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Corrosion Science 77 (2013) 265–272

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Corrosion Science
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Inhibition properties of self-assembled corrosion inhibitor talloil
diethylenetriamine imidazoline for mild steel corrosion
in chloride solution saturated with carbon dioxide
- Nešić b, Vesna Mišković-Stanković a,⇑
Ivana Jevremović a, Marc Singer b, Srdan
University of Belgrade, Faculty of Technology and Metallurgy, Karnegijeva 4, 11000 Belgrade, Serbia
Institute for Corrosion and Multiphase Technology, Ohio University, 342 West State St. Athens, OH 45701, USA

a r t i c l e i n f o a b s t r a c t

Article history: The inhibition effect of talloil diethylenetriamine imidazoline (TOFA/DETA imidazoline) on corrosion of
Received 30 April 2013 mild steel in chloride solutions saturated with CO2 was investigated by weight loss measurements
Accepted 17 August 2013 (WL) and atomic force microscopy (AFM). Adsorption mechanism and kinetics of self-assembled
Available online 27 August 2013
(TOFA/DETA imidazoline) monolayers formation on gold were studied using the quartz crystal microbal-
ance measurements (QCM). WL and AFM results demonstrated that TOFA/DETA imidazoline can effec-
Keywords: tively protect mild steel surface from corrosion. QCM measurements shown that the adsorption of
A. Mild steel
TOFA/DETA imidazoline onto gold follows Langmuir adsorption isotherm and further investigation of
B. Weight loss
the adsorption process will be carried out on a corroding metal surface.
C. Acid corrosion Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction Imidazolines are organic compounds with two nitrogen atoms in
the heterocycle and three different sites suitable for bonding: pyr-
Corrosion caused by CO2 in aqueous phase is a major problem idine like nitrogen atom N3, pyrrole like nitrogen atom N1 and aro-
encountered in multiphase carbon steel pipelines used in oil and matic ring [12]. Some modeling studies propose that the head and
gas industry. One of the most practical methods for protection of the pendent groups enable bonding of the inhibitor molecules to
carbon steels exposed to CO2, mainly due to economical reasons, the metal surface while the hydrocarbon tail limits the transport
is the addition of organic substances as corrosion inhibitors [1– of corrosive species from solution to the metal surface and forms
3]. Investigation of corrosion inhibition mechanism by adsorption the monolayer. These corrosion inhibitors are believed to form
of inhibitor on the metal surface is very difficult due to the com- self-assembled films that protect the steel surface against corro-
plexity of chemical structure of inhibitors used in petroleum indus- sion [13]. Self-assembled systems are ordered molecular assem-
try. Low concentrations at which these inhibitors are used as well blies formed spontaneously by the adsorption of an active
as the diversity of the environment surrounding the inhibitor un- surfactant molecules on a solid surface, as a result of competing
der real conditions make this research especially challenging [4]. intermolecular, molecules–substrate and molecules–solvent inter-
Corrosion inhibitors contain different functional groups, usually actions [14,15]. Because of the surfactant properties of corrosion
polar head (fatty acids, amines, imidazolines, oxyalkylated amines, inhibitors, when dissolved in a solution the free energy of the sys-
oxygen, sulfur or phosphorus containing species, quaternary tem increases resulting in the corrosion molecules concentrating at
amines) and long hydrocarbon chain (typically C14–C18), which the solution interface. The surfactant molecules accumulate favor-
promote the binding of inhibitor molecules to the metal surface ably at the solution/air interface and consequently the surface ten-
[5–10]. Imidazolines are widely used in oil industry as corrosion sion decreases. The surface tension continues to fall as the
inhibitors, but their properties and behavior are not yet fully surfactant concentration increases until the critical micelle con-
known. They are classified as cationic surfactants with positive centration (CMC) is attained. The shape and size of a micelle is de-
charge on imidazoline nucleus, which is unaffected by change in fined by surfactant nature, concentration, temperature, pH, and
pH of the environment, thereby easily adsorbed on the metal sur- ionic strength of the solution. The full coverage of the exposed me-
face, which is negatively charged [11]. It is of great importance to tal surface by protective inhibitor film is usually established after
determine which functional groups bind to the metal in order to saturation of the surfactant molecules in the medium [16]. Some
gain better understanding of the corrosion inhibition mechanism. studies have shown that inhibitor solutions at concentrations
greater than the CMC are more effective in corrosion protection
⇑ Corresponding author. Tel.: +381 11 3303 737; fax: +381 11 3370 387. than solutions at concentrations below the CMC [17].
