Egyptian Journal of Petroleum xxx (2017) xxx–xxx

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Experimental and theoretical studies on the corrosion inhibition of

vitamins – Thiamine hydrochloride or biotin in corrosion of mild steel in
aqueous chloride environment
Albin Aloysius a, Rajajeyaganthan Ramanathan b,c,⇑, Auxilia Christy a, Sambath Baskaran d, Noreen Antony e
a
Department of Chemistry, BWDA Arts and Science College, Kolliyanguam 604304, Tamil Nadu, India
b
Department of Chemistry, M.Kumarasamy College of Engineering, Karur 639113, Tamil Nadu, India
c
Department of Chemistry, Kalasalingam Academy of Research and Education, Kalasalingam University, Krishnankoil 626126, Tamil Nadu, India
d
Department of Chemistry, Tsinghua University, Beijing 100084, People’s Republic of China
e
Department of Chemistry, Holy Cross College, Tiruchirappalli 620002, Tamil Nadu, India

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

Article history: The corrosion inhibition of thiamine hydrochloride (vitamin B1) or biotin (vitamin B7) on corrosion of
Received 22 February 2017 mild steel in 240 ppm chloride ions solution was studied using weight loss method, potentiodynamic
Revised 23 May 2017 polarization curves and electrochemical impedance spectroscopy. UV–Vis, FTIR and surface analysis using
Accepted 18 June 2017
SEM and EDS characterization were carried out to understand the corrosion inhibition property of these
Available online xxxx
inhibitors in 240 ppm aqueous chloride medium. Experimental results show that both thiamine
hydrochloride and biotin act as a good corrosion inhibitors. Quantum chemical parameters obtained from
Keywords:
density functional theory (DFT) calculations were discussed with experimental results.
Green corrosion inhibitor
Vitamin
Ó 2017 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V. This is an open
Thiamine hydrochloride access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Biotin
Mild steel
240 ppm chloride medium

1. Introduction affect the corrosion resistance of most metals and the presence
of 100 ppm chloride ions in the water causes pitting corrosion of
Cooling water is needed for most industrial production pro- steel [5]. The chloride ions cause the passive film to break down
cesses for efficient and proper operation. The operation of cooling at certain weak spots on the metal surface and assist corrosion.
water circulation systems is faced with several challenges; one of Organic compounds like natural products, drugs act as corro-
the most significant is corrosion of the metal equipment. Various sion inhibitors in different environment for various metals [6–8].
dissolved substances in cooling water may have different influ- Extensive research on organic compounds reveals that compounds
ences on the corrosion of metals. For water-cooled systems, com- containing hetero atoms such as sulphur, phosphorous, nitrogen or
monly corrosion is of an electrochemical nature and there are oxygen and compounds containing double bonds and triple bonds
several major types of corrosion [1]. The corrosion of iron in corro- inhibit corrosion of metal by surface adsorption [9–18]. Corrosion
sive environments, especially in cooling water containing chloride, inhibitors for cooling water systems are several types and are stud-
limits its uses. The mechanisms of pitting and crevice corrosion are ied in detail [19]. Vitamins are used as green inhibitors [20] on cor-
similar and they most commonly occur in chloride environments rosion of metals and their inhibition efficiency of vitamins on
[2–4]. But crevice corrosion occurs more readily because it is corrosion of metals in chloride [21] and acid [22–27] medium were
helped by the existence of a physical crevice, whereas pitting has studied in detail. Among vitamins, B vitamins are a class of eight
to initiate on a flat surface. Chloride and sulfate ions adversely water-soluble chemically distinct vitamins but their use as corro-
sion inhibitors are not much studied in aqueous chloride
environment.
Peer review under responsibility of Egyptian Petroleum Research Institute. Thiamine hydrochloride (vitamin B1) and Biotin (vitamin B7 or
⇑ Corresponding author at: Department of Chemistry, Kalasalingam Academy of vitamin H), are members of the water soluble B vitamins family
Research and Education, Kalasalingam University, Krishnankoil 626126, Tamil needed in our health system. The structure of thiamine hydrochlo-
Nadu, India.
ride, Fig. 1(a) consists of two rings, an amino pyrimidine and a
E-mail address: rajajeyaganthan.r@gmail.com (R. Ramanathan).

http://dx.doi.org/10.1016/j.ejpe.2017.06.003
1110-0621/Ó 2017 Egyptian Petroleum Research Institute. Production and hosting by Elsevier B.V.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article in press as: A. Aloysius et al., Experimental and theoretical studies on the corrosion inhibition of vitamins – Thiamine hydrochloride
or biotin in corrosion of mild steel in aqueous chloride environment, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.003
2 A. Aloysius et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx

Fig. 1. Structure of (a) thiamine hydrochloride and (b) biotin.

