Corrosion Science 63 (2012) 275–286

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Evaluation of some phenothiazine derivatives as corrosion inhibitors for bronze

in weakly acidic solution
Roxana Bostan a,b, Simona Varvara b,⇑, Luiza Găină c, Liana Maria Muresßan a
a
Department of Physical Chemistry, ‘‘Babes-Bolyai’’ University, 11 Arany Janos St., 400028 Cluj-Napoca, Romania
b
Department of Topography, ‘‘1 Decembrie 1918’’ University, 11-13 Nicolae Iorga St., 510009 Alba-Iulia, Romania
c
Department of Organic Chemistry, ‘‘Babes-Bolyai’’ University, 11 Arany Janos St., 400028 Cluj-Napoca, Romania

a r t i c l e i n f o a b s t r a c t

Article history: Four phenothiazine derivatives have been tested as inhibitors for bronze corrosion in a solution contain-
Received 15 February 2012 ing Na2SO4 and NaHCO3 (pH 5).
Accepted 13 June 2012 Electrochemical investigations (potentiodynamic polarisation and impedance measurements) revealed
Available online 20 June 2012
that all phenothiazine derivatives exert a protective effect against bronze corrosion and, in some cases
their inhibition efficiency exceeds 90% at concentration level as low as 75 lM. An adherent layer of
Keywords: organic molecules chemisorbed on bronze surface is responsible for the protective effect of the investi-
A. Bronze
gated compounds. Adsorption of phenothiazine derivatives on bronze obeys Langmuir isotherm. Correla-
B. EIS
B. Modelling studies
tion between quantum chemical calculations and inhibition efficiency of the investigated compounds
C. Corrosion was discussed using DFT method.
Ó 2012 Elsevier Ltd. All rights reserved.

1. Introduction tronic density of donor atoms and orbital character of donating

Due to the frequent use of copper and copper-based alloys in
various structural, architectural, electrical and electronic applica-
tions, the corrosion phenomena occurring on these materials have
been studied for long time [1].
The use of organic inhibitors is one of the most practical alter-
natives for preventing metal dissolution, especially in acidic media.
The inhibiting properties of the organic molecules on metal corro-
sion are often associated with their molecular structures. Thus, it
has been shown that organic compounds containing heteroatoms
with high electronic density (i.e. nitrogen, sulphur and oxygen)
or those containing multiple bonds which are considered as
adsorption centres are effective corrosion inhibitors for copper
and copper-based alloys.
In the last years, the anticorrosive properties of several classes of
innoxious compounds such as azoles [2–12], amino acids [13–20],
amines [21], imidazole [22–25], indole and their derivatives [26]
on the corrosion of copper and its alloys in different aggressive
media have been investigated. The inhibiting action of these com-
pounds is attributed to their interactions with the metallic surface
via adsorption. In general, the adsorption of the inhibitors on the
electrodic surface depends on the nature and charge of metal,
electrolyte type and physicochemical and electronic properties of
the inhibitor molecule such as functional groups, steric effects, elec-
⇑ Corresponding author. Tel.: +40 258 806263; fax: +40 258 806329.
E-mail address: svarvara@uab.ro (S. Varvara).
electrons [24]. Thus, it has been shown that certain molecules con-
taining both nitrogen and sulphur atoms in their structure, i.e. mer-
capto-functionalized thiadiazole derivatives [27–31] and Schiff
bases [32,33] provide better inhibition efficiency compared to dif-
ferent organic inhibitors containing only sulphur or nitrogen.
Another class of heterocyclic compounds possessing two donor
atoms in their core which are expected to show good anticorrosive
properties are phenothiazine derivatives. A perusal of literature re-
vealed that phenothiazine and its derivatives have been already re-
ported as efficient corrosion inhibitors for zinc in NH4Cl solution
[34] and cadmium in HClO4, H2SO4 and CH3COOH solutions [35],
but their inhibitive performances towards copper or copper-based
alloys corrosion have never been reported. It has to be emphasized
that phenothiazine derivatives are relatively cheap substances,
easy to produce in high purity and have useful applications, such
as: dyes, pesticides, pharmaceuticals [36], additives for stabilizing
organic products that are subjected to oxidative, thermal, and/or
light-induced degradation (lubricants, polymers) [37–39] and
more recently, redox active components for materials science
investigations (electrically conducting charge transfer composites
[40], redox active fluorophores [41,42]).
In the present paper, four phenothiazine derivatives (Table 1)
have been investigated for the first time as bronze corrosion inhib-
itors in a solution containing Na2SO4 and NaHCO3 (pH 5) that
simulates acid rain in an urban environment.
Electrochemical techniques, such as potentiodynamic polariza-
tion and electrochemical impedance spectroscopy measurements
(EIS) corroborated with SEM–EDX observations were used to

0010-938X/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2012.06.010
276 R. Bostan et al. / Corrosion Science 63 (2012) 275–286

Table 1
Names and chemical structures of the phenothiazine derivatives under study.