E-mail address: (V. Mišković-Stanković).

0010-938X/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.

were sequentially grinded using 240.001 0. The purpose of investigating steel surface. adsorption.1 mg). scan points 256 and scan lines 256 using an MFP-3d Stand- surface. very suitable for the investigation of the influence of tem. In this research the measurement of the surface tension of Molecular structure of TOFA/DETA imidazoline. AT-cut Stanford Research Systems) coated with ner for 1–2 min and then air-dried. ygenated sodium bicarbonate solution.8 Corrosion inhibitor TOFA/DETA imidazoline Inhibitor concentration (ppmv) 0. as shown in 3 wt.1 mm y1 when 70 ppmv of TOFA/DETA imidazoline was added by a thermocouple.007 0. USA in a glass cell shown in Fig. 1.% NaCl procedure may not be completely adequate since knowledge purged with CO2 gas at 20 °C.002 0. Jevremović et al. pH 5. QCM measurements 2. 1. the topography of the surface was to characterize the surface faces are needed in order to successfully study corrosion inhibitor roughness on a microscale. After 24 h the samples ings. ing Alone AFM instrument.% aqueous NaCl solution saturated The analysis of the morphology of the mild steel surface was with CO2 using the quartz crystal microbalance (QCM). as a model angle 0.2 mm y1 by adding 70 ppmv the pH of the test solution was adjusted to 5 by addition of a deox- of TOFA/DETA imidazoline at 70 °C. 320. sence of TOFA/DETA imidazoline was studied by atomic force microscopy (AFM). When the required temperature was achieved.1. using drop count method. gold coated quartz crystals were cleaned for 2 min in Table 1 Chemical composition of X65 mild steel (mass% balance is Fe). high-resolution mass sensing tech- Weight-loss specimens.36 0. at a scan rate 0.009 <0. Images of the perature and inhibitor concentration on the adsorption process. The device included a 7. a crystal oscillator. wiped TOFA/DETA imidazoline for mild steel corrosion in 3 wt. The X65 carbon steel composition is shown in Table 1. dm3 1. Corrosion measurements All the adsorption measurements were carried out using a quartz crystal microbalance (QCM) Stanford Research Systems. 2. circular disks with an exposed area of nique. Asylum Research. then air dried and accurately weighed on an analytic NaCl solution saturated with CO2 using weight loss measurements. The test matrix for this experimental while the surface morphology of mild steel in the presence and ab.% NaCl to use.7 Hz. Molecular structure of TOFA/DETA imidazoline. The frequency of the used crystals was 5 MHz.% NaCl Solution volume. 2.5 cm2. Further at 20 °C. However well defined and characterized model sur. In order to determine the critical micelle concentra- investigation was conducted by fitting the experimental data with tion (CMC) for corrosion inhibitor TOFA/DETA imidazoline the sur- analytical equations in order to define the adsorption isotherm and face tension was measured in the concentration range from to calculate the thermodynamic parameters. Determination of CMC value using the drop count method and evaluate the corrosion inhibitor adsorption on steel surface as well. (2. 70 imidazoline for mild steel corrosion in 3 wt% NaCl saturated with pH 5 CO2 was investigated at 20 °C and 70 °C. The carbon steel API X65 was used in all corrosion measure. Test solution 3 wt. and at 70 °C.017 P Pb S Sb Si Sn Ta Ti V Zr Cu 0. carried out using atomic force microscopy (AFM). scan ophiles centres makes gold coated quartz crystals. Model QCM200. The quartz crys- ments.001 0. and at 70 °C without and with gained from gold surface may not be directly applicable to mild 70 ppmv of TOFA/DETA imidazoline. 10 ppmv to 90 ppmv. balance (accuracy ± 0.266 I.3.