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Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

2 Ascorbic acid as corrosion inhibitor for Q235 mild steel in acidic

3 environments
4 Q1 Maduabuchi A. Chidiebere a,b, Emeka E. Oguzie b, Li Liu a, Ying Li a,*, Fuhui Wang a
5 a
Institute of Metal Research, Chinese Academy of Sciences, 62 Wencui Road, Shenyang 110016, China
6 b
Electrochemistry and Materials Science Research Laboratory, Department of Chemistry, Federal University of Technology, PMB 1526 Owerri, Nigeria

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 ascorbic acid (AA) on mild steel corrosion in 1 M HCl and 0.5 M H2SO4 was
Received 11 September 2014 estimated using electrochemical and surface probe techniques. Potentiodynamic polarization results
Received in revised form 29 October 2014 showed AA to be a mixed type inhibitor in both acidic environments, whereas the impedance results
Accepted 2 November 2014
revealed adsorption of the AA species on the steel surface. Atomic force microscopy (AFM) and scanning
Available online xxx
electron microscopy (SEM) studies revealed the formation of a protective lm adsorbed AA on the steel
surface. Quantum chemical calculations were used to conrm the ability of AA to adsorb on a steel
Keywords:
surface.
Mild steel
2014 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering
Corrosion
Inhibition Chemistry.
Adsorption
Impedance
Polarization

7
8 Introduction found in biochemical compounds used as drugs [13]. Accordingly, a 28
number of such compounds have been investigated for corrosion 29
9 Q2 Introduction of corrosion inhibitors into acid solutions com- inhibition efcacy. Sekine et al. [14] studied the inhibitive effect of 30
10 monly employed in cleaning iron and steel surfaces is a useful ascorbic acid (AA) and folic acid (FA) on mild steel corrosion in 0.3% 31
11 method to protect such surfaces from corrosion damage [1,2]. As NaCl environment and observed chemisorption of both com- 32
12 regards to the adsorption strength of these inhibitors, certain pounds as the primary mechanism of corrosion inhibition. 33
13 factors are of signicant consideration, including: the nature and Efciency of inhibition diminished at high concentrations due to 34
14 surface charge of the metal, composition of the electrolyte and the formation of soluble iron (II) chelates. AA has as well been 35
15 structure of the inhibitor [3,4]. Most effective inhibitors are organic investigated as corrosion inhibitor in diverse systems, with varying 36
16 compounds that contain heteroatoms like nitrogen, sulfur and results [1519]. 37
17 oxygen in a conjugated system [510]. The inhibitors function at Currently, the complex processes involved with metal 38
18 the interface between the metal and aqueous corrosive solution, inhibitor interactions have been studied at the molecular level 39
19 their interaction with the metal surface through adsorption, results by means of computer simulations of suitable models and the 40
20 in a modication in the mechanism of the electrochemical process. density functional theory (DFT) has been used widely in this 41
21 Polar functional groups are regarded as the reaction center that regard [2024]. Accordingly, DFT-based quantum chemical 42
22 stabilizes the adsorption process [11], this helps to reduce the calculations and molecular dynamics simulations have also been 43
23 corrosion susceptibility of the metal surface [9,12]. As a result, the used to show the adsorption of inhibitor molecules on metal 44
24 service life of the metal is prolonged. surfaces at a molecular level and to compute the corresponding 45
25 The requisite electronic structural characteristics of corrosion interaction energies, which is related to the adsorption strength 46
26 inhibitors such as substituted heterocycles like imidazoles, [2527]. 47
27 pyridines, furans, thiophenes, isoxazoles, and others are readily The aim of this research is to further understudy the corrosion 48
inhibition and adsorption behavior of AA (Fig. 1), using combined 49
experimental and computational techniques to investigate the 50
* Corresponding author. Tel.: +86 24 2399 2875; fax: +86 24 2392 5323. corrosion inhibition performance on Q235 mild steel in 1 M HCl 51
E-mail address: liying@imr.ac.cn (Y. Li). and 0.5 M H2SO4 environment. 52

http://dx.doi.org/10.1016/j.jiec.2014.11.029
1226-086X/ 2014 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering Chemistry.

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15 mm  15 mm  2 mm were dipped in the different test 96

solutions for 24 h in the absence and presence of 0.01 M AA at 97
30  1 8C. After removal, the specimens were cleaned with double 98
distilled water, dried in warm air and submitted for AFM observation. 99

Computational details 100

The quantum chemical computations were performed using the 101

DFT electronic structure programs and DMol3 as contained in the 102
Materials Studio 4.0 software. 103

Results and discussion 104

Fig. 1. Structure of ascorbic acid. Potentiodynamic polarization measurements 105

