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Corrosion Science, 1971, Vol. 11, pp. 223 1o 229. Pergamon Press.

'Printed in Great Britain






J. VosTA a n d J. ELI~SEK
Institute of Chemical Technology, Prague
Abstract---The physico-chemical properties of corrosion inhibitors are one of the principal criteria
for the determination and selection of inhibitors, and it is apparent that such quantities as the dipole
moment or electron density play an important role. Issuing from these and other assumptions, an
attempt has been made to apply quantum-chemicalvalues to the selection and evaluation of corrosion
inhibitors. The calculation was carried out by the LCAO (Linear Combination of Atomic Orbitals)
method for the homologous series of substituted pyridine derivatives. Molecular diagrams and other
quantum values were obtained and correlated with the inhibition of corrosion produced by these
substances as evaluated by polarization curves.
R6sum6----Lespropri6tfs physico-chimiques des irthibiteurs de corosition repr6sentent un des aspects
~ la ddterminationet sdlection des inhibiteurs. II est clair que telles grandeurs comme p.ex. un moment
dipolaire, une densit6 61ectroniquejouent un role important. Partant de ces et d'autres pr&nisses on
a 6labor6 un trait6 expdrimentant la mise en valeur des grandeurs quantiques h la s6lection et estf
marion des inhibiteurs de corrosion. On a cffectu6 le calcul par m6thode LCAO dans une s~rie
homologue de ddrivds substitu~s pyridiques. On a obtenu des diagrammes moldculaires ensemble
avec des grandeurs quantiques suivantes mises en corr61ation avec rexamination inhibitivement
corrosive de ces substances-lb, au moyen des courbes de polarisation.
Zusammenfassung--Ffirdie Bestimmung und Auswahl tier Korrosionsinhibitoren sind die physikalisch-chemische Eigenschaften etnscheidend. Dabei spielen das Dipolmoment und die Elektronendichte eine wichtige Rolle. Aug dieser Grundlage wurden die Korrosionsinhibitoren nach den
QuantengdSssen ausgewahlt und ausgewertet. An den homologen Reihe yon substituierten Pyridinderivaten wurde die Berechnung mit der LCAO-Methode durchgefiihrt. Es wurden Molekulardiagramme neben anderen Quantengrfssen gewonnen. Mit Hilfe yon Polarisationskurven wurden
sic mit den Irthibitions--und Korrosionsuntersuchungenin einen Zusammenhang gebracht.

OROANIC substances utilized as corrosion inhibitors are selected and judged on the
basis of their physico-chemical properties, 1.5 and relatively little attention has been
paid to the quantitative evaluation of the internal and sterie effect of these substances
upon their inhibition efficiency. For this reason we have been interested in the relation
between the quantum-chemical values 6,7 and inhibition efficiency, which could assist
in the selection and quantitative evaluation of corrosion inhibitors.

Homologous series of pyridine N-oxide carrying various substituents in the

7-position, were studied. Quantum-chemical values ol'these substances were calculated
by the method of Linear Combination of Atomic Orbitals (LCAO) ~ which is used for
the q u a n t u m calculation o f molecular diagrams and other q u a n t u m - c h e m i c a l values
a n d provides a c o m p a r i s o n between the chemical reactivity of a substance. Substances
studied were: pyridine, pyridine N-oxide, 4-dimethylaminopyridine N-oxide, 4-mer*Presented at the 4th International Congress on Metallic Corrosion, Amsterdam, 1969.
Manuscript received 7 January 1970. Received in revised form 28 July 1970.


J. VOltA and J. ELI,~EK

captopyridine N-oxide, 4-cyanopyridine N-oxide, 4-methylpyridine N-oxide, 4-nitropyridine N-oxide together with dibenzyl sulphoxide in a hyperconjugation model. The
above homologous series was chosen because of the possibility of observing the effect
of y-substituents upon the inhibition efficiency of the N-oxide group, and also with
regard to the structural similarity with the S-oxide group, which may be compared
with the well-known and already studied dibenzyi sulphoxide. At the same time, it was
possible to use the LCAO method for calculating the quantum-chenlical values of
these substances.
The polarization curves s,9 were measured at 25~ in 5% HCI which was prepared
by dilution of distilled analytical pure acid with demineralized water (Amberlite
MB-1). For the polarization experiments, an Armco Fe electrode was used. The
substances used for the experiments were recrystallised, and their purity was examined
by their melting point and by chemical analysis. The results obtained agreed with the
theoretical values.
Some polarization curves of the electrode in HC! alone and ill HCI containing
dibenzyl sulphoxide, 4-nitro-pyridine N-oxide, and 4-dimethylaminopyridine N-oxide
in concentrations of 10--~ in 5% HCI are shown for illustration in Fig. 1.







E vs, SCE [Volts]

Fro. i. Polarization curves of Armco iron electrode in: Graph I, 5% ]ICI; Graph 2,
5% HCi + I0-2M dibenzyl sulphoxide (DBSO); Graph 3,5% HC! + 10-=M 4-nitropyridine N-oxide; Graph 4, 5% ttCI + 10-"M 4-dimethylaminopyridine N-oxide.

The results of correlation of the quantum-chemical quantities with the log icorr
showed that the inhibition efficiency depends mostly upon the energy of the Highest
Occupied Molecular Orbital (HOMO); k(l), which is a theoretical analogue to the
ionization potential of a substance, and the energy of the Lowest Free Molecular

Study on corrosion inhibition from aspect Of quantum chemistry

-/3 - '




Fzo. 2. Energy level diagram for LCAO's.









