Journal of Molecular Structure 1214 (2020) 128231

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Journal of Molecular Structure

journal homepage: http://www.elsevier.com/locate/molstruc

Chondroitin sulfate as potent green corrosion inhibitor for mild steel

in 1 M HCl
Megha Basik , Mohammad Mobin *
Corrosion Research Laboratory, Department of Applied Chemistry, Faculty of Engineering and Technology, Aligarh Muslim University, Aligarh, 202002, India

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

Article history: Chondroitin sulfate (CS) was studied as an effective green corrosion inhibitor for mild steel in 1 M HCl
Received 18 February 2020 using gravimetric (303e333 K), potentiodynamic polarization (PDP), electrochemical impedance spec-
Received in revised form troscopy (EIS), SEM/EDAX, FT-IR, UVeVisible spectroscopy, DFT analysis and molecular dynamics (MD)
4 April 2020
simulation. The gravimetric parameters revealed that inhibition efficiency depends both on the tem-
Accepted 8 April 2020
perature of corrosive solution and concentration and further supports its long term stability in aggressive
Available online 13 April 2020
solution. The maximum %IE of 95.4% is observed at concentration of 500 ppm at 333 K. PDP analysis
suggests that compound acts as mixed type of inhibitor with anodic dominance. EIS data revealed the
Keywords:
EIS
formation of a protective film by the adsorbed inhibitor. SEM/EDAX studies adequately supported the
PDP existence of protective layer on mild steel surface in inhibited acid solution. The binding of Chondroitin
FTIR sulfate with mild steel surface in aggressive acid solution was further supported by DFT and MD simu-
DFT lation studies.
MD Simulation © 2020 Elsevier B.V. All rights reserved.

1. Introduction However these compounds are carcinogenic and poisonous for

Low cost and sufficient mechanical strength of mild steel make
it a widely used material in many industrial applications including
construction and oil-refining industries. However, mild steel un-
dergoes oxidation easily in presence of moisture, acids, bases etc.,
thus degrade and corrode at the surface. Corrosion doesnot affect
the material immediately but it slowly affects the mechanical
strength, physical appearance and mechanical operation which
cause severe and serious accidental conditions. Many industries use
acids for pickling, degreasing, descaling and acidizing. Use of acids
in these industries deteriots the mild steel surface and thus
dissolution process occurs. So to minimize or retard the corrosion
process and to increase materials longevity, inhibitors are added.
Corrosion inhibitors mainly contains heteroatoms such as S, N, O
and conjugated pi electron system in their structure. Inhibitors are
beleived to protect the surface by process of adsorption resulting in
the formation of thin protective film over the metals surface [1].
Inorganic compounds such as chromates, nitrates, phosphates etc.
are used for protecting metal against corrosion. They form a passive
film on metal surface and thus retard the corrosion process.
* Corresponding author.
E-mail address: drmmobin@hotmail.com (M. Mobin).
environment, thus their usage is restricted [2]. One of the approach
to stop corrosion without harming the environment is the use of
natural inhibitors available in the environment. They are easily
available, harmless to ecosystem, biodegradable and are economi-
cally viable. Recently, plant extracts and natural polymers have gain
attention as corrosion inhibitors due to their excellent inhibitive
property, biodegradability, easy availability and economic feasi-
bility. Plant extracts contains various active species which get
adsorbed on steel surface and thus protect steel against corrosion
[3e5]. Various exudate gum and other natural polymeric com-
pounds like, xanthan gum,tragacanth gum, starch, chitosan, pectin,
carboxymethyl cellulose have been tested and found as potent
corrosion inhibitors [6,7]. Natural gums and polymers comprise of
long chain with various heteroatoms attached in it. These polymer
chain covers large surface area in the form of blanket over mild
steel surface and thus act as shielding agent and protects steel
against corrosion. Here, in present study we are using a glycos-
aminoglycan known as Chondroitin sulfate. It is found both in
vertebrates and invertebrates abundantly in bones, cartilage, nerve
tissue and blood vessels [8,9]. It is mucopolysaccharide which
comprise of alternating units of glucuronic acid and acetylga-
lactosamine with sulfate group attached to galactosamine residue
[10]. It is widely used in curing osteoarthritis and has good anti-
inflammatory activity. It also helps in developing central nervous

