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Journal of Molecular Structure (Theochem) 625 (2003) 3138

www.elsevier.com/locate/theochem

Tautomeric studies on 2-mercapto pyrimidines and their


significance in corrosion process
gretir, M. Yaman, E. Hur
G. Bereket*, C. O
Department of Chemistry, Faculty of Arts and Science, Osmangazi University, Eskisehir 26480, Turkey
Received 30 August 2002; accepted 11 October 2002

Abstract
Thermodynamic parameters of some 2-mercapto pyrimidine derivatives were calculated by semi-empirical quantum
chemical calculation methods. Full geometry optimization of the molecules in aqueous phase were made and any possible
parallelism with the reported experimental data were searched The observed confidence levels of correlations for both
tautomerism and corrosion process were satisfactory.
q 2002 Published by Elsevier Science B.V.
Keywords: Corrosion; Inhibitor; 2-Mercapto pyrimidine; Quantum calculations; Tautomerism

1. Introduction
Sulphuric acid solutions have been used for some
treatments of metallic materials. Inhibiting action of
several families of organic compounds were reported
in literature. Inhibitors should be added in order to
prevent corrosion and acid consumption during these
treatments. The compounds usually reported are the
conventional sulphur containing inhibitors such as
thiourea derivatives, aliphatic mercaptans and generally the heterocyclic substances containing sulphur
atoms in the ring or SH substituents in the lateral
chains. Among the nitrogen containing compounds the
quaternary ammonium cations having halide ion as a
counterion have been the most used [1 3]. Several
* Corresponding author. Tel.: 90-222-2290433; fax: 90-2222393578.
E-mail address: gbereket@ogu.edu.tr (G. Bereket).

derivatives of 2-mercapto pyrimidine (Table 1) have


been studied as corrosion inhibitors for ARMCO iron
in 1 M sulphuric acid solution. Among the studied
pyrimidine derivatives 2-mercaptopyrimidine, 2,4dimercaptopyrimidine and 2-mercapto-4-methylpyrimidine has been found to behave as inhibitor.
Whereas the remaining studied compounds were
founded to accelerate the corrosion. Accelerating
effect of these compounds was devoted to the
presence of OH or NH 2 in 4 position of
heterocyclic ring, which presumably stabilize thione
form. The decomposition of this form in acid solution
occurs with removal of the sulphur atom as H2S which
stimulate iron dissolution. Conversely, derivatives
having CH3 or SH in 4-position of the ring found
to stabilize the mercapto form instead of thione form
and inhibiting effect of these compounds were
explained by presence of mercapto group at 2-position

0166-1280/03/$ - see front matter q 2002 Published by Elsevier Science B.V.


PII: S 0 1 6 6 - 1 2 8 0 ( 0 2 ) 0 0 7 4 2 - X

32

G. Bereket et al. / Journal of Molecular Structure (Theochem) 625 (2003) 3138

Table 1
Nomenclature and the experimental acidity constants, pKa, of studied compounds 18
Molecule

1
2
3
4
5
6
7
8

H
SH
CH3
NH2
OH
OH
NH2
NH2
a

H
H
H
H
H
H
H
NyO

H
H
H
H
H
CH3
OH
OH

pKaa

IUPAC name

2-Mercaptopyrimidine
2,4-dimercaptopyrimidine
2-Mercapto-4-methylpyrimidine
2-Mercapto-4-amino-pyrimidine
2-Mercapto-4-hydroxypyrimidine
2- Mercapto-4-amino-6-methylypyrimidine
2- Mercapto-4-amino-6-hydroxypyrimidine
2- Mercapto-4-amino-5-nitroso-6-hydroxypyrimidine

Proton-loss

Proton-gain

7.14
11.19
8.00
10.63
12.70
8.10

1.35
6.46
2.20
3.32
7.74

Taken from Ref. [19].

which the possibility of interaction with the metal


surface by some adsorption process [4].
The use of quantum chemical methods as an
additional tool in studying corrosion inhibitor is
becoming so common in the last decade [5 16].
The aim of this paper is to investigate the applicability
of quantum chemical calculations to predict inhibition
and accelerating effect of some 2-mercapto pyrimidine derivatives for the corrosion of ARMCO iron in
sulphuric acid and determine the possible tautomeric
forms to elucidate the mechanism of corrosion
process.

2. Method of calculations
All calculations were carried out with the full
geometry optimization. Theoretical calculations were
carried out at the Restricted Hartree-Fock Level
(RHF) using AM1, PM3 and MNDO semiempirical
SCF-MO methods in the MOPAC 7.0 packed program
[17]. Implemented on Pentium IV.

the inhibition of corrosion by those molecules. In one


of our earlier work we had studied the tautomeric
equilibra for 2-mercapto pyrimidine and demonstrated 50% preference of thione and thiol forms by
using experimental values. Whereas gas phase
quantum chemical calculations had indicated the
predominance of thiol form 1a with PM3 and
MNDO methods. The AM1 method however
had indicated the predominance of thione form 1b
(Fig. 1, Table 1) [18].
The aqueous phase calculated stability
values indicate the stability of thione forms (1b 8b)
(Table 2) with AM1 and PM3 methods, whereas the
gas phase calculations indicate the opposite, for all
studied molecules 1 8. MNDO method however both
in gas and aqueous phase calculations indicate the
predominance of thiol forms 1a 8a for all studied
molecules.
3.2. Corrosion
To study the relationship between corrosion
rates and quantum chemical parameters of mercaptopyrimidine derivatives systematically they were

3. Results and discussion


3.1. Tautomerism
Since the tautomeric forms of organic molecules
play an important role in structure reactivity relationships, we have concentrated primarily on the proton
tautomerism of the studied 2-mercapto pyrimidine
derivatives to be able to explain the mechanism of

Fig. 1. Structure of the investigated compounds.

G. Bereket et al. / Journal of Molecular Structure (Theochem) 625 (2003) 3138


Table 2
Comparison of semiempirical (AM1, PM3 and MNDO) aqueous
phase and gas phase calculated relative stability (RS, kcal mol21)
for the investigated compounds

33

5 or 6 positions which behave as activator (i.e.


compounds 4, 7, 8).

Series 1: 2-Mercapto pyrimidine derivatives which


behave as inhibitor (i.e. compounds 1,2,3)
Series 2: 2-Mercapto pyrimidine derivatives having different substitutients at 5-position and behave
as (i.e. compounds 1,2,3,4, 5).
Series 3: 2-Mercapto pyrimidine derivatives having NH2 in 4-position but different substituents at

The nomenclature and the experimental acidity


constants of studied 2-mercapto pyrimidine derivatives are collected in Table 1. The experimental
corrosion rate of ARMCO iron in 1 M H2SO4 in
the presence of 1023 M 2-mercapto pyrimidine
derivatives and AM1, PM3, MNDO gas and
aqueous phase calculated relative stabilities,
RS, are given in Table 2. Using the obtained data
graphs of corrosion rates, CR, against relative
stability, RS, graphs were constructed. Corrosion
rates were found to decrease as relative stability
increase. Since RS value is the measure of stability
of molecules these results indicate that corrosion
rates were decrease as the stability of molecules
increase. The best correlations were found for AM1
gas and aqueous phase calculations for series 2
(Figs. 2 and 3).
Values of total energy, ET, energy of lowest
unoccupied molecular orbital, ELUMO, and energy of
highest unoccupied molecular orbital, EHOMO, and
charges on active centres of 2-mercaptopyrimidine
ring N(3), N(1) were calculated using semiemprical
AM1, PM3 and MNDO methods gas and aqueous
phases. Results are given in Tables 3 and 4,
respectively. In order to evaluate the relation
between corrosion rate, CR, and total energy, ET,
graphs of CR ET were constructed. As it can be
seen from Figs. 4 and 5 the corrosions rates
decrease as ET values increase. With series 1
which consists of inhibitor molecules, correlations
are excellent. However, CR vs. ET graphs for series
2 are not good (Figs. 6 and 7). Deviation from the
line of molecules 4 and 5 is probably due to
presence of NH 2 and OH as substituent.

Fig. 2. Graph of corrosion rates and gas phase relative stabilities


(AM1).

Fig. 3. Graph of corrosion rates and aqueous phase relative


stabilities (AM1).

Molecules
Aques phase
1a1b
2a2b
3a3b
4a4b
5a5b
6a6b
7a7b
8a8b
Gas phase
1a1b
2a2b
3a3b
4a4b
5a5b
6a6b
7a7b
8a8b

MNDO

CRa

27.930
27.370
28.249
212.297
28.245
27.889
27.783
24.948

2.431
2.703
2.637
1.069
0.955
2.568
5.610
4.710

1.17
2.42
2.27
21.30
10.96
20.23
16.46
18.84

19.131
18.208

16.332
15.810
16.471
15.352
14.811
15.449
21.276
21.347

1.17
2.42
2.27
21.30
10.96
20.23
16.46
18.84

AM1

PM3

29.025
29.038
29.404
212.899
29.726
29.672
210.502
28.733
10.626
9.460
10.405
8.836
9.086
7.840
11.257
11.177

17.491
17.309
16.245
23.283

RS DHf (thione) 2 DHf (mercapto) The minus sign indicates


that thione form is more stable.
a
Taken from Ref. [4].

classified into three series with respect to different


substitutients.

34

G. Bereket et al. / Journal of Molecular Structure (Theochem) 625 (2003) 3138

Table 3
Gas phase AM1, PM3 and MNDO calculation data for studied molecules
Molecules

AM1
1a
1b
2a
2b
3a
3b
4a
4b
5a
5b
6a
6b
7a
7b
8a
8b

Total energy,
ET (eV)

EHOMO
(eV)

ELUMO
(eV)

Charge on
nitrogen atom 1, qN(1)

Charge on
nitrogen atom 3, qN(3)

Corrosion rates
(mg/cm2/h)

21174.71
21174.24
21369.24
21368.83
21330.53
21330.08
21395.70
21395.31
21495.30
21494.91
21651.13
21650.79
21716.30
21715.81
22228.43
22247.95

28.99
28,67
28.92
28.65
28.92
28.58
28.81
28.33
29.06
28.68
29.0
28.61
28.90
28.45
28.27
28.83

20.44
20.90
20.51
21.07
20.36
20.87
20.17
20.49
20.47
20.86
20.39
20.81
20.16
20.56
21.02
21.11

20.15
20.25
20.16
20.25
20.15
20.25
20.18
20.26
20.17
20.26
20.18
20.26
20.26
20.31
20.29
20.31

20.19
20.15
20.22
20.19
20.20
20.16
20.26
20.25
20.27
20.26
20.28
20.25
20.28
20.27
20.31
20.29

1.17
1.17
2.42
2.42
2.27
2.27
21.30
21.30
10.96
10.96
20.23
20.23
16.46
16.46
18.84
18.84

21045.39
21044.56
21231.57
21230.78
21195.10

29.26
28.85
29.27
28.90
29.21

20.72
21.39
20.85
21.60
20.64

20.08
0.22
20.09
0.22
20.09

20.14
20.8
20.16
20.12
20.14

PM3
1a
1b
2a
2b
3a
3b
4a
4b
5a
5b
6a
6b
7a
7b
8a
8b

21223.45
21222.69
21339.43
21338.68
21489.15
21488.44
21517.52

29.07
28.57
29.30
28.82
29.25
28.76
29.14

20.52
21.14
20.74
21.28
20.67
21.24
20.47

20.13
0.20
20.12
0.19
20.12
0.19
20.22

20.19
20.18
20.24
20.21
20.25
20.22
20.24

21955.93
21954.92

29.44
28.88

21.21
21.42

0.26
0.08

20.28
20.24

1.17
1.17
2.42
2.42
2.27
2.27
21.30
21.30
10.96
10.96
20.23
20.23
16.46
16.46
18.84
18.84

MNDO
1a
1b
2a
2b
3a
3b
4a
4b
5a
5b
6a
6b
7a
7b
8a
8b

21210.66
21209.95
21439.59
21438.90
21367.30
21366.59
21432.45
21431.79
21533.46
21532.82
21690.10
21689.43
21755.27
21754.35
22268.86
22267.93

29.52
28.78
29.46
28.80
29.478
28.730
29.37
28.62
29.51
28.77
29.47
28.72
29.38
28.63
29.72
28.97

20.51
20.82
20.63
21.02
20.50
20.85
20.40
20.68
20.51
20.77
20.52
20.82
20.36
20.71
21.16
21.18

20.247
20.304
20.249
20.304
20.244
20.303
20.27
20.31
20.27
20.31
20.27
20.31
20.35
20.36
20.38
20.35

20.29
20.26
20.31
20.29
20.28
20.26
20.34
20.33
20.37
20.36
20.37
20.36
20.37
20.35
20.39
20.37

1.17
1.17
2.42
2.42
2.27
2.27
21.30
21.30
10.96
10.96
20.23
20.23
16.46
16.46
18.84
18.84

G. Bereket et al. / Journal of Molecular Structure (Theochem) 625 (2003) 3138

35

Table 4
Aqueous phase AM1, PM3 and MNDO calculation data for studied molecules
Molecules

Total energy, ET
(eV)

EHOMO
(eV)

ELUMO
(eV)

Charge on nitrogen
atom 1, qN(1)

Charge on nitrogen
atom 3, qN(3)

Corrosion rates
(mg/cm2/h)

AM1
1a
1b
2a
2b
3a
3b
4a
4b
5a
5b
6a
6b
7a
7b
8a
8b

21174.71
21175.65
21369.25
21370.21
21330.54
21331.47
21396.47
21397.03
21495.5
21496.38
21651.77
21652.19
21717.16
21717.62
22229.38
22229.76

29.48
29.96
29.32
29.64
29.47
29.98
29.38
29.84
29.52
210.02
29.53
210.02
29.41
29.79
29.65
210.12

20.58
21.12
20.75
21.38
20.59
21.19
20.47
20.75
20.61
21.07
20.62
21.14
20.49
20.80
21.28
21.36

20.26
20.12
20.27
20.14
20.26
20.13
20.31
20.20
20.29
20.16
20.29
20.17
20.36
20.25
20.39
20.25

0.12
20.27
0.11
20.28
0.12
20.27
20.34
20.35
20.33
20.32
20.33
20.32
20.36
20.35
20.38
20.35

1.17
1.17
2.42
2.42
2.27
2.27
21.30
21.30
10.96
10.96
20.23
20.23
16.46
16.46
18.84
18.84

PM3
1a
1b
2a
2b
3a
3b
4a
4b
5a
5b
6a
6b
7a
7b
8a
8b

21045.39
21046.30
21231.57
21232.51
21195.11
21196.01
21224.18
21224.71
21340.10
21340.48
21489.79
21490.14
21518.32
21518.66
21957.02
21957.23

29.80
210.14
29.64
29.87
29.78
210.13
29.22
29.19
29.77
210.13
29.78
210.16
29.15
29.23
29.26
29.51

20.75
21.33
21.03
21.61
20.77
21.37
20.59
20.81
20.77
21.24
20.78
21.28
20.57
20.86
21.18
21.41

20.22
0.58
20.21
0.58
20.23
0.57
20.31
0.37
20.26
0.51
20.25
0.48
20.37
0.28
20..43
0.25

0.03
20.18
0.05
20.16
0.05
20.17
20.33
20.35
20.30
20.26
20.31
20.27
20.36
20.33
20.36
20.29

1.17
1.17
2.42
2.42
2.27
2.27
21.30
21.30
10.96
10.96
20.23
20.23
16.46
16.46
18.84
18.84

MNDO
1a
1b
2a
2b
3a
3b
4a
4b
5a
5b
6a
6b
7a
7b
8a
8b

21210.66
21211.07
21439.59
21439.98
21367.30
21367.67
21433.15
21453.10
21534.10
21534.06
21690.70
21690.58
21756.06
21755.82
22269.77
22269.57

29.74
29.49
29.60
29.53
29.72
29.50
29.60
29.53
29.69
2958
29.69
29.61
29.58
29.47
29.75
29.74

20.44
20.92
20.65
21.19
20.51
21.06
20.43
20.53
20.46
20.84
20.54
20.97
20.45
20.57
21.19
21.16

20.37
20.21
20.37
20.22
20.37
20.21
20.40
20.27
20.40
20.24
20.39
20.24
20.44
20.31
20.49
20.31

0.14
20.42
0.14
20.41
0.13
20.40
20.41
20.48
20.43
20.47
20.43
20.46
20.43
20.49
20.48
20.50

1.17
1.17
2.42
2.42
2.27
2.27
21.30
21.30
10.96
10.96
20.23
20.23
16.46
16.46
18.84
18.84

36

G. Bereket et al. / Journal of Molecular Structure (Theochem) 625 (2003) 3138

Fig. 4. Graph of corrosion rates and gas phase toplam energy


mercapto form (AM1).

Fig. 6. Graph of corrosion rates and gas phase calculated toplam


energy mercapto form (AM1).

Abnormal behaviour of molecule 4 and molecule 5


might be due to not considering imine and oxo
tautomeric forms of these compounds. No correlation was found between the CR vs. ET
graphs for series 3 also because of not
considering imine and oxo tautomeric forms of
this compounds.
In order to be able to propose mechanism of
inhibition of studied compounds relations between
corrosion rates and charges of active sites, relation
between corrosion rates and EHOMO or ELUMO
energies should be discussed. Using calculated data
given in Tables 3 and 4 graphs of corrosion rate
and charges CR qN(3), CR qN(1), CR EHOMO,
CR ELUMO were constructed. Corrosion rates were
found to decrease as the charge densities on N(3)
atoms were increasing for inhibitor molecules. No
correlation between charge densities on N(1) atom
was found. Fig. 8 shows CR qN(3) graphs
obtained from PM3 aqueous phase calculation
which gives the best correlations. No correlations
between corrosion rate and charge found for the
other molecules. The obtained good correlations in
CR qN(3) graphs can be interpreted as physical

adsorption of inhibitor molecule on metal surface.


Physical adsorption although weak is usually an
inevitable stage precede to chemisorption. Variation
of charge density on N(3) atom for inhibitor
molecules with their proton gain pKa values are
linear. The best correlation was found with PM3
aqueous phase calculation (Fig. 9). The parallel
results obtained in CR vs. qN(3) graphs and
indicates that most probable centre of protonation
is pyridine like nitrogen. After physical absorption
inhibitor molecules are chemisorped subsequently
on metal surface. Chemisorption of organic molecules occur due to chelation on metal surface.
Organic molecules may offer electrons to unoccupied d-orbitals of metals and accept the electrons in
the in the d-orbitals of metals by using antibonding
orbital to form feedback bounds [20]. CR vs.
EHOMO graphs are linear and corrosion rates are
increase as EHOMO values are increase (Figs. 10
and 11). Variation of CR with ELUMO are also
linear (Figs. 12 and 13). Corrosion rates are
decrease as ELUMO values are increase. Taking
into account that EHOMO values which are equal to
negative of ionization potentials and ELUMO values
which are equal to electron affinity of

Fig. 5. Graph of corrosion rates and aqueous phase calculated


toplam energy thion form (AM1).

Fig. 7. Graph of corrosion rates and aqueous phase calculated


toplam energy thion form (AM1).

G. Bereket et al. / Journal of Molecular Structure (Theochem) 625 (2003) 3138

Fig. 8. Graph of corrosion rates aqueous phase calculated qN3 thion


form (PM3).

Fig. 9. Graph of pKa and aqueous phase calculated qN3 thion form
(PM3).

37

Fig. 12. Graph of corrosion rates and aqueous phase EHOMO thion
form (AM1).

molecules. This type of variation in CR-EHOMO and


CR-ELUMO indicate that chelation on metal surface
occurs because studied inhibitor molecules are
accepting electrons from metal that means
they behave as acceptor. Similar acceptor
behavior is recorded for the inhibition
effect of protanated pyridine derivatives for
the inhibition of aluminium in hydrochloric
acid [21].
When regression analysis was performed on CR
and EHOMO and ELUMO the following equations were
obtained.
CR 21:84; 686EHOMO 9:6ELUMO 2 1570:801
R2 1AM1; gas phase

CR 52:021EHOMO 27:083ELUMO 580:880

Fig. 10. Graph of corrosion rates and gas phase calculated EHOMO
mercapto form (AM1).

The coefficients of EHOMO and ELUMO are negative and


positive, respectively. These values indicate the
acceptor properties of 2-mercapto pyrimidine derivatives which are acting as inhibitor.

Fig. 11. Graph of corrosion rates and gas phase calculated EHOMO
mercapto form (MNDO).

Fig. 13. Graph of corrosion rates and aqueous phase calculated


ELUMO mercapto form (MNDO).

38

G. Bereket et al. / Journal of Molecular Structure (Theochem) 625 (2003) 3138

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