% aqueous NaCl solution in the absence and presence of vari- Fig. Al As B C Ca Co Cr Mn Mo Ni Nb 0. Surface morphology tigation of mechanism and kinetics of TOFA/DETA imidazoline adsorption onto gold from 3 wt.2.54 cm diameter.001 <0. Prior weighed before immersion of the specimen into the 3 wt.131 . is comprised of long-chain nitrogenous surfactant and its ous concentrations of TOFA/DETA imidazoline was performed properties at the solution/air interface were investigated by mea. electrochemical impedance spectroscopy (EIS) and potentiodynamic sweep measurements (PDS).26 0. 70 In our previous study [10] the inhibition effect of TOFA/DETA Liquid temperature (°C) 20.008 0. The cleaned samples were sputtered gold.032 0.% aqueous with a cloth. contact mode under ambient conditions.007 <0. a crystal holder and quartz crystals silicon carbide paper. The cell temperature was followed 0.047 <0. Materials and methods 2. To further confirm these find. based upon the piezoelectric effect.009 0. pH 5. Low reac. This specimens were recorded after 24 h exposure time in 3 wt. tal microbalance is a simple. / Corrosion Science 77 (2013) 265–272 Table 2 Experimental conditions for corrosion measurements. and from 4 mm y1 for bare steel to 0. Inc.001 0.16 0. All the experiments were carried out suring the surface tension using the drop count method. 2. Parameters Conditions Total pressure (bar) 1 Fig. 400 and 600 grit controller. The results shown purged with CO2 gas without and with 70 ppmv of TOFA/DETA imi- that the corrosion rate decreased from 1 mm y1 for bare steel to dazoline at 20 °C.16 0.009 0. operated in the tivity and surface roughness of gold and its affinity towards nucle. The focus of our current research was the inves.001 0.13 0. without and with Measurements Weight loss 70 ppmv of TOFA/DETA imidazoline using linear polarization resis- tance (LPR).14 1. series is shown in Table 2. rinsed with isopropanol in an ultrasonic clea. in the present study we investigated the inhibition effect of were then taken out of the solution rinsed with isopropanol. Further advances in this research would be greatly supported by the obtained results that would be used to check 2.4.

60. Surface morphology start of each experiment and during the whole test in order to maintain positive CO2 partial pressure. respectively [18].% NaCl. g.% NaCl 3. which causes the decrease of the steel surface rough- ness and effectively protects mild steel from corrosion.% aqueous NaCl solution. was calcu. Using the obtained results from weight loss measurements. immersion period. 25 °C.3.4 3 wt. m0corr where vcorr and vocorr are the mild steel corrosion rates with and piranha solution (1:3 by volume of 30% H2O2 and H2SO4) rinsed without TOFA/DETA imidazoline.53 – 3 wt. was determined by the following equation: mcorr  m0corr g¼  100% ð3Þ Fig.2. The AFM Table 3 Experimental conditions for QCM measurements. In the presence of 70 ppmv TOFA/DETA imi- dazoline the RMS value at 20 °C was 42 nm. I. Solution DW (mg) vcorr (mm y1) g (%) 3 wt. 2. In the absence of inhibitor (Fig. The purity of the crystals after cleaning procedure was the addition of TOFA/DETA imidazoline corrosion inhibitor at both ensured by checking their frequency response in air. q is the density of iron and t is the exposure time. 165 nm. 25. the mild steel 3.0045 0. Jevremović et al. Results and discussions surface was strongly damaged due to metal dissolution in the cor- rosive solution. derived from AFM height where W1 and W2 are the average weight of the specimens before profile images (Fig.0780 4. at 20 °C and 70 °C. The weight loss method was used in order to The graphs of the average height of the entire image (the aver- estimate average corrosion rates. Nevertheless.% NaCl.