53 Experimental Polarization experiments were performed to investigate the 106

effect of AA on the anodic and cathodic half reactions of the 107
54 Materials preparation corrosion process. 108
Parts a and b of Fig. 2 show typical potentiodynamic 109
55 Mild steel specimens with chemical composition (wt.%) C 0.30, polarization curves for mild steel specimens in 1 M HCl and 110
56 Si 0.30, Mn 0.30, P 0.045, S 0.050, Cr 0.064, Cu 0.040, Ti 0.5 M H2SO4, in the absence and presence of AA. Accordingly, 111
57 0.04 and the balance Fe were used for the experiments. The metal the mild steel specimen in both acidic environments displayed 112
58 specimens were wet-polished with silicon carbide abrasive paper active dissolution with no distinctive transition to passivation 113
59 (from grade #150to #1000), degreased in acetone and dried in warm within the studied potential range. 114
60 air. All chemicals and reagents used in preparation of the test The corresponding electrochemical parameters, namely, corro- 115
61 solutions were of analytical grade (Sinopharm Chemical Reagent Co., sion potential (Ecorr), corrosion current density (Icorr), anodic (ba) 116
62 Ltd.). The aggressive solutions were prepared using HCl and H2SO4 and cathodic (bc) Tafel slopes were obtained and their values are 117
63 (Sinopharm Chemical Reagent Co., Ltd.) and double distilled water. shown in Table 1. The data presented therein shows that in both 118
64 For experiments containing ascorbic acid, the salt was added to
65 blank solutions to obtain concentrations of 0.0005 M, 0.002 M, 1 M HCl (a)
-0.2
66 0.005 M and 0.01 M, respectively. For all synergistic experiments 0.0005 M AA
67 0.0005 M KI was used. All experiments were carried out at 30  1 8C. 0.002 M AA
0.005 M AA
-0.3
0.01 M AA
68 Electrochemical measurements
-0.4
E vs SCE (V)

69 Electrochemical tests were conducted using a PAR-2273

70 Advanced Electrochemical System workstation, with a conventional
-0.5
71 three-electrode corrosion cell. A platinum sheet and a saturated
72 calomel electrode (SCE) were used as a counter and reference
73 electrodes, respectively. A metal specimen xed in epoxy resin with -0.6

74 a surface area of 1 cm2 exposed to the test solution, served as the

75 working electrode. Electrochemical measurements were carried out -0.7
76 in aerated and unstirred solutions at the end of 1800 s of immersion,
77 which allowed the OCP values to attain steady state. Temperature -0.8
78 was xed at 30  1 8C. Impedance measurements were performed at -7 -6 -5 -4 -3 -2 -1
79 corrosion potentials (Ecorr) over a frequency range of 100 kHz0.1 Hz, A/cm
2

80 with a signal amplitude perturbation of 5 mV. Potentiodynamic

0.5 M H2SO4
81 polarization studies were conducted in the potential range 250 mV -0.2 (b)
0.0005 M AA
82 versus corrosion potential at a scan rate of 0.333 mV/s [28].
0.002 M AA
-0.3 0.005 M AA
83 Scanning electron microscopy 0.01 M AA

-0.4
84 The XL-30FEG scanning electron microscope was used to study
E vs SCE (V)

85 the surface morphology of the metal specimens after immersion in

86 1 M HCl and 0.5 M H2SO4 in the absence and presence of AA. Mild -0.5
87 steel specimens of dimensions 3 cm  3 cm  0.25 cm were
88 prepared as mentioned earlier (Section Materials preparation) -0.6
89 and immersed for 24 h in both acidic solutions, in the absence and
90 presence of 0.01 M AA. The specimens were then removed and
-0.7
91 cleaned with double distilled water, dried in warm air and
92 submitted for SEM analysis.
-0.8
-6 -5 -4 -3 -2 -1
93 Atomic force microscopy 2
A/cm

94 AFM observation was carried out with the aid of Picoplus 2500 Fig. 2. Potentiodynamic polarization curves of mild steel in: (a) 1 M HCl and (b)
95 surface probe microscope. Mild steel specimens with dimensions 0.5 M H2SO4 solution in the absence and presence of AA, respectively.

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Table 1
Polarization parameters for mild steel in 1 M HCl and 0.5 M H2SO4 in the absence and presence of AA.

System Ecorr (mV vs SCE) Icorr (mA cm2) ba (mV dec1) bc (mV dec1) IE (%)

0.5 M H2SO4 465.2 1340 135.68 204.2

0.0005 M AA 458.3 715.6 121.2 192.4 46.6
0.002 M AA 461.2 654.9 111.5 184.3 51.1
0.005 M AA 469.9 473.7 103.7 179.4 64.6
0.01 M AA 475 341.8 99.8 172.6 74.5

1 M HCl 466.4 183 124.6 162.7 42.4

0.0005 M AA 456.2 105.4 110.4 122.6 63.4
0.002 M AA 458.1 66.9 102.3 114.8 75.3
0.005 M AA 462.7 45.2 94 121.8 82.9
0.01 M AA 468.5 31.2 91.6 119.5