HOMO [/3']

FIG. 3. Correlation of ItOMO orbitals with log iL-o~:1. Pyridine; 2.4-Methylpyridine

N-oxide; 3. Pyridine N-oxide; 4. 4-Cyanopyridine N-oxide; 5. 4-Mercaptopyridine
N-oxide; 6.4-Dimethylaminopyridine N-oxide.



J. VO~,TAand J. EI.I.~EK

Orbital (LFMO); k(--l), which illustrates the electron affinity of the molecule. Both
orbitals are schematically demonstrated in Fig. 2. From Fig. 3 it is consequent that
the inhibition efficiency increases with the increase of energy of the HOMO orbital,
that is with the decrease of the ionization potential. It has to be said that the least
firmly bonded electrons in the limit H O M O orbital are the richest ones in energy. It
is further evident that the inhibition efficiency increases with the ease of the ionization
of the molecule, which means that the molecule acts as an electron donor when blocking the corrosion reaction. For 4-nitropyridine N-oxide which according to the
polarization curve is a stimulator of corrosion, the dependence of log icorr upon the
energy of H O M O orbitals does not correspond to the marked linear dependence and,
therefore, its action in the corrosion process is controlled by a different mechanism.
This presumption was, to a certain extent, corroborated by the dependences of energy
of L F M O orbitals upon log icorr with the exception of pyridine and 4-cyanopyridine
N-oxide. These energies which represent the electron affinity had shown that effective
inhibitors are bad acceptors of electrons. On the contrary, the substances which are
easily reduced, like 4-nitro-pyridine N-oxide, may operate as stimulators of corrosion.
Pyridine which does not fulfil the stated dependence, is on one side difficult to reduce,
but with regard to its stability which is evident even from its low ionization potential,





-0 E





L F M O [B]

Fro. 4. Correlation o f L F M O orbitals with log i ~ : I. 4-Methylpyridine N-oxide;

2. Pyridine N-oxide; 3. 4-Mercaptopyridine N-oxide; 4. 4-Dimethylaminopyridine

Study on corrosion inhibition from aspect o[ quantum chemistry


it is a very ineffective inhibitor. 4-cyanopyridine N-oxide is reduced easily because

of the presence of the cyano-group. Its inhibition efficiency is obviously caused mainly
by its relatively easy ionization (see Fig. 4).
Some other values obtained by the quantum-chemical calculation verified these
principal concepts. Electron densities (Q), free valences (F), and bond orders (P) for
each atom of the studied substances were obtained from the molecular diagrams.






C ,-5,2

FIG. 5.


Molecular diagram of 4-cyanopyridine N-oxide.

Figure 5 shows the molecular diagram of 4-cyanopyridine N-oxide. The most

interesting turned out to be the electron densities (Q) in the N-oxide and S-oxide
inhibition centres, which related to the inhibition efficiency are shown in Table 1. The
comparison indicates the fact that inhibitors with higher efficiency have even a higher
electron density in the presumed inhibition centre. That means, from the point of view
of the general chemical reactivity, that these centres are able to participate by their
own electrons when forming a chemical bond between a substance (inhibitor) and a
metal. It also means that an electrophilic substitution from the standpoint of a reaction
between the metal and the inhibitor, may take place. In this case, the metal will be an
electrophilic agent (with a cation or an atom with an incompleted electron octet).
The values of free valences (F) which are quantum-chemical indicators of the radical
reactions, do not exclude the possibility of a radical reaction taking place. For comparison, only the most reactive sites in the considered substances were chosen. The
predisposition towards a radical reaction, that is a maximum free valence (F), is shown
by oxygen in the N-O and S-O groups, as may be seen in Table 1. In these parts of the
molecule also the bond order (P) decreases with the increase of the inhibition, and this
is a sign of a considerable localization of electrons (see Table 1).


J. Vogr^ and J. ELIAgEK












































Study on corrosion inhibition from aspect of quantum chemistry


The presented quantum-chemical parameters, that means the electron densities,

free valences and bond orders belong to the so-called static indices of the chemical
reactivity, because they characterize the reactivity of a substance by means of quantities in its basic state. In order to have the estimate and subsequent prognosis of chemical reactivity as precise as possible the static indices must be in harmony with the
dynamic indices of the chemical reactivity which agree with the structure of an
activated complex. These are the atomic localization energy (A) and the superdelocalizability (S).
The values of these quantities confirmed the assumed considerations, and were in
harmony with the static indices of the chemical reactivity. They verified the fact that
the most reactive site of the studied compounds is the oxygen in the N-O and S-O
groups, because here is the minimum atomic localization energy (AE), and this indicates the most reactive position, for the largest reaction rate may be expected in sites,
where the required energy for eliminating the conjugation of a certain centre is the
lowest one. The same parts of the molecules had also high values of the electrophilic
(Se) and radical super-delocalizability (SR) on the oxygen atom. The nucleophilic
super-delocalizability was not expressive for any atom in the molecules and, therefore,
it was not taken into account for the comparison (see Table I).
As for the influence of 7-substituents upon the N-oxide inhibition centre, the
dimethylamino-group appeared to be the most effective one, from the point Of view of
the inhibition, in comparison with such groups as --SH, --C----N, --CHa, and --NO.,.
This kind of evaluation of the metal corrosion inhibitors by means of quantumchemical values may, to a great extent, eliminate an empirical approach to the research
work in this sphere, and also facilitate a rational selection of the new inhibitors.
Acknowledgeulent--Sincere thanks are due to Dr. Zahradnik, of The Institute for Physical Chemistry
of the Czechoslovak Academy of Science, for his help in calculating the quantum-chemical parameters and the moral support without which this work would never have been done.
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