thiazole ring linked by a methylene bridge. On the contrary, the In this study, the CR value is calculated using the formula,
structure of biotin, Fig. 1(b) also consists of two rings, an ureido
2 1 2
and a thiophene ring but fused together through one of its sides. CRðmg  dm  day Þ ¼ DWðmgÞ=½0:096ðdm Þ
1day
Thiamine is naturally present in cereal grains, sun flower seed
where, the surface area S takes the value of 0.096 dm2.
and eggs and biotin is also naturally present in peanuts and leafy
green vegetables. In this research, corrosion inhibition effect of thi-
amine hydrochloride and biotin on corrosion of mild steel in 240 2.3. Potentiodynamic polarization studies
ppm chloride ions solution was studied using weight loss method,
potentiodynamic polarization curves, electrochemical impedance, Electrochemical experiments were carried out using conven-
UV–Vis and FT-IR spectroscopy. tional three electrode cell assembly. The working electrode was a
mild steel specimen with an exposed surface area of 1 cm2 was fit-
ted to a holder and the rest of the area was covered with epoxy
2. Experimental
coating. Saturated calomel electrode and platinum wire were used
as reference and counter electrode. The working electrode was ver-
2.1. Material and specimens
tically immersed in the test solution and open circuit potential was
recorded by using Princeton Applied Research (2 channels) ana-
The test material was mild steel with a chemical composition
(mass%) of 0.10 C, 0.06 P, 0.40 Mn, 0.026 S, and the balance of Fe. lyzer. The samples were immersed in the test solution for 30 min
for stabilization of open circuit potential and then potentiody-
Specimens with a size of 1
4
0.2 cm3 were cut and their sur-
faces were abraded using 150–600 grit emery papers. Prior to test- namic polarization tests were performed. The open circuit poten-
tial test was conducted for 30 min for every sample and with
ing, the specimens were degreased with acetone and rinsed with
de-ionized pure water. Thiamine hydrochloride and biotin were respect to open circuit potential value, the Tafel polarization stud-
ies were carried out at a scan rate of 0.5 mV/s. The reason for
purchased from Loba Chemie, India. FeSO4 and NaCl were pur-
chased from Merck, India and used as such without further purifi- choosing slow scan rate (0.5 mV/s) was to reduce the disturbance
of the charging current to avoid distortion of potentiodynamic
cation. Double-distilled water was used to prepare solution of
chloride ions concentration of 240 ppm and various concentrations polarization curves. This will extend the polarization time and
the polarization potential will cause some irreversible changes to
of ferrous ions, thiamine hydrochloride and biotin inhibitors solu-
tion. Corrosion medium was an aqueous solution having a fixed the interfacial structure especially in the anodic region. Corrosion
current (Icorr) and corrosion potential (Ecorr) were obtained by
concentration of 240 ppm of chloride ions in water. The corrosion
tests were carried out with inhibitors concentration of 25, 50, 100, extrapolating the anodic and cathodic curves of Tafel plot. Inhibi-
tion efficiency was calculated by using respective Icorr values. Elec-
150 and 200 ppm in the corrosion medium.
trochemical impedance analyses were performed in the frequency
range from 1 Hz to 1 MHZ with amplitude of 10 mV peak-to-peak
2.2. Weight loss method
using AC signal at Ecorr. The mild steel specimens used for this
study have a surface area of 1 cm2, which were exposed to the cor-
For weight loss measurements, each run was carried out in a
rosive solution. All these measurements were done at the atmo-
glass vessel containing 100 mL of 240 ppm chloride ion solution.
spheric conditions without any stirring. The experiments were
The experiments were carried out at an ambient temperature of
conducted in the absence and presence of inhibitor with different
30 °C by immersing the mild steel specimen using glass hooks in
concentration in the 240 ppm chloride ion medium.
100 mL of the blank solutions or solution with respective inhibitor.
After 24 h immersion, the specimens were taken out from solution,
rinsed with double distilled water, dried thoroughly and weighed. 2.4. Characterization of surface morphology
The weight loss (DW) was used to calculate the corrosion rate
denoted as CR, (mg.dm2day1) and the inhibition efficiency as Surface morphologies of the films were mainly observed under
IE, (%): scanning electron microscopy, SEM (TESCAN Vega 3) using elec-
2 1
tron acceleration between 5 and 10 kV.
CRðmg  dm  day Þ ¼ M 1  M 2 =SP
where, M1 and M2 is the mass of the specimen before and after the 2.5. Fourier transforms infrared (FT-IR) spectroscopy
corrosion respectively, S is the surface area of the specimen in dm2
and P is the period of immersion in days. The IE was calculated by FT-IR spectra were recorded in Perkin Elmer Spectrum RX I with
using the following equation: a spectral range of 4000 cm1 to 400 cm1 and a spectral resolu-
tion of 4 cm1. The mild steel specimens were immersed for 24 h
IEð%Þ ¼ ðW 0  W i Þ=W 0
100
in 100 mL of 240 ppm of aqueous chloride ion medium containing
Here DW = (W0  Wi), where W0 and Wi are the corrosion rate of various concentrations of vitamins. After 24 h, the specimens were
mild steel in the absence and presence of inhibitor respectively, taken out and dried. Finally, the specimens were rubbed with a

Please cite this article in press as: A. Aloysius et al., Experimental and theoretical studies on the corrosion inhibition of vitamins – Thiamine hydrochloride
or biotin in corrosion of mild steel in aqueous chloride environment, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.003
 A. Aloysius et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx 3

small amount of KBr powder and made into a disk for FTIR polarization curves of mild steel immersed in the absence and in
characterization. presence of thiamine hydrochloride and biotin at 30 °C were
obtained and shown in Fig. 2. The potentiodynamic polarization
2.6. UV–visible spectroscopy curves of VB1 and VB7 show both anodic and cathodic half-
reactions of the mild steel corrosion in 240 ppm aqueous chloride
The UV–visible absorption spectra of 240 ppm chloride ion environment. The change in the anodic and cathodic half-reaction
solution containing various concentrations of vitamin (Thiamine curves was observed by the introduction of various concentrations
hydrochloride or Biotin) and the same solution with 300 ppm of of VB1 and VB7 in the 240 ppm aqueous chloride corrosion med-
ferrous ion were recorded using Perkin Elmer’s Lambda 35 UV– ium. The extrapolation of linear Tafel segments in these Tafel
Vis spectrophotometer with a spectral range of 190 nm–1100 nm. curves of VB1 and VB7, the electrochemical corrosion parameters
such as corrosion potential (Ecorr), corrosion current (Icorr), cathodic
2.7. Computational methods slope (bc), anodic slope (ba), surface coverage area (h) and percent-
age of inhibition efficiency were calculated from Tafel plots and
All calculations were done by using the Gaussian 09 software were summarized in Table 2. In Table 2, the percentage of inhibi-
[28]. The molecular structure optimization was done by quantum tion efficiency (IEPDP) calculated from Tafel plots are compared
chemical calculations performed using density function theory with percentage of inhibition efficiency (IEWL) calculated from
(DFT)/B3LYP method (Becke’s three parameter hybrid Hartree- weight loss method.
Fock and Lee-Yang-Par correlation functional theory) with basis The percentage of inhibition efficiency was then calculated
set 6-31G⁄. Energy of highest occupied molecular orbital (HOMO) using the equation [29]
and lowest unoccupied molecular orbital (LUMO), the energy gap
IE ¼ ði corr  icorr =i corr Þ
100
between ELUMO and EHOMO (DE = ELUMO  EHOMO), dipole moment
(m), and other parameters were obtained from the theoretical stud- where i°corr and icorr are the corrosion current density values in the
ies for vitamins. absence and presence of VB1 and VB7, respectively.
On increasing the concentration of VB1 and VB7 from 25 to
3. Result and discussion 200 ppm in the aqueous chloride medium, the corrosion current
density was reduced significantly (see Fig. 2 and Table 2) and cor-
3.1. Weight loss study rosion current density reached the minimum value for 200 ppm of
VB1 or VB7. The Icorr value decreases from 23.871 mA/cm2 for
For further discussion instead of thiamine hydrochloride (vita- blank and reached the minimum value of 2.249 mA/cm2 and
min B1) and Biotin (vitamin B7), VB1 and VB7 was used to make 2.103 mA/cm2 for 200 ppm of VB1 and VB7, respectively. This sug-
it simple. The results obtained for variation of weight loss for mild gests that both anodic dissolution of mild steel and cathodic reduc-
steel immersed in 240 ppm of aqueous chloride medium in the tion reaction were inhibited by the inhibitor VB1 and VB7. The
absence and presence of VB1 and VB7 are summarized in Table 1. presence of inhibitor was blocking the active sites and modifying
The additions of VB1 and VB7 in the aqueous chloride medium are the mild steel surface. This leads to the shift of anodic and cathodic
varied in concentration of 25, 50, 100, 150 and 200 ppm. It is evi- slope areas toward lower current densities (Icorr). The percentage of
dent from the data in Table 1 that the corrosion rate decreases inhibition efficiency (IE) values obtained from the potentiodynamic
and the inhibition efficiency increase with the increase in concen- polarization studies increased with increase in the concentration of
tration of VB1 and VB7. The inhibition efficiencies at 200 ppm for the VB1 or VB7 added to the corrosion medium. This implies that
VB1 and VB7 are almost same which indicate that these vitamins the corrosion inhibition of mild steel was due to the formation of
can effectively prevent mild steel from dissolving in the aqueous the adsorption film of VB1 or VB7 formed on the surface of the mild
chloride medium probably through their adsorption on the mild steel. The IE values obtained from polarization studies also agreed
steel surfaces. well with the values of weight loss measurements.
The type of behavior of inhibitors VB1 and VB7 was determined
3.2. Potentiodynamic polarization by relating the corrosion potential (Ecorr) values. Generally, if the
value of Ecorr is greater than 85 mV/SCE the inhibitor can be classi-
The corrosion of mild steel in aqueous chloride environment is fied as cathodic or anodic type and in addition, if the value of Ecorr
an electrochemical corrosion comprises a simultaneous anodic dis- is lower than 85 mV/SCE the inhibitor can be classified as mixed-
solution of mild steel and cathodic reduction reaction. To under- type [30,31]. The trend in the values of Ecorr for VB1 showed a
stand this mechanism of corrosion, the potentiodynamic change not greater than 85 mV/SCE and was within the range