% NaCl solutions without for this experimental series is shown in Table 3. Data was collected over inhibitor concentration range from microscopy (AFM) in order to characterize the mild steel surface 50 ppmv to 90 ppmv. Fig. The solutions were deoxygenated by purging CO2 gas for 1 h before the 3. Further investigation of the corrosion resistance ability of TOFA/ formed at the following temperatures: 20 °C. for the bare steel after exposure at 20 °C was and after exposure. 70. 35 count method for different concentrations of corrosion inhibitor pH 5 in 3 wt. the appearance of steel surface was 3. WL ¼ W1  W2 ð1Þ The value of surface roughness (RMS). 30.0182 1. The high inhibition efficiency can be explained by by a thermocouple. results are in a good agreement with the weight loss results and electrochemical measurements [10].017 98.3 where S is the surface area of specimens. suggesting that TOFA/DETA imidazoline forms an inhibi- by weight loss measurements at 20 °C and 70 °C after a 24 h tive film on the mild steel surface. The CMC Measurements QCM concentration corresponds to the point where the surfactant first .26 94. while the inhibition efficiency was calculated to be was stirred (150 rpm) and the cell temperature was monitored around 95%. 70 °C 0. It can be seen with distilled water and isopropanol. 20 °C 0. 5. The results obtained from the weight loss measurements are in dium bicarbonate solution.% NaCl solution without and with inhibitor TOFA/DETA imidazoline. The three-dimensional AFM images of mild steel the QCM holder was immersed into the solution. 4 were given to show general height variation.1. Once the desired conditions were achieved microstructure. age of 512 line profiles across the scanned area) of the mild steel lated as follows: surface in the presence and absence of TOFA/DETA imidazoline shown in Fig. the inhibition efficiency. The corrosion rate. When temperature was achieved. the pH of the adsorption of TOFA/DETA imidazoline on the mild steel surface. vcorr. 30 °C and DETA imidazoline films was carried out by means of atomic force 35 °C. cinh = 70 ppmv.% NaCl saturated with CO2 are shown in Fig. Experimental setup for QCM measurements. cinh = 70 ppmv. The test matrix surface after 24 h of exposure to 3 wt. accordance with the previously obtained results from the electro- Corrosion inhibitor TOFA/DETA imidazoline was adsorbed onto chemical measurements [10]. The solution temperatures. 90 The values of the surface tension determined using the drop Liquid temperature (°C) 20. Determination of CMC value using drop count method Corrosion inhibitor TOFA/DETA imidazoline Inhibitor concentration (ppmv) 50.% NaCl. gold coated quartz crystals from 3 wt. 3a and b). respectively.% NaCl solution was studied peared. 4). and with TOFA/DETA imidazoline at 20 °C and at 70 °C are shown in Fig. while the RMS value after exposure at 70 °C significantly lated using the equation: increased to 712 nm. and dried under a stream of from Table 4 that the corrosion rate significantly decreased after nitrogen. the test solution was adjusted to 5 by adding a deoxygenated so.0003 0. 3.05 – 3 wt. Parameters Conditions Total pressure (bar) 1 Test solution 3 wt. Weight loss measurements significantly different after the introduction of TOFA/DETA imidaz- oline to the corrosive solution. while at 70 °C RMS va- WL mcorr ¼ ð2Þ lue was 97 nm due to the formation of inhibitor film on the mild t qS steel surface. 3c and d clearly shows that the The effect of addition of the TOFA/DETA imidazoline inhibitor corrosion rate of mild steel decreased and very flat surface ap- on the corrosion of mild steel in 3 wt. The weight loss (WL) was calcu. / Corrosion Science 77 (2013) 265–272 267 Table 4 Weight loss measurements after 24 h for mild steel in 3 wt. 70 °C 0. 20 °C 0.% NaCl. Experiments were per.