119 acidic environments the Icorr decreases in the presence of the ascribed to the charge transfer resistance (Rct). In a 0.5 M H2SO4 167
120 inhibitor compared to the uninhibited solution and the trend environment, the Nyquist plots in the presence of AA are 168
121 continues with an increase in the concentration of the inhibitor. In characterized by a capacitive loop at high-to-medium frequency 169
122 1 M HCl environment, it was obvious, that the anodic curves show and an inductive arc at low frequency. The capacitive loop at high 170
123 that the inhibition mechanism of AA depends upon the electrode frequencies shows the phenomenon associated with the double 171
124 potential; for instance, at overvoltages higher than circa 300 mV electric layer. This arises from the time constant of the electrical 172
125 SCE, the presence of AA does not change the currentpotential double layer and charge transfer in the corrosion process [30]. It is 173
126 characteristics, when compared to the uninhibited solution, which evident in Figs. 3 and 4 that addition of AA to both acidic 174
127 means that the observed steel dissolution dominates the AA environments result in an increase in the charge transfer 175
128 adsorption. Therefore, in the area of Ecorr and below 300 mV SCE resistance, the Bode phase angle and the impedance of the 176
129 to more cathodic potentials, the increase of AA concentration leads interface, which all points toward inhibition of the corrosion 177
130 to a decrease in the current density. In this case, the adsorption rate process. 178
131 of AA remains higher than its desorption rate. In 0.5 M H2SO4 the In order to determine the numerical values of the various 179
132 polarization curves in presence of AA (Fig. 2b) show evidence of impedance parameters presented in Table 2, the impedance 180
133 inhibition. AA has no signicant effect on Ecorr, however, a shift of spectra were analyzed by tting to the equivalent circuit models 181
134 both the cathodic and anodic curves to lower corrosion current Rs(QdlRct) and Rs(QdlRct) (LRL) which have been used before to 182
135 densities was observed even at an overvoltage higher than model the mild steel/acid interface [32,33]. An example of the 183
136 300 mV SCE. And this effect becomes more signicant with tting diagrams, with the equivalent circuit models are presented 184
137 increasing AA concentration. in Fig. 5. From the data presented in Table 2, it is clear that addition 185
138 The results obtained show that the rate of mild steel dissolution of AA lead to an increase in the Rct values at all concentrations in 186
139 in 0.5 M H2SO4 is higher than that in 1 M HCl, which is in 1 M HCl and 0.5 M H2SO4, respectively. The values of double-layer 187
140 agreement with previous reports [29,30]. The differences in the capacitance (Cdl) were determined using the relation: 188
141 polarization proles in hydrochloric and sulphuric acid solutions
1
142 possibly suggest that the acid anions inuenced the processes in f Z immax (2)
2pC dl Rct
143 different ways.
144 The values of the corrosion current density in the absence and Due to a modication on addition of AA, the values of Cdl 191
190
189
145 presence of AA were used to determine the inhibition efciency decrease more than observed in the absence of the inhibitor. 192
146 from polarization data as follows: Charge transfer resistance and double layer capacitance also show 193
! the opposite trend, according to Helmholtz model: 194
Icorrbl  Icorrinh
IE%  100 (1)
Icorrbl eeo A
C dl (3)
d
149
148
147 The values obtained are presented in Table 1. The observed e represents the dielectric constant of the medium, eo is the 196
195
150 reduction in anodic and cathodic corrosion current densities show vacuum permittivity, A is the electrode area, and d is the thickness of 197
151 that the inhibitor reduced the mechanism of H2 gas evolution the interfacial layer. The decrease in Cdl value which occurs due to a 198
152 reaction [31] and also the anodic dissolution of mild steel. If the decrease in the dielectric constant and/or an increase in the double 199
153 displacement in Ecorr is greater than 85 mV with reference to Ecorr layer thickness can be ascribed to the adsorption of AA species on a 200
154 (in the absence of the inhibitor) the inhibitor may act as a cathodic corroding metal surface. The increase in resistance with inhibitor 201
155 or anodic type and if the displacement is less than 85 mV the concentration, suggests enhanced adsorption of AA molecules on the 202
156 inhibitor may be regarded as a mixed-type. mild steel surface and efcient blocking of the steel surface [34]. 203
Again, the inhibition efciency (IE%) from impedance data was 204
157 Electrochemical impedance spectroscopy measurements calculated by comparing the values of the charge transfer resistance 205
in the absence and presence of AA using relation: 206
158 Figs. 3 and 4 represent the Nyquist plots for mild steel in 1 M !
159 HCl and 0.5 M H2SO4 in the absence and presence of different Rctinh  Rct
160 concentrations of AA. As mentioned earlier, the experiment was IE%  100 (4)
Rctinh
161 performed at the open circuit potential. In 1 M HCl environment,
162 the corresponding Nyquist plots show single semicircles for all The obtained inhibition efciency values are presented in 209
207
208
163 systems over the frequency range studied, relating to one time Table 1. The slight variations in computed corrosion rate and 210
164 constant in the Bode plots. The high frequency intercept with inhibition efciency values from polarization and impedance 211
165 the real axis in the Nyquist plots is assigned to the solution measurements could be related to the processes associated with 212
166 resistance (Rs) and the low frequency intercept with the real axis is the different techniques. For instance, the metal surfaces were held 213