Table 1
Weight loss studies for mild steel immersed in 240 ppm of aqueous chloride medium in the absence and presence of VB1 and VB7.

Inhibitor concentration (PPM) Weight Loss (mg) Corrosion rate (mg cm2 day1) Surface Coverage (h) Inhibition Efficiency (%)
Blank 3.9332 39.3324 – –
VB1
25 3.1514 31.5146 0.1988 19.88
50 2.8046 28.0463 0.2870 28.70
100 1.9255 19.2551 0.5105 51.05
150 1.1851 11.8511 0.6987 69.87
200 0.3366 3.3668 0.9142 91.42
VB7
25 1.6567 16.5672 0.5787 57.87
50 1.4196 14.1964 0.6391 63.91
100 1.1171 11.1715 0.7160 71.60
150 0.6783 6.7834 0.8275 82.75
200 0.3391 3.3917 0.9138 91.38

Please cite this article in press as: A. Aloysius et al., Experimental and theoretical studies on the corrosion inhibition of vitamins – Thiamine hydrochloride
or biotin in corrosion of mild steel in aqueous chloride environment, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.003
4 A. Aloysius et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx

Fig. 2. Potentiodynamic polarization curves for mild steel in 240 ppm aqueous chloride medium in the absence and presence of VB1 and VB7.

Table 2
Potentiodynamic polarization(PDP) parameters for mild steel immersed in 240 ppm of aqueous chloride medium in the absence and presence of VB1 and VB7.

Inhibitor concentration Blank Icorr Inhibitor Icorr Ecorr (mV)/ ba (mV bc (mV Surface coverage IEPDP IEWL
(PPM) (mA cm2) (mA cm2) SCE dec1) dec1) (h) (%) (%)
Blank 23.871 – 316.816 162.689 128.447 0 – –
VB1
25 23.871 19.575 367.728 114.684 72.856 0.17996 17.99 19.88
50 23.871 18.164 332.835 99.514 72.996 0.23907 23.91 28.70
100 23.871 11.754 362.629 352.128 1.939 0.50760 50.76 51.05
150 23.871 6.600 392.523 126.005 83.604 0.72351 72.35 69.87
200 23.871 2.249 290.024 62.455 46.781 0.90578 90.57 91.42
VB7
25 23.871 10.473 199.832 126.594 76.74 0.56126 56.12 57.87
50 23.871 7.579 265.324 86.468 93.031 0.68250 68.25 63.91
100 23.871 4.179 182.549 69.199 97.653 0.82493 82.49 71.60
150 23.871 3.424 223.089 98.629 72.365 0.85656 85.66 82.75
200 23.871 2.103 182.478 87.453 77.082 0.91190 91.19 91.38

(316.816 mv/SCE to 392.523 mV/SCE) of 75.707 mV/SCE for cathodic reduction reaction. This shows that the VB7 inhibits the
VB1. The type of behavior of VB1 was attributed to mixed-type corrosion mechanism by controlling anodic reaction predomi-
inhibitor from the Ecorr values of VB1. It was also confirmed by nantly which indicates that the VB7 was acted as anodic inhibitor
the trend in the Ecorr values of VB1which did not increase or in 240 ppm aqueous chloride corrosion medium.
decrease in a regular manner from the blank values. However,
the anodic current densities were less sensitive and in the cathodic 3.3. Electrochemical impedance spectroscopy
range, a significant increase in the cathodic current densities com-
pared to anodic current densities for various concentration of VB1 Electrochemical impedance spectroscopy provides information
leads to the shift of the Ecorr toward cathodic direction. These about the kinetics of mild steel corrosion in 240 ppm aqueous chlo-
observations confirmed that addition of VB1 in 240 ppm aqueous ride corrosion medium and about the surface properties of the mild
chloride corrosion medium will reduce anodic dissolution of mild steel in the absence and in presence of VB1 or VB7. Fig. 3 shows the
steel less than the cathodic reduction reaction. This shows that Nyquist plots represented by imperfect semicircles for the impe-
the VB1 inhibits the corrosion mechanism by controlling cathodic dance data of mild steel in 240 ppm aqueous chloride corrosion
reaction predominantly which indicates that the VB1 was a medium in the absence and presence of VB1 or VB7 at 30 °C. The
mixed-type but dominantly acted as a cathodic inhibitor in charge transfer resistance (Rct) and double layer capacitance (Cdl)
240 ppm aqueous chloride corrosion medium. On the other hand, values were obtained from Nyquist plots and summarized in the
the trend in the values of Ecorr for VB7 showed a change greater Table 3. The nature of impedance for the mild steel corrosion in
than 85 mV/SCE and was within the range (316.816 mv/SCE to 240 ppm of aqueous chloride medium was explained using simple
182.478 mV/SCE) of 134.338 mV/SCE for VB7. This type of behav- electrical equivalent circuit [32,33] comprising the resistor (Rs),
ior of VB7 was attributed to either cathodic or anodic type inhibi- resistance of charge transfer (Rct) and a double layer capacitance
tor. But, the trend in the Ecorr values of VB7 was not consistent with (Cdl). The equivalent electrical circuit used to fit the impedance
the increase or decrease in Ecorr values from the blank value which spectra for corrosion of mild steel in 240 ppm of aqueous chloride
suggested that VB7 was a mixed-type indicator in 240 ppm aque- medium in the presence and absence of VB1 or VB7 was shown in
ous chloride corrosion medium. However, the cathodic current Fig. 4.
densities were less sensitive and in the anodic range, a significant Rct is the charge transfer resistance, CPEdl is the constant phase
increase in the anodic current densities compared to cathodic cur- equivalent of double layer and Rs is the solution resistance shown
rent densities for various concentration of VB7 leads to the shift of in the equivalent electrical circuit [34,35]. The diameter of imper-
the Ecorr toward anodic direction. These observations confirmed fect semicircles (Rct) in Nyquist plots increased on increasing the
that addition of VB7 in 240 ppm aqueous chloride corrosion med- concentration of VB1 or VB7 which implied the formation of
ium will reduce anodic dissolution of mild steel more than the adsorption film and indicated the strengthening of inhibitor film