Inhibitor name Structure Abbreviation

10-(Toluene-4-sulfonyl)-10H-phenothiazine H3C TSP

SO2
N

S
10-(4-Amino-benzenesulfonyl)-10H-phenothiazine H2N AmSP

SO2
N

S
10-(4-Acetanido-benzenesulfonyl)-10H-phenothiazine CH3 AcaSP
O
HN
SO2
N

S
10-(4-Methyilcarbamate-benzenesulfonyl)-10H-phenothiazine H3C MecSP
O
O
HN
SO2
N

elucidate the inhibition mechanism of phenothiazine derivatives
on bronze corrosion. Several adsorption isotherms were tested
for their potential relevance in explaining the adsorptive behaviour
of these compounds on the metallic surface. A quantum chemical
calculation method was also applied in an attempt to correlate
the structural and electronic characteristics of the studied pheno-
thiazine derivatives with their efficiencies as bronze corrosion
inhibitors in acidic solution.
2. Experimental
2.1. Inhibitors
The phenothiazine derivatives examined in the present study
(Table 1) were synthesized according to a procedure previously re-
ported by Karpinskii and Konovalova [43], summarized in Scheme
1. After their synthesis, the phenothiazine compounds were fully
characterized for the first time by spectroscopic and spectrometric
measurements.
Thus, the structure assignment was supported by NMR spectro-
scopic data. Proton and carbon 1D-NMR spectra, as well as 2D-NMR
homocorrelation (COSY) and heterocorrelation (HMQC and HMBC)
spectra were employed for complete structural assignments.
1
H- and 13C-NMR spectra were recorded at room temperature
using CDCl3 as solvent in 5 mm tubes; spectra were recorded using:
300, 400 and 500 MHz Brucker Anvance NMR spectrometers.
Melting points were measured with an Electrothermal 9200
melting point apparatus and are uncorrected. FT-IR spectra were
recorded on a Brucker Vector 22 spectrometer. Elemental analysis
was recorded with Thermo Flash EA 1112 equipment. Mass spectra
was recorded with GC–MS Spectrometer Shimadzu QP 2010 Plus.
The results of FT-IR, 1H- and 13C-NMR, elemental analysis and
GC–MS investigations performed on the studied phenothiazine
derivatives are presented below:
10-(toluene-4-sulfonyl)-10H-phenothiazine (TSP): m.p.: 152–
153 °C. m/z (EI): 353 (M+, 100%); calculated: C19H15NO2S2
(353.05) C: 64.56%, H: 4.28%, N: 3.96%, S: 18.14%, found: C:
63.89%, H: 4.39%, N: 3.88%, S: 18.55%.
IR (ATR cm1): 1384(–SO2–N–); 2988; 2949(as./s. CH)
1
H-RMN (300 MHz, CDCl3): d(ppm): 2.31(s, 3H); 6.98(d, 2H,
J = 8.4 Hz); 7.04(d, 2H, J = 8 Hz); 7.69(d, 2H, J = 8 Hz); 7.15(td, 2H,
J = 1.1 Hz, J = 7.4 Hz, J = 7.8 Hz); 7.27(td, 2H, J = 8.4z, J = 7.4 Hz,
J = 1.1 Hz); 7.08(dd, 2H, J = 1.1 Hz, J = 7.4 Hz).
13
C-RMN (75 MHz CDCl3): d(ppm): 21.3; 117.7(2C); 128.1(2C);
126.9(2C); 127.2(2C); 136.7(Cq); 128.3; 129.9; 137.6(Cq); 145.7
(2Cq); 127.2(2Cq);
10-(4-acetamido-benzenesulfonyl)-10H-phenothiazine (AcaSP):
m.p. 203–204 °C. m/z (EI): 396 (M+, 100%); calculated C20H16N2O3S2
(396.06) C: 60.59%, H: 4.07%, N: 7.07%, S: 1632%, found: C: 60.48%,
H: 4.07%, N: 7.03%, S: 16.53%.
IR (ATR cm1): 3373(NH), 1352(–SO2–N–), 1584, 1529(–CO–
NH–).
1
H-RMN (400 MHz, CDCl3): d(ppm): 6.83(s, 1H); 2.19(s, 3H);
7.11(d, 2H, J = 8 Hz); 7.18(d, 2H, J = 8.8 Hz); 7.73(d, 2H,
J = 8.8 Hz); 7.2(td, 2H, J = 8 Hz, J = 7.4 Hz, J = 1 Hz); 7.33(dt, 2H,
J = 8 Hz, J = 1.2 Hz, J = 8.4 Hz); 7.34(d, 2H, J = 8.4 Hz).
13
C-RMN (100.6 MHz, CDCl3): d(ppm): 24.3; 117.7(2C);
128.1(2C); 126.9(2C), 127.2(2C); 135.8(Cq); 129.0; 132.9;
142.5(Cq); 168.9(Cq); 142,8(2Cq); 127.2(2Cq).
10-(4-methyilcarbamate-benzenesulfonyl)-10H-phenothiazine
(MecSP): m.p. = 197.5 °C. m/z (EI): 412 (M+, 100%), calculated:
 R. Bostan et al. / Corrosion Science 63 (2012) 275–286 277

R
NH2

H SO2Cl
N Py NaOH/EtOH
SO2
+ refluxe 12h refluxe 1h SO2
N R=NHCOOCH3
S N
R
S
TSP: R=CH3, S
AcaSP: R=NHCOCH3, AmSP
MecSP: R=NHCOOCH3:

Scheme 1. Preparation scheme of phenothiazine derivatives.

