Journal of Molecular Liquids 328 (2021) 115421

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Synthesis and evaluation of nonionic surfactants based

on dimethylaminoethylamine: Electrochemical investigation
and theoretical modeling as inhibitors during electropolishing
in-ortho-phosphoric acid
Asia A. Taha a,⁎, Samy M. Shaban b,c,⁎⁎, H.A. Fetouh a, Salma T. Taha a, V.M. Sabet a, Dong-Hwan Kim c,⁎⁎
a
Chemistry Department, Faculty of Science, Alexandria University, Alexandria, Egypt
b
Petrochemical Department, Egyptian Petroleum Research Institute, Egypt
c
School of Chemical Engineering, Sungkyunkwan University (SKKU), Suwon 16419, Republic of Korea

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

Article history: Three non-ionic surfactants had synthesized through one simple direct reaction between N,
Received 16 November 2020 N-dimethylethylenediamine and three fatty acids: octanoic, palmitic and oleic acid. The chemical structures of
Received in revised form 4 January 2021 the synthesized non-ionic surfactants had been confirmed by FTIR & 1HNMR spectroscopy. The surface and ther-
Accepted 17 January 2021
modynamic behavior of the surfactant were determined at different temperatures based on surface tension (γ)
Available online 21 January 2021
measurments. The critical micelle concentration (CMC) is dependent on both of the hydrophobic chain length
Keywords:
and solution temperature. The change in free energy of micellization (ΔG°mic) and adsorption (ΔG°ads) referring
Carbon steel that the synthesized surfactants favor adsorption at interfaces than constructing a micelle. The performance of
Non-ionic surfactants the synthesized surfactants on the dissolution behavior of carbon steel in 8 M H3PO4 acid have been investigated
Surface parameters at temperature range 15 to 45 °C via weight loss and polarization measurements. The dissolution rate (limiting
Galvanostatic polarization current IL) decreases with increasing the surfactants concentrations confirming a mass transport-controlled pro-
Corrosion inhibition cess and a salt-film mechanism. Polarization curves showed that the prepared surfactants are good anodic inhib-
Electro-polishing itors and the adsorption on the carbon steel surface obeys the Langmuir isotherm. The examining the surface
morphology, topography and brightness of the carbon steel in a 8 M H3PO4 containing the synthesized surfac-
tants using scanning electron microscope (SEM), atomic force microscope (AFM) and gloss meter, disclosed
the adsorption of the prepared inhibitors surfactant on the steel surface. The data obtained from theoretical cal-
culations support empirical results.
© 2021 Elsevier B.V. All rights reserved.

1. Introduction
The electropolishing (EP) is the controlled corrosion of a metallic
component to reduce metal surface roughness in order to obtain a
smooth and bright surface [1]. This technique is simple, inexpensive
and effective in treating metals and alloys of different shapes and geom-
etries. The EP of the metals is conducted by polarization in the potential
located in the limiting current plateau of its anodic polarization curve. In
spite of the different grain orientations, phases and different crystalline
imperfections confined in the metal surface, the levelling and brighten-
ing could be obtained by EP [2]. therefore, there are two acceptable
⁎ Corresponding author.
⁎⁎ Corresponding authors at: School of Chemical Engineering, Sungkyunkwan University
(SKKU), Suwon 16419, Republic of Korea.
E-mail addresses: asia.taha@alexu.edu.eg (A.A. Taha), dr.samyshaban@yahoo.com
(S.M. Shaban), dhkim1@skku.edu (D.-H. Kim).
theories that explain the limiting current plateau, based on either the
acceptor mechanism or the salt film [3]. The generation of a salt layer
could minimize the effect of both crystallographic orientation and
roughness on the dissolution process which leads to micro-finishing
and specular reflectance of the metal surface.
Solutions of concentrated acids media are frequently employed for
EP, according to metal type, such as H3PO4, H2SO4 and their mixture.
CH3OH is sometimes used as solvent instead of H2O [4]. Other formula-
tions have been developed using H3PO4 baths containing various classes
of organic compounds as inhibitors, reducing the etching action of acid
and increasing the brightness of metal surface. Several studies were
conducted on the inhibition of anodic corrosion of cupper in H3PO4 at
high concentration levels [5–12] but there is little information available
on the inhibition of anodic corrosion of steel in H3PO4. Recently H3PO4
acid baths containing additives such as plant extract [13], amines [14]
and pharmaceutical compounds [15] have been reported for study of
EP of steel.