submerged into the water phase [22]. formation: vation time. 6) indicate that the Langmuir at 20 °C. as shown following. ka and of quartz. According to the literature monolayers insoluble in water are only formed when alkyl chain consists of at least The QCM is a mass sensing device which is used to measure the 12 carbon atoms [21].268 I. change depends on the surface coverage. The equilibrium was tension remains relatively constant. Inte- direct result of the formation of inhibitor film. shows the lowest surface tension. pH 5. Since the frequency is a linear relationship [19]. While. respectively. (c) containing 70 ppmv TOFA/DETA imidazoline at 20 °C and (d) containing 70 ppmv TOFA/DETA imidazoline at 70 °C. since the Langmuir imidazoline was added in the 3 wt. 5 the increase in inhibitor concentration imidazoline introduction.% NaCl solution in a very dilute isotherm is based on the assumption that the adsorption process solution state (from 50 ppmv to 90 ppmv which is close to CMC va. is limited to one monolayer. which tion of the inhibitor monolayer [23. The frequency decreased and the exponential mass hðtÞ ¼ K 0 ½1  expðktÞ ð6Þ increase indicated the presence of an adsorbed inhibitor layer at . and after this point the surface the gold coated quartz crystal surface. was recorded after TOFA/DETA was fitted to the Langmuir adsorption model. the rate of surface reaction can be described using the fol- Df ¼  pffiffiffiffiffiffiffiffiffiffiffi Dm ð4Þ lq qq lowing equation: where Df is the frequency change. / Corrosion Science 77 (2013) 265–272 Fig. Dm is the change in mass per dh ¼ ka ð1  hÞc  kd h ð5Þ unit area. which is defined as the ratio between occupied sites and available sites on the sur- 2f02 face. lue of 65 ppmv in 3 wt. the fre. The correlation between mass and frequency is dependence of frequency change is a direct result of the forma- described by the Sauerbrey equation. formed horizontal plateau corresponds to the formation of 3. These n-alkyl chains are oriented perpen- frequency shift caused by a small mass changes in the region near dicular to the water surface while the hydrophilic head group is the QCM solution interface. Obtained experimental data lation frequency of the QCM. consequently the obtained time lue of 65 ppmv). achieved within a certain period of time following the TOFA/DETA As it can be seen in Fig. TOFA/DETA imidazoline has been found to have CMC va. (b) without inhibitor at 70 °C. The use of QCM for determination of thermodynamic parameters a monolayer of TOFA/DETA imidazoline on a gold coated quartz of adsorption crystal surface. adsorption isotherm can be used to describe the kinetics of pends on the pH of the solution and its ionic strength. It should be taken into account that CMC value de.% NaCl saturated with CO2 (a) without inhibitor at 20 °C. As expected. [20]. adsorption process over a concentration range close to CMC value. c is inhibitor concentration. gration of this equation gives the time course of the monolayer quency change was found to decrease continuously with the obser. The TOFA/DETA imidazoline molecule leads to the accumulation of inhibitor at the solution/air interface contains two nitrogen atoms and p-electrons which enable the mol- and consequently decreases the value of the surface tension of the ecule to be adsorbed on the metal surface via lone-pair electrons solution.% aqueous NaCl solution saturated with CO2 Obtained experimental data (Fig. 3. The obtained time dependence of frequency change is a kd are the adsorption and desorption constants. lq is the shear modulus of quartz and qq is the density where h is the surface coverage. In this research the change of the oscil.24]. Atomic force microscopy three-dimensional images of mild steel surface in 3 wt.4. Jevremović et al. f0 is the resonant frequency of the fundamental mode of dt the crystal. Df.

% NaCl saturated with CO2. 4. where k and K0 are the constants presented by the following equa. of QCM for different concentration of TOFA/DETA imidazoline in 3 wt. c. 20 °C (solid Fig. in 3 wt. 6. Df for dif- tions. Jevremović et al. 6 the time dependences of frequency change. Graphs of the average height of the entire image profiles of mild steel surface in 3 wt. 5. respectively: ferent concentrations of TOFA/DETA imidazoline at 20 °C are shown in solid lines while the dashed line represents the k ¼ ka c þ kd ð7Þ c K0 ¼   ð8Þ c þ kkda Fig. dashed line –fitting for the concentration of 60 ppmv of TOFA/ ln c. pH 5. . (b) without inhibitor at 70 °C. Dependence of surface tension. lines – experimental. In Fig. on TOFA/DETA imidazoline concentration. DETA imidazoline).% NaCl saturated with CO2 (a) without inhibitor at 20 °C. Df.% NaCl saturated with CO2 on a gold surface. I. Frequency change. (c) containing 70 ppmv TOFA/DETA imidazoline at 20 °C and (d) containing 70 ppmv TOFA/DETA imidazoline at 70 °C. / Corrosion Science 77 (2013) 265–272 269 Fig.