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-350 1 M HCl 0.5 M H2SO4

(a) 0.0005 M AA
(a)
-80 0.0005 M AA
-300 0.002 M AA
0.002 M AA
0.005 M AA
0.005 M AA
0.01 M AA
-250 -60
0.01 M AA
Zim (ohms)

-200

Zim (ohms)
10.54 Hz 21.9 Hz
-40
-150

136.9 Hz 410.8 Hz
-100 1.17 Hz
-20
0.01 Hz
-50

0
0

0 50 100 150 200 250 300 350

0 10 20 30 40 50 60 70 80 90
Zre (ohms)
Zre (ohms)
-160
(b) 1 M HCl -40
0.0005 M AA 0.5 M H2SO4
-140 (b)
0.002 M AA 0.0005 M AA
-120 0.005 M AA 0.002 M AA
0.01 M AA -30
0.005 M AA
-100 0.01 M AA
Phase of Z (deg)

-80
Phase of Z (deg) -20
-60

-40
-10
-20

0
0
20
0.01 0.1 1 10 100 1000 10000 100000
Frequency (Hz) 10
0.01 0.1 1 10 100 1000 10000 100000
350 (c) 1 M HCl Frequency (Hz)
0.0005 M AA 90
300
0.002 M AA (c) 0.5 M H2SO4
0.005 M AA 80 0.0005 M AA
0.01 M AA 0.002 M AA
250
70 0.005 M AA
200 0.01 M AA
/Z/ (ohms)

60

150 50
/Z/ (ohms)

100 40

50 30

0 20

10
0.1 1 10 100 1000 10000 100000
Frequency (Hz) 0

Fig. 3. Electrochemical impedance spectra of mild steel in 1 M HCl solution in the 0.1 1 10 100 1000 10000 100000
absence and presence of AA: (a) Nyquist, (b) Bode phase angle plots and (c) Bode Frequency (Hz)
modulus plots.
Fig. 4. Electrochemical impedance spectra of mild steel in 0.5 M H2SO4 solution in
the absence and presence of AA: (a) Nyquist, (b) Bode phase angle plots and (c) Bode
modulus plots.
214 close to the equilibrium corrosion potential for impedance
215 measurements, but taken far away from the equilibrium potential
216 during polarization measurements, which should inuence the environments (1 M HCl and 0.5 M H2SO4). The impedance spectra 221
217 measured values from both techniques. again show that immersion time has a signicant effect on the 222
corrosion resistance of mild steel. The data are presented in Tables 3 223
218 Effect of immersion time and 4, respectively. In 1 M HCl environment, it is apparent from the 224
219 Figs. 6 and 7 present the impedance response obtained over a Nyquist (Fig. 4a), Bode phase angle (Fig. 4b) and Bode modulus 225
220 period of 144 h in the presence of 0.01 M AA in both acidic (Fig. 4c) plots that corrosion resistance increased considerably, going 226

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Table 2 steel by formation of a protective lm on its surface. Close scrutiny 252