Please cite this article in press as: A. Aloysius et al., Experimental and theoretical studies on the corrosion inhibition of vitamins – Thiamine hydrochloride
or biotin in corrosion of mild steel in aqueous chloride environment, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.003
 A. Aloysius et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx 5

is calculated is mentioned in the state of equivalent circuit contains

constant phase element (ZCPE) is given by

0 ðjxÞ
ZCPE ¼ Y1
n

where Y0 is the CPE constant, x is the angular frequency, j is the

imaginary number and n is the phase shift which is related to the
degree of surface inhomogeneity. Depending on the value of n,
CPE can represent resistance (n = 0, Y0 = R), capacitance (n = 1,
Y0 = C), inductance (n = 1, Y0 = L) or Warburg impedance (n = 0.5,
Y0 = W) [38]. Double layer capacitance (Cdl) is related to the thick-
ness of the adsorbed protective layer (d) by the equation: [39]
C dl ¼ ðeeo AÞ=d
where eo is the free space permittivity, e is the dielectric constant of
the medium and A is the surface area of the electrode. The increase
in thickness of the double layer was confirmed by the decrease in
double layer capacitance values by the effective adsorption of VB1
and VB7 which reduced the dissolution of mild steel in aqueous
chloride medium.

3.4. Analysis of adsorbed film

The scraped samples collected from specimen immersed in

240 ppm aqueous chloride medium was labeled as ‘‘MS in Cl”
Fig. 3. Nyquist plots for mild steel in 240 ppm aqueous chloride medium in the and scraped samples collected from specimen immersed in the
absence and presence of VB1 and VB7.
same chloride medium with VB1 or VB7 were labeled as ‘‘MS in
VB1+Cl” or ‘‘MS in VB7+Cl”, respectively and were used in the
on the surface of mild steel with increasing concentration of the below discussion. The FT-IR spectra in Fig. 5 were recorded for
MS in Cl, MS in VB1+Cl and VB1 samples. The strong peaks at
VB1 or VB7. As a result of increase in concentration of VB1 or
VB7, charge transfer resistance (Rct) enhanced and decreased the 3504 cm1 and 3427 cm1 correspond to –NH stretching of the
amine group in pyrimidine ring and –OH stretching present in
Cdl values. This was due to the adsorption of VB1 or VB7 on the
metal surface leading to the formation of a protective layer on the hydrocarbon side chain which is attached to the thiazole ring.
The strong peaks at 1614 cm1 and 1381 cm1 and medium peak
the mild steel surface and decreased the extent of dissolution reac-
tion which prevented the further corrosion of mild steel [36]. Fur- at 1531 cm1 were due to the pyrimidine [40–42] ring stretching
vibration and a strong peak at 1480 cm1 was because of -C-N-C
thermore, the decrease in Cdl was due to decrease in dielectric
constant because of increase in the thickness of the electrical dou- stretching in pyrimidine ring [40] of VB1. The disappearance of
the peaks mentioned above emphasized that some interaction or
ble layer by the adsorption of VB1 or VB7 on mild steel. The per-
centage of inhibition efficiency (IE) was calculated from Rct adsorption of VB1 occurred on the surface of the mild steel. The
medium peaks at (i) 1186 cm1, (ii) 540 cm1 and (iii) 506 cm1
values by the following equation
were assigned to the (i) stretching of -C-CH2 bridge of pyrimidine
IE ¼ ðRctðiÞ  RctðbÞ =RctðiÞ Þ
100 ring, (ii) -NH out of plane deformation of NH2 group and (iii) -
SCN and –SCC out of plane deformation of thiazole ring of VB1,
where Rct (b) and Rct (i) were uninhibited and inhibited charge trans- respectively [41]. The disappearance of these medium peaks
fer resistance, respectively. The values of IE were summarized in the clearly indicated the interactions with nitrogen in the pyrimidine
Table 3. The value of IE increased due to the increase in the charge ring and sulphur in the thiazole ring of VB1 with the metal surface.
transfer resistance value and the corresponding decrease in the FTIR spectra in Fig. 6 were recorded for MS in Cl, MS in VB7+Cl
double layer capacitance values when increasing the concentration and VB7 samples. The strong bands at 1708 cm1 and 1240 cm1
of VB1 and VB7. The double layer capacitance (Cdl) is replaced with were assigned to the ureido carbonyl stretching and cyclic urea
CPEdl in the equivalent electrical circuit in Fig. 4 for more accurate stretching of fused rings of VB7 [43,44]. The strong peaks at
fit [37] and the equation which the double layer capacitance (Cdl) 1571 cm1 and 1408 cm1 were due to the carboxylate group of

Table 3
Electrochemical impedance parameters for mild steel immersed in 240 ppm of aqueous chloride medium in the absence and presence of VB1 and VB7.