% NaCl solution saturated with CO2 onto gold constant. the adsorption of the inhibitor increases assembly formation have been calculated according to Eq. ka and kd. experimental data to the Langmuir adsorption model Eq. where R is the gas constant and T is the absolute temperature.63 26. the time required tion.270 I. 6 the required exposure time to reach the steady state at each concentration decreased with increasing DG0ads ¼ RT ln K eq ð10Þ TOFA/DETA imidazoline concentration.47 35 308 28. 7.70 7.69 20 293 3.98 10. increases of DG0ads around 20 kJ mol1 or less negative indicate physisorp- with increase in temperature. In the present 50 ppmv of TOFA/DETA imidazoline in 3 wt. As it can be seen in Fig. Jevremović et al. Standard adsorption equilibrium constant. higher than 40 kJ mol1 but lower than 20 kJ mol1.41 23. 8 time required to reach equilibrium cates that adsorption of TOFA/DETA imidazoline is governed by state decreased at higher temperatures.29].% NaCl solution satu.58 23. in the presence of TOFA/DETA imidazoline in 3 wt. and standard Gibbs free energy of adsorption. 7 the values of the higher temperature accelerates the adsorption of TOFA/DETA the adsorption and desorption constants. which is due to the charge sharing between tion isotherms for experimental data recorded after the injection of inhibitor molecules and the metal surface [25–27]. both chemisorption and physisorption mechanism. DG0ads . The values equilibrium process while the adsorption constant. suggesting that From the slopes and intercepts of the lines in Fig. equilibrium constant increases with temperature.67 25 298 14. work. seen as chemisorption. 8.% NaCl solution sat. The tempera- cate that the adsorption of TOFA/DETA imidazoline from 3 wt. using the van’t Hoff equation [28.63 4. while the values around 40 kJ mol1 or more negative are in Fig. (7) and with the temperature increase.28 .% ture dependence of Keq allows the calculation of the standard en- NaCl solution saturated with CO2 onto gold coated quartz crystal thalpy of adsorption. where we compare the obtained fits of Langmuir adsorp. 8. electrostatic interactions between the inhibitor and the metal to reach saturation is shorter. Cal- dence of k for TOFA/DETA imidazoline in 3 wt. The fit obtained at this concentration determined from the following equations. is an endothermic reaction since an increase in temperature drives an endothermic reaction forward to products. ka.% NaCl solution at a concentration of 50 ppmv at different temperatures. and consequently.476 19. were of TOFA/DETA imidazoline. The obtained results indi.98 30 303 13. / Corrosion Science 77 (2013) 265–272 Fig.94 35 29. 7.75 30 10. ka and desorption constant. the calculated values of DG0ads at different temperatures are rated with CO2 at different temperatures. Fig. (6) is It can be noticed from Table 6 that the standard adsorption shown in Fig. corded in Table 6 indicate that the adsorption of TOFA/DETA imi- It can be observed from Table 5 the positive value of desorption dazoline from 3 wt. for TOFA/DETA imidazoline adsorption indicates the coated quartz crystals is spontaneous and favorable.81 4. The fitting procedure was repeated K eq ¼ ð9Þ kd for all the temperatures from 20 °C to 35 °C (data not shown). for monolayer imidazoline. temperature. The concentration dependence of k for TOFA/DETA imidazoline in 3 wt. culated values of Keq and DG0ads determined from collected data are urated with CO2 at different temperatures obtained by fitting the summarized in Table 6. at different temperatures. The concentration depen. corresponding curve obtained by fitting the experimental data to Langmuir adsorption isotherm for the concentration of 60 ppmv Keq. The required time to DH0ads ln K eq ¼  þ constant ð11Þ reach saturation decreased from approximately 100 min at 293 K RT to 30 min at 308 K. The negative values of DG0ads as re- presented in Table 5. Table 5 Table 6 The values of adsorption constant. This is evident as shown by the lines surface.% NaCl solution saturated with CO2. which indi- As it can be seen in Fig. Df. kd.86 25 6. therefore. The frequency change. kd at different The values of Keq and DG0ads determined from collected data as a function of temperatures. t (°C) ka (M1 s1) kd (104 s1) t (°C) T (K) Keq (103 M1) DG0ads (kJ mol1) 20 1. respectively: shows that the proposed model is in a good accordance with the ka recorded experimental data. DH0ads .