Electrochemical impedance parameters of mild steel in 1 M HCl and 0.5 M H2SO4 in
of the images presented in Fig. 8 reveals that the metal surface was 253
the absence and presence of AA.
more protected in 1 M HCl (Fig. 8a) compared to 0.5 M H2SO4 254
System Rct (V cm2) n Cdl (F cm2) IE (%) (Fig. 8b) environment, which corroborates with the values of 255
0.5 M H2SO4 28.05 0.92 1.131E4 inhibition efciency obtained in both environments. Thus, one 256
0.0005 AA 45.29 0.90 6.647E5 38 might conclude that the adsorption lm can efciently inhibit the 257
0.002 M AA 56.45 0.89 5.092E5 50.3 corrosion of steel. 258
0.005 AA 63.11 0.89 4.559E5 55.5
0.01 M AA 75.32 0.89 3.919E5 62.7
Atomic force microscopy 259
1 M HCl 102.6 0.89 2.340E5 24.6 AFM is a very useful technique to investigate the surface 260
0.0005 M AA 136.1 0.90 1.684E5 58.1
0.002 M AA 244.8 0.89 9.173E6 69.1
morphology at nano - to micro-scale and has become a new choice 261
0.005 M AA 332.4 0.88 6.745E6 69.6 to study the inuence of inhibitor on the generation and the 262
0.01 M AA 337.4 0.88 6.572E6 progress of the corrosion at the metal/solution interface [3537] . 263
3D AFM images of polished mild steel surface (reference sample) 264
and surfaces immersed in 1 M HCl and 0.5 M H 2SO4 in the absence 265
and presence of 0.01 M AA are presented in Fig. 9. It is clear from 266
227 from 0.5 h (Rct = 337.4 V cm2) to 72 h of immersion the images that the specimens immersed in the uninhibited acid 267
228 (Rct = 2753 V cm2). Corrosion resistance decreased steadily there- solutions present rougher surfaces ( Fig. 9b(i) and c(i) compared 268
229 after, but still remained lower than that obtained after 0.5 h of to the reference specimens, as well as those immersed in the 269
230 immersion. While in 0.5 M H2SO4 solution a pronounced increase in solutions containing 0.01 M AA [ Fig. 9a, b(ii) and c(ii)], 270
231 the corrosion rate occurred steadily from 75.32 V cm2 (0.5 h) to respectively. AFM image analysis was carried out to obtain the 271
232 16.54 V cm2 (144 h). Accordingly, the trend of corresponding Qdl average roughness, Ra (the average deviation of all points 272
233 values in 1 M HCl solution suggests that processes occurring at the roughness prole from a mean line over the evaluation length), 273
234 metal/solution interface initially increased the compactness (or root-mean-square roughness, Rq (the average of the measured 274
235 thickness) of the inhibitor lm within the initial 72 h, whereas Qdl height deviations taken within the evolution length and measured 275
236 values in 0.5 M H2SO4 suggests a decreased compactness of the from the mean line) and the maximum peak-to-valley (P V) 276
237 inhibitor, which could be considered as opposed to the inhibitor height values (largest single peak-to-valley height in ve 277
238 adsorption process. Such phenomena could result from desorption adjoining sampling heights) [35]. The average roughness of the 278
239 of adsorbed AA molecules due to increasing solubility of the polished mild steel surface, and those immersed in uninhibited 279
240 corrosion product and/or slower formation of stable corrosion 1 M HCl and 0.5 M H 2SO4 were found to be 44.55 nm, 226.68 nm 280
241 product, suggesting a competitive adsorption between the aggres- and 487.84 nm respectively. The addition of 0.01 M AA to the 281
242 sive acid ions and the organic inhibitor on a mild steel surface. aggressive solutions reduced the roughness to 106.13 nm (in 1 M 282
HCl) and 143.71 nm (in 0.5 M H 2SO4), respectively. The Rq values 283
243 Scanning electron microscopy in the presence of the inhibitor reduced by a factor of 166.06 nm 284
244 The surface morphologies of mild steel immersed in the from 303.58 nm (in 1 M HCl) and 424.54 nm from 606.87 nm (in 285
245 absence and presence of 0.01 M AA in both acidic environments are 0.5 M H 2SO4). The maximum peak-to-valley height (P V) also 286
246 presented in Fig. 8. As can be seen, the surface of the mild steel was reduced to 163.82 and 198.23, respectively. These parameters 287
247 appears rough due to active dissolution in the absence of the suggest that the surface appears smoother and hence less 288
248 inhibitor, evidence of pits was observed in 1 M HCl environment. corroded, due essentially to the inhibiting action of AA. The 289
249 However, the roughness reduced considerably after the introduc- details are presented in Table 5. The data presented therein 290
250 tion of AA to the acid environments. The ndings reveal that the indicates that the surface of mild steel has been protected by AA 291
251 presence of AA molecules reduced the active dissolution of mild species adsorbed on its surface. 292

Red = experimental fit

CPE 14
Green = modeled fit
(a) 12
10
8
6

Rs Rct 4
2
0
RL -2
L
-4
0 5 10 15 20 25 30 35 40
Z ', ohm
24
22
CPE 20
(b) 18
16
14
12
10
8
6
4
Rs 2
0 Red = experimental fit
-2 Green = modeled fit
Rct -4
0 5 10 15 20 25 30 35 40 45 50 55 60
Z ', ohm

Fig. 5. Equivalent circuit models with their respective tting diagrams.

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-3500 -80
0.5 h 0.5 h
(a) 24 h
(a)
24 h
-3000 -70
48 h 48 h
72 h 72 h
-60
-2500 96 h 96 h
120 h 120 h
144 h -50
144 h
-2000
Zim (ohms)

Zim (ohms)
-40
-1500
-30
0.81 Hz 31.6 Hz
-1000 2.43 Hz
-20
15.2 Hz 0.01 Hz
-500 0.01 Hz
-10

0 0

0 500 1000 1500 2000 2500 3000 3500

10 20 30 40 50 60 70 80
Zre (ohms)
Zre (ohms)
(b) 0.5 h
0.5 h
24 h (b)
-800 48 h 24 h
72 h -30 48 h
96 h 72 h
120 h 96 h
-600
144 h 120 h
Phase of Z (deg)

Phase of Z (deg) -20 144 h

-400

-10
-200

0
0

0.01 0.1 1 10 100 1000 10000 100000

0.01 0.1 1 10 100 1000 10000 100000
Frequency (Hz)
Frequency (Hz)
3500
0.5 h
(c) 24 h 80 (c) 0.5 h
3000 24 h
48 h
70 48 h
72 h
2500 72 h
96 h
60 96 h
120 h
120 h
2000 144 h
50 144 h
/Z/ (ohms)

/Z/ (ohms)

1500
40

1000 30

500 20

0 10

0
-500
0.1 1 10 100 1000 10000 100000
0.1 1 10 100 1000 10000 100000
Frequency (Hz)
Frequency (Hz)

Fig. 6. Electrochemical impedance spectra of mild steel in 1 M HCl showing the Fig. 7. Electrochemical impedance spectra of mild steel in 0.5 M H2SO4 showing the
effect of time in 0.01 M AA for 144 h: (a) Nyquist, (b) Bode phase angle plots and (c) effect of time in 0.01 M AA for 144 h: (a) Nyquist, (b) Bode phase angle plots and (c)
Bode modulus plots. Bode modulus plots.

