Available online at www.sciencedirect.

com

Thin Solid Films 516 (2008) 1020 – 1024

www.elsevier.com/locate/tsf

Experimental and theoretical elucidation on the inhibition mechanism of

1-methyl-5-mercapto-1,2,3,4-tetrazole self-assembled films on corrosion
of iron in 0.5 M H2SO4 Solutions
Hongfang Ma ⁎, Tao Song, Hua Sun, Xiao Li
Department of materials, Shandong Jianzhu University, Jinan 250101, PR China
Received 19 June 2006; received in revised form 15 June 2007; accepted 30 June 2007
Available online 13 July 2007

Abstract

The self-assembled films of 1-methyl-5-mercapto-1,2,3,4-tetrazole (MMT) were prepared on the iron surface. By means of electrochemical
impedance spectroscopy in 0.5 M H2SO4 solutions, the inhibition ability of the film was investigated. Results were discussed through changing
the concentrations of the inhibitor and the pH values of the self-assembly solutions. Quantum chemical calculation was applied to elucidate the
adsorption mechanism of the inhibitor molecule to iron atom. The study shows that MMT is a good inhibitor for iron in 0.5 M H2SO4 solutions.
The self-assembled films formed in 10−2 M acidic solutions have the best protection effect and the inhibition efficiency in 0.5 M H2SO4 solutions
is 98.0%. Density functional theory proves that MMT molecule is adsorbed on the iron surface by the most negatively charged nitrogen atom and
the adsorption can occur spontaneously.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Self-assembled films; Inhibition efficiency; Adsorption mechanism; Quantum chemical calculation

1. Introduction atmosphere. K. Nozawa et al. [12] used self-assembled films of

Organic compounds are usually used to protect metal against
corrosion as inhibitors in acidic media [1–5]. Heterocyclic
compounds containing N and S atoms, such as azoles and their
derivatives, have attracted much attention because of the effi-
cient inhibition abilities to the metal [6–8]. Heteroatoms, for
example, N and S, usually become the active center. When me-
tal is immersed in the inhibiting solutions, N and S atoms donate
lone pair electrons to the unoccupied orbits of the metal atom.
Strong and stable bonds are formed between the inhibitor and
the metal surface during the self-assembling process. Iron is a
widely used metal with extensive applications in industry and
the study of its corrosion inhibition has attracted lots of interest
[9–11]. But it is difficult to form self-assembled films on the
iron surface because of its spontaneous oxidation trend in
⁎ Corresponding author. Tel.: +86 531 86367035; fax: +86 531 886367034.
E-mail address: mahongfangsd@yahoo.com.cn (H. Ma).
0040-6090/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.tsf.2007.06.225
alkanethiols for corrosion protection to iron. But the application
of thiol-compounds is limited due to their toxicity [13]. Ilona
Felhösi et al. [13] studied the formation of self-assembled films
of alkane monophosphonic acids on the iron surface and ex-
plored the protection mechanism. Considering the characteristic
of the heteroatoms, 1-methyl-5-mercapto-1,2,3,4-tetrazole
(MMT) was used as the inhibitor for iron.
Electrochemical impedance spectroscopy (EIS) is often used
to study the inhibiting process and to probe the action
mechanism [14,15]. Quantum chemical calculation is usually
used to study the correlations between the corrosion inhibition
and molecular properties of the inhibitor [16–18]. The properties
include orbital energies, charge density and combined energies,
etc. [19].
The purpose of this study is to determine the inhibition
efficiency of MMT self-assembled films to iron with EIS. Ab
initio quantum chemical calculation is used to gain insight into
the mechanism of the corrosion inhibition. It shows that the self-
assembled films formed in 10−2 M acidic solutions have the best
 H. Ma et al. / Thin Solid Films 516 (2008) 1020–1024
Fig. 1. Measured Nyquist impedance diagrams for iron electrodes in 0.5 M H2SO4 solutions: (a) modified with 10−3 M MMT neutral solution, (b) modified with 10−3 M MMT acidic solution, (c) modified with 10−2 M
MMT neutral solution, (d) modified with 10−2 M MMT acidic solution.