Inhibitor concentration (ppm) Rct(blank) (X cm2) Rct(i) (X cm2) Ymax Cdl (mF cm2) IE (%) h(imp)
VB1
25 62.316 172.42 86.21 1.07E-05 63.85802 0.63858
50 62.316 193.86 96.93 8.47E-06 67.85515 0.678552
100 62.316 225.47 112.735 6.26E-06 72.36173 0.723617
150 62.316 272.68 136.34 4.28E-06 77.14684 0.771468
200 62.316 517.45 258.725 1.19E-06 87.9571 0.879571
VB7
25 62.316 197 98.5 8.21E-06 68.36751 0.683675
50 62.316 252.43 126.215 5E-06 75.31355 0.753136
100 62.316 318.79 159.395 3.13E-06 80.45234 0.804523
150 62.316 362.19 181.095 2.43E-06 82.79467 0.827947
200 62.316 465.37 232.685 1.47E-06 86.60936 0.866094

Please cite this article in press as: A. Aloysius et al., Experimental and theoretical studies on the corrosion inhibition of vitamins – Thiamine hydrochloride
or biotin in corrosion of mild steel in aqueous chloride environment, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.003
6 A. Aloysius et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx

carboxylic group in VB7 exists in ionized form in the 240 ppm chlo-
ride ion medium.
The UV–Vis absorption spectroscopy is a suitable method for
identification of complex ions in solution and with the change in
position of the absorption maximum indicates the formation of a
complex between two species in solution. The UV–Vis absorption
spectrum in Fig. 7 was taken for 240 ppm chloride ion medium
containing 200 ppm of vitamin (VB1 or VB7) and 300 ppm of Fe
(FeSO4). The absorption spectrum of VB1 in chloride ion medium
had three adsorption bands with maxima at 198, 233 and
267 nm. The last two absorption maxima 233 and 267 nm were
mainly due to the excitation in pyrimidine component of VB1
Fig. 4. Equivalent electrical circuit used to fit the impedance spectra obtained for
[46,47] because thiazole component exhibited absorption maxi-
mild steel immersed in 240 ppm aqueous chloride medium in the absence and mum at 253 nm [48]. After 24 h, there was a change in the position
presence of VB1 or VB7. of the absorption maxima to 194 and 246 nm for VB1+Fe in chlo-
ride ion medium which indicated the formation of a complex
VB7 in completely ionized form [45]. The disappearance of between VB1 and Fe. Similarly, the absorption spectrum for VB7
1708 cm1 and 1240 cm1 peaks implied that there was an interac- in chloride ion medium had absorption maximum at only
tion of ureido ring with the mild steel surface and appearance of 193 nm. After 24 h, the absorption curve for VB7+Fe in chloride
strong peaks at 1571 cm1 and 1408 cm1 indicated that the ion medium exhibited very small shift in absorption band, which

Fig. 5. FTIR spectra of MS in chloride medium, MS in VB1 and chloride medium and VB1.

Fig. 6. FTIR spectra of MS in chloride medium, MS in VB7 and chloride medium and VB7.

Please cite this article in press as: A. Aloysius et al., Experimental and theoretical studies on the corrosion inhibition of vitamins – Thiamine hydrochloride
or biotin in corrosion of mild steel in aqueous chloride environment, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.003
 A. Aloysius et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx 7

Fig. 7. UV–Vis spectrum for VB1 and VB7 system in 240 ppm chloride ion medium.

indicated the complex formation between VB7 and Fe. However,

the shift of absorption band for VB1 was greater than the shift of
absorption band for VB7 confirming that VB1 adsorbed better on
the mild steel surface than VB7.

3.5. Surface analysis

Scanning Electron Microscopy (SEM) images and their corre-

sponding Energy Dispersive Spectroscopy (EDS) spectra were
obtained and shown in Figs. 8and 9. The smooth surface with
scratches due to abrasion with emery sheets was the mild steel
surface before immersion (see Fig. 8(a)). After immersion in
240 ppm aqueous chloride medium, the roughness due to pits
was observed in the mild steel surface shown in Fig. 8(b). (c) and
(d) represent the images of mild steel immersed in VB1 and VB7,
respectively.
On comparing the SEM images, it was evident that the VB1 and
VB7 was adsorbed on the surface of the mild steel which was indi-
cated by the smooth surface in the Fig. 8(c) and (d). In (c), the
patches were due to accumulated VB1 on the adsorbed mild steel
surface. The corresponding EDS spectra to the SEM image Fig. 8
(a)–(d) were shown in Fig. 9(a)–(d). In Fig. 9(b), the presence of
chloride ion was responsible for the pitting in the mild steel seen
in Fig. 8(b). Sodium ions were confirmed to have no influence on
the corrosion behavior [49]. The absence of chloride ion in Fig. 9
(c) and (d) implied that the inhibitor VB1 or VB7 was adsorbed
on the mild steel which was indicated by the presence of nitrogen
Fig. 8. SEM images of surface of mild steel: a) polished mild steel, b) mild steel
and sulphur in EDS spectra (see Fig. 9(c) and (d)) and smooth SEM
immersed in 240 ppm of aqueous chloride medium and mild steel immersed in
images of VB1 and VB7 (see Fig. 8(c) and (d)). The protective 240 ppm of aqueous chloride medium in presence of c) VB1 and d) VB7.
adsorbed film of VB1 or VB7 prevented the contact of chloride
ion to the metal surface and prevented the further corrosion of
mild steel.
of VB1 and VB7 such as the energy of the highest occupied
3.6. Quantum chemical calculation molecular orbital (EHOMO), the energy of the lowest unoccupied
molecular orbital (ELUMO), the gap energy DEgap, the dipole
The quantum chemical calculation plays a vital role in selecting moment (l), the electronegativity (v), the global hardness (c),
the best corrosion inhibitor with required structural characteris- the global softness (r) and the total energy (ET) were calculated
tics. This theoretical approach helps to find the corrosion inhibition and listed in Table 4. The optimized geometry, HOMO and LUMO
effectiveness which depends on the molecular structure. The calcu- of VB1 and VB7 were shown in Fig. 10. The electrostatic potential
lated quantum chemical parameters related to the inhibition effect surface of VB1 and VB7 were shown in Fig. 11.

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or biotin in corrosion of mild steel in aqueous chloride environment, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.003
8 A. Aloysius et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx

Fig. 9. EDS spectra of the surface of mild steel: a) polished mild steel b) mild steel immersed in 240 ppm of aqueous chloride medium and mild steel immersed in 240 ppm of
aqueous chloride medium in presence of c) VB1 and d) VB7.

Table 4
Quantum chemical parameters for VB1 and VB7 calculated by DFT/B3LYP/6-31G* method.

Vitamin EHOMO (eV) ELUMO (eV) DΕgap (eV) m (Debye) v c r Total Energy (a.u)
VB1 9.661 5.892 3.769 7.096 7.776 1.884 0.531 1159.70
VB7 6.250 0.305 6.555 2.999 3.277 2.972 0.336 1124.10

Fig. 10. Optimized geometries for (a) VB1 and (b) VB7, distribution of HOMO energy of (c) VB1 and (d) VB7 and distribution of LUMO energy of (e) VB1 and (f) VB7.

Please cite this article in press as: A. Aloysius et al., Experimental and theoretical studies on the corrosion inhibition of vitamins – Thiamine hydrochloride
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 A. Aloysius et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx 9

Fig. 11. Electrostatic potential surface of compound VB1 and VB7.