https://doi.org/10.1016/j.molstruc.2020.128231
0022-2860/© 2020 Elsevier B.V. All rights reserved.
2 M. Basik, M. Mobin / Journal of Molecular Structure 1214 (2020) 128231
system [11]. Gravimetric, electrochemical, surface characterization
and theoretical (DFT, MD simulation) studies were used to establish
the corrosion inhibition characteristics of Chondroitin sulfate.
2. Experimental
2.1. Sample and solution preparation
Chondroitin sulfate was commercially procured. The corrosion
inhibition testing of Chondroitin sulfate was carried out on A1020
low carbon steel of rectangular (2.5
2
0.1 cm) and circular
(1 cm2) shaped specimens of chemical composition reported else-
where [12]. The coupons were properly cleaned and polished with
SiC papers of Nº320, Nº400, Nº600 and Nº1200 grade. After that
coupons were rinsed with distilled water, acetone (de-greased) and
then dried. Test solution was prepared by using 37% analytical
grade HCl. 500 ppm stock solution of chondroitin sulfate was pre-
pared in 1 M HCl and the desired concentration was obtained by
diluting the stock solution.
2.2. Gravimetric analysis
The pre-prepared mild steel coupons of rectangular shape were
weighed accurately before immersion in test solution. The coupons
were immersed in triplicate set in 250 ml test solution of each
concentration maintained at 303 K, 313 K, 323 K and 333 K using
thermostated water bath for duration of 6 h. After 6 h, the coupons
were taken out, washed with double distilled water and cleaned to
remove the corrosion product present on their surface. After
cleaning coupons were dried with warm air and weigh again to
record the loss in weight. The average corrosion rate was taken to
calculate the inhibition efficiency at various concentration and
temperature as:
DW
CR ¼
At
w0  wi
%I:E ¼
100
w0
where wo and w’i are the average weight loss values in absence and
presence of various concentration of inhibitor. DW is the weight
loss expressed in mg. ‘A’ is the area of the specimen and ‘t’ is the
time in h.
2.3. Electrochemical analysis
Polished circular coupons were exposed to three electrode glass
cell system operating with Potentiostat/Galvanostat (model:
128 N). The cell comprises a working electrode as mild steel
coupon, reference electrode as Ag/AgCl (saturated KCl) and plat-
inum wire as counter electrodes. The system was allowed to attain
steady state potential in test solution for 60 min. Electrochemical
impedance (EIS) measurements were carried out in the frequency
range of 102 Hze105 Hz with 10 mV peak to peak amplitude sig-
nals. The potentiodynamic polarization curves were recorded by
sweeping the potential ±250 mV at scan rate of 0.001 V/s. The I.E
was calculated by equation reported elsewhere [13].
2.4. Characterization
2.4.1. FT-IR analysis
The functional groups involved in the adsorption process was
assessed by FTIR, which was recorded over 4000 - 400 cm1 using
PerkinElmer Spectrometer.
2.4.2. Surface analysis
Scanning electron microscope (JEOL JSM-6510 LV) attached with
INCA Oxford EDX was used to evaluate the surface morphology and
for identification of elemental composition.
2.4.3. UVeVis analysis
PerkinElmer spectrophotometer Lambda 25 was used to carry
out the UVeVis analysis. Also the data was analyzed by using UV
Winlab Data Processor and Viewer.
2.5. DFT analysis
DFT calculations have been performed utilizing Dmol3 module
implemented in Materials Studio software. GGA (generalized
gradient approximation) level and DNP basis set (double numeric
with polarization) have been used [14,15]. All calculations have
been performed in aqueous phase by applying the Conductor-like
Screening Model (COSMO) model. Moreover, the Fukui indices
have been calculated based on Hirshfeld population analysis using
the same module and parameters.
2.6. Molecular dynamics (MD) simulation
Molecular dynamics (MD) data have been generated with Ma-
terials Studio software. A simulation box has been created in which
the molecules are placed directly contacting the surface of the iron.
Before starting the simulation, there are some important steps to
take, firstly we import Fe into the cleaved on a surface following the
plane (110) with a slab of 6 Å. In the interest of clarifying the re-
actions involved among the inhibitory molecule and the Fe surface,
the crystal reaching the supercell (10
10) is enlarged. Then we
build a cell of size 24.82
24.82
25.14 Å3 in which each inhibitor
molecule is placed with 491 water molecules, 9 molecules of H3Oþ
and 9 of Cl. After that, the set is simulated at a temperature of
303 K, in a simulated volume element (24.82
24.82
35.69 Å3)
(1)
and with a timing increment of 1 fs and simulation duration of
5000 ps. For all molecular simulations, systems built up by applying
the COMPASS force field and the NVT set (constant number of
(2)
molecules, volume and temperature) [16]. The methodology is now
established in metal-inhibitor interaction analysis in order to
compute the correlation and binding energies using the following
Equations [17,18]:
 
Einteraction ¼ Etotal e EsurfaceþH2 OþH3 Oþ þCl þ Einhibitor (3)
Ebinding ¼  Einteraction (4)
where Etotal presents the all-system energy, EsurfaceþH2 OþH3 Oþ þCl
designates the iron energy (110) surface including H2O, H3Oþ, and
Cl, Einhibitor implies the energy of the studied molecule in HCl
medium, and Esurface signifies the energy of Fe (110).
3. Results and discussion
3.1. Gravimetric analysis
3.1.1. Effect of concentration and temperature
The corrosion rate and inhibition efficiency for different con-
centration of inhibitor at temperature range of 303e333 K is listed
in Table 1. The inhibition efficiency increases on increasing the
concentration of inhibitor till 500 ppm. Also the inhibition efficency
increases on increasing the electrolyte temperature, which suggest
chemical adsorption. Here, a strong chemical bond is formed be-
tween the mild steel surface and inhibitor molecules at high
 M. Basik, M. Mobin / Journal of Molecular Structure 1214 (2020) 128231 3

Table 1
Corrosion parameters for mild steel in 1 M HCl in absence and presence of the Chondroitin sulfate from weight loss measurements at different temperatures.