293 Adsorption considerations the metal surface can be explained by nding a suitable isotherm, 299
294 Some of the constituents of AA are protonated in 1 M HCl and which describes the variation of experimentally obtained values of 300
295 0.5 M H2SO4 solutions, whereas the rest remain in the molecular the amount of adsorbed substance by unit area of the metal surface 301
296 form. Therefore, the observed inhibiting efciency of AA can be with its concentration in bulk solution at a constant temperature. 302
297 attributed to the participation of both protonated and molecular In order to determine the adsorption mode of AA molecules on the 303
298 species in the adsorption process. The adsorption of AA species on metal surface in the different acid solutions, experimental data 304

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Table 3 Table 4
Electrochemical impedance parameters of mild steel in 1 M HCl showing the effect Electrochemical impedance parameters of mild steel in 0.5 M H2SO4 showing the
of time in 0.01 M AA for 144 h. effect of time in 0.01 M AA for 144 h.

System Rct (V cm2) n Cdl (F cm2) IE (%) System Rct (V cm2) n Cdl (F cm2) IE (%)

0.5 h 0.5 h
0.01 M AA 337.4 0.88 6.572E6 69.6 0.01 M AA 75.32 0.89 3.919E5 62.7
24 h 24 h
0.01 M AA 730.5 0.84 3.079E6 84.7 0.01 M AA 24.54 0.97 1.302E4 51.5
48 h 48 h
0.01 M AA 2333 0.82 9.627E7 96.4 0.01 M AA 36.6 0.88 8.884E5 77.6
72 h 72 h
0.01 M AA 2753 0.82 8.069E7 97.2 0.01 M AA 31.71 0.85 1.109E4 84.5
96 h 96 h
0.01 M AA 2278 0.84 9.583E7 96.9 0.01 M AA 23.13 0.82 1.732E4 77.7
120 h 120 h
0.01 M AA 2127 0.83 1.033E6 97 0.01 M AA 19.93 0.76 2.322E4 73.3
144 h 144 h
0.01 M AA 2083 0.83 1.055E6 97.2 0.01 M AA 16.54 0.76 2.941E4 64.4

305 were tested by tting to several adsorption isotherms (not shown) the slopes from the predicted values of 1.00 can be attributed to the 318
306 and the best t was obtained from the Langmuir isotherm. Surface interactions between adsorbate species on the metal surface as 319
307 coverage values (u) dened as u = IE/100 were evaluated from well as changes in the adsorption heat with increasing surface 320
308 inhibition efciency obtained from polarization measurements coverage, factors which were not taken into consideration in 321
309 [38]. According to the Langmuir adsorption isotherm: deriving the isotherm. The obtained values for Kads in 0.5 M H2SO4 322
C inh 1 and 1 M HCl are 1015 and 1211, respectively. The higher value of 323
C inh (5) Kads obtained in 1 M HCl environment shows strong adsorption 324
u K ads
ability of protonated AA on the metal surface [38] due to the 325
311
310 where C(inh) represents the inhibitor concentration, u is the degree presence of chloride ions, which form bridges between the 326
312 of surface coverage on the metal surface and Kads is the equilibrium positively charged metal surface and the protonated species. Such 327
313 constant for the adsorptiondesorption process. Fig. 10 shows the ability is not very pronounced with sulphate ions. 328
314 plot of C/u against C to be linear in both acid environments, with It is generally accepted that the values of DGads8 up to 329
315 slopes of 1.09 (0.5 M H2SO4), and 1.03 (1 M HCl) respectively, 20 kJ mol1 are accordant with electrostatic interaction between 330
316 showing that the adsorption of AA species onto a mild steel surface the charged molecules and the charged metal surface (physisorp- 331
317 obeys Langmuir adsorption isotherm. The observed deviations of tion) whereas those ranging 40 kJ mol1 or more negative 332

Fig. 8. Scanning electron micrographs of a mild steel surface immersed for 24 h in 1 M HCl and 0.5 M H2SO4 in the presence and absence of 0.01 M AA.

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Fig. 9. Three-dimensional AFM images of: (a) abraded mild steel, and mild steel immersed in: (b) (i) 1 M HCl, (b) (ii) 1 M HCl containing 0.01 M AA, and (c) (i) 0.5 M H2SO4, (c)
(ii) 0.5 M H2SO4 containing 0.01 M AA.

