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Original Article

Two ditetrazole derivatives as effective inhibitors

for the corrosion of steel in CH3 COOH solution

Shuduan Deng a,∗ , Xianghong Li b , Guanben Du a

a Faculty of Materials Science and Engineering, Southwest Forestry University, Kunming 650224, PR China
b College of Chemical Engineering, Southwest Forestry University, Kunming 650224, PR China

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

Article history: The inhibition performance of two ditetrazole derivatives of blue tetrazolium (BT) and
Received 22 February 2018 nitrotetrazolium blue chloride (NTBC) on cold rolled steel (CRS) in 2.5 M CH3 COOH solution
Accepted 30 September 2018 was studied by weight loss, electrochemical techniques and scanning electron microscope
Available online xxx (SEM). Quantum chemical calculations of BT2+ and NTB2+ were performed to theoretically
investigate the adsorption mechanism. The results show that both BT and NTBC behave as
Keywords: effective inhibitors, and their maximum inhibition efficiency values are higher than 92%
Corrosion inhibitor at 0.20 mM. The inhibition follows the order of NTBC > BT. The adsorption of either BT or
Acetic acid NTBC on steel surface follows Langmuir isotherm. BT and NTBC can be arranged as mixed-
Steel type inhibitors. The presence of BT or NTBC increases the charge transfer resistance, and
Blue tetrazolium decreases the corrosion degree of steel surface in CH3 COOH. The adsorption centers are
Nitrotetrazolium blue chloride mainly focused on two tetrazole rings as well as the linkers of two benzene rings.
Adsorption © 2018 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier
Editora Ltda. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

could strongly interact with metal surface. The tetrazole

1. Introduction ring is a five-member ring with four N atoms, and so
tetrazole derivatives meet the structural characteristics of
A large number of N-heterocyclic compounds have been
potential good corrosion inhibitors, and their inhibitions
already used as effective inhibitors to retard the steel cor-
have been increasingly received some attentions. Kertit
rosion in various acids media [1–3]. The adsorption of
and Hammouti [4] reported that 1-phenyl-5-mercapto-1,2,3,4-
N-heterocyclic inhibitor onto steel surface is mainly through
tetrazole (PMT) was an effective inhibitor for pure iron in
the N-heterocyclic ring, in which coordinate bonds could be
1.0 M HCl with inhibition efficiency () of 98% at 2.0 mM,
formed between Fe 3d empty orbits and electron pairs of
but other two tetrazole derivatives of 1-H-tetrazole (TTZ)
N hetero-atom(s) as well as ␲ electrons of N-heterocyclic
and 1-methyl-5-mercapto-1,2,3,4-tetrazole (MMT) reversely
ring. If a N-heterocyclic ring contains more N atoms, it
accelerates steel corrosion with negative  values of −1.5%
and −0.5% at 2.0 mM, respectively. Also, the optimum 
of 1.0 mM PMT was as high as 98% for the corrosion of
∗
Corresponding author. steel in both 1/2 M H2 SO4 and 1/3 M H3 PO4 solutions [5].
E-mail: dengshuduan@163.com (S. Deng). According to another previous work studied by Morales-Gil
https://doi.org/10.1016/j.jmrt.2018.09.010
2238-7854/© 2018 Brazilian Metallurgical, Materials and Mining Association. Published by Elsevier Editora Ltda. This is an open access
article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

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et al. [6], 5-mercapto-1-tetrazoleacetic sodium salt (MTAc)

is a moderate inhibitor for steel 1.0 M H2 SO4 , and the
maximum  was about 69% at 200 mg l−1 . Although these
tetrazole derivatives are widely studied as corrosion inhibitors
for steel in inorganic acids (HCl, H2 SO4 and H3 PO4 ), there is
little work in organic acid medium.
Acetic acid (CH3 COOH) is widely used in acid pickling
and acidification in the oil and gas industry [7]. Most impor-
tant of all, CH3 COOH accounts for about 50%–90% of the
total organic acids in produced fluids during oil and gas sys-
tems [8]. Despite CH3 COOH is weak acid (Ka  = 1.8 × 10−5 ),
it still shows strong corrosive attack on steel. During past
decades, many studies [9–11] have been dedicated to inves-
tigating the corrosion behavior and mechanism of steel
in CH3 COOH media. Regarding protection of steel from
CH3 COOH corrosion, organic inhibitors are always added
to the acetic acid solution. The inhibition performance of
some N-heterocyclic compounds on steel in CH3 COOH media
have been reported, such as pyridine derivative [12], thia-
diazole derivatives [13], thiazoles [14] and triazoles [15].
Obviously, there is no published literature regarding the
tetrazole derivatives as corrosion inhibitors in CH3 COOH solu-
tion.
Our work team has been doing some research work about Fig. 1 – Chemical molecular structures of two ditetrazole
the corrosion inhibition of tetrazole derivatives of steel in inor- derivatives: (a) blue tetrazolium (BT); (b) nitrotetrazolium
ganic acid media, like red tetrazolium [16], 5-aminotetrazole blue chloride (NTBC).
[17], triazolyl blue tetrazolium bromide [18], blue tetrazolium
(BT) [19] and nitrotetrazolium blue chloride (NTBC) [20]. It is
found that the type of tetrazole compound with double N- 2.2. Weight loss method
heterocyclic rings exhibits more inhibitive efficiency than the
traditional tetrazole compound with only one tetrazole ring. For each gravimetric test, three parallel CRS (the dimen-
Here, in continuation of our previous work, the aim of the sion of one CRS specimen is 2.5 cm × 2.0 cm × 0.06 cm) were
present work is study the inhibition effect of two ditetra- weighed accurately by digital balance (±0.1 mg) to obtain the
zole derivatives of BT and NTBC on cold rolled steel (CRS) initial mass, then suspended using glass rods and hooks, and
in 2.5 M CH3 COOH solution. Besides experimental methods then totally immersed in a beaker with 250 ml CH3 COOH test
of weight loss, electrochemical techniques and SEM, quan- solution at a constant temperature kept by a water ultra-
tum chemical calculation was applied to further explore the thermostat (±0.1 ◦ C). After immersion for 24 h, CRS sheets
adsorption mechanism and structural–property relationship. were taken out, subsequently immersed in ASTMG1-90 stan-
It is expected to fully elucidate the inhibitive action and dard solution (Clark solution: 100 ml HCl + 2% Sb2 O3 + 5%
mechanism of ditetrazole derivatives on steel in acetic acid SnCl2 ) to remove the corrosion products, then washed with
media. distilled water and acetone, dried and reweighed accurately
to obtain the final mass. The average weight loss of three par-
2. Experimental allel CRS sheets is obtained, and then both corrosion rate (v)
and inhibition efficiency (w ) are calculated [20].
2.1. Materials
2.3. Electrochemical measurements
The element compositions (wt.%) of tested CRS specimens
are 0.07% C, 0.3% Mn, 0.022% P, 0.010% S, 0.01% Si, 0.030% All electrochemical tests were performed on PARSTAT
Al and the remainder Fe. Both BT (C40 H32 N8 O2 Cl2 , molecular 2273 advanced electrochemical system (Princeton Applied
weight: 727.7 g mol−1 ) and NTBC (C40 H30 N10 O6 Cl2 , molecular Research) with PowerSuite software. The electrochemical
weight: 817.6 g mol−1 ) are purchased from Sinopharm Chemi- three-electrode cell is used for all electrochemical measure-
cal Reagent Co. Ltd. of China, and their chemical molecular ments. A platinum electrode is used as counter electrode, a
structures are illustrated in Fig. 1. Both BT and NTBC are saturated calomel electrode (SCE) coupled to a fine Luggin
easily dissolved in water, and the additive inhibitor concen- capillary as reference electrode, and a square CRS embedded
trations are 0.01–0.20 mM. The aggressive solution of 2.5 M in PVC holder using epoxy resin as working electrode (WE).
CH3 COOH (calculated pH = 2.17, measured pH = 2.10) were pre- The exposed surface (1.0 cm × 1.0 cm) of WE was treated as
pared by dilution of analytical grade 99.5% acetic acid glacial described above (Section 2.1). The electrolyte is the corrosive
(Sinopharm Chemical Reagent Co. Ltd. of China) with distilled media of 250 ml 2.5 M CH3 COOH solution without or with a
water. A freshly prepared corrosive electrolyte was used for certain concentration of ditetrazole maintained at 20 ◦ C under
each experiment. non-stirred conditions. The tip of Luggin capillary was located

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about 3 mm close to WE to minimize the ohmic drop of the
solution, and the exposed surface of WE was put right against
the platinum plate to form uniform electric field. Prior to elec-
trochemical measurements, WE was immersed in corrosive
electrolyte for 2 h at OCP to reach a stationary value (±0.5 mV).
The polarization curves were conducted in the potential range
from −250 to +250 mV versus OCP at a sweep rate of 0.5 mV s−1 .
EIS was carried out at stable OCP within the frequency range
from 100 kHz to 10 mHz, and the signal amplitude is 10 mV root
mean square. Each test was run at least three times to verify
the reliable results. Inhibition efficiency values of polarization
curves (p ) and EIS (p ) are calculated according to corrosion
current density and charge transfer resistance, respectively
[20].
2.4. SEM examinations
The morphologies of CRS samples after 24 h of immersion
in 2.5 M CH3 COOH solutions without and with 0.2 mM BT or
NTBC at 20 ◦ C were examined by FEI QUANTA 200 scanning
electron microscope (America).
2.5. Quantum chemical calculations
Quantum chemical calculations were respectively performed
with DMol3 in Materials Studio 7.0 software from Accelrys
Inc. [21]. Quantum chemical calculations based on den-
sity function theory (DFT) of BT2+ and NTB2+ were done
at the GGA/BLYP [22]/DND [23]/COSMO [24] level without
any symmetry and spin constraints. Both optimized geo-
metric structures of BT2+ and NTB2+ are verified that their
vibrations have no imaginary frequency through frequency
calculations. The parameter criteria for the convergence tol-
erances of energy, maximum force, maximum displacement
and SCF convergence criteria k-point set are 1.0 × 10−5 Ha,
2.0 × 10−3 Ha/Å, 5.0 × 10−3 Å and 1.0 × 10−6 , respectively [25].
3. Results and discussion
3.1. Weight loss measurements
The relative standard deviation (RSD) values of both v and w
for three parallel CRS specimens obtained from weight loss
method are below 5%, which confirms that the reproducibility
for experimental data in present system is very precise.
3.1.1. Effect of BT and NTBC on corrosion inhibition
In blank 2.5 M CH3 COOH solution, v is 1.296 g m−2 h−1
(RSD = 3.4%), but it greatly decreases for all additive concen-
trations of ditetrazoles. To directly understand the inhibitive
ability, the corresponding inhibition efficiency (w ) values
against inhibitor concentrations of BT and NTBC (c) for CRS
in 2.5 M CH3 COOH solution at 20 ◦ C are plotted in Fig. 2.
Inspection of Fig. 2 reveals that w sharply increases with
increasing the inhibitor concentration from 0.01 to 0.08 mM,
but it mildly changes within the inhibitor concentration from
0.08 to 0.20 mM. This behavior is attributed to that the adsorp-
tion amount of inhibitor covering steel surface increases to
more extent firstly, but when it is near to the saturated state,
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3
100
90
80
ηw (%)
70
BT
NTBC
60
50
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 0.16 0.18 0.20 0.22
c (mM)
Fig. 2 – Relationship between inhibition efficiency (w ) and
concentration of inhibitor (c) in 2.5 M CH3 COOH at 20 ◦ C
(weight loss method, immersion time is 24 h).
it slightly changes with the further increase of added inhibitor
concentrations from 0.10 to 0.20 mM. At the inhibitor concen-
tration of 2.0 mM, the maximum w values of BT and NTBC
are 96.4% and 92.6%, respectively. Thus, both BT and NTBC
act as effective inhibitors for steel in CH3 COOH. It is apparent
that NTBC has higher inhibitive performance than BT, which
could be assigned to two additional substituted nitro-groups
in NTBC as compared to BT.
3.1.2. Adsorption isotherm and standard adsorption free
energy (G0 )
Two ditetrazoles of BT and NTBC exhibit their inhibitive abil-
ity via the adsorption on steel surface. In order to elucidate
the adsorption behavior of inhibitor on steel surface, some
adsorption isotherms such as Frumkin, Langmuir, Temkin,
Freundlich, Bockris–Swinkels and Flory–Huggins are utilized
to fit the experimental data. By far, Langmuir adsorption
isotherm is found to be the best description for the present
adsorption behavior, and it is described by Eq. (1) [26]:
c 1
= +c (1)
 K
where c is the inhibitor concentration (mM) and K is the
adsorptive equilibrium constant (M−1 ).  is the degree of sur-
face coverage, and its value approximately equals to inhibition
efficiency [27].
Two linear fitted straight lines and experimental data of
c/ versus c for BT and NTBC at 20 ◦ C are plotted in Fig. 3,
and the corresponding linear regression parameters and the
adsorption parameter of K are listed in Table 1. From Table 1,
both linear correlation coefficients (r) and slope are very close
to 1, confirming the adsorption of either BT or NTBC on
steel surface completely obeys Langmuir adsorption isotherm.
Larger K is generally related to stronger interaction of inhibitor
molecule with metal surface. As can be seen from Table 1, K
(NTBC) > K (BT) means that NTBC exhibits a stronger tendency
to be adsorbed onto steel surface than BT.
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A
-0.2
a --- blank d c b a
b --- 0.02 mM
-0.3 c --- 0.10 mM
d --- 0.20 mM

-0.4

E (V vs. SCE)
-0.5

-0.6

-0.7
d c b a
-0.8
-7 -6 -5 -4 -3 -2

B log i (A cm-2)
Fig. 3 – Langmuir adsorption isotherm modes of BT and
-0.2
NTBC on CRS surface in 2.5 M CH3 COOH at 20 ◦ C from d b a
a --- blank c
weight loss measurement. b --- 0.02 mM
-0.3
c --- 0.10 mM
d --- 0.20 mM
-0.4

E (V vs. SCE)
Table 1 – Parameters of the straight lines of c/ − c and
standard adsorption free energy (G0 ) in 2.5 M CH3 COOH -0.5
at 20 ◦ C (weight loss method, immersion time is 24 h).
Inhibitor r Slope K (M−1 ) G0 (kJ mol−1 ) -0.6

BT 0.9997 1.02 8.16 × 10 4

−37.35
NTBC 0.9999 1.01 1.42 × 105 −38.71 -0.7
d b a
c
-0.8
Another important thermodynamic parameter of standard -7 -6 -5 -4 -3 -2
adsorption free energy (G0 ) could be obtained from K given log i (A cm-2)
by the following equation [28]:
Fig. 4 – Potentiodynamic polarization curves for CRS in
  2.5 M CH3 COOH without and with different concentrations
1 −G0
K= exp (2) of inhibitors at 20 ◦ C (immersion time is 2 h): (A) BT; (B)
55.5 RT
NTBC.

where the value 55.5 is the concentration of water in test solu-

tion expressed in M [28].
permission and anodic ferrous dissolution are activatedly con-
The calculated G0 values of BT and NTBC as shown in
trolled. The cathodic reaction of steel in CH3 COOH solution is
Table 1 ranges from −40 to −20 kJ mol−1 , it is thus to deduce
the hydrogen evolution reaction [9–11]. Accordingly, the pro-
that the adsorption of BT and NTBC on steel surface could be
posed cathodic mechanism follows the steps (4)–(6) [30]:
the mixed adsorption process that involves both physical and
chemical adsorption [29]. G0 (NTBC) < G0 (BT) again demon-
Fe + H+ ↔ (FeH+ )ads (3)
strates that NTBC has more stronger adsorptive ability on steel
surface than BT between two studied ditetrazole derivatives.
(FeH+ )ads + e− ↔ (FeH)ads (4)
3.2. Potentiodynamic polarization studies
(FeH)ads + H+ + e− ↔ Fe + H2 (5)
Potentiodynamic polarization curves for CRS electrode in 2.5 M
CH3 COOH media at 20 ◦ C with the addition of different concen- Two (FeH)ads may combine together to liberate hydrogen
trations (0.02, 0.10 and 0.20 mM) of BT and NTBC are shown in (H2 ) via following reaction [31]:
Fig. 4(A) and (B). Comparing with uninhibited 2.5 M CH3 COOH
bank solution, the addition of either BT or NTBC moves both (FeH)ads + (FeH)ads ↔ 2Fe + H2 (6)
anodic and cathodic curves to the lower current densities,
which indicates that both anodic and cathodic reactions of According to the mechanism for the corrosion of mild steel
the corrosion of CRS are significantly inhibited by two ditetra- in aqueous solutions of CH3 COOH [9–11], the anodic dissolu-
zole compounds of BT and NTBC. Each potentiodynamic curve tion of CRS in CH3 COOH solutions may be assumed as follows:
is parallel with each other, which suggests that the electro-
chemical reactions of CRS in CH3 COOH are not changed upon Fe + CH3 COO− → (FeCH3 COO− )ads (7)
with the addition of the tested ditetrazoles. The appearance
of polarization curves indicates that both cathodic hydrogen (FeCH3 COO− )ads → (FeCH3 COO)ads + e− (8)

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Table 2 – Potentiodynamic polarization parameters for the corrosion of CRS in 1.0 M CH3 COOH containing different
concentrations of BT and NTBC at 20 ◦ C.
Inhibitor c Ecorr icorr −bc ba p
(mM) (mV vs. SCE) (␮A cm−2 ) (mV dec−1 ) (mV dec−1 ) (%)

— 0 −481 225.4 305 95 —

BT 0.02 −478 92.8 313 102 58.83
0.10 −484 30.8 312 107 86.34
0.20 −471 22.1 328 103 90.20
NTBC 0.02 −476 70.5 282 87 68.72
0.10 −482 26.7 328 103 88.15
0.20 −477 15.5 303 80 93.12

(FeCH3 COO)ads → (FeCH3 COO+ ) + e− (9) A

1200 90
+ 2+ − 0.02 mM blank
(FeCH3 COO ) → Fe + CH3 COO (10) 0.10 mM 60

0.20 mM
900 Fitting Curves 30

Thus, the adsorption of CH3 COO− ions on the CRS surface

0
would be the prerequisite for the anodic steel dissolution to 100 150 200 250 300

Zim (Ω cm2)
be occurred. 600

The corrosion parameters including corrosion current den-

sities (icorr ), corrosion potential (Ecorr ), cathodic Tafel slope (bc )
300
and anodic Tafel slope (ba ) are obtained by extrapolation of
the Tafel lines. Table 2 lists the fitting corrosion parameters
and inhibition efficiency (p ). As can be seen from the data in 0
Table 2, icorr decreases prominently after adding BT or NTBC
to CH3 COOH media, and it decreases gradually with increas- 0 300 600 900 1200 1500 1800 2100

ing of the concentration of ditetrazoles. icorr is as high as B Zre (Ω cm2)

225.4 ␮A cm−2 in CH3 COOH blank solution, but it falls to only 1500

22.1 ␮A cm−2 in the presence of 2.0 mM BT; and 15.5 ␮A cm−2 0.02 mM
0.10 mM
in the presence of 2.0 mM NTBC. Correspondingly, p increases 1200
0.20 mM
with the inhibitor concentration, and the best p of 2.0 mM BT ___ Fittting Curves
and 2.0 mM NTBC are 90.20% and 93.12%, respectively. Thus, 900
Zim (Ω cm2)

both BT and NTBC are good inhibitors in 2.5 M CH3 COOH, and
NTBC is a better inhibitor than BT. Ecorr is not changed in the
presence of either BT or NTBC with respect to blank solu-
tion, which indicates both ditetrazole compounds of BT and
NTBC behave as mixed-type inhibitors for CRS in CH3 COOH
[32]. Moreover, the electrochemical mechanism of ditetrazole
inhibitors of BT and NTBC is caused by geometry blocking
effect [32]. In the other words, both BT and NTBC diminish the
available reactive surface areas to be corroded in CH3 COOH.
Two Tafel constants of bc and ba are not changed with the addi-
tion of BT and NTBC, again indicating that both BT and NTBC
impedes the electrode corrosion by merely blocking the reac-
tion sites of electrode surface without affecting both anodic
dissolution of steel and cathodic hydrogen evolution reaction
mechanism [33].
3.3. Electrochemical impedance spectroscopy (EIS)
Fig. 5(A) and (B) represents the Nyquist plots for CRS electrode
in 2.5 M CH3 COOH without and with the addition of BT and
NTBC at 20 ◦ C after an exposure immersion time of 2 h, respec-
tively. It is evident that all Nyquist spectra obtained exhibit one
single capacitive loop, which indicates that the corrosion of
steel in CH3 COOH solution is mainly controlled by the charge
transfer process [34]. The diameter of the capacitive loop in the
presence of BT or NTBC is much bigger than that in the absence
of inhibitor (blank solution), and increases with the inhibitor
600
300
0
0 300 600 900 1200 1500 1800 2100 2400
Zre (Ω cm2)
Fig. 5 – Nyquist plots for CRS in 2.5 M CH3 COOH without
and with different concentrations of inhibitors at 20 ◦ C
(immersion time is 2 h): (A) BT; (B) NTBC.
concentration from 0.02 to 0.20 mM. Thus, the impedance of
inhibited substrate is enhanced owing to the introduction of
ditetrazole compound BT or NTBC.
The Bode modulus and phase angle plots for CRS in 2.5 M
CH3 COOH containing different concentrations of BT and NTBC
at 20 ◦ C are given in Figs. 6 and 7, respectively. Comparing with
the Bode of the blank solution, the absolute impedance in the
presence of ditetrazole compound is drastically increased at
low frequencies in Bode modulus, which corresponds slowing
down the corrosion of steel and confirms the higher protec-
tion of ditetrazole compounds of BT and NTBC, owing to the
adsorption of the inhibitor molecules on the CRS surface. As

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A A
3.5 50 blank
blank 0.02 mM
0.02 mM 0.10 mM
40 0.20 mM
0.10 mM
0.20 mM Fitting Curves

phase angle (º)

3.0 Fitting Curves 30
log Z (Ω cm2)

20

2.5 10

-2 -1 0 1 2 3 4 5
2.0
-2 -1 0 1 2 3 4 5 log f (Hz)
log f (Hz) B
B 60
3.5 blank
0.02 mM
blank
50 0.10 mM
0.02 mM
0.20 mM
0.10 mM
40 Fitting Curves
0.20 mM

phase angle (º)

3.0 Fitting Curves
30
log Z (Ω cm2)

20

2.5
10

2.0 -2 -1 0 1 2 3 4 5
-2 -1 0 1 2 3 4 5
log f (Hz)
log f (Hz)
Fig. 7 – Bode phase angle plots for CRS in 2.5 M CH3 COOH
Fig. 6 – Bode modulus for CRS in 2.5 M CH3 COOH without
without and with different concentrations of inhibitors at
and with different concentrations of inhibitors at 20 ◦ C
20 ◦ C (immersion time is 2 h): (A) BT; (B) NTBC.
(immersion time is 2 h): (A) BT; (B) NTBC.

can be seen from Fig. 7(A) and (B), there is only one phase
peak in phase angle plots, which confirms that there is only
one time constant related to the capacitive loop. Irrespective
of adding any concentrations of BT or NTBC to CH3 COOH, the
shapes of Nyquist and Bode plots are not altered through-
out all tested inhibitor concentrations. Thus, there is almost
no alter in the corrosion mechanism whether the inhibitor is
added to the corrosive media [35,36].
Noticeably, all these capacitive loops in Nyquist grams
are not perfect semicircles, and the peak angles are lower
than 90◦ in phase angle plots (Fig. 7), which could be
attributed to the frequency dispersion effect as a result of
the roughness and inhomogeneousness of electrode surface
or electrode/solution interface [37].
In summary, the hydrogen depolarisation of CRS in
CH3 COOH solution is the charge transfer controlling step with
only one time constant. Thus, the simplest model of EIS could
be the electrochemical resistance in parallel to the double
layer capacitance connected with the resistance of the elec-
trolyte. However, there is the frequency dispersion effect that
will result in a deviation from ideal double layer capacitance.
Accordingly, constant phase element (CPE) is more accurate to
CPE
Rs
Rt
Fig. 8 – The equivalent circuit model of EIS.
replace the double layer capacitance (Cdl ), and then EIS data
are simulated using the equivalent circuit shown in Fig. 8,
in which Rs and Rt are the solution resistance and charge
transfer resistance, respectively. The fitted solid lines in
Figs. 5–7 agrees well with experimental data, which confirms
that this equivalent circuit best fit the experimental data.
CPE is composed of a component Qdl and a dispersion
coefficient a that quantifies the inhomogeneousness degree
of electrode/solution interface resulting from surface rough-
ness, inhibitor adsorption, porous layer formation, etc. The
double layer capacitance (Cdl ) can be obtained via CPE from
the following equation [38]:
a−1
Cdl = Qdl × (2fmax ) (11)

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Table 3 – EIS parameters for the corrosion of CRS in 2.5 M CH3 COOH containing BT and NTBC at 20 ◦ C.
Inhibitor c Rs Rt CPE a 2 Cdl R
(mM) ( cm2 ) ( cm2 ) (␮−1 sa cm−2 ) (␮F cm−2 ) (%)

– 0 132.2 139.1 288.2 0.7049 5.48 × 10−5 117 —

BT 0.02 131.4 307.3 205.4 0.8036 5.44 × 10−5 106 54.73
0.1 130 1008 106.8 0.7799 1.78 × 10−4 51 86.2
0.2 129.7 1860 75.6 0.823 4.41 × 10−4 46 92.52
NTBC 0.02 130 546.6 125.3 0.8637 2.01 × 10−4 82 74.55
0.1 133.8 1385 94.6 0.8995 3.81 × 10−4 49 89.96
0.2 133.5 2131 68.7 0.89 4.64 × 10−4 44 93.47

where fmax represents the frequency at which the imagi-
nary value reaches a maximum on the Nyquist plot. The
electrochemical parameters of Rs , Rt , CPE, a, Cdl , fmax , chi-
squared (2 ) and R are summarized in Table 3.
All 2 values are rather as low as 10−5 to 10−4 , which ver-
ifies that the fitted data are in good coincidence with the
experimental data. It is observed that Rs is about 100  cm2
for 2.5 M CH3 COOH test solution, which implies that the test
solution is not very conductive owing to the weak deionization
of CH3 COOH. Rt is about 139.1  cm2 for the blank solution,
and is increased to remarkable about 1860  cm2 in the pres-
ence of 2.0 mM BT; and 2131  cm2 in the presence of 2.0 mM
NTBC. A large charge transfer resistance (Rt ) is associated with
a slower corroding system. Rt of two ditetrazole compounds
follows the order: Rt (BT) < Rt (NTBC), which again confirms
that inhibitive performance of NTBC is better than that of
BT.
If the electrode surface is homogeneous and plane, the
dispersion coefficient of a equals to 1 and the electrode sur-
face can be treated as an ideal capacitance. The value of a
is used to account for the roughness of the electrode. The
lower the value of a is related to the rougher electrode sur-
face. All a values are lower than 1, which confirms that there
is frequency dispersion on electrode surface. In presence of
BT or NTBC, the value of a increases to some extent, which
suggests that CRS electrode surface becomes smoother due to
formation of a non-porous and dense monolayer of inhibiting
film.
As shown in Table 3, Cdl becomes lower when BT or NTBC
is added to CH3 COOH medium, which can be explained on
Helmholtz model:
ε0 ε
Cdl = S (12)
d BT → BT2+ + 2Cl−
Inhibition efficiencies obtained from EIS are in good accor-
dance with those from weight loss and polarization methods.
3.4. SEM surface examination
In order to further determine the inhibitive action of dite-
trazole compounds, SEM microstructures of CRS surfaces are
shown in Fig. 9. It can be seen from Fig. 9(A) that CRS sur-
face after immersion in uninhibited 2.5 M CH3 COOH blank
system for 24 h is drastically damaged by the aggressive media.
The corrosion products distributed on the whole steel surface
appear too uneven, and are rather rough. Fig. 9(B) shows that
corrosion degree of the steel surface decreases in the pres-
ence of 2.0 mM BT, and the surface seems much smoother.
Fig. 9(C) clearly shows that the corrosion of steel surface in
the presence of 2.0 mM NTBC is significantly hindered; where
the corrosion specimen surface is more flat and compact.
Both observations in Fig. 9(B) and (C) reveals that there are
compact and rigid layers on steel surfaces treated with dite-
trazoles, which could efficiently protect steel from corrosion in
CH3 COOH. In summary, either BT or NTBC could be adsorbed
onto steel surface to form a good protective film, thus imped-
ing the corrosion of steel surface in CH3 COOH media.
3.5. Quantum chemical calculations of DFT
Quantum chemical calculation has been proved the useful
method to theoretically elucidate the metal-inhibitor and
inhibitive mechanism of inhibitor molecule [40]. Both BT and
NTBC could be easily ionized in water solution to cationic parts
of BT2+ and NTB2+ and anionic chloride ion (Cl− ):
(13)

where ε0 is dielectric constant of vacuum, ε the dielectric con-

stant of electrolyte, d the thickness of the electrical double
layer, and S is the surface area. Comparing CRS electrode in
uninhibited solution with that in inhibited solution, ε0 and S
remain unchangeable, thus the decrease in Cdl in inhibited
solution, which could result from a decrease in ε and/or an
increase in d, suggests that the inhibitor molecules function
by adsorption at the metal/solution interface to replace the
adsorbed water molecules [39]. R increases with the concen-
tration of ditetrazole derivative, and follows the consequence:
R (NTBC) > R (BT). The maximum R values at 2.0 mM are
92.52% and 93.47% for BT and NTBC, respectively. Thus, two
ditetrazole derivatives act as effective inhibitors for CRS in
CH3 COOH solution.
NTBC → NTB2+ + 2Cl− (14)
The organic parts of BT2+ and NTB2+ could be deemed
as vital effective components for BT and NTBC, respec-
tively. Accordingly, quantum chemical calculations of BT2+
and NTBC2+ based on DFT were done to elucidate the adsorp-
tion inhibitive mechanism on molecular level. Fig. 10 shows
the full optimized spatial molecular structures of BT2+ and
NTB2+ under BLYP/DND/GGA/COSMO level. For either BT2+ or
NTB2+ , two tetrazole rings and four benzene rings are not
in one plane. In view of molecular structures of BT2+ and
NTB2+ , the adsorption involves two main adsorption modes:
physisorption and chemisorption.