Temperature

303 K 313 K 323 K 333 K

2 1 2 1 2 1
Inhibitor concentration (ppm) CR (mgcm h ) q % I.E CR (mgcm h ) q % I.E CR (mgcm h ) q % I.E CR (mgcm2h1) q % I.E

Blank 0.19 e e 0.44 e e 2.93 e e 6.80 e e

50 0.12 0.35 35.28 0.24 0.45 45.08 1.30 0.55 55.65 2.31 0.66 66.06
100 0.10 0.43 43.50 0.20 0.53 53.29 1.08 0.63 63.03 1.80 0.73 73.43
200 0.09 0.50 50.13 0.17 0.59 59.42 0.90 0.69 69.11 1.42 0.79 79.14
300 0.08 0.58 58.09 0.14 0.67 67.16 0.67 0.76 76.98 1.02 0.84 84.93
400 0.06 0.65 65.52 0.11 0.73 73.52 0.58 0.80 80.00 0.67 0.90 90.03
500 0.05 0.69 69.23 0.09 0.78 78.38 0.42 0.85 85.46 0.30 0.95 95.48

temperature. The maximum inhibition efficiency obtained is 95.4%

at 333 K at 500 ppm.

3.1.2. Effect of immersion time

To check the stability of the studied inhibitor in the aggressive
solution the mass loss experiment at optimum inhibitor concen-
tration was extended for 168 h. The obtained results are shown in
Fig. 1. It was indicative from the plot that initially inhibition effi-
ciency was improved at certain time interval which suggest strong
bond was building up between mild steel surface and inhibitor
molecules. After that constancy in inhibition efficiency was ach-
ieved till the end of immersion period. After completion of im-
mersion test the inhibition efficency of 88.2% was retained, which
confirms the stability of the inhibitor.

Fig. 2. Log CR vs 1/T plots in absence and presence of different concentration of

3.1.3. Activation parameters
Arrhenius equation helps us in finding various activation pa-
rameters such as activation energy (Ea), enthalpy of activation
(DH*) and entropy of activation (DS*) at temperature range
(303e333 K). It was conducted to find out the effect of temperature
on mild steel dissolution in uninhibited and inhibited medium. Plot
of log CR vs. 1/T was constructed which are shown in Fig. 2. The
value of ‘Ea’ and ‘A’ was obtained from the slope and intercept of
linear section of plot. The calculated activation parameters are re-
ported in Table 2. The value of Ea was lower in inhibited medium as
compared to uninhibited medium suggesting chemical adsorption.
Other activation parameters such as DH* (enthalpy) and
DS*(entropy) was obtained from plot of log CR/T vs. 1/T (Fig. 3)
using Eyring transition state equation in absence and presence of
different concentration of Chondroitin sulfate [19]. The enthapic
Chondroitin sulfate.
parameter was calculated from the slope (DH*/2.303R) and
entropic parameter was calculated from the intercept (log R/
NhþDS*/2.303R) of the log CR/T vs. 1/T plot. Calculated activation
parameters are listed in Table 2. The value of DH* is positive which
shows that steel dissolution is slow and endothermic in nature [20].
The value of DS* move towards negative in presence of inhibitor.
This indicates that disorderness decreases on going from reactant
to activated complex state (rate determining step).
3.1.4. Adsorption isotherms
The nature of adsorption of an inhibitor on mild steel surface can
be predicted by employing various isotherms. In present study, it is
found that C/q vs.C (Fig. 4) gives straight line with regression co-
efficient close to unity (R2 ¼ 0.9945) suggesting best fitting for
Langmuir adsorption isotherm [21]. The value of Kads was obtained
from the intercept of the Langmuir plot. With increasing the tem-
perature of the solution, the value of Kads increases suggesting in-
crease in adsorption of inhibitor molecule on mild steel surface. The
value of DGads was obtained by using following relation with Kads.
 