Fig. 12. The gas phase optimized geometries of Fe-Vitamins (VB1 or VB7) complexes.

A molecule to be effective corrosion inhibitor, it must donate inhibitor is less due to low reactivity with the metal surface and
electrons to the vacant d orbital of the metal for bonding and/or lower the DE value implies that the inhibitor is having higher inhi-
receive free electrons from the metal surface [50]. The frontier bition efficiency due to high reactivity with metal surface [50–53].
molecular orbital are involved in the bonding between the corro- The dipole moment (l) and electronegativity (v) are important
sion inhibitor and the metal surface. The frontier molecular orbital quantum chemical parameter which represents the distribution of
are highest occupied molecular orbital (HOMO) and lowest unoc- electrons in the molecular structure and electron attracting capac-
cupied molecular orbital (LUMO). The difference in energies i.e. ity of the molecule, respectively. High value of l probably
energy gap (DE = ELUMO  EHOMO) of the HOMO and the LUMO of increases the inhibitor adsorption through electronic force [54].
the corrosion inhibitor is considered for the effective chemical The dipole moments in Table 4 of VB1 and VB7 are 7.096 and
adsorption of the inhibitor (reactivity) on the metal surface. Higher 2.999 Debye, which indicates that there are strong dipole–dipole
energy of the HOMO (EHOMO) indicates the electron donating interactions between VB1 and metal surface when compared to
ability of the inhibitor molecule to the unoccupied d-orbital of the interactions of VB7 with metal surface. In addition to that,
the metal and lower energy of the LUMO (ELUMO) indicates the VB1 possess high electronegativity (vVB1 (7.776) > vVB7 (3.277))
electron accepting ability of the inhibitor molecule from the metal. than VB7 and so VB1 gets adsorbed on the metal surface strongly
Larger the DE value implies that the inhibition efficiency of the and has high inhibition efficiency. Global hardness (c) and global

Please cite this article in press as: A. Aloysius et al., Experimental and theoretical studies on the corrosion inhibition of vitamins – Thiamine hydrochloride
or biotin in corrosion of mild steel in aqueous chloride environment, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.003
10 A. Aloysius et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx

softness (r) are another important property to measure the reac- 8. The theoretical studies are in close agreement with the experi-
tivity of an inhibitor. A hard molecule has a large energy gap while mental results; it showed that both VB1 and VB7 are good
a soft molecule is characterized by a small energy gap. Soft mole- organic corrosion inhibitors.
cules are more reactive than hard ones because they could easily
offer electrons to an acceptor. According to HSAB principle, soft
acids react with soft bases and hard acid reacts with hard bases. References
Bulk metals are soft acids and so the corrosion inhibitor must be
soft base for high adsorption on the metal surface and to have high [1] M.J. Esmacher, Corrosion control in industrial water systems, in: Z. Amjad
corrosion inhibition efficiency. Generally, if the inhibitors has low- (Ed.), The Science and Technology of Industrial Water Treatment, CRC Press,
New York, 2010, pp. 319–342.
est global hardness (c) and highest global softness (r), they have
[2] Z. Szklarska-Smialowska, J. Mankowski, Crevice corrosion of stainless steels in
higher reactivity towards the metal surface [55]. The calculated sodium chloride solution, Corros. Sci. 18 (1978) 953–960.
values of softness follow the order: VB1 > VB7 (see Table 4), which [3] J.W. Oldfield, Test techniques for pitting and crevice corrosion resistance of
stainless steels and nickel-base alloys in chloride-containing environments,
further supports the better adsorption power of VB1 on the metal
Int. Mater. Rev. 32 (1987) 153–172.
surface when compared with VB7. [4] G.S. Frankel, Pitting corrosion of metals: a review of the critical factors, J.
To find the active site for the metal interaction with vitamins, Electrochem. Soc. 145 (1998) 2186–2198.
the different electron rich centre (i.e., amino pyrimidine and thia- [5] L.-B. Niu, K. Nakada, Effect of chloride and sulfate ions in simulated boiler
water on pitting corrosion behavior of 13Cr steel, Corros. Sci. 96 (2015) 171–
zole rings of VB1 and ureido and thiophene ring and carboxyl 177.
group of VB7) of the vitamins were taken into consideration and [6] B. Sanyal, Organic compounds as corrosion inhibitors in different
the resulting input geometry was optimized. The optimized environments—a review, Prog. Org. Coat. 9 (1981) 165–236.
[7] P.B. Raja, M.G. Sethuraman, Natural products as corrosion inhibitor for metals
geometries and binding energies (DE) are given in Fig. 12. The cal- in corrosive media—a review, Mater. Lett. 62 (2008) 113–116.
culated binding energy suggested that the favored site for interac- [8] G. Gece, Drugs: a review of promising novel corrosion inhibitors, Corros. Sci. 53
tion with the metal surface is the N atom in the amino pyrimidine (2011) 3873–3898.
[9] M. Bouklah, B. Hammouti, A. Aouniti, T. Benhadda, Thiophene derivatives as
of VB1 and ureido ring and S atom of the thiophene ring. These effective inhibitors for the corrosion of steel in 0.5 M H2SO4, Prog. Org. Coat.
results also revealed that the lone pair electron on the N atoms 49 (2004) 225–228.
has the utmost affinity with the metal atom/surface than the p [10] L. Yohai, M. Vázquez, M.B. Valcarce, Phosphate ions as corrosion inhibitors for
reinforcement steel in chloride-rich environments, Electrochim. Acta 102
electrons of the pyrimidine and ureido rings. These findings sug- (2013) 88–96.
gested that the VB1 shows the strong affinity towards the metal [11] A. Kosari, M.H. Moayed, A. Davoodi, R. Parvizi, M. Momeni, H. Eshghi, H.
atom, compared to the VB7 and also good agreement with the Moradi, Electrochemical and quantum chemical assessment of two organic
compounds from pyridine derivatives as corrosion inhibitors for mild steel in
experimental results.
HCl solution under stagnant condition and hydrodynamic flow, Corros. Sci. 78
(2014) 138–150.
4. Conclusions [12] M. Yadav, S. Kumar, R.R. Sinha, I. Bahadur, E.E. Ebenso, New pyrimidine
derivatives as efficient organic inhibitors on mild steel corrosion in acidic
medium: electrochemical, SEM, EDX, AFM and DFT studies, J. Mol. Liquids 211
1. The vitamin VB1 and VB7 act as worthy corrosion inhibitors for (2015) 135–145.
mild steel in 240 ppm chloride ion solution. Their inhibition [13] A.A. Al-Sarawy, A.S. Fouda, W.A.S. El-Dein, Some thiazole derivatives as
corrosion inhibitors for carbon steel in acidic medium, Desalination 229
efficiencies increase with increasing concentration of inhibitors. (2008) 279–293.
The values of the inhibition efficiency of 200 ppm VB1 and VB7 [14] S. Hejazi, S. Mohajernia, M.H. Moayed, A. Davoodi, M. Rahimizadeh, M.
acquired from the weight loss measurement at 240 ppm chlo- Momeni, A. Eslami, A. Shiri, A. Kosari, Electrochemical and quantum chemical
study of thiazolo-pyrimidine derivatives as corrosion inhibitors on mild steel
ride ion solution were 91.42% and 91.38%, respectively.
in 1 M H2SO4, J. Ind. Eng. Chem. 25 (2015) 112–121.
2. The vitamin VB1 and VB7 act as mixed-type inhibitors without [15] G. Bereket, E. Hür, C. Öğretir, Quantum chemical studies on some imidazole
changing the mechanism of hydrogen evolution that is con- derivatives as corrosion inhibitors for iron in acidic medium, J. Mol. Struct.
(Thoechem) 578 (2002) 79–88.
firmed by potentiodynamic polarization studies.
[16] J. Fang, J. Li, Quantum chemistry study on the relationship between molecular
3. The electrochemical impedance studies of VB1 and VB7 in structure and corrosion inhibition efficiency of amides, J. Mol. Struct.
240 ppm chloride ion solution confirmed that the charge trans- (Thoechem) 593 (2002) 179–185.
[17] R. Yıldız, A. Döner, T. Doğan, I. _ Dehri, Experimental studies of 2-
fer resistance increases, whereas the double layer capacitance
pyridinecarbonitrile as corrosion inhibitor for mild steel in hydrochloric acid
reduces. This is due to the thickness of electrical double layer solution, Corros. Sci. 82 (2014) 125–132.
formed by the adsorption of VB1 or VB7 on the surface of mild [18] M.S.S. Morad, A.E.-H.A. Hermas, M.S.A. Aal, Effect of amino acids containing
steel. sulfur on the corrosion of mild steel in phosphoric acid solutions polluted with
Cl, F and Fe3+ ions–behaviour near and at the corrosion potential, J. Chem.
4. The formation of Fe–VB1 or Fe–VB7 complex was undoubtedly Technol. Biotechnol. 77 (2002) 486–494.
indicated by UV–visible spectrophotometric studies and [19] A. Chirkunov, Y. Kuznetsov, Chapter 4 - corrosion inhibitors in cooling water
adsorption of VB1 or VB7 on the mild steel surface was con- systems, in: Z.A.D. Demadis (Ed.), Mineral Scales and Deposits, Elsevier,
Amsterdam, 2015, pp. 85–105.
firmed by FT-IR spectra. [20] N. Patni, S. Agarwal, P. Shah, Greener approach towards corrosion inhibition,
5. The adsorption of VB1 or VB7 on the mild steel was also con- Chin. J. Eng. 2013 (2013) 10.
firmed by the presence of nitrogen and sulphur signal in EDS [21] I. Sekine, Y. Nakahata, H. Tanabe, The corrosion inhibition of mild steel by
ascorbic and folic acids, Corros. Sci. 28 (1988) 987–1001.
spectra.
[22] S. Malhotra, G. Singh, Vitamins: potential inhibitors for nickel in acidic media,
6. The difference in surface morphology of mild steel surface due Surf. Eng. 21 (2005) 187–192.
to formation of protective layer by VB1 or VB7 was confirmed [23] R. Solmaz, Investigation of corrosion inhibition mechanism and stability of
by SEM image. Vitamin B1 on mild steel in 0.5 M HCl solution, Corros. Sci. 81 (2014) 75–84.
[24] R. Fuchs-Godec, G. Zerjav, Corrosion resistance of high-level-hydrophobic
7. From the DFT calculations, the frontier molecular orbitals such layers in combination with Vitamin E – (a-tocopherol) as green inhibitor,
as HOMO and LUMO showed that the studied inhibitors adsorb Corros. Sci. 97 (2015) 7–16.
through the active centers (O, S and N atoms) and p electrons of [25] O.K. Abiola, M.O. John, P.O. Asekunowo, P.C. Okafor, O.O. James, 3-[(4-amino-2-
methyl-5-pyrimidinyl) methyl]-5- (2-hydroxyethyl)-4-methyl thiazolium
the amino pyrimidine and thiazole rings of VB1 and ureido ring chloride hydrochloride as green corrosion inhibitor of copper in HNO3
and carboxyl group of VB7. Inhibition efficiency of VB1 was bet- solution and its adsorption characteristics, Green Chem. Lett. Rev. 4 (2011)
ter when compared to VB7 and it can be understood on the 273–279.
[26] R.F. Godec, M.G. Pavlović, M.V. Tomic, The inhibitive effect of vitamin-C on the
basis of the quantum chemical parameters value such as EHOMO, corrosive performance of steel in HCl solutions, Int. J. Electrochem. Sci. 8
ELUMO, DE, and l. (2013) 1511–1519.

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 A. Aloysius et al. / Egyptian Journal of Petroleum xxx (2017) xxx–xxx 11