https://doi.org/10.1016/j.molliq.2021.115421
0167-7322/© 2021 Elsevier B.V. All rights reserved.
A.A. Taha, S.M. Shaban, H.A. Fetouh et al.
The corrosion is known by the destructive attack of steel and its al-
loys mainly in aqueous-acidic medium. Therefore the using of inhibitors
consider the most effectively probable method for controlling the de-
structive attack of acidic solutions, therefore suppressing the dissolution
of metals rate [16–18]. Inhibitors are also used in the surface treatment
of metals to improve the corrosion resistance. Owing to raising the en-
vironmental regulations, a more attention is now paid forward for the
development of substitute nontoxic compared to hazardous inorganic
inhibitors [19–21]. Today organic inhibitors fully play this role and
new series of them are developing as alternatives to inorganic ones.
Recently the application of surfactants (surface active agents, SAA)
as potential corrosion inhibitors has concerned the awareness of re-
searchers. SAA are special kind of organic compounds; they are bifunc-
tional molecules (amphiphilic compounds) therefore they exhibit
unique properties [22–27]. The non-ionic SAA inhibitors has many ad-
vantages such as easy and low-price production, high inhibition effi-
ciency at lower CMC than the corresponding ionic SAA and low
toxicity which provide them as a suitable candidate in many applica-
tions such as cosmetic, corrosion inhibitors and detergents [28–31].
Also, they have the ability to orient themselves at the interfaces; there-
fore they can give better corrosion inhibition efficiencies. Due to high
adsorption ability of SAA molecules, they are commonly added to acidic
environment to act at the metal/solution interface to decrease the corro-
sion rate of the metal [32–35].
The N,N-dimethylethylenediamine and dimethylamino-1-
propylamine species consider as potentials intermediate in preparing
many products through simple and direct reaction, that involved in
many application as carrion inhibitors, biocide, enhancing some fluores-
cent quantum dot, and a green process for anticancer drug delivery ap-
plication [36–44].
The present study represents an attempt to focus on preparing some
of non-ionic surfactants via simple method in order to manage them as:
(a) a corrosion inhibitors for steel in 8 M H3PO4 acid with intensive
study their inhibition performance using weight loss and galvanostatic
technique with a theoretical calculations using density functional the-
ory (DFT) at B3LYP/6-311G(d, p) basic set level of the theory,
(b) Assessing the extent of polishing (brightening) through elaborating
study that investigate the influence of SAA concentration on the
resulting surface morphology, surface topography and brightness (in-
vestigated by measuring the gloss value and reflectance).
2. Experimental
2.1. Chemicals and aggressive solution
The involved chemicals in the synthesis of the water soluble
materials SAA were used as purchased without any pre-treatments.
The 1-bromooctane, 1-bromohexadecane, oleic acid, and N,N-
dimethylethylenediamine were purchased from Sigma-Aldrich
(Germany). All solvents that used like xylene, and diethyl ether with
high grade were purchased from Al-Gomhoria (Egypt) chemical
company.
The aggressive solution, 8 M H3PO4 was prepared by dilution of an-
alytical grade H3PO4 (85% W/W), supplied by BDH Chemicals Ltd., with
doubly distilled water with a measured resistivity >18 MΩ/cm. All ex-
periments were carried out in absence and presence of different con-
centrations of the synthesized non-ionic SAA. The concentrations of