C20H16N2O4S2 (412,48) C:58,24%, H: 3,91%, N:6,79%, S: 15,68%,
found: C: 58,08%, H: 3,92%, N: 6,71%, S: 16,18%
IR (ATR cm1): 3351; 3330(NH); 1346(–SO2–N–); 1588;
1531(–CO–NH–).
1
H-RMN (400 MHz, CDCl3): d(ppm): 3.77(s, 3H); 7.12(d, 2H,
J = 7.6 Hz); 7.17(d, 2H, J = 8 Hz); 7.73(d, 2H, J = 8 Hz); 7.22(td, 2H,
J = 6.8 Hz, J = 7.6 Hz, J = 1 Hz); 7.3(dd, 2H, J = 7.6 Hz, J = 1.2);
7.34(dd, 2H, J = 6.8 Hz, J = 1,2 Hz); 6.85(s, 1H).
13
C-RMN (100.6 MHz, CDCl3): d(ppm): 52.6; 117.4(2C);
127.7(2C); 126.9(2C); 127.2(2C); 135.8(Cq); 129; 132.9; 142.5(Cq);
153.3(Cq); 143.8(2Cq); 127.2(2Cq).
10-(4-amino-benzenesulfonyl)-10H-phenothiazine (AmSP):
m.p 165 °C. m/z (EI): 354 (M+, 100%)
1 of the bronze electrode in the corrosive medium. The impedance
H-RMN (500 MHz, CDCl3): d(ppm): 4.08 (s, 2H); 7.01(d, 2H,
J = 9 Hz); 6.41(d, 2H J = 8.5 Hz), 7.72(d, 2H, J = 8.5 Hz), 7.20(td,
2H, J = 7.5 Hz, J = 1 Hz); 7.3(dd, 2H, J = 7.5 Hz, J = 1,5); 7.11(d, 2H,
J = 7.5 Hz).
13
C-RMN (125 MHz, CDCl3): d(ppm): 114.1(2C); 128.1(2C);
127.1(2C); 127.4(2C); 130.44(Cq); 130.49; 129.4; 151.5(Cq);
136.5(2Cq); 127.3(2Cq).
2.2. Electrochemical measurements
Polarization curves were recorded at constant sweep rate of
10 mV/min in a potential range of ±200 mV vs. open circuit
potential.
The corrosion inhibition efficiency (z) was calculated from the
polarization curves according to following equation:
0
icorr  icorr
zð%Þ ¼ 0
 100 ð1Þ
icorr
0
where icorr and icorr are the values of the corrosion current densities
in absence and in presence of the inhibitor, respectively.
Electrochemical impedance spectroscopy measurements (EIS)
were carried out at the open circuit potential after 1 h immersion
spectra were acquired in the frequency range 10 kHz to 10 mHz
at 10 points per hertz decade with an AC voltage amplitude
of ± 10 mV. The impedance data were interpreted on the basis of
equivalent electrical circuits, using the ZSimpWin V3.21 software
for fitting the experimental data.
The degree of surface coverage (h) and the percentage of inhibi-
tion efficiency (z) were calculated from the polarization resistance
values determined from the impedance spectra, according to the
following equations:

A three-electrode cell was used for the electrochemical experi-
ments. The counter-electrode was a large platinum grid and an Ag/
AgCl, KClsat was used as reference electrode. An electrode made of
bronze (Cu-94.03%, Sn-3.31%, Pb-0.24%, Zn-1.44%, Ni-0.25, Fe-0.22,
S-0.51, at.%) was used as working electrode.
In order to avoid the electrolyte infiltration, the lateral part of
the bronze rod was firstly protected by a cataphoretic paint layer,
cured at 150 °C for 30 min. The rod specimen was embedded in
epoxy resin (Buhler, EpoxycureTM) with an exposed area of
0.28 cm2. Prior to measurements, the working electrode was a
mechanically ground using successive grade of silicon carbide pa-
per up to grade 2400, and then rinsed thoroughly with distilled
water and ethanol.
The bronze sample was transferred into the electrochemical cell
and the measurements were carried out in an aqueous solution of
0.2 g L1 Na2SO4 + 0.2 g L1 NaHCO3, acidified to pH 5 by addition
of dilute H2SO4.
Appropriate weighted amounts from each phenothiazine deriv-
ative were dissolved in ethanol to prepare a 0.01 M stock solution.
From each inhibitor, low concentration range (10–100 lM) was
employed and, due to the low water solubility of the compounds,
a calculated volume of ethanol kept at the same level (10%) for
all inhibitor concentrations was added to each test solution.
Electrochemical experiments were performed at room temper-
ature, using a PAR model 2273 potentiostat controlled by a PC
computer. Before each experiment, the bronze electrode was left
at the open circuit potential for 1 h in the corrosive solution.
Rp  R0p
h¼ ð2Þ
Rp
zð%Þ ¼ 100  h ð3Þ
where Rp and R0p
are the polarization resistances in electrolytes with
and without inhibitors, respectively.
2.3. SEM–EDX measurements
For morphological studies, the bronze surface was prepared by
keeping the electrodes for 72 h in the corrosive solution in the ab-
sence and in the presence of organic inhibitors. Then, the specimens
were washed gently with water, carefully dried and analyzed with-
out any further treatment, by scanning electron microscopy using a
Jeol JEM5510LV (Japan) microscope coupled with an Oxford Instru-
ments EDX Analysis System, INCA 300 (UK).
2.4. Calculation methods
In an attempt to determine the most stable geometry of the
inhibitors molecules, the minimum energy has been evaluated
starting with molecular mechanics optimization of the conformers
generated within the Confanal module of Spartan’06 [44], followed
by semi-empirical (PM3) and 6–31G(d) B3LYP DFT calculations
[45–47] on all such obtained conformers.
The following quantum chemical indices were considered: the
energy of the highest occupied molecular orbital (EHOMO), the
278 R. Bostan et al. / Corrosion Science 63 (2012) 275–286

energy of the lowest unoccupied molecular orbital (ELUMO),
absolute energy band gap (DEgap = ELUMO  EHOMO) and the dipole
moment (l).
3. Results and discussion
3.1. Potentiodynamic polarization measurements
Fig. 1 shows representative Tafel polarisation curves for bronze
immersed in 0.2 g L1 Na2SO4 + 0.2 g L1 NaHCO3 (pH 5) solution at
25 °C in the absence and presence of different concentrations of
phenothiazine derivatives.
Electrochemical kinetic parameters, such as corrosion potential
(Ecorr), cathodic and anodic Tafel slopes (bc and ba) and corrosion
current density (icorr) were estimated by extrapolation of the Tafel
lines and are presented in Table 2. The inhibition efficiencies (z) of
the phenothiazine derivatives calculated according to Eq. (1) are
also given in Table 2. The polarisation resistance (Rp) values (Table
2) were determined as the slopes of the linear polarization curves
recorded over Ecorr ± 30 mV potential ranges, after 1 h immersion
of the bronze in the corrosive solution [48].
From Fig. 1, it is clear that both the anodic metal dissolution and
oxygen reduction reactions are hindered when phenothiazine
compounds are added to the corrosive solution. The values of the
corrosion density significantly decrease with increasing phenothi-
azine derivatives concentrations up to 75 lM; then the icorr values
start to slightly increase at higher concentration of inhibitors
(Table 2).
The decreasing of the current density values also reflects different
protective behaviour of phenothiazine derivatives on bronze corrosion,
as shown in the following sequence: AcaSP > TSP > MecSP > AmSP.
In all cases, the inhibition degree of the studied compounds de-
pends on their concentrations and molecular structures. Thus, the
increase of the inhibitor concentration from 10 to 75 lM was
accompanied by an increase of the inhibition efficiency values,
i.e. from 78.9% to 91.5% for the most efficient compound, AcaSP.
These results suggest that the phenothiazine derivatives act as
fairly efficient inhibitors on bronze corrosion, i.e. they reduce the
anodic dissolution and also retard the oxygen evolution reaction,
probably as a consequence of their ability to adsorb and to form
a protective layer on the metallic surface. However, it should be
mentioned that an increase of phenothiazine derivatives concen-
trations to 100 lM leads to a decrease of the z values.
Moreover, the polarization resistances (Rp) values increase with
the inhibitors concentration and they were the highest in solutions
containing the optimum concentration of phenothiazine deriva-
tives (75 lM).
The changes of the anodic (ba) and cathodic (bc) Tafel slopes ob-
served on the addition of phenothiazine derivatives indicate that
the kinetics of anodic and cathodic processes are affected by the
presence of the inhibitors in the corrosive media. Since no definite
trend was observed in the shift of (ba) and (bc) values in the pres-
ence of different inhibitors, it was assumed that the investigated
compounds act mainly as mixed-type inhibitors for bronze corro-
sion in solution containing Na2SO4 and NaHCO3 at pH 5 and a pos-
sible change of the reaction path could also take place as a
consequence of their adsorption on the electrode surface.

-4 -4

-5 -5
log (i / A cm )

log (i / A cm )
-2

-2

-6 -6

TSP (μΜ) AmSP (μΜ)

0 0
-7 -7
10 10
25
25
50
-8 50 -8
75
75
100
100
-9 -9
-0.2 -0.1 0.0 0.1 0.2 -0.2 -0.1 0.0 0.1 0.2
E (V / Ag/AgCl) E (V / Ag/AgCl)

-4 -4

-5 -5
log (i / A cm )
log (i / A cm )

-2
-2

-6 -6

-7 -7
AcaSP (μΜ) MecSP (μΜ)
0 0
-8 10 -8 10
25 25
50 50
-9 -9
75 75
100 100
-10 -10
-0.2 -0.1 0.0 0.1 0.2 -0.2 -0.1 0.0 0.1 0.2
E (V / Ag/AgCl) E (V / Ag/AgCl)
Fig. 1. Anodic and cathodic polarization curves (Tafel curves) for bronze in Na2SO4/NaHCO3 (pH 5) solution without and with various concentrations of phenothiazine
derivatives.
 R. Bostan et al. / Corrosion Science 63 (2012) 275–286 279

Table 2
Corrosion parameters obtained from the polarization curves of the studied phenothiazine derivatives.

Inhibitor Cin Ecorr icorr bc ba Rp z

(lM) (mV/Ag/AgCl) (mA/cm2) (mV/dec) (mV/dec) (kX cm2) (%)
Blank 0 22 659.0 172.8 46.4 22.4 –
TSP 10 66 189.1 49.0 15.5 79.7 71.3
25 27 138.3 118.3 100.2 110.3 79.0
50 32 85.9 77.4 75.5 120.1 86.9
75 17 57.4 77.4 66.8 202.6 91.3
100 7 67.2 84.6 72.1 121.1 89.8
AmSP 10 23 243.1 129.9 79.3 51.4 63.1
25 31 181.3 108.9 166.9 79.2 72.5
50 17 144.1 140.9 169.1 93.5 78.1
75 14 120.6 97.7 91.5 118.3 81.7
100 5 174.2 85.8 99 75.8 73.6
AcaSP 10 38 139.1 45.4 18.8 90.1 78.9
25 34 89.0 125.8 167.3 112.1 86.5
50 8 69.9 119.1 132.1 133.3 89.4
75 40 55.8 128.4 489.1 288.6 91.5
100 64 93.3 92.6 128.3 121.9 85.9
MecSP 10 28 259.8 69.8 66.1 53.1 60.5
25 32 160.8 80.9 35.0 101.3 75.6
50 18 108.1 49.0 11.1 106.3 83.6
75 1.2 67.7 108.3 118.1 157.3 89.7
100 7 219.8 131.2 187.4 131.1 66.6

Nevertheless, the shifts of Ecorr values towards positive direction of the corrosion potential on the inhibitor concentration since they
in the presence of low concentrations (10–25 lM) of phenothia- inhibit both the anodic and cathodic reactions.
zine derivatives could be probably explained by a small domina-
tion of the anodic dissolution reaction. At higher concentrations
of inhibitors (50–100 lM), the corrosion potentials shift towards 3.2. Electrochemical impedance spectroscopy
more negative values as compared to the Ecorr value calculated
for blank solution and a predominant control of the cathodic The corrosion behaviour of bronze after 1 h immersion in the
reduction reaction could be assumed. This variation of the corro- corrosive solutions without and with various concentrations of
sion potential values could be due to a competition between the phenothiazine derivatives was further investigated by electro-
anodic and the cathodic inhibiting reactions and/or to the metal chemical impedance spectroscopy (EIS). The measurements were
surface condition, as a consequence of the phenothiazine deriva- conducted at the open-circuit potentials and the obtained Nyquist
tives adsorption. Therefore, it is difficult to explain the dependence diagrams are depicted in Fig. 2.

60 0.01
0.01
30
- ZIm (kΩ cm )

0.01
2
- ZIm (kΩ cm )

45 0.1
2

0.01 0.01
TSP ( μΜ) AmSP ( μΜ)
20 0.1
0 0
0.01
30 0.1
0.01
0.1 10
10
0.01 0.01 25
25 10
0.1 0.1 50
15 0.1 50 1
1 75
1 75
1 0.1 100
0.01 100 0
0.01
0
0 10 20 30 40 50 60
0 25 50 75 100 125
2 2
Z Re (kΩ cm ) Z Re (kΩ cm )
75
50 0.01

0.01 0.01
- ZIm (kΩ cm )

- ZIm (kΩ cm )
2

50 AcaSP (μΜ)
0.01
0.01 MecSP (μΜ)
0.1
0 0.1 0
0.01
0.01
10 25 10
0.01
25 25 25
0.1
50 0.1 50
1 75 1 75
0.1 100 0.1 100
0.01 0.01
0 0
0 25 50 75 100 125 150 0 25 50 75 100
2 2
Z Re (kΩ cm ) Z Re (kΩ cm )

Fig. 2. Nyquist impedance diagrams of bronze electrode in Na2SO4/NaHCO3 (pH 5) solution without and with various concentrations of phenothiazine derivatives. (– + –)
simulated diagrams. Frequencies are expressed in Hz.
280 R. Bostan et al. / Corrosion Science 63 (2012) 275–286

resistor with the resistance, R (n = 0); a capacitor with the capaci-

Fig. 3. Equivalent electrical circuits used for computer fitting of the experimental
results: 2RQ (left) and 3RQ (right).
The impedance response of bronze was changed after the addi-
tion of phenothiazine derivatives in the solution; the significant in-
creases of the low frequency limit of the impedance (polarization
resistance) observed in the presence of the organic compounds
confirming their inhibiting effect on bronze dissolution.
The experimental impedance spectra for bronze in blank solu-
tion was appropriately analyzed by fitting to the (2RQ) equivalent
electrical circuit, which was previously used to model bronze
[9,30] and copper/acid interface [22], while a (3RQ) circuit was
used for solution containing various phenothiazine derivatives
(Fig. 3).
As can be seen in Fig. 2, the experimental impedance loops are
depressed semicircles with their centres below the real axis, as a
result of the roughness and other non-homogeneities of the solid
surface. This phenomenon is known as the ‘‘dispersing effect’’
[31] and similar results have been reported for the corrosion of
copper in HCl in the presence of different amino acids [16] and
Schiff bases [33].
Consequently, in order to get more accurate fit of experimental
data, constant phase elements (CPEs) represented by the terms, Q
and n were substituted for the pure capacitive elements. The coef-
ficient n characterizes different physical phenomena, like surface
inhomogeneity, resulting from surface roughness, impurities,
inhibitor adsorption etc.
The impedance of the CPE is given by [49]:
Q ¼ Z CPEðxÞ ¼ ½CðjxÞn 1
where j is an imaginary number and x is the angular frequency in
rad s1; depending on the value of the exponent n, CPE could be: a
tance, C (n = 1); a Warburg impedance, W (n = 0.5) or an inductance,
L (n = 1).
In the equivalent circuits from Fig. 3, Re stands for the solution
resistance and the high-frequency parameters Qf and Rf are attrib-
uted to the dielectric character of the corrosion products due to the
formation of a surface layer (oxide and/or oxide with adsorbed
inhibitor) that is reinforced by the presence of the inhibitor and
by the ionic conduction through the pores of the film. The param-
eter Rct coupled with Qd describe the charge transfer process at the
electrolyte/bronze interface, while the low frequency elements, RF
and QF correspond to an oxidation–reduction process taking place
at the electrode surface, probable involving the corrosion products
layers accumulated at the interface.
The used equivalent circuits properly reproduce the experimen-
tal data corresponding to bronze corrosion in the absence and in
the presence of the phenothiazine derivatives as revealed in
Fig. 2, where the symbols and dashed lines represent the measured
data and their best fits, respectively. The parameters obtained by
fitting the equivalent electrical circuits and the calculated inhibi-
tion efficiencies are given in Table 3.
The values of the pseudo-capacitances associated with the con-
stant phase elements from Table 3 were recalculated using the
general equation: C ¼ ðR1n Q Þ1=n ðn 2 ½0:54  0:99Þ and the varia-
tion of the double layer capacitance (Cd) and faradaic capacitance
(CF) as a function of the organic inhibitors concentration are pre-
sented in Fig. 4.
The data in Table 3 show tha t the film resistances are relatively
high in the presence of phenothiazine derivatives and their values
increases by increasing the inhibitors concentration while, in many
cases, the values of film capacitance decreases. This suggests that
the surface layer covering the electrode surface in presence of
the organic inhibitors is probable more protective than in their ab-
sence, which makes the ionic conduction through this layer more
difficult.
The values of Rct and inhibition efficiency increase when the
phenothiazine derivatives are added to the blank solution, indicat-
ð4Þ
ing a marked anticorrosion effect of these compounds on bronze
dissolution, probably as a consequence of their absorption on the
bronze surface. This effect is enhanced upon increasing the com-

Table 3
Electrochemical parameters of bronze corrosion in Na2SO4/NaHCO3 (pH 5) solution obtained in the absence and in the presence of various concentrations of inhibitors.

Inhibitor Cin Re Rf Qf Cf Rct Qd RF QF z

(lM) (kX cm2) (kX cm2) (lF sn1 cm2) (lF cm2) (kX cm2) (lF sn1 cm2) (kX cm2) (lF sn1 cm2) (%)
Blank 0 0.15 – – – 1.7 143.2 17.1 231.3
TSP 10 3.25 17.8 8.2 5.1 34.1 34.5 30.1 230.8 77.0
25 0.90 24.5 22.4 16.9 53.8 21.4 53.8 95.1 85.7
50 0.48 33.2 22.5 20.9 59.2 14.9 60.1 208.0 87.6
75 2.10 39.7 14.9 12.6 61.9 13.2 89.9 91.4 90.1
100 0.84 37.1 41.2 48.5 30.2 43.4 43.8 172.7 83.1
AmSP 10 0.37 4.9 35.4 7.3 17.4 46.8 22.5 243.5 58.0
25 0.77 11.4 22.3 6.5 37.7 36.4 29.8 214.9 76.1
50 1.04 33.4 19.4 9.5 43.1 26.9 37.2 245.0 83.4
75 0.99 37.5 15.3 8.6 45.1 23.9 42.5 243.0 84.9
100 5.98 6.7 36.1 12.7 32.4 44.9 33.5 474.2 74.1
AcaSP 10 0.63 20.9 21.3 17.1 41.5 32.4 30.1 230.8 79.6
25 0.31 26.4 19.2 15.8 49.1 21.8 58.8 95.1 86.0
50 0.10 39.6 23.8 23.2 68.7 17.1 69.1 208.0 89.4
75 0.53 44.8 18.4 17.7 88.2 15.1 99.9 91.4 91.9
100 0.36 41.9 22.8 22.6 47.5 24.7 43.8 172.7 85.9
MecSP 10 0.34 11.9 61.4 55.3 25.5 75.3 23.4 721.3 69.1
25 0.57 16.2 28.2 23.3 44.7 35.3 40.9 204.5 81.5
50 0.97 32.8 26.7 25.5 50.4 30.3 48.2 215.7 85.7
75 1.14 30.5 24.6 22.9 63.7 26.6 67.8 104.3 88.4
100 1.43 18.1 21.8 15.9 54.7 30.4 36.4 460.4 82.8
 R. Bostan et al. / Corrosion Science 63 (2012) 275–286 281

100 1.00
TSP TSP
AmSP AmSP
80 AcaSP AcaSP
MecSP 0.75 MecSP
Cd (μF cm )

CF (mFcm )
-2

-2
60

0.50

40

0.25
20

0 0.00
0 25 50 75 100 0 25 50 75 100
Cin (μM) Cin (μM)

Fig. 4. Capacitances Cd and CF calculated from impedance data as a function of the phenothiazine derivatives concentrations.

pounds concentration, suggesting that the protective effect of the

inhibitors is due most likely to decreases of the surface area in con- 250
tact with the corrosive solution. The highest inhibition efficiency TSP
reaches 91.9% for AcaSP at 75 lM concentration level. Further in- AmSP
200 AcaSP
crease in all investigated inhibitors concentration leads to a slight
MecSP
decrease of the z values, in agreement with the results obtained by
Rp (kΩ cm )
polarisation measurements. This phenomenon is also consistent
2

with the results obtained for other inhibitors [14,50] and could
be a consequence of deterioration or dissolution of the adsorbed
layer on bronze surface [17].
As seen in Fig. 4, the double layer capacitances are smaller in the
presence of phenothiazine derivatives compared to the Cd value ob-
tained for blank solution and progressively diminish as the inhibitors
concentration increases. The decrease of the Cd values may be due to
the gradual replacement of water molecules in the double layer by the
adsorbed inhibitors molecules which form probably an adherent
layer on the bronze surface and leads to a smaller area of the electrode
directly in contact with the electrolyte and/or to a decrease in the local
dielectric constant of the metal/solution interface.
The faradaic resistance, RF that can be linked to the redox process
involving corrosion products increases in the presence of the organ-
ic inhibitors, while simultaneously the CF decreases. Consequently,
it can be assumed that the adsorption of the organic compounds on
the bronze surface hinders the formation of the corrosion products
and stabilizes the species covering the electrode, which became less
susceptible to redox processes and give better protection to the
electrodic surface.
Taking into consideration that the polarization resistance Rp,
calculated as the sum Rf + Rct + RF is the parameter most closely
associated to corrosion rate, the protective effectiveness of the
investigated compounds could be also assessed by Rp values [51].
The variation of the Rp value as a function of inhibitors concentra-
tion is shown in Fig. 5.
In absence of any inhibitor, the value of Rp is 18.8 kX cm2; it sig-
nificantly increases with all phenothiazine derivatives concentra-
tion and reaches the maximum at 75 lM level. However, at a
given inhibitor concentration, the corrosion rates of the
investigated phenothiazine derivatives lay in the following order:
AcaSP < TSP < MecSP < AmSP, in agreement with the results ob-
tained from polarization measurements.
The efficiency order of these compounds reflects the important
role played by the substituent group and the type of the chemical
bonds formed between the metal surface and the phenothiazine
compounds in the inhibition processes. In the last part of the work,
these differences will be interpreted by using quantum chemical
calculation.
150
100
50
0
0 20 40 60 80 100
Cin ( μM)
Fig. 5. Variation of the polarization resistance as a function of phenothiazine
derivatives concentration.
3.3. SEM–EDX analysis
In order to establish if the phenothiazine derivatives are ad-
sorbed on bronze, the surface morphology and the composition
of the corrosion products covering the electrode was examined
by SEM and EDX.
Fig. 6a presents the bronze surface morphology after 72 h of
immersion in the blank solution; it can be seen that the bronze sur-
face is already covered with a layer of corrosion products. The
bronze surface analysis by EDX (results not shown) reveals the
presence of oxygen and sulphur in addition to the major elements
(Cu, Sn and Zn). The corrosion products would be mainly in oxides
form.
Fig. 6b shows the bronze surface protected after adding AcaSP
at a concentration level of 75 lM, where it is clear that the surface
damage was diminished in comparison to the blank material.
Moreover, the analysis of the bronze surface after its immersion
for 72 h in the corrosive solution containing the optimal concentra-
tion of AcaSP allows the identification of the nitrogen atoms, as
shown in the EDX spectra presented in Fig. 7. This result confirms
the adsorption of the inhibitor on the bronze surface.
The oxides are still present on the bronze surface, although a
decrease of the peak due to oxygen was noticed in the EDX spectra.
The presence of oxides is reasonable since the inhibiting efficiency
of phenothiazine derivatives was lower than 100%, therefore there
282 R. Bostan et al. / Corrosion Science 63 (2012) 275–286

Fig. 6. SEM images of bronze surface obtained after 72 h immersion in Na2SO4/NaHCO3 (pH 5) solution in the absence (left) and in the presence of 75 lM AcaSP (right).

Fig. 7. EDX spectra of bronze surface obtained after 72 h immersion in Na2SO4/NaHCO3 (pH 5) solution in the presence of 75 lM AcaSP.

are some small active zones on bronze surface where corrosion 140
could start again [52]. TSP
120 AmSP
3.4. Adsorption isotherm AcaSP
MecSP
100
Since the corrosion inhibition process is based on the adsorp-
Cin / θ (μΜ)

tion of phenothiazine derivatives molecules on bronze surface, it

80
is important to elucidate their adsorption behaviour (physisorption
or chemisorption) and to establish the isotherm that best fits the
60
experimental data. For this purpose, the values of surface coverage
degree, h, could be calculated as a function of the inhibitor concen-
tration, assuming that the inhibitor efficiency is mainly due to the 40
blocking effect of the adsorbed species on bronze electrode [53].
The electrochemical impedance spectroscopy results at different 20
concentrations of phenothiazine derivatives were used to calculate
the adsorption isotherm parameters. 0
Different attempts were made to fit the h values to various adsorp- 0 20 40 60 80 100
tion isotherms, including Langmuir, Frumkin and Temkin isotherms. Cin ( μM)
Plots of the data for each isotherm showed that all investigated com-
Fig. 8. Langmuir isotherm for adsorption of phenothiazine derivatives on bronze
pounds agreed with the Langmuir isotherm that is given by [53]:
surface.
C in 1
¼ þ C in ð5Þ
h K
where K is the adsorption equilibrium constant. (Table 4), confirming that the adsorption of organic compounds on
Relation (5) was applied for all investigated phenothiazine bronze obeys Langmuir isotherm.
derivatives adsorbed on bronze surface. It was found that the plots The standard free energy of adsorption DG0ads was calculated
C in from the adsorption equilibrium constant, K according to the fol-
of versus Cin (Fig. 8) yield to straight lines with nearly unit slope
h lowing equation [31]:
 R. Bostan et al. / Corrosion Science 63 (2012) 275–286 283

Table 4
Thermodynamic parameters for the adsorption of phenothiazine derivatives in 92 AcaSP
Na2SO4/NaHCO3 (pH 5) on bronze surface at 250 C.
91
Inhibitor Slope K (dm3 mol1) DG0ads (kJ mol1) R2
TSP 1.09 9.3  106 49.6 0.9980 90 TSP
AmSP 1.16 1.9  106 45.8 0.9917
AcaSP 1.10 51.8  106 53.9 0.9983 89

z (%)
MecSP 1.08 2.8  106 46.7 0.9981 MeSP
88
!
1 DG0ads 87
K¼ exp ð6Þ
55:5 RT 86
AmSP
where 55.5 represents the molar concentration of water in solution 85
(mol dm3), R is the gas constant and T is the thermodynamic
84
temperature.
4.40 4.45 4.50 4.55 4.60 4.65 4.70 4.75
The calculated standard free energies of adsorption of phenothi-
ΔEgap (eV)
azine derivatives are given in Table 4.
Generally, the values of DG0ads of –20 kJ mol1 or less negative
Fig. 9. Correlation between energies gap and inhibition efficiencies of phenothia-
are associated with an electrostatic interaction between charged zine derivatives.
inhibitor molecules and charged metal surface, i.e. physical adsorp-
tion; those of –40 kJ mol1 or more negative involve charge sharing
or charge transfer from the inhibitor molecules to the metal sur- phenothiazine inhibitors, the minimum energy geometry of each
face to form a coordinate covalent bond, chemisorption [16]. The derivative has been estimated starting with molecular mechanics
calculated DG0ads values indicate that the adsorption mechanism optimization of the conformers generated within the Confanal
of the phenothiazine compounds on bronze surface in electrolyte module of Spartan’06 [44], followed by semi-empirical (PM3) and
containing Na2SO4 and NaHCO3 (pH 5) is chemisorption in nature 6–31G(d) B3LYP DFT [45–47]. The generated lowest energy con-
(Table 4). Furthermore, the absolute values of the standard free en- formers were further used in order to calculate the quantum
ergy of adsorption follow the order: AcaSP > TSP > MecSP > AmSP, molecular parameters such as EHOMO, ELUMO, HOMO–LUMO energy
in accordance with the range of the inhibition efficiency values ob- gap (DEgap) and the dipole moment (l) which are given in Table 5.
tained from both polarization curves and electrochemical imped- Frontier molecular orbital theory suggests that the formation of
ance spectroscopy techniques. a transition state is due to an interaction between frontier orbitals
(HOMO and LUMO) of reacting species. It is well-known that low
3.5. Quantum chemical calculations absolute values of the energy band gap gives good inhibition effi-
ciencies, because the ionization potential will be low [54,55].
In order to find a possible correlation between the experimental The theoretical data obtained by B3LYP, 6–31G(d) level of the-
inhibition efficiencies and the electronic structure of the ory (Table 5) show that the absolute values of the energy band

Table 5
Calculated quantum chemical parameters of the studied phenothiazine derivatives and the repartition of HOMO and LUMO densities.

Compound HOMO LUMO EHOMO (eV) ELUMO (eV) DEgap (eV) l (Debye)
TSP 5.6546 1.1554 4.4992 5.37

AmSP 5.5721 0.8658 4.7063 7.18

AcaSP 5.6706 1.2671 4.4035 3.07

MecSP 5.7173 1.1735 4.5438 6.51

284 R. Bostan et al. / Corrosion Science 63 (2012) 275–286
Table 6
Theoretical quantum chemical parameters of the studied Cu-phenothiazine complexes and the repartition of HOMO densities.
Aca-Cu complex DEgap (eV) Repartition of HOMO densities on Cu-inhibitor complex molecule
AcaSP-Cu 5.81103
AcaSP-CuO 2.22957
AcaSP-Cu2O 2.77644
gap for phenothiazine derivatives lay in the following order:
AcaSP < TSP < MecSP < AmSP, which is consistent with the calcu-
lated values of the inhibition efficiencies obtained from both,
polarization curves and EIS techniques (Tables 2 and 3).
The correlation between the energies gap and the inhibition
efficiencies of phenothiazine compounds is shown in Fig. 9.
It can be seen that the plot of DEgap vs. z is linear with a corre-
lation coefficient of R = 0.9869 and the values of DEgap decreases
from AmSP to AcaSP. This result suggests that electron transfer be-
tween molecular orbital HOMO and LUMO is facilitated in the case
of AcaSP with the maximum inhibition efficiency [18].
The dipole moment (l) is another indicator of the electronic
distribution in a molecule and is one of the properties used to dis-
cuss and to rationalize the structure [54] and reactivity of many
chemical systems. A survey of literature revealed a lack of agree-
ment on the correlation between the dipole moment and inhibition
efficiency values [54]. Thus, some authors [56,57] state that the
inhibition efficiency increases with increasing value of the dipole
moments, other consider that lower values of the inhibitor dipole
moment will favor accumulation of the compound in the surface
layer and therefore higher inhibition efficiency [58,59], but in most
cases no significant relationship has been found between the two
parameters [55].
The results obtained in the present study showed that the cal-
culated dipole moments of the phenothiazine derivatives mole-
cules are in the order: AcaSP < TSP < MecSP < AmSP (Table 5),
which means that the adsorption of the organic inhibitors possess-
ing low values of the dipole moments is facilitated on the bronze
surface and lead to better inhibition efficiency values.
In the bronze alloy, the predominant metal is copper, a d type
transition metal containing unoccupied atomic orbitals, character-
ized by a pronounced tendency to form coordination complexes
with donor molecules. We suppose that the inhibition process is
based on the formation of an insoluble and highly adherent do-
nor–acceptor (DA) complex between the inhibitor and the copper
EHOMO (eV) ELUMO (eV)
11.68060 4.62146
9.43349 1.48025
8.1333 1.4238
and copper (I or II) oxide. The formation of these DA complexes im-
ply the electron donation from the occupied p-molecular orbitals
of the ligand into the vacant copper centred orbitals, possibly
accompanied by retrodonor bonds formed by the donation from
the metal to the vacant p-orbitals of the ligand.
An examination of the frontier molecular orbitals which could
be involved in the bonding between the inhibitor and copper,
shows that at HOMO participate all the atoms in the phenothiazine
core of the inhibitor, while LUMO is preponderantly distributed on
the substituent, with one exception which occurs in the case of
AmSP with a LUMO shared by the whole molecule, which shows
the poorest inhibitor activity.
In order to better understand the inhibition of copper dissolu-
tion process by phenothiazine derivatives chemisorption on the
bronze surface, molecular mechanics and semi-empirical (PM3)
optimization were performed using model complexes such as
Cu-, CuO- and Cu2O - phenothiazine derivatives respectively. The
well known electron donor properties of the phenothiazine core
may lead to electronic interactions between the sulphur atom of
the donor heterocyclic and the acceptor Cu or Cu oxides, as shown
for example in the Table 6, where one can see the distribution of
HOMO orbital between the sulphur atom from phenothiazine moi-
ety and copper nucleus [60].
4. Conclusions
All investigated phenothiazine derivatives are fairly efficient
inhibitors towards bronze corrosion in weak acidic solution con-
taining Na2SO4 and NaHCO3 at pH 5, even in lM concentration
range. Their inhibition efficiency increases with increasing the
inhibitor concentrations up to the optimum value (75 lM) and,
at any given conditions, it decreases according to the following or-
der: AcaSP > TSP > MecSP > AmSP.
The protection afforded by phenothiazine derivatives is due to
their adsorption on the bronze surface forming a blocking barrier
 R. Bostan et al. / Corrosion Science 63 (2012) 275–286
to corrosion process. The EDX analysis of the bronze surface ex-
posed to inhibitor-containing solution confirmed the presence of
nitrogen atoms on the electrode surface. The adsorption of
these molecules on bronze in the corrosive solution obeys the
Langmuir isotherm and the adsorption mechanism is typical of
chemisorption.
The stability of the Cu-phenothiazine derivative complex de-
pends essentially on the difference between interacted orbital
energies. The absolute values of the standard free energy of adsorp-
tion and the dipole moments are in good agreement with the order
of inhibition efficiency values calculated from the polarisation
curves and EIS techniques. A correlation between the energy gap
of the phenothiazine derivatives molecules and their inhibition
efficiencies was also put on evidence.
Acknowledgements
The authors thank to Dr. Emese Gál from the Department of Or-
ganic Chemistry, ‘‘Babes-Bolyai’’ University, for synthesizing the
phenothiazine derivatives.
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