333 involve charge sharing or transfer from the inhibitor molecules to (PW) local correlation density functional and restricted spin 343
334 the metal surface to form a coordinate type of bond (chemisorp- polarization using the DND basis set. For core electrons at the 344
335 tion) [3943]. The obtained DGads8 values are 28 kJ mol1 (1 M lowest atomic orbitals the DFT semicore pseudopotentials (DSPP) 345
336 HCl) and 26 kJ mol1 (0.5 M H2SO4), respectively. The negative was active [45]. The quantum chemical parameters were calculated 346
337 values of free energy of adsorption suggest spontaneous adsorp- for AA molecules in neutral as well as protonated forms. Solvent 347
338 tion of the inhibitor molecules on the metal surface. effects have been included in our calculations. Self-consistent 348
reaction eld (SCRF) methods were used to perform calculations in 349
339 Computational studies aqueous solution. These methods model the solvent as a continuum 350
of uniform dielectric constant, and the solute is placed in the cavity 351
340 DFT calculations were carried out using the electronic structure within it. The self-consistent eld (SCF) procedure was performed 352
341 program DMol3 using a Mulliken population analysis [44]. The with a convergence of 105 and a Fermi smearing parameter of 353
342 electronic parameters for the simulation involve the PerdewWang 0.005 Ha to increase the rate of SCF convergence. We achieved the 354

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Table 5 Table 6
AFM data for mild steel immersed in 1 M HCl and 0.5 M H2SO4 in the absence and Some molecular properties of AA calculated using DFT.
presence of 0.01 M AA.
Quantum chemical properties Neutral form Protonated form
Samples Average Root-mean-square, Maximum-peak-to
Total energy (au) 605.1 680.4
roughness, Rq (nm) valley height,
EHOMO 6.329 3.723
Ra (nm) PV (nm)
ELUMO 2.391 3.027
Control 44.55 66.96 101.24 DE 3.938 0.696
1 M HCl 226.68 303.58 246.11 Molecular surface area (A2) 173.1 195.7
0.01 M AA 106.13 137.56 163.82 Molecular weight (amu) 160.1 179.1
0.5 M H2SO4 487.84 606.87 577.19 Ionization potential (eV) 6.329 3.723
0.01 M AA 143.71 182.33 198.23 Electron afnity (A) (eV) 2.391 3.027
Absolute electronegativity (x) (eV) 4.36 3.375
Hardness (h) 1.969 0.348
Softness (s) 0.508 2.874

355 geometry optimization using the COMPASS force eld and Smart
356 minimization method. Quantum chemical parameters such as
357 EHOMO, ELUMO, the energy gap DE (ELUMO  EHOMO), and adsorption the p-electrons of heterocyclic compound and the vacant d-orbital 386
358 energy were obtained for the AA molecule in order to predict its of the metal surface atoms [46,47]. 387
359 activity toward the Fe surface. The aforementioned parameters were It is obvious from Table 6 that AA has higher EHOMO in the 388
360 determined after geometric optimization with respect to all nuclear neutral form than in the protonated form, showing that the 389
361 coordinates. Fig. 11(ivi) depicts the optimized structure, total electron-donating tendency of AA is greater in the neutral form. 390
362 electron density, highest occupied molecular orbital (HOMO), Also, the LUMO energy is directly related to the electron afnity 391
363 lowest unoccupied molecular orbital (LUMO), and the Fukui and shows the susceptibility of the molecule toward attack by 392
364 functions for electrophilic F and nucleophilic F+. From our results, nucleophiles. The lower the value of ELUMO, the stronger the 393
365 the HOMO and LUMO energy orbitals are mostly localized on the electron accepting ability of the molecule. It is also clear from 394
366 heteroatoms (O) and carbonyl groups present in the AA molecule. Table 6 that the protonated form of AA shows the lowest EHOMO, 395
367 Mulliken charge analysis was used to determine the adsorption making the neutral form the most likely form for the interaction of 396
368 centers of the inhibitor. The adsorption of AA molecules on the Fe mild steel with AA molecule. Again, low values of the energy gap 397
369 surface results from donoracceptor interactions between the AA will provide good inhibition efciencies, because the energy 398
370 and the Fe surface. The electron donating ability ofAA is related with needed to excite an electron from the last occupied orbital will be 399
371 the EHOMO. EHOMO shows the tendency of AA molecule to donate low [48]. A molecule with a low energy gap (DE) is expected to be 400
372 electrons to the acceptor species with empty molecular orbitals. The more polarizable and is generally associated with high chemical 401
373 tendency of a molecule to accept the electrons is related to ELUMO. reactivity and low kinetic stability, being regarded to as a soft 402
374 As can be seen from Fig. 11(ii) and (iii), the HOMO and molecule [49]. The adsorption of inhibitor onto a metallic surface 403
375 the LUMO are distributed over the entire AA molecule due to occurs at the part of the molecule which has the greatest softness 404
376 the presence of lone electron pairs in the O atoms and the and lowest hardness [50]. The result from Table 6 reveals that AA in 405
377 delocalization of p-electrons. Due to the presence of these the protonated form has the lowest energy gap value and lowest 406
378 adsorption centers one would expect a at orientation of AA hardness. If the AA molecules donate electrons to unoccupied d- 407
379 molecules on the surface of Fe, thus high degree of surface coverage orbital of metals and the electrons are accepted in the d-orbital of 408
380 and inhibition efciency is expected for AA from the theoretical metals by using antibonding orbital to form covalent bond, the 409
381 point of consideration. The result so far suggests that the O atoms adsorption process is regarded as chemisorption, and there will 410
382 are the probable reactive sites for adsorption of AA on the metal be a relationship between the quantum chemical parameters and 411
383 surface. As mentioned earlier, the adsorption of an inhibitor on the inhibitive effect of AA in the neutral or molecular form only. 412
384 metal surface can occur on the basis of donoracceptor interac- However, it is evident from the theoretical calculations that no 413
385 tions between the lone electron pairs in heteroatoms together with direct correlation can be obtained in the neutral or protonated 414
form. 415
The local reactivity of AA molecule was analyzed by means of 416
0.014 the Fukui indices (FI) to also assess the reactive regions in terms of 417
nucleophilic (F+) and electrophilic (F) behavior. Fig. 11(iv) shows 418
0.012 that the F functions correspond with the HOMO locations, 419
indicating the sites through which the molecules could be 420
0.010 adsorbed on the metal surface, whereas F+(Fig. 11(v) corresponds 421
with the LUMO locations, showing sites through which the 422
0.008 molecules could interact with the nonbonding electrons in the 423