SAA cover a range from 1 × 10−5 to 5 × 10−3 M. The chemical compo-
sition of studied carbon steel (C-steel), (%wt) is 0.185C, 0.015 S, 0.205
Mn, 0.008 P, 0.11 Si, and the remainder is Fe.
2.2. Synthesis of non-ionic water soluble SAA
Three non-ionic water soluble SAA with variable hydrophobic hy-
drocarbon tail have been prepared through one step click chemistry.
The N,N-Dimethylethylenediamine (0.01 mol, 0.88 g) was reacted
2
Journal of Molecular Liquids 328 (2021) 115421
with 0.01 mol from octanoic acid (1.44 g), palmitic acid (2.56 g) and
oleic acid (2.82 g) individually in 100 mL xylene and 0.01% p-tolene
sulphonic acid (PTSA) as a catalyst. The experiment had been conducted
using Dean-stark system for 24 h at 137 °C until the pre-estimated the-
oretical amount of water (0.01 mol., 0.18 mL) has been received in bot-
tom of the Dean-Stark. The vacuum rotary evaporator was used for
solvent evaporation. The petroleum ether was used to get rid of catalyst
[45] and get on the synthesized non-ionic surfactant abbreviated as
DMAC, DMAP and DMAO with yield percent 92.6, 91.8 and 89.4%
respectively (Scheme 1).
2.3. Instruments
The structure of SAA was characterized by FTIR spectra using A
Bruker tensor 37 (central lab at Faculty of science-Alexandria univer-
sity) and 1HNMR using Jeol-500 MHz, model ECA-500 II, Field strength
11.74 T., Japan in DMSO-D6 (Faculty of science-Mansoura university).
The surface tension was conducted via K6 Krüss tensiometer (Hamburg,
Germany). The degree of brightness (Gloss value) of the investigated
samples was obtained by measuring gloss value using Gloss meter
(ERICHSEN PICOGLOSS; Model No 68-50-0002). A Shimadzu UV-3101
PC spectrophotometer (UV-VIS-NIR) was conducted to get the reflec-
tion spectra in the range of 200–700 nm. Finally the chemical composi-
tion of the C- steel was analyzed by optical emission spectrophotometer
(Egyptian Copper Co., Alexandria, Egypt). The surface morphology of C-
steel surface was performed via scanning electron microscope (SEM)
(JSM-IT 200 SEM, Jeol, Japan). The Atomic force microscope (AFM)
(AP-0100 Autoprobe CP-Research, Thermomicroscobe, 1171 Borregas
Avenue Sunnyvale, California USA) was used to investigate the average
surface roughness factor of the C-steel with and without the
synthesized SAA.
2.4. Surface tension measurements (γ)
The surface tension of DMAC, DMAP and DMAO non-ionic SAA had
been conducted using a platinum ring detachment method at 20, 40
and 60 ± 0.1 °C with accuracy of ±0.5 mNm−1. The solutions were
discharged into the Teflon cup of a 28 mm diameter. Before starting
each run, the platinum ring was cleaned with a diluted chromic acid
followed by washing with a double distilled water. Each run was re-
peated triple with 20 min till stabilization before starting the measure-
ment and the average was considered in calculating the surface
parameters [46,47].
The CMCs values of the DMAC, DMAP and DMAO non-ionic SAA at
the inspected temperature, correspond to the inflection in surface ten-
sion (γ) versus logarithm concentration [log C] curve.
The effectiveness (πCMC) DMAC, DMAP and DMAO anionic SAA was
estimated using the Eq. (1), corresponding to the difference in (γ)values
of both distilled water (γo) without and with the DMAC, DMAP and
DMAO non-ionic SAA at their corresponding CMC [48].
π CMC ¼ γ o –γ CMC ð1Þ
The efficiency (C20) of DMAC, DMAP and DMAO non-ionic SAA cor-
respond to a specific concentration that has a tendency to induce a de-
pression in the surface tension by a value of 20 mN/m.
The maximum surface excess (Γmax) of DMAC, DMAP and DMAO
non-ionic SