J. Chirn. Phys.

(1998) 95, 45-55

0 EDP Suences. Les Ulis

Inhibition of corrosion of copper in

nitric acid solution by some arylmethylene
cyanothioacetamide derivatives

A.S. oud da*, A.K. Mohamed and H.A. Mostafa

Chernistry Department. Faculty of Science, El-Mansoura University, El-Mansoura, Egypl

(Received 18 February 1997; accepted 15 Septernber 1997)

Correspondenceand reprints.

RÉSUMÉ
L'inhibition de la corrosion du cuivre dans des solutions 2M HNO, par
quelques dérivés d'arylméthylène cyanothioacétamides a été testée par des mesures
de polarisation. Les résultats montrent que ces composés se comportent comme des
inhibiteurs mixtes. Des efficacités d'inhibition jusqu'à 90 % peuvent être obtenues.
L'inhibition est supposée se produire par l'adsorption des molécules d'inhibiteur
suivant une isotherme de Fmmiun. L'influence du groupe substituant sur l'efficacité
de l'inhibiteur a été interprétée en terme de densité du nuage électronique sur la
partie cyanothioacétamide et de mode d'adsorption. L'augmentation de la
température augmente la corrosion en l'absence et en présence d'inhibiteur.
Certaines fonctions thermodynamiques ont également été calculées et discutées.
Mots-clés : dérivés d'arylméthylène cyanothioacétamides, inhibiteur de corrosion,
cuivre.
ABSTRACï
The uihibition of corrosion of copper in 2M HNO3 solution by some arylmethylene
cyanothioacetamide derivatives was tested using polarization measurements. The
results showed that these compounds act as mixed type inhibitors and inhibition
effîciencies up to 90% can be obtained. The uihibition was assurned to occurvia
physical adsorption of the uihibitor molecules fitting a Frurnkm isotherm. The influence
of the substituent group on the inhibition eficiency of the inhibitor was explained in
terms of the density of the electron cloud on the cyanothioacetamide moiety and the
mode of adsorption. The increase in temperature was found to increase the corrosion
in absence and in presence of inhibitors. Some thermodynamic functions were also
computed and discussed.
Key words: Arylmethylene cyanothioacetamide derivatives, corrosion inhibitors,
copper.
46 A.S. Fouda et al.

INTRODUCTION
Copper and copper alloys are wdely employed in industnes due to their remarkable
physical and mechanical properties. Nitrogen- and sulphur-containing compounds
encompass a large section of the important organic corrosion inhibitors [l].
Compounds containing both nitrogen and suiphur are of parhcular interest since they
are otten able to provide enhanced adsorption and dubition characteristics compared
with compounds contianing only nitrogen or sulphur [2]. Added improvements in
inhibitor performance can also be acheved by the substitution and addition of
appropnate group. The electron donation or inductive effect has been the subject of a
nurnber of reviews [3-91. Thiourea and thiosemicarbazide are possibly the simplest of
the nitrogen-and sulphur-containing group of compounds. The use of thourea and its
denvatives [ 1O] and thiosemicarbazide and its derivatives [ I l - 131 as corrosion
dubitors of metals have been studied. The extent of adsorption of uihibitors depends
on many factors [14-161: a) the nature of the metal, b) the mode of adsorption of the
inhibitors, and c) the surface conditions, the adsorption theory of corrosion inhibition,
postulating that adsorption is general over the entire surface, was first proposed by
Hackermann [ 1 7- 191
The aim of t h s paper is to descnbe an investigation of the inhibition of corrosion of
copper in 2M HNO3 solution by some arylmethylene cyanothoacetamide denvatives
using polarizaiton measurements and to elucidate the mechanism of inhibition of the
corrosion of copper.

E,VERIMENTAL DETAlLS
Commercial-grade copper (composition %: 0.001 Fe, 0.01, Cd, 0.1 Pb, Cu
remainder) was used. All chemicals used were of BDH grade except the inhibitors
w h c h were chemically pure substances. The solutions were made fiom bi-distilled
water.
Polarization experiments were camed out under unstirred conditions with a fine
luggin capillary to avoid ohmc polarization. Galvanostatic condition was maintained
using a constnat current (WP-704 AX). Copper was taken in the form of cylindrical
rod with a surface area of 0.37 cm2. The surfaces to be exposed were successively
mechanically polished with e m e y paper up to 410 grade using an alcohol as lubricant,
degreased in 1:1 HNO3 and washed thoroughly with distilled water. A saturated
calomel electrode and platinum electrode were used as reference and a u x i l i a ~
electrodes, respectively. The potentials were recorded using an Orion digital ionalyzer
(mode1 701A). For each experiment a new specimen was used. Al1 experiments were
carried out in thermostat at temperature 25f 0.2"C.
 INHIBITION OF CORROSION OF COPPER

The mhibitors used and their structures are s h o w in scheme 1

1) 4-methowphenyhethylene cyanothoacetamide.

2) 4-methylphenyhethylene cyanothioacetamide

3) 4-chlorophenyhethylene cyanothioacetamide

S=C-NH?
4) 4-bromophenylmethylene cyanothioacetamide.

-
5) 4-nitrophenyhethylene cyanothioacetamde.

RESULTS AND DISCUSSION

Effect of type and concentration of inhibitor
The two substituted groups studied were methoxy, methyl, as electron donating, and
chloro, bromo, nitro, as electron withdrawing groups, located in the para-position of
the phenyl ring. The inhibition of such denvatives were obtianed using galvanostatic
polarization measurement. The results of anodic and cathodic polarization
measurements on copper in 2M HNO3 contianing different concentrations of d u b i t o r
4 are plotted in Figure 1. The results obtianed for the other mhibitors were quite
sirnilar. As the ùihibitor concentration increases, the Tafel lines of the hydrogen
evolution rate are shfted to more negative values relative to the blank curve in case of
cathodic polanzation and to more positive values relative to the blank in case of anodic
polanzation. These results suggest that al1 the tested rnatenals act as rnixed &pe
inhibitors. In the inhibitor molecules, the sulphur and nitrogen of C=S and C-N<
groups are the active centres involved in the cathodic and anodic adsorption.
respectively (S>N>O in basicity). Addition of cornpounds tested induce a decrease in
48 A.S. Fouda et al.

ico,, ths indicates that these compounds act as inhibitors for copper dissolution in
nitnc acid.

O .4 1.2 2.0 2.8

Log i,,,,, m A cm-2

Fzg. 1. Calvanostatic polarization cuwes of copper in 2M HNO3 solution containmg

various concentraitons of 4-bromophenylmethylenecyanothioacetamide.

The percent inhibition eficiency, 1%, was calculated using equation 1 :

I % = ( l - i h . / i o ) x 100 (1)
where io and i d , are the corrosion currents in the absence and presence of inhibitor
and the results are surnrnarized in Table 1. The uihibition eficiencies of the senes
follow the order: 1>2>3>4>5. Also, the results of Table 1 indicate that:
i) as the concentration of the additive increases, the value of ico, decreases and hence
the 1% increases. This indicates that the inhibition eficiency depends on the
concentration of the inhibitors.
ii) the slopes of anodic and cathodic Tafel lines (ba and bc) remain almost unchanged
on increasing the concentration of the tested compounds. This indicates that these
molecules have no effect on the mechanism of the dissolution of copper, but cause
only inactivation of a part of the surface with respect to the corrosive medium.
 INHIBITION OF CORROSION OF COPPER 49

Table 1. Corrosion currents, Tafel slopes and percentage of inhibition efficiency for
copper in 2M HNO3 solution in the absence and presence of differnet
concentrations of awlmethylene cyanothioacetamide derivatives at 25OC.
Miibitor Conc. lcorr ba bc 1%
m~cm-2 (mV) (mV)
Blank 0.00 31.62 58.00 63.20
(1) 1x10-3 1.66 50.3 60.4 94.8
5x1o - ~ 2.00 50.3 61.3 93 7
1x10-4 3.55 50.3 65.0 88.8
5x10-5 4.37 50.3 61.3 86.2

A plot of 0 vs. log C (Fig. 2) of arylmethylene cyanothioacetamide derivatives

has the character of an S-shaped adsorption isotherm. This variation fits a Fnunkin
isothenn at intermediate coverage [20]. The data obey the equation:
50 A.S Fouda et al.

where C 1s the concentration of the adsorbed substance in the bulk of the solution and
0 is the d e g e e of surface coverage of the metal surface by the inhibitor. B is the
rnodified equilibriurn constant of the adsorption process and f is a constant depending
on intermolecular interactions in the adsorption layer and on the heterogeneity of the
surface.

Fig. 2. Variation of suvace coverage (B) with the loganthm of the inhibitors
concentrations.

Effect of temperature
An Arrhenius plot of log ico, agianst 1/T is shown in Fig. 3. The variation is linear
and obeys the following equation:
log ic0, = A - ~ a 1 2 . 3 0 3RT (4)
where A is a constant depending on the metal Gpe and electrolyte. The activation
energy, E: , calculated frorn the slope [d log ico,/d(l/T)] is equal to 7.3 Kcal mol-1.
Amrnar et al. [21] found that the activation e n e r p was 2 Kcal mol-1 for copper in
O. 1 M HCI solution.
 INHIBITION OF CORROSION OF COPPER

Free 7.3
1 20.7
- 2 16.1
3 14.7
4 14.5
5 12.0
-

Fig. 3.Arrhenius plot of log. i,,, against I/Tfor copper in 2M H M 3 solutions in

presence and in absence .of 1 x 1 0 - 4inhibitors.
~

Fouda et al. [22,23] found that the activation energy for copper in 4M HNO3
solution was 4.6 Kcal mol-1, whereas 11.7 Kcal mol-1 for copper in 3M HNO3.
Generally, one can Say that the nature and concentration of the electrolyte greatly
affect the activation energy for the corrosion process.
Table 2 shows the variation of Eco,., i,, and 0 for copper in 2M HNO3 solution
containing 1x10-JM of dubitor 2 with temperature. The results show that ic0,
increases and 0 decreases with with increasing the temperature. These results are
characterizing for the physical adsorption. The above results can be proved from the
magnitude of the heat of adsorption Q (as below). The variation of the logarithrn of the
surface coverage, 0, with 117' for 1 x 1 0 - 4 ~al1 inhibitors are linear with slopes
1.0~103,1 . 1 ~ 1 0 3 1, . 2 ~ 1 0 31, . 2 5 ~ 1 0 3and 1 . 3 ~ 1 0 respectively.
3
The heat of adsorption Q for mhibitors 1,2,3,4 and 5 have been found to be 4.6, 5.1,
5 5, 5.8 and 6.0 Kcal mol-] respectively. These values of Q lie in the range which
characterizing physical adsorption. So, the adsorption of the additives on the surface of
copper is likely to be of a physical nature.
52 A.S. Fouda et al

Table 2. Variation of Eco,,, ico, and surface coverage (8) for copper in 231 HNO3
solution containing 1x10-4~of inhibitor 2 with temperature.
Temp Eco,. lcorr (0)
OC (V) m A cm-?
-7 5
d 0.020 3.98 0.874
3O 0.018 7.08 O 797
35 0.016 11.75 0.696
40 0.013 19.95 0.546
45 0.010 28.18 0 175

Effect of molecular structure

Fig. 4 shows the relationshp behveen the logarithm of inhibitor efficiency and the
Hammett substituent constant (o)of compounds 1,2,3:4 and 5, with concentration of
1x10-3 and 5 x 1 0 - 3 ~ .

Fig. 4.Relationship benveen inhibitor eficiency (log. i,/i) and Hammett constants
(a) of al1 compozlnds Onhibitor concentraitons are: 1x10-344 and 5.~1CI-~~L.~)).
 INHIBITION OF CORROSION OF COPPER 53

Linear Free E n e r p Relationships (LFER) have pre~iouslybeen used to correlate the

dubition efficiency of organic compounds with their Hammett substituent constants
[24]. The LFER or Hammett relation is given by [24-261:
log (io 1 i) = -PO (5)
where p is the reaction cosntant [27]. The slope of the plot of log (rate) vs. O: and its
sign indicates whether the process is inhbited by an increase or a decrease of electron
density at the reaction centre. The magmtude of p indicates the relative sensitivity of
the dubition process to electronic effects. The small negative slope of the correlation
Iine (p =-0.40, -0.26) shows a strong dependence of the adsorption character of the
reaction centre on the electron density of the ring, with electron releasing substituents
increasing dubition. This may be due to the fact that in this type of compounds the
centre of adsorption (C = S grouping) is throughly conjugated to the ring.
Mechanism of inhibition
The order of increasing inhibition eficiency of the arylmethylene
cyanothoacetamide derivatives (Table 1) in 2M HNO3 solution is: 1>2>3>4>5. The
inhibition efficiency of additive compounds depends on many factors whch include
the nurnber of adsorption sites and their charge density, molecular size, mode of
interaction with the metal surface and formation of metallic complexes. The inhibition
of corrosion of copper in acid solution by the investigated arylmethyiene
cyanothioacetamide derivatives was found to depend on the concentration and nature
of the dubitor. Variation in structure of the dubitor molecules take places through
the arylmethylene side chain, the cyanothoacetamide moiety being the same. The
electron charge density of the adsorption centers would depend on substituents in the
arylmethylene conjugated with the thioketo sulphur atom. Also, substituents on the
phenyl ~g may participate in adsorption [28].
Skeletal representation of the mode of adsorption of the compounds is s h o w by
Fig. 5.

Fig. 5. SkeIetal representation of the mode of adorption of the tested compoiindri.

J Chrrn Phys
54 A.S. Fouda et al.

The previously mentioned order of increased inhibition efficiency can be accounted

for in terms of the obviously operating factors, including the polar effect [27] of the
substituents on the phenyl nng. Based on Hammett's [24] polar substituent constant (O)

OCH3 > CH3 > Cl -

the electron - donating character of the substituents used is increased in the order:
Br > NO?. This order is almost concordant hith the observed
order of inhibition efficiency. The p-OCH3 compound is the most efficient inhibitor.
This may be attnbuted to the higher electom donating character of -OCH3 compared
to the other substituents. On the other hand, p-NO2 compound is the least effective
inhibitor in this senes. This may be attnbuted to the coplanarity of the p-NO2 group
with the phenyl ring brings about maximum electron ~lthdrawal.Also, the NO- g o u p
is easily reduced in acid medium and t h s process is exothermic, the evolved heat aids
the desorption of the compound on copper surface [28,29]. p-CH3 compound comes
after. p-OCH3 compound in inhibition efficiency. This due to the lower electron -
donating character of p-CH3 group compared to p-OCH3 group. The p-Cl and p-Br
compounds comes after p-CH3 compound in inhbition efficiency, t h s atrtributed to
the dual nature of Cl and Br [the mesomenc effect (+M) involving electron pairs on Cl
or Br may oberate in a direction opposite to the -1 effect]. Thus, the overall mechamsm
constituents electron release which maintains sufficient electron charge density on the
molecule [30,3 11.
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