metal. 424
C/

0.006 Molecular dynamics simulation was carried out to model 425

different low energy adsorption congurations of the AA molecule 426
0.004
on the Fe surface [5154]. The Fe crystal was cleaved along the 427
(1 1 0) plane because it has a density packed surface and the most 428
stabilization at this position. Calculations were carried out in a 429
0.002
0.5 M H2SO4 12  10 supercell using the COMPASS force eld and the Smart 430
1 M HCl algorithm with NVE (microanonical) ensemble, a time step of 1 fs, 431
0.000
and simulation time 5 ps. The geometry of the lower layers of the 432
0.000 0.002 0.004 0.006 0.008 0.010
slab was constrained. The temperature was xed at 350 K. 433
C
Simulation was done using the optimized structure of the AA 434
Fig. 10. Langmuir adsorption isotherm plots for AA in 1 M HCl and 0.5 M H2SO4 and Fe. The system was quenched every 250 steps. Fig. 11(vii) and 435
solution. (viii) shows the top and side views of the optimized (lowest 436

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Fig. 11. Electronic properties of ascorbic acid: (i) optimized structure, (ii) HOMO orbital, (iii) LUMO orbital, (iv) F function, (v) F+ function, (vi) total electron density, (vii) top
view: snapshot from the molecular dynamics model of ascorbic acid adsorption on Fe (1 1 0), (viii) side view: snapshot from the molecular dynamics model of ascorbic acid
Q3 adsorption on Fe (1 1 0), atom legend: white = H; gray = C; red = O. The blue and yellow isosurfaces depict the electron density difference; the blue regions show electron
accumulation while the yellow regions show electron loss. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this
article.)

437 energy) adsorption structures for AA on the Fe (1 1 0) surface from (2) The polarization result shows that AA is a mixed-type inhibitor 456
457
438 our simulation. The binding energy (EBind) which is important in in both 1 M HCl and 0.5 M H2SO4 environments, which the 458
439 characterizing the adsorption of AA molecules onto the Fe surface impedance data indicate was achieved via adsorption of the AA 459
440 was estimated using the equation: species on the mild steel surface. 460
(3) The adsorption process obeys the Langmuir adsorption 461
462
Ebind Etotal  Einhibitor Esurface (6) isotherm. The negative values obtained for DGads8 shows that 463
AA species were strongly adsorbed on the metal surface. 464
442
441 where Einhibitor, Esurface, and Etotal represent the energy of a single (4) SEM and AFM studies revealed the formation of a protective 465
466
443 molecule of AA, the Fe slab without adsorption, and the total lm adsorbed on the steel surface. 467
444 energy of the system containing a molecule and Fe surface, (5) Quantum chemical calculation results reveal that the oxygen 468
469
445 respectively. The obtained adsorption energy value is 81.55 kcal/ atoms of the AA molecule are the active sites by which the 470
446 mol. The obtained value was calculated by averaging the energies inhibitor molecules can directly adsorb on a mild steel surface. 471
447 of ten structures of lowest energy. The estimated negative value of (6) DFT-based quantum-chemical computations of parameters 472
473
448 Ebind points toward the adsorption ability of AA on the Fe surface. associated with the electronic structures of specic compo- 474
nents of AA conrmed its ability to adsorb on a steel surface. 475
450
449 Conclusions
References 476
453
452 (1) Ascorbic acid proved to be a good inhibitor for Q235 mild steel
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