1021
1022 H. Ma et al. / Thin Solid Films 516 (2008) 1020–1024

EIS measurements were conducted with an IM6 impedance

and electrochemical measurement system (ZAHNER, Ger-
many). EIS tests were performed in a frequency range of 60 kHz
to 20 mHz under excitation of a sinusoidal perturbation signal
of 5 mV amplitude at open circuit potential.
Fig. 2. Equivalent circuit of the iron/solution interface.
2.3. Calculation method

protection effect for iron and the inhibition efficiency in 0.5 M
H2SO4 solutions is 98.0%.
2. Experimental details
2.1. Preparation of the samples and films
MMT (A.R. grade) was dissolved in tridistilled water with
the controlled concentrations (10−3 M and 10−2 M). The 0.5 M
H2SO4 solutions were prepared with concentrated H2SO4 and
tridistilled water. The working electrode was made from a
99.9% pure iron rod. The electrode was embedded in epoxy
resin and only its top surface was exposed to the solution. The
exposed surface was ground with emery paper of different grit
sizes up to 1600, and polished with 1 μm diamond spray until a
mirror surface was obtained. After rinsed with tridistilled water
and absolute ethanol, the electrode was etched in a 0.2 M H2SO4
solution for 15 s in order to obtain an active iron surface. Then it
was rinsed with water again as soon as possible, and immersed
in MMT solutions (pH = 2 and pH = 6.5) immediately. The pH
value of the solution was adjusted by 0.5 M H2SO4. After the
formation of the self-assembled films, the electrode was rinsed
with tridistilled water again.
2.2. EIS measurement
Considering the accuracy and convenience of ab initio method,
B3LYP method of density functional theory (DFT) on the basis
set of LANL2DZ was used to perform a full geometry
optimization of the MMT molecule and the accomplished system
after the MMT molecule adsorbed on the iron surface. All
quantum calculations were accomplished by program Gaussian
98 [20].
3. Results and discussion
3.1. Electrochemical impedance spectroscopy
Fig. 1 represents the Nyquist impedance spectra for bare iron
electrode and the electrodes modified with MMT self-assembled
films. All spectra exhibit capacitive loops. The diameter of the
capacitive loop is associated with the corrosion resistance of the
self-assembled films [21]. All impedance spectra can be
analyzed and fitted with the equivalent circuit in Fig. 2.
In Fig. 2, Rs is the solution resistance between the work
electrode and the reference electrode, while Rct is the charge
transfer resistance at the iron/solution interface [22]. Consider-
ing that the capacity of the double layer is different from the ideal
capacitor, a constant phase element (CPE) is used as a substitute
for the capacitor. Q represents CPE in Fig. 2. The measured and
calculated data of the electrode modified by MMT films

EIS experiments were carried out in a three-electrode cell.

The reference electrode was a saturated-calomel electrode Table 1
(SCE). It was in a separate compartment connected with the Impedance data of iron in 0.5 M H2SO4 solutions with and without the MMT
films
main part by a fine Luggin capillary to minimize ohmic resis-
tance. And all potential values were referred to the SCE. The Iron electrodes Immersion time Rct (Ω cm2) P%
counter electrodes were two sheets of platinum placed in two Bare – 39.9 –
sides of the working electrode respectively. All tests were carried 10−3M neutral solution 15 min 79.7 49.9
30 min 146.2 72.7
out in 0.5 M H2SO4 solutions.
3 hour 251.2 84.1
8 hour 218.4 81.7
12 hour 190.5 79.0
10−3 M acidic solution 15 min 103.8 61.5
30 min 98.3 59.4
3 hour 72.2 44.7
8 hour 53.8 25.9
12 hour 52.1 23.3
10−2 M neutral solution 15 min 140.4 71.6
30 min 359.2 88.9
3 hour 434.1 90.8
8 hour 267.9 85.1
12 hour 109.0 63.4
10−2 M acidic solution 15 min 693.6 94.2
30 min 1848.4 97.8
3 hour 2006.2 98.0
Fig. 3. Measured and fitted Nyquist impedance diagrams for iron electrode in
8 hour 1244.2 96.8
0.5 M H2SO4 solutions (electrode modified with 10−2 M MMT acidic solution
12 hour 1222.6 96.7
for 8 hours).
 H. Ma et al. / Thin Solid Films 516 (2008) 1020–1024 1023

Fig. 4. Optimized structure of 1-methyl-5-mercapto-1,2,3,4-tetrazole. Fig. 5. Optimized complex of 1-methyl-5-mercapto-1,2,3,4-tetrazole molecule

and iron atom.

(immersed in 10−2 M MMT acidic solution for 8 h) are both

displayed in Fig. 3. From Fig. 3, we can see that the calculated concentration (10−3 M) of the inhibitor cannot produce compact
values fit the measured data well. The inhibition efficiency (P%) films on the electrode in a short time, and the iron will dissolve
of the self-assembled films can be calculated by the following immediately at the beginning of the self-assembling process if it
formula [23]: is immersed in 10−3 M solutions.
According to the experimental data, the corrosion inhibition
P% ¼ 100ðRct  R0ct Þ=Rct of the film first increases with the self-assembling time and then
decreased. The self-assembling process is a dynamic process,
Where R0ct and Rct are charge transfer resistances of bare which includes the adsorption of the inhibitor to the electrode
electrode and electrode modified with self-assembled films and desorption from the electrode. It is good for the film
respectively. formation when time is prolonged until equilibrium is attained.
The fitted data and inhibition efficiencies of the films are However further increase of the self-assembling time cause
listed in Table 1. desquamation of the films formed on the iron surface, hence too
In this self-assembled system, both the concentration of the long film formation time is detrimental to the quality of the
inhibitor and the pH value of the solution affect the formation of films. In these systems, 3 h may be characterized as the appro-
the film. From Fig. 1 and Table 1, we can see that the self- priate self-assembly time.
assembled films formed in 10−2 M solutions have more effec-
tive inhibition efficiency than that of 10−3 M. The reason is that 3.2. Quantum chemical calculations
the self-assembled films are formed on the iron surface by the
molecules of the inhibitor spontaneously. In the 10−2 M In order to investigate the adsorption mode between the
solutions, large quantities of molecules can form condense films MMT and the iron, we carried quantum chemical calculations.
on the iron surface. At first, a full geometry optimization of the MMT molecule is
Good quality films can be obtained in 10−2 M MMT solutions performed with the B3LYP/LANL2DZ method, and the result is
with pH = 2. The highest inhibition efficiency is 98.0%, which is shown in Fig. 4. It shows that the MMT molecule has a planar
better than the inhibition efficiency of the neutral solution
(pH = 6.5). In acidic self-assembly solutions, some protonated Table 3
nitrogen atoms are positively charged and iron surface is nega- Bond properties of the MMT molecule and the complex including MMT and
tively charged because of the adsorption of sulphate ions from iron
the solution [24]. So the MMT molecules can adsorb on the iron MMT molecule Complex
surface through positively charged nitrogen atoms by electro- Bond distance (Å) N4–C1 1.3640 1.4893
static action and the protection barrier is formed. However, when N4–C2 1.4628 1.4718
using the 10−3 M solutions, good inhibition efficiency is N4–N6 1.4057 1.5271
observed in the neutral solution. The reason is that low C1–S8 1.8024 1.8225
C1–N5 1.3490 1.4605
N4–Fe – 1.8483
Table 2 Band angle (°) N6–N4–C1 108.04 100.28
Mulliken charges of the MMT molecule C1–N4–C2 131.03 128.66
S8–C1–N4 124.10 121.42
Atom δ(C1) δ(C2) δ(N3) δ(N4) δ(N5) δ(N6) δ(S8)
N5–C1–S8 126.46 119.49
Charge −0.0525 0.1952 −0.0846 −0.1225 −0.1074 −0.0428 0.0616 Fe–N4–C2 – 143.67
1024 H. Ma et al. / Thin Solid Films 516 (2008) 1020–1024
Table 4
Calculated results of enthalpies (H), entropies (S) and free energy changes (ΔG)
of the MMT and iron system
H(hartree)
Iron atom −123.251
MMT molecule −307.493
Complex (MMT–Fe) −430.792
ΔH (J/mol) −125901.6
ΔS (J/mol·K)
ΔG (J/mol) −90597.1
structure, that is, four nitrogen atoms, two carbon atoms and one
sulfur atom are all in one plane. Mulliken charges of the atoms
in MMT molecule are calculated and listed in Table 2, which
shows that atom 4 N has the biggest electron density and it may
be the reactive center of the MMT molecule. Because 4N atom
of the MMT molecule will donate its lone electron pair to the
unfilled orbit of the metal atom, the MMT molecule can be
adsorbed on the metal surface.
In order to simplify the calculation, we use one iron atom
instead of iron surface to investigate the adsorption mechanism.
We consider this simplification is permitted and sound in the
quantum chemical calculation. The adsorption structure for the
complex of MMT molecule and iron atom is optimized with the
same method, which is shown in Fig. 5. From Fig. 5, we find
that the MMT molecule is connected with the iron atom through
its 4 N atom, which accords completely with the former theo-
retical predication. Moreover, the planar structure of the MMT
molecule is changed and distorted. Bond distance and bond
angle of the MMT molecule before and after the adsorption are
listed in Table 3. After adsorption, corresponding bond distance
became long and bond angle became small, which might be
caused by the intensive interactions between the MMT mole-
cule and the iron atom.
In order to investigate the spontaneity of the self-assembly
process, we calculated the free energy changes by:
DG ¼ DH  T DS
where ΔG is the free energy change, ΔH is the enthalpy change,
ΔS is the entropy change of the self-assembly process, and T is
the absolute temperature. The self-assembling process is
performed at the room temperature. The calculated results of
enthalpies (H), entropies (S) and free energy changes (ΔG) of
MMT and iron system are presented in Table 4. The calculated
result of ΔG is −90597.1 J/mol, therefore the self-assembling
process is spontaneous.
4. Conclusion
The self-assembled films of heterocyclic compound MMT
are found to be effective in inhibiting corrosion of iron in 0.5 M
H2SO4 solutions. The best inhibition efficiency of MMT for iron
is 98.0%. The most important explanation of the adsorption
mechanism is obtained by the DFT. The MMT molecule links to
S(J/mol·K) the iron surface by sharing of electrons between the nitrogen and
158.8 the iron atoms. Another kind of adsorption is by electrostatic
341.4 action in acidic solution. Some nitrogen atoms can be protonated
381.8
in acidic solution and be adsorbed on the negatively charged iron
−118.4 surface. The adsorption is enhanced by these two actions in
10−2 M MMT acidic solutions and the best inhibition efficiency
is obtained. This study is helpful in exploring the protection of
self-assembled films to iron in practice.
Acknowledgement
This work was supported by the Outstanding Middle-
aged Scientists Foundation of Shandong Province of China
(2005BS009).
References
[1] G. Trabanelli, Corrosion 47 (1991) 410.
[2] K. Aramaki, Corros. Sci. 41 (1999) 1715.
[3] Lj M. Vračar, D.M. Dražić, Corros. Sci. 44 (2002) 1669.
[4] S. Kerit, B. Hammouti, Appl. Surf. Sci. 93 (1996) 59.
[5] Martin Stratmann, Adv. Mater. 2 (1990) 191.
[6] X.R. Ye, X.Q. Xin, J.J. Zhu, Z.L. Xue, Appl. Surf. Sci. 135 (1998) 307.
[7] R. Singh, S.K. Dikshit, Polyhedron 12 (1993) 759.
[8] E.S. Raper, Coord. Chem. Rev. 129 (1994) 91.
[9] G. Lendvay-Győrik, L. Mészáros, G. Mészáros, B. Lengyel, Corros. Sci.
42 (2000) 79.
[10] N. Tsuji, K. Nozawa, K. Aramaki, Corros. Sci. 42 (2000) 1523.
[11] K.F. Khaled, N. Hackerman, Electrochim. Acta 48 (2003) 2715.
[12] K. Nozawa, H. Nishihara, K. Aramaki, Corros. Sci. 39 (1997) 1625.
[13] I. Felhösi, J. Teleddi, G. Pálinkás, E. Kálmán, Electrochim. Acta 47 (2002)
2335.
[14] E. Maccafferty, Corros. Sci. 39 (1997) 243.
[15] H.Y. Ma, X.L. Cheng, G.Q. Li, S.H. Chen, Corros. Sci. 42 (2000) 1669.
[16] A. Stoyanova, G. Petkova, S.D. Peyrimhoff, Chem. Phys. 279 (2002) 1.
[17] E. Lazarova, T. Yankova, B. Aleksiev, Langmuir 11 (1995) 2231.
[18] E. Lazarova, S. Kalcheva, G. Neykov, T. Yankova, N. Stoyanov, J. Appl.
Electrochem. 30 (2000) 561.
[19] N. Khalil, Electrochim. Acta 48 (2003) 2635.
[20] M.J. Frisch, G.W. Trucks, H.B. Schlegel, P.M.W. Gill, B.G. Johnson, M.A.
Robb, J.R. Cheeseman, T. Keith, G.A. Petersson, J.A. Montgomery, K.
Raghavachari, M.A. Al-Laham, V.G. Zakrzewski, J.V. Ortiz, J.B. Fores-
man, C.Y. Peng, P.Y. Ayala, W. Chen, M.W. Wong, J.L. Andres, E.S.
Replogle, R. Gomperts, R.L. Martin, D.J. Fox, J.S. Binkley, D.J. Defrees, J.
Baker, J.P. Stewart, M. Head-Gordon, C. Gonzalez, J.A. Pople, Gaussian
98, Revision A.9, Gaussian Inc., Pittsburgh, PA, 1999.
[21] M. Gojić, Corros. Sci. 43 (2001) 919.
[22] C.T. Wang, S.H. Chen, H.Y. Ma, C.S. Qi, J. Appl. Electrochem. 33 (2003)
179.
[23] Z.L. Quan, S.H. Chen, Y. Li, X.G. Cui, Corros. Sci. 44 (2002) 703.
[24] K.F. Khaled, N. Hackerman, Mater. Chem. Phys. 82 (2003) 949.