DGads ¼  RT ln 1
106 Kads (5)

where R ¼ universal gas constant, T ¼ temperature in Kelvin,

Fig. 1. Plot of %I.E vs. immersion time for mild steel in 1 M HCl with 500 ppm con-
centration of Chondroitin sulfate at 303 K.
1
106 ¼ concentration of water in mgL1 [22]. The value of DGads
is negative and hence process is spontaneous. The value DGads less
than 20 kJ/mol suggests physical adsorption, the value of DGads
greater than 40 kJ/mol suggests chemical adsorption while in
present study the value of DGads lies between 20 kJ/mol
and 40 kJ/mol suggesting mixed type of adsorption. The plot of ln
Kads vs. 1/T (Fig. 5) was constructed and other adsorption parame-
ters such as DHads (slope) and DSads (intercept) was calculated. All
the obtained parameters are mentioned in Table 3. The obtained
4 M. Basik, M. Mobin / Journal of Molecular Structure 1214 (2020) 128231

Table 2
Activation parameters for mild steel in 1 M HCl in the absence and presence of different concentrations of the Chondroitin sulfate.

Inhibitor concentration (ppm) Pre-exponential factor (A) Ea (kJ mol1) DH* (kJ mol1) DS* (J mol1K1)
(g m2 h1)

Blank 37,021,153 105.63 102.99 79.91

50 1400024.1 87.65 85.01 17.19
100 804519.11 84.76 82.12 6.59
200 438011.31 81.51 78.87 5.06
300 187212.57 77.01 74.37 21.33
400 77265.282 72.27 69.62 38.28
500 3532.2841 54.44 51.80 97.37

Fig. 5. Plot of ln Kads versus 1/T for mild steel in 1 M HCl solution containing different
concentration of Chondroitin sulfate.

Fig. 3. Log CR/T vs 1/T plots in absence and presence of different concentration of
Chondroitin sulfate.
namely Rs (solution resistance), Rp (polarization resistance) and Cdl
(double layer capacitance). For uninhibited medium Rp consist of
Rct (charge transfer resistance) and Rd (double layer resistance)
while for inhibited medium Rp consists of Rct, Rf (film resistance)
and Ri (resistance of all accumulated species) at metal-solution
interface [25]. The Nyquist plots shows single semi-circle (capaci-
tive loop). The diameter of loop increases on increasing the con-
centration of the inhibitor. The loops are depressed and are not
accurate semicircles because of surface roughness and irregularity.
A constant phase element (CPE) is introduced to overcome these
irregularities. CPE is defined by following relationship:

1
ZCPE ¼ (6)
YoðjuÞn

where Yo ¼ CPE magnitude, j ¼ imaginary number, u ¼ angular

frequency and n ¼ phase shift. From the value of CPE, Cdl can be
Fig. 4. Langmuir adsorption isotherm graphs of C/q versus C of WL data at 303e333 K
calculated as:
for mild steel in 1 M HCl solution containing different concentration of Chondroitin
sulfate.

Cdl ¼ Yoðumax Þn1 (7)

value of DHads is positive (endothermic nature). Also the value of
DHads > 0 suggests chemical adsorption process. The value of DSads
obtained is positive which shows more water molecules are des-
orbed by one inhibitor molecule [23,24].
3.2. Electrochemical impedance measurements
The electrochemical processes occurring at the metal-solution
interface in absence and presence of different concentration of
inhibitor was predicted by impedance spectra. Fig. 6(a and b) shows
Nyquist and Bode plots in 1 M HCl (Blank) and at different con-
centration of inhibitor. The randles circuit (Fig. 7) was used to fit the
impedance data accurately. The circuit comprises of three elements
where umax ¼ 2pfmax (fmax denotes the impedance at maximum
frequency). All the calculated impedance parameters obtained are
listed in Table 4. It can be seen from Table that value of Rp increases
on increasing the concentration of inhibitor which was due to in-
crease in surface coverage by the molecules of inhibitor. Also, the
value of Cdl decreases on increasing the inhibitor concentration.
This can be attributed by the increase in thickness of layer of
molecules adsorbed at metal-solution interface [26]. Bode plots
shows single phase maxima which corresponds to corrosion pro-
cess occurring in one step at one time constant. On increasing the
concentration of the inhibitor the value of phase angle approach
towards 90 . This indicates that on increasing concentration
inhibitive performance increases [27].
 M. Basik, M. Mobin / Journal of Molecular Structure 1214 (2020) 128231 5

Table 3
The thermodynamic parameters of adsorption of the Chondroitin sulfate at different concentrations for mild steel in 1 M HCl solution.

Temperature (K) R2 Kads (Lmg1) DGads (kJ/mol) DHads (kJ/mol) DSads (kJ/K.mol)
303 0.99 0.009 23.00 29.01 0.172
313 0.99 0.013 24.68 29.01 0.172
323 0.99 0.019 26.57 29.01 0.172
333 0.99 0.025 28.09 29.01 0.172

Fig. 6. (a) Nyquist plot of Chondroitin sulfate at 303 K and (b) Bode modulus and bode phase of Chondroitin sulfate at 303 K.

obtained parameters from polarization curves are listed in Table 5.