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Fig. 9 – SEM micrographs of CRS surface: (a) after 24 h of immersion at 20 ◦ C in 2.5 M CH3 COOH; (b) after 24 h of immersion at
20 ◦ C in 0.20 mM BT + 2.5 M CH3 COOH; (c) after 24 h of immersion at 20 ◦ C in 0.20 mM NTBC + 2.5 M CH3 COOH.

A The physisorption is correlated with the quantum param-

eter of dipole moment ( ) that is used to determine the
polarity of a molecule [41]. The physisorption of organic
inhibitor molecules on metal surface arises as a result of
electrostatic attraction between the organic dipole and the
charged metal surface. The inhibitor molecules incorporated
in the electric double layer on the metal/solution interface
compete with the adsorbed H2 O molecules for sites at the
metal surface. The inhibitor molecules with a high dipole
BT2+ moment exert significant effect on the dielectric properties
of the electric double layer. Thus, the inhibitor molecule with
B larger value is more likely to interact with steel surface
through electronic force [42]. The calculated value of BT2+
is 18.3615 D, and that of NTB2+ is 18.6669 D. As mentioned
above in Section 3.2, CH3 COO− could be firstly adsorb on elec-
trode surface during the anodic reaction process in CH3 COOH
media. Meanwhile, the chloride ions (anionic part of dite-
trazole derivative) can penetrate into the inner layer of the
double-layer structure, and could specifically adsorb on steel
surface.
The adsorption of these anions (CH3 COO− and Cl− ) on steel
NTB2+ surface create negative charged steel surface. Then, the posi-
tive charged molecules of BT2+ and NTB2+ could adsorb on the
Fig. 10 – Optimized molecular structures of two ditetrazole
negatively charged metal surface through electrostatic inter-
derivatives: (a) BT2+ ; (b) NTB2+ .
actions. In other words, the adsorption of CH3 COO− and Cl−
leads to the enhancement of the adsorption of BT2+ and NTB2+

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A reflects two tetrazole rings could be acceptor of electrons
BT2+ (HOMO)
B conjugation systems for either HOMO parts of two benzene
BT2+ (LUMO)
C The quantum parameters of energy of highest occupied
NTB2+ (HOMO)
D owing to that the HOMO distribution of BT2+ (Fig. 11(A)) is
NTB2+ (LUMO)
Fig. 11 – The frontier molecule orbital density distributions
of two ditetrazole derivatives: (a) BT2+ (HOMO); (b) BT2+
(LUMO); (c) NTB2+ (HOMO); (d) NTB2+ (LUMO).
at the steel electrode. It should be noted that (NTB2+ ) > [47]:
(BT2+ ), which indicates that the better inhibitive action of
NTB2+ than BT2+ may be arisen from intermolecular electro-
static force.
The frontier molecular orbitals are applied to study the
global reactivity of two ditetrazoles studied. HOMO (the high-
est occupied molecular orbital) is related to the capacity of
a molecule to donate electrons, whereas LUMO (the low-
) and global softness (s) of
est unoccupied molecular orbital) represents the ability of
the molecule to accept electrons [40]. The electric/orbital
density distributions of HOMO and LUMO for BT2+ and
NTB2+ molecules are shown in Fig. 11. As can be seen from
Fig. 11(A) and (C), that the electron densities of HOMO for
both BT2+ and NTB2+ are mostly localized on the linkers
of two benzene rings and two oxygen atoms in methoxy
= (18)
groups, which could be deemed as the donor of the elec-
trons to the metal surface. For BT2+ , LUMO as shown in
Fig. 11(B) is mostly located on two tetrazole rings, which
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J Mater Res Technol. 2018. https://doi.org/10.1016/j.jmrt.2018.09.010
9
from steel surface. Inspection of Fig. 11(D) reveals that the
distributions of LUMO for NTB2+ are found on two tetra-
zole rings and two nitro-groups (–NO2 ). Thereby, comparing
with BT2+ , it is reasonable to assume that the two substi-
tuted –NO2 groups of NTB2+ have extra additional ability
to accept electrons from d-orbitals of metal to form back-
donating bond, which could be assigned to the main reason
of inhibition order of NTB2+ > BT2+ . Noticeably, there are ␲
rings (Fig. 11(A) and (C)) or LUMO parts of two tetrazole
rings (Fig. 11(B) and (D)), which make them suitable for ␲-
interaction with metal surface [43] and back donation of
metal d-electrons to the ␲*-orbitals of inhibitor molecule [44].
The aromatic ␲-electrons intensify the chemisorption, which
make two studied ditetrazoles to be considered as efficient
inhibitors.
molecular orbital (EHOMO ), energy of lowest unoccupied molec-
ular orbital (ELUMO ) and the separation energy (ELUMO − EHOMO ,
E) are also presented in Table 4. Higher value of EHOMO
causes more tendency of inhibitor molecule to donate elec-
trons to empty 3d orbitals of Fe [45], while lower ELUMO
suggests more probable of inhibitor molecule to accept elec-
trons from steel [45]. From Table 4, EHOMO has a slight
difference value of 0.055 eV between two studied ditetrazoles
same as that of NTB2+ (Fig. 11(C)). In contrast, ELUMO obeys
the order: NTB2+ < BT2+ , which is in complete agreement with
the experimental inhibition consequence of NTBC > BT. Thus,
there is a good correlation between ELUMO and inhibition
efficiency.
The parameter of E means the reactivity of inhibitor
molecule toward the adsorption on metallic surface. The
lower E is, the higher reactivity of inhibitor molecule is
reversely, and facilitates the adsorption, then improves higher
inhibitive performance [46]. E values of two ditetrazole com-
pounds follow the order: NTB2+ < RT2+ , which confirms that
NTB2+ exhibits adsorptive ability on steel surface preferably to
RT2+ .
The energy parameters of EHOMO and ELUMO are related to
ionization potential (I) and electron affinity (Y), respectively
I = −EHOMO (15)
Y = −ELUMO (16)
With obtained I and Y, three parameters of absolute elec-
tronegativity (ˇ), global hardness (
inhibitor molecule are approximately calculated as following
equations [48]:
I+Y
ˇ= (17)
2
I−Y
2
1
s= (19)
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Table 4 – Quantum chemical parameters for inhibitor molecules at GGA/BLYP/DND/COSMO level.