[27] R. Hoseizadeh Ali, I. Danaee, H. Maddahy Mohammed, Thermodynamic and [38] L.C. Murulana, M.M. Kabanda, E.E. Ebenso, Experimental and theoretical
adsorption behaviour of vitamin B1 as a corrosion inhibitor for AISI 4130 steel studies on the corrosion inhibition of mild steel by some sulphonamides in
alloy in HCl solution, Zeitschrift für Physikalische Chemie International Journal aqueous HCl, RSC Adv. 5 (2015) 28743–28761.
of Research in Physical Chemistry and Chemical Physics (2013) 403. [39] W.-K. Lu, R.L. Elsenbaumer, B. Wessling, Corrosion protection of mild steel by
[28] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman coatings containing polyaniline, Synth. Met. 71 (1995) 2163–2166.
Jr., J.A. Montgomery, T. Vreven, K.N. Kudin, J.C. Burant, J.M. Millam, S.S. Iyengar, [40] S. Breda, I.D. Reva, L. Lapinski, M.J. Nowak, R. Fausto, Infrared spectra of pyrazine,
J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G.A. pyrimidine and pyridazine in solid argon, J. Mol. Struct. 786 (2006) 193–206.
Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, [41] N. Leopold, S. Cîntă-Pînzaru, M. Baia, E. Antonescu, O. Cozar, W. Kiefer, J. Popp,
M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.E. Knox, H. Raman and surface-enhanced Raman study of thiamine at different pH values,
P. Hratchian, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Vib. Spectrosc. 39 (2005) 169–176.
Stratman, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, P.Y. [42] G.V. Joshi, H.A. Patel, B.D. Kevadiya, H.C. Bajaj, Montmorillonite intercalated
Ayala, K. Morokuma, G.A. Voth, P. Salvador, J.J. Dannenberg, V.G. Zakrzewski, S. with vitamin B1 as drug carrier, Appl. Clay Sci. 45 (2009) 248–253.
Dapprich, A.D. Daniels, M.C. Strain, O. Farkas, D.K. Malick, A.D. Rabuck, K. [43] G. Socrates, Infrared and Raman Characteristic Group Frequencies, John Wiley
Raghavachari, J.B. Foresman, J.V. Ortiz, Q. Cui, A.G. Baboul, S. Clifford, J. & Sons Ltd, West Sussex, England, 2001.
Cioslowski, B.B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R.L. [44] N.A. Lapin, Y.J. Chabal, Infrared characterization of biotinylated silicon oxide
Martin, D.J. Fox, T. Keith, M.A. Al-Laham, C.Y. Peng, A. Nanayakkara, M. surfaces, surface stability, and specific attachment of streptavidin, J. Phys.
Challacombe, P.M.W. Gill, B. Johnson, W. Chen, M.W. Wong, C. Gonzalez, J.A. Chem. B 113 (2009) 8776–8783.
Pople, Gaussian 03, Revision E.01, Gaussian Inc., Wallingford CT, 2004. [45] R. Barbucci, A. Magnani, C. Roncolini, S. Silvestri, Antigen–antibody recognition
[29] H. Ashassi-Sorkhabi, Z. Ghasemi, D. Seifzadeh, The inhibition effect of some by Fourier transform IR spectroscopy/attenuated total reflection studies:
amino acids towards the corrosion of aluminum in 1 M HCl + 1 M H2SO4 biotin–avidin complex as an example, Biopolymers 31 (1991) 827–834.
solution, Appl. Surf. Sci. 249 (2005) 408–418. [46] R.R. Williams, A.E. Ruehle, J. Finkelstein, Studies of crystalline vitamin B1. XV.
[30] A.K. Singh, M.A. Quraishi, Investigation of adsorption of isoniazid derivatives at C-methylated 6-amino- and 6-oxypyrimidines, J. Am. Chem. Soc. 59 (1937)
mild steel/hydrochloric acid interface: Electrochemical and weight loss 526–530.
methods, Mater. Chem. Phys. 123 (2010) 666–677. [47] F.M. Uber, F. Verbrugge, Photochemistry and absorption spectroscopy of the
[31] C. Verma, M.A. Quraishi, A. Singh, 5-Substituted 1H-tetrazoles as effective pyrimidine component of vitamin B1, J. Biol. Chem. 134 (1940) 273–282.
corrosion inhibitors for mild steel in 1 M hydrochloric acid, J. Taibah Univ. Sci. [48] A.E. Ruehle, Studies of crystalline vitamin B1. XIII. Ultraviolet absorption of
10 (2016) 718–733. some derivatives of the basic cleavage product and their synthetic analogs 1, J.
[32] D.V. Ribeiro, C.A.C. Souza, J.C.C. Abrantes, Use of electrochemical impedance Am. Chem. Soc. 57 (1935) 1887–1888.
spectroscopy (EIS) to monitoring the corrosion of reinforced concrete, Revista [49] M. Hirano, S. Itaba, T. Sakurada, Y. Imaizumi, T. Minami, L.-B. Niu, H. Takaku,
IBRACON de Estruturas e Materiais 8 (2015) 529–546. Accelerated corrosion behavior due to alternating dry-wet conditions for LP
[33] F. Mansfeld, Electrochemical impedance spectroscopy (EIS) as a new tool for steam turbine materials of fossil power plants, ISIJ Int. 45 (2005) 373–379.
investigating methods of corrosion protection, Electrochim. Acta 35 (1990) [50] G. Gece, The use of quantum chemical methods in corrosion inhibitor studies,
1533–1544. Corros. Sci. 50 (2008) 2981–2992.
[34] B. Xu, Y. Ji, X. Zhang, X. Jin, W. Yang, Y. Chen, Experimental and theoretical [51] N. Khalil, Quantum chemical approach of corrosion inhibition, Electrochim.
studies on the corrosion inhibition performance of 4-amino-N, N-di- (2- Acta 48 (2003) 2635–2640.
pyridylmethyl)aniline on mild steel in hydrochloric acid, RSC Adv. 5 (2015) [52] M.S. Masoud, M.K. Awad, M.A. Shaker, M.M.T. El-Tahawy, The role of structural
56049. chemistry in the inhibitive performance of some aminopyrimidines on the
[35] M.A. Hegazy, A.S. El-Tabei, A.H. Bedair, M.A. Sadeq, Synthesis and inhibitive corrosion of steel, Corros. Sci. 52 (2010) 2387–2396.
performance of novel cationic and gemini surfactants on carbon steel [53] T. Ghailane, R.A. Balkhmima, R. Ghailane, A. Souizi, R. Touir, M. Ebn Touhami,
corrosion in 0.5 M H2SO4 solution, RSC Adv. 5 (2015) 64633–64650. K. Marakchi, N. Komiha, Experimental and theoretical studies for mild steel
[36] S.A. Umoren, M.M. Solomon, U.M. Eduok, I.B. Obot, A.U. Israel, Inhibition of corrosion inhibition in 1 M HCl by two new benzothiazine derivatives, Corros.
mild steel corrosion in H2SO4 solution by coconut coir dust extract obtained Sci. 76 (2013) 317–324.
from different solvent systems and synergistic effect of iodide ions: ethanol [54] F. Zhang, Y. Tang, Z. Cao, W. Jing, Z. Wu, Y. Chen, Performance and theoretical
and acetone extracts, J. Environ. Chem. Eng. 2 (2014) 1048–1060. study on corrosion inhibition of 2-(4-pyridyl)-benzimidazole for mild steel in
[37] K.B. Samardzija, C. Lupu, N. Hackerman, A.R. Barron, A. Luttge, Properties and hydrochloric acid, Corros. Sci. 61 (2012) 1–9.
surface morphology of a group of heterocyclic diazoles as inhibitors for acidic [55] X. Li, X. Xie, S. Deng, G. Du, Inhibition effect of two mercaptopyrimidine
iron corrosion, Langmuir 21 (2005) 12187–12196. derivatives on cold rolled steel in HCl solution, Corros. Sci. 92 (2015) 136–147.

Please cite this article in press as: A. Aloysius et al., Experimental and theoretical studies on the corrosion inhibition of vitamins – Thiamine hydrochloride
or biotin in corrosion of mild steel in aqueous chloride environment, Egypt. J. Petrol. (2017), http://dx.doi.org/10.1016/j.ejpe.2017.06.003