It is clearly visualized from Tafel plots (Fig. 8) that both anodic
(metal dissolution) and cathodic (hydrogen ion discharge) reaction
get affected. The addition of inhibitor decrease the corrosion cur-
rent density (Icorr) and corrosion rate (CR), this declining effect
continues as we increase the concentration of inhibitor. On
increasing the amount of inhibitor, the inhibition efficiency in-
creases. The maximum efficiency of 75.39% was obtained at
500 ppm concentration of inhibitor. The values of ba and bc does
not shows specific trend and no significant change was observed on
increasing the inhibitor concentration which suggests no modifi-
cation in the mechanism of both anodic and cathodic reaction. The
Fig. 7. Equivalent circuit.
value of Ecorr shifts towards more positive direction in presence of
inhibitor, the extent of shift is less than 85 mV as compared to
uninhibited medium suggesting mixed type of adsorption with
3.3. Potentiodynamic polarization anodic dominance.

The curves of mild steel polarization in absence and presence of

various concentration was shown in Fig. 8. The inhibition efficiency 3.4. FTIR analysis
can be obtained by using equation mentioned elsewhere [28]. The
The spectrum of Chondroitin sulfate (Fig. 9) indicates

Table 4
Electrochemical parameters of impedance for mild steel in 1 M HCl without and with different concentrations of Chondroitin sulfate at 303 K.

Inhibitor conc. (ppm) Rs (U cm2) Rp (U cm2) Cdl (Fcm2) c2 slope Phase angle % I.E
5
Blank 1.63 17.89 7.96
10 0.0238 0.57 46.07
50 1.73 29.44 5.89
105 0.0293 0.58 51.24 39.21
100 1.32 33.32 7.05
106 0.0270 0.59 54.73 46.28
200 1.97 37.98 6.69
106 0.0404 0.70 56.01 52.87
300 1.80 41.68 6.55
106 0.0050 0.62 59.14 57.05
400 1.84 55.59 5.73
106 0.0040 0.63 60.17 67.80
500 1.18 66.07 5.44
106 0.0316 0.78 62.10 72.91
6 M. Basik, M. Mobin / Journal of Molecular Structure 1214 (2020) 128231

Fig. 8. Tafel plots of mild steel in 1 M HCl in the absence and presence of different
concentrations of Chondroitin sulfate at 303 K.

characteristic sharp peak at 3309 cm1 corresponds to hydroxyl Fig. 9. FTIR spectra of Chondroitin sulfate and Chondroitin sulfate adsorbed on mild
group (-OH). The peak at 2936 cm1 is due to presence of -C-H steel in 1 M HCl.
group. The peak at 1616 cm1 corresponds to C]O group, peak at
1544 cm1 is due to deformation of NeH group, peak at 1251 cm1
corresponds to the OeSO3 group (vibration of the sulfate group).
The peak at 1028 cm1 corresponds to carboxyl group -C-O. The
characteristic peaks at 884 cm1 and 849 cm1 is due to CeOeS
axial and equatorial bending vibration [29,30]. The FTIR spectrum
of Chondroitin sulfate adsorbed on mild steel surface (scrapped
sample) was also conducted to evaluate the functional group
involved in binding with mild steel surface. The spectrum shows all
the characteristics peaks which was present in pure chondroitin
sulfate. The intensity of the characteristic peaks were reduced in
scrapped sample and shifted towards higher or lower wavenumber.
This was due to binding of inhibitor molecule to metal surface. The
reduction and shifting of peaks confirms the formation of inhibitor
film on mild steel surface.

3.5. UVeVis analysis

The complex formation between inhibitor molecule and mild

Fig. 10. UVeVis spectra of pure Chondroitin sulfate and mild steel coupon dipped in
steel surface is examined by performing UVeVis analysis. Fig. 10
Chondroitin sulfate at 303 K.
shows the UVeVis spectrum of pure chondroitin sulfate solution
and solution containing 500 ppm concentration of chondroitin
sulfate with mild steel coupon dipped in it. The spectrum shows the 3.6. Surface analysis
peak at 207 and 285 nm with relative absorbance at 0.59 and 0.12
while the spectrum containing mild steel coupons shows shifting in SEM Analysis has been conducted to know the surface condition
wavelength and increase in absorbance i.e., 222 nm and 337 nm of mild steel in uninhibited and inhibited medium. Fig. 11 (a) shows
with relative absorbance of 2.48 and 0.65 respectively. The increase the SEM micrographs of polished mild steel surface, the surface is
in absorbance value and shifting in the wavelength indicates the smooth and free from pits and defects. Fig. 11(b) shows surface of
good complex formation between inhibitor and mild steel surface.

Table 5
Potentiodynamic polarization results for mild steel in 1 M HCl without and with different concentrations of the Chondroitin sulfate at 303 K.

Inhibitor conc. (ppm) Ecorr (mv) Icorr (A/cm2) ba (mV/dec) bc (mV/dec) % I.E

Blank - 487.94 1.07
103 117.08 73.88

50 - 452.65 7.98
104 85.10 67.70 33.47
100 - 417.82 5.06
104 112.23 127.01 51.74
200 - 421.52 4.81
104 102.69 123.50 56.46
300 - 435.46 4.13
104 91.08 87.77 61.38
400 - 480.93 3.27
104 113.87 81.97 69.39
500 - 466.74 2.63
104 83.30 62.52 75.39
 M. Basik, M. Mobin / Journal of Molecular Structure 1214 (2020) 128231
mild steel dipped in 1 M HCl for 6 h at room temperature. The
surface is severely corroded with visible pits and defects. Fig. 11(c)
shows surface of mild steel dipped in 500 ppm concentration of
inhibitor for 6 h at room temperature. The surface shows lesser pits
and defects as compared to uninhibited medium which confirms
the protective film formation on mild steel surface.
EDAX Analysis has been conducted to know the elemental
confirmation and to know the element taking part in adsorption
process. Polished mild steel shows the elemental peaks consti-
tuting mild steel (Fig. 12 a). Mild steel in uninhibited medium
shows additional elemental peak of Cl along with peaks of elements
present in steel composition (Fig. 12 b). The mild steel in inhibited
medium shows additional peaks of N and S and absence of Cl peak
(Fig. 12 c) which confirms that these heteroatom’s are responsible
for inhibition process.
3.7. DFT: Global reactivity descriptors
Experimental results demonstrated the effectiveness of chon-
droitin-6-sulfate (CS) in retarding corrosion rate of mild steel in HCl
solution. To show more evidence in this conclusion, and to further
explain the interaction between CS and the iron surface, global
reactivity descriptors have been computed using DFT calculations.
Considering the presence of heteroatom such as oxygen, sulphur
and nitrogen in CS structure, which can lead to a higher suscepti-
bility of CS for protonation in acidic medium, DFT calculations were
performed for one monomer in its neutral and protonated form. An
effective corrosion inhibition requires inhibitors that can not only
accept electrons from d-orbital of iron but also act as good electron
donors [31]. Detailed insights into electron donor and acceptor
abilities of an inhibitor can be obtained by frontier molecular
orbital theory [32]. According to this theory, the HOMO orbital
Fig. 11. SEM images for mild steel (a) polished state (b) exposed to 1 M HCl solution (c)exposed to 1 M HCl solution containing 500 ppm of Chondroitin sulfate for 6 h at 303 K.
7
distribution is usually used to predict zones that are potentially
responsible for electron donation, whereas LUMO orbital is used as
an indicator of the lower electron density area, therefore these
zones are expected to be responsible for accepting electron from
iron surface [33].
Optimized molecular structures, HOMOs and LUMOs distribu-
tion of neutral and protonated CS monomer are shown in
Figs. 13e15 respectively.
From Fig. 14(a), we can observe that the HOMO orbital of neutral
form is mainly located on N-acetylgalactosamine and glucuronic
acid moieties, which means that are both can donate electron to d-
orbital of iron. In contrast, HOMO distribution of protonated
monomer (Fig. 14(b)) reveals that, when monomer is protonated,
the glucuronic acid moiety becomes the only responsible for elec-
tron donation. On the other hand, the LUMO orbital distribution of
neutral monomer in Fig. 15(a) indicates that the carboxyl group
present in the glucuronic acid moiety is the preferred area for
electron accepting. Unsurprisingly, protonated group, which are
present in the N-acetylgalactosamine moiety, are the main electron
accepting area. Overall, these results indicate that the entire neutral
molecule could be in contact with the surface of iron and donate its
electrons while, in contrast, its electron accepting ability is limited
to the carboxyl group of the glucuronic acid moiety. It should be
noted that a change in the chemical state of the monomer alters
significantly its reactivity.
Inside the framework of the DFT method, our purpose is to
calculate the different intrinsic molecular parameters, that are
assumed to transform the global reactions linking the interacting
systems [34]. These parameters include EHOMO and ELUMO, which
can be briefly defined as the energies of the highest occupied
molecular orbital and the lowest unoccupied molecular orbital [35].
These are required to calculate the gap energy DE, which designates
8 M. Basik, M. Mobin / Journal of Molecular Structure 1214 (2020) 128231

Fig. 12. EDAX spectra for mild steel (a) polished state, (b) exposed to 1 M HCl solution and (c) exposed to 1 M HCl solution containing 500 ppm Chondroitin sulfate at 303 K.

Fig. 13. The optimized geometry obtained using DFT of (a) neutral and (b) protonated structure of Chondroitin sulfate.

the reactivity or stability indices of the molecule, IP (ionization

potential) and EA (electronic affinity) by the following equations
IP þ EA
[36]: c¼ (11)
2
DE ¼ ELUMO  EHOMO ¼ IP  EA (8)

IP  EA
IP ¼  EHOMO (9) h¼ (12)
2

EA ¼  ELUMO (10)
1 2
Additionally, absolute electronegativity (c), chemical hardness s¼ ¼ (13)
h IP  EA
(ɳ), softness (s) and the electron transfer fraction (DN) have been
deduced by applying the following equations [16]:
 M. Basik, M. Mobin / Journal of Molecular Structure 1214 (2020) 128231 9

Fig. 14. HOMO orbital distribution obtained using DFT of (a) neutral and (b) protonated structure of Chondroitin sulfate.

Fig. 15. LUMO orbital distribution obtained using DFT of (a) neutral and (b) protonated structure of Chondroitin sulfate.

compound to accept electrons and the other way around [38]. The
∅  cinh electrophilicity also provides information about electron accepting
DN ¼ Fe (14)
2ðhFe þ hinh Þ capability of a molecule while nucleophilicity is a measure of Lewis
basicity [39]. Results in Table 6 clearly shows that the neutral
where ∅Fe ¼ 4.82 eV, and the value of the global hardness of iron, monomer has the maximum ability to donate electrons. These re-
hFe is considered as zero [37]. sults can be further confirmed from the DN values, which, ac-
The comparison between the neutral and protonated monomer cording to previous studies [40,41], indicate the ability of an
parameters (Table 6) shows that the neutral form has the highest inhibitor to donate its electron to metal if DN > 0 and vice versa if
electron donation ability with HOMO value of 5.759 eV and the DN < 0. Results in Table 6 clearly show that CS monomer can donate
lowest electron accepting ability with LUMO value of 2.317 eV in or share electron in neutral and protonated form.
comparison with the achieved parameters for protonated form. Considering the value of the energy gap (DE), which is consid-
Inferior ELUMO value implies an improved capacity of a chemical ered as a useful parameter to prove the reactivity of chemical
molecule and its capacity to be a powerful inhibitor against the
corrosion phenomenon [42]. Although, the low value of the energy
Table 6 gap signifies a higher activity towards the mild steel surface [43].
Quantum chemical parameters of neutral and protonated monomers obtained by
Considering this significant factor, it is observed that the neutral
DFT.
form of monomer has maximum reactivity than protonated form.
Parameter Neutral CS-NHþ Bearing in mind that both protonated and neutral forms of the
EHOMO, (eV) 5.759 6.354 monomer could be present in solution, these results strengthen the
ELUMO, (eV) 2.317 2.197 hypothesis that effective corrosion inhibition is a result of complex
DE, (eV) 3.442 4.157
interactions between inhibitor molecules and metal surface. These
IP, (eV) 5.759 6.354
EA, (eV) 2.317 2.197
involve, on one hand, chemical interactions through lone pair of
, (eV) 1.721 2.079 electrons of heteroatoms and p-electrons, and on the other hand,
c, (eV) 4.038 4.275 electrostatic interactions between protonated molecules and
s, (eV1) 0.581 0.481 positively charged surface of metals [44].
DN 0.227 0.131
10 M. Basik, M. Mobin / Journal of Molecular Structure 1214 (2020) 128231

Table 7 3.8. DFT: Fukui function

The Fukui indices and dual descriptor of investigated monomer estimated using
DFT/GGA/DNP.
The condensed Fukui functions permit the identification of local
Atoms fkþ fk Df ðkÞ reactive sites of an inhibitor molecule in terms of nucleophilic (f þ)
C (1) 0.2 2 2.2 and electrophilic (f -) behavior [45]. Fukui indices of investigated
C (2) 0.4 1.5 1.1 inhibitor are listed in Table 7. The higher positive charges (f þ) of an
C (3) 0.3 1.1 1.4 atomic site notify that this site is privileged to have a nucleophilic
C (4) 0 0.4 0.4 attack character, whereas a site with a significant negative charge (f
O (5) 0.5 0.9 0.4 -
C (6) 1.2 1.8 3
) have the ability to produce an electrophilic attack [46]. For
O (7) 2 5.8 3.8 nucleophilic and electrophilic attack, the condensed Fukui func-
C (8) 0.7 1.5 0.8 tions are proposed as:
C (9) 0.6 1.3 0.7
C (10) 0.6 3.3 2.7 fkþ ¼ qk ðN þ 1Þ  qk ðNÞ (15)
C (11) 1.5 2.8 1.3
O (12) 1.6 8.8 7.2
C (13) 4.3 1.7 2.6 fk ¼ qk ðNÞ  qk ðN  1Þ (16)
C (14) 25.2 1 24.2
O (15) 23.4 1.9 21.5
O (16) 14 1.3 12.7
where qk is the electronic population of an atomic site within a
O (17) 1.1 4.3 3.2 molecule in its neutral (N), anionic (Nþ1) or cationic (N-1) state.
O (18) 2.7 2.3 0.4 The dual descriptor introduced by Morell et al. [47] is given via the
O (19) 1.2 10.4 9.2 following equation:
O (20) 0.8 5.9 6.7
0.1
C (21)
S (22)
0.2
0.3
0.3
0.7 1
Df ðkÞ ¼ fkþ  fk (17)
O (23) 0.7 1.3 2
It is a useful parameter used to distinguish between sites
O (24) 0.2 0.3 0.1
O (25) 0.1 0.7 0.8 preferred for the electrophilic attack and nucleophilic attack.
H (26) 0.2 0.1 0.1 Atomic sites having positive and negative dual descriptor values are
O (27) 0.7 0.2 0.5
N (28) 0.2 1.8 1.6
C (29) 0 1.5 1.5 Table 8
C (30) 0.1 0.8 0.9 Interaction energies of neutral and protonated
O (31) 0.8 3.7 4.5 monomer with Fe(110) obtained by MD simulations in
presence of solvent.
Note that Fukui indices have been multiplied by a factor of 100 for easier direct
comparison. System Einter (kJ/mol)