Molecule EHOMO (eV) ELUMO (eV) E (eV) ˇ (eV)
(eV) s (eV−1 ) N

RT 2+
−6.096 −3.975 2.121 5.036 1.061 0.943 0.926
NTB2+ −6.151 −4.350 1.801 5.250 0.900 1.110 0.972

The number of electrons transferred from the inhibitor

molecule to metallic surface (N) is calculated through ˇ and
Conflicts of interest

values [49]:
The authors declare no conflicts of interest.

ˇFe − ˇinh
N = (20) Acknowledgements
2(
Fe +
inh )

This work was carried out in the frame of research projects

The theoretical values of ˇFe and
Fe are 7 eV and 0 eV
funded by National Natural Science Foundation of China
for Fe atom, respectively [50]. The values of ˇ,
, s and
(51361027) and Training Program of Young and Middle Aged
N are also listed in Table 4. According to some studies
Academic and Technological Leaders in Yunnan Province
[50], the parameter of ˇ is related to the chemical potential,
(2015HB049, 2017HB030).
and higher ˇ corresponds to better inhibitive performance.
Comparing Eq. (18) with Eqs. (15) and (16),
is equal to
E/2, and so the lower
implies more polarizability and references
higher inhibitive action. The parameter of s is reciprocal to

, thus high value of s is related to more efficiency. The

parameter of N exhibits inhibitive performance resulted
from electrons donations. If N < 3.6, the chemisorption and
inhibition efficiency increase with increasing in electron-
donation ability to the metal surface [50]. For the present
studied two ditetrazoles, the inhibition action follows the
order: NTB2+ > BT2+ . Thus, there is a good correlation between
inhibition efficiency with the parameters of ELUMO , E, ˇ,
, Sci 2015;101:47–55.
s and N.
4. Conclusions
(1) Two ditetrazole derivatives of NTBC and BT act as effective
inhibitors for the corrosion of CRS in 2.5 M CH3 COOH solu-
tion, and the inhibitive action follows the order: NTBC > BT.
Inhibition efficiency (w ) increases with the inhibitor con-
centration, and the maximum w values of BT and NTBC
at 0.20 mM are 96.4% and 92.6% at 20 ◦ C. The adsorption
of either BT or NTBC on CRS surface completely obeys
Langmuir adsorption isotherm.
(2) Both BT and NTBC are arranged as mixed-type inhibitors
in CH3 COOH, and the electrochemical inhibitive mecha-
nism is caused by geometry blocking effect. EIS spectra
exhibit one depressed capacitive loop with one time con-
stant, and the presence of each ditetrazole derivative
enhances Rt while reduces Cdl . SEM micrographs clearly
confirms that the corrosion of steel surfaces are promi-
nently retarded by ditetrazoles.
(3) The higher values of BT2+ and NTB2+ facilitates their
physisorption. For both BT2+ and NTB2+ , the nucleophilic
attack sites and LUMO are mainly located on two tetrazole
rings, while the electrophilic sites and HOMO densities are
focused on the linker of two benzene rings as well as two O
atoms in –OCH3 . As compared with BT2+ , two substituted
–NO2 groups of NTB2+ have extra ability to accept electrons
from steel surface to form back-donating bond.
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