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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).
32
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
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.
33
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
34
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
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
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).
Fig. 10. Graph of corrosion rates and gas phase calculated EHOMO
mercapto form (AM1).
Fig. 11. Graph of corrosion rates and gas phase calculated EHOMO
mercapto form (MNDO).
38
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