CS 334.24
CS-NHþ 225.97

Fig. 16. Side views of equilibrium configurations of neutral and protonated monomer obtained by MD simulations.

Fig. 17. Top views of equilibrium configurations of neutral and protonated monomer obtained by MD simulations.
 M. Basik, M. Mobin / Journal of Molecular Structure 1214 (2020) 128231
suitable sites for nucleophilic and electrophilic attack, respectively.
From results in Table 7, we can mention that the most favorable
sites for nucleophilic attack are positioned on C(14), O(15) and
O(16), while O(12), O(19), O(20) and O(31) atoms, would be most
preferred sites for electrophilic attack. These highlight the signifi-
cant contribution of heteroatoms in enhancing the interactivity of
CS monomer, thus its interaction with iron surface.
3.9. Molecular dynamics simulations
Molecular dynamics simulations were used to directly simulate
the corrosion inhibition process. These simulations can provide
useful insights on how the monomer can interact with the iron
surface [48]. In fact to make the simulations more realistic, neutral
and protonated form of the monomer were simulated in solvent
containing all active species (like H2O, H3Oþ, Cl). MD simulations
were performed for 5000 ps where both temperature and energy of
simulated system were in the equilibrium state and remained
constant during the simulation process. Fig. 16 (side views) and
Fig. 17 (top views) show the equilibrium configurations of neutral
and protonated form of the monomer absorbed on the iron surface.
Results depicted in Fig. 16 reveal that neutral and protonated
monomers can adsorb nearly parallel to the iron surface via both N-
acetylgalactosamine and glucuronic acid moieties, which could
obviously favor the formation of insulating layer onto the iron
surface, ensuring therefore high coverage and better protection.
The visual inspection of results provides information about how an
inhibitor molecule adsorb on the metal surface, however, strength
of the interaction between this inhibitor and metal surface cannot
be observed. To this end, inhibitor-metal interaction should be
interpreted in view of interaction and binding energies. As we can
see in Table 8, the interaction energy (which is the opposite value of
the binding energy) of the neutral monomer is very large than the
protonated monomers. Higher negative interaction energies reveal
higher stability of adsorbed molecules and a strong affinity to the
iron surface [49]. As we noticed in the previous section, the entire
neutral monomer is responsible for the electron donating, which
means that neutral monomer can has a strong interaction with the
iron surface as compared to protonated form where only small
zones in the monomer can build interaction with iron atoms. It has
been shown also that reactivity of protonated monomer is limited
to protonated groups, which could explain the low interaction
energy of protonated monomer. That is to say, the neutral monomer
could be strongly adsorbed on metal surface than protonated
monomer, which is expected since the chemical adsorption occurs
through neutral molecules, and it is in accordance with previous
investigations.
4. Conclusion
The following points can be drawn from whole study:
(1) The water soluble Chondroitin sulfate act as a good corrosion
inhibitor in 1 M HCl. The inhibition efficiency were found to
be dependent on both concentration and temperature.
(2) The electrochemical measurements reveal the successful
adsorption of Chondroitin sulfate molecules at metal-
solution interface followed by mixed type of adsorption
mechanism.
(3) The adsorption of Chondroitin sulfate on metal surface obeys
Langmuir adsorption isotherm.
(4) According to FTIR, the presence of eOH, eNH, eC]O, eOSO3
and aromatic ring are the active sites for inhibitor interaction
with metal surface.
11
(5) SEM analysis justify that the presence of inhibitor reduce the
corrosive effect and smoothened the surface of the specimen
as compared to uninhibited medium.
(6) DFT study carried out for neutral as well as protonated forms
of Chondroitin sulfate molecules provide good insight about
the metal-inhibitor interaction as well as support the
experimental order of inhibition efficiency.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
CRediT authorship contribution statement
Megha Basik: Conceptualization, Methodology, Software, Vali-
dation, Writing - original draft. Mohammad Mobin: Writing - re-
view & editing, Validation, Supervision.
Acknowledgment
One of the authors Megha Basik thankfully acknowledges the
financial assistance from DST PURSE, New Delhi.
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