the enthalpy of adsorption. further confirmed by AFM measurements. line in the temperature range from 293 K to 308 K. Additional experiments will be carried by means of QCM on obtained results are not of direct relevance for imidazoline adsorp- iron coated quartz crystals in order to investigate the mechanism tion on steel. DETA imidazoline adsorbs on the oppositely charged hydrophilic philic gold surface through the electrostatic interactions. 9.07 kJ mol1. followed by desorption of small molecules or non-corroding substrate provides useful information for the fur. TOFA/ tive charges. Although it is com. Additional experiments will be carried by means of of adsorption of TOFA/DETA imidazoline on a real corroding metal QCM on iron coated quartz crystals in order to investigate the surface. 9. therefore adsorb on the oppositely charged hydro. mechanism of adsorption of TOFA/DETA imidazoline on a real cor- ing surfaces never reaches the real equilibrium and tends to an roding metal surface. where we have shown that time required to reach equilib- rium state decreased at higher temperatures. The adsorption study on inert.44 kJ mol1. between the followed by desorption of small molecules or ions such as H2O TOFA/DETA imidazoline head group or pendent group and the gold and Cl from the gold surface. / Corrosion Science 77 (2013) 265–272 271 Fig. while TOFA/DETA imidazoline decreases the steel surface roughness and 0 DHads was 93. gold surface through the electrostatic interactions. since it is reported that the inhibitor adsorption on corrod. QCM measurements confirmed that TOFA/ monly believed that simple adsorption on bare surface is generally DETA imidazoline forms self-assembled monolayers on gold coated an exothermic process which is followed by a decrease in entropy quartz crystals. The entropy of molecular structure of TOFA/DETA imidazoline (Fig. 10. which is in agreement with the results presented 4. Gold surface was employed as well defined and [31. The obtained values of DG0ads at different tem- in the bulk.389 kJ mol1K1. that is in agreement with the value of effectively protects mild steel from corrosion due to the formation DH0ads . Van’t Hoff plot for adsorption of TOFA/DETA imidazoline in the temperature Fig. of the inhibitor film.32]. DG0ads . According to chemisorption and physisorption mechanism. the face. Conclusions in Fig. as the tempera- ture increase. DETA imidazoline adsorption. I.% ven temperature.389 kJ mol1 K1. adsorption steady state. Temperature dependence of DG0ads for adsorption of TOFA/DETA imidazo- range from 293 K to 308 K.% NaCl solution significantly reduced the corro- The temperature dependence of DG0ads for adsorption of TOFA/ sion rate. The inhibition effects of talloil diethylenetriamine imidazoline In order to determine standard entropy of adsorption at any gi- (TOFA/DETA imidazoline) on the corrosion of mild steel in 3 wt. tion on gold coated quartz crystal is only for process modeling. may be written from the definition of the Gibbs loss measurements and AFM surface analysis. the change in standard Gibbs free energy of NaCl solution saturated with CO2 was further studied using weight adsorption. 1) N1 atom adsorption. obtained using the van’t Hoff equation. The inhibition effect of TOFA/DETA imidazoline was is shown in Fig. It is shown that adsorption kinetics oline on a gold surface is endothermic and driven by entropy gain of this self-assembled system can be described by Langmuir associated with the breaking down of inhibitor structures formed adsorption isotherm. The value of DH0ads was calculated to be 94. while the inhibition efficiency was calculated to be DETA imidazoline in the temperature range from 293 K to 308 K around 95%. while in imidazoline ring and N atom in the pendent group carry nega. Weight loss mea- surements shown that the addition of the TOFA/DETA imidazoline DG0ads ¼ DH0ads  T DS0ads ð12Þ inhibitor to 3 wt. ions such as H2O and Cl. the gold surface is spontaneous and favorable governed by both chemical properties of inhibitor compound [33]. was around 94 kJ mol1. meaning that the equilibrium constant increases. where. surface active sites. Van’t Hoff plot for adsorption of TOFA/DETA imidazoline in the temperature range from 293 K to 308 K is shown in Fig. . the obtained positive value of DH0ads and the positive value characterized model surface in order to successfully study TOFA/ of DS0ads indicate that the adsorption process of TOFA/DETA imidaz. DH0ads . 10. was calculated to be 0. Jevremović et al. where it was shown that The value of DS0ads was calculated to be 0. whereas the potential and the surface the negative slope indicates an endothermic adsorption process. The study by QCM of imidazoline adsorp- ther investigation of adsorption process on a corroding metal sur. while the focus of free energy as [30]: our research was the investigation of mechanism and kinetics of TOFA/DETA imidazoline adsorption onto gold. DS0ads . 8. It has been proven that local electron densities or peratures indicate that adsorption of TOFA/DETA imidazoline on charges are important in many chemical reactions and physico. changes with time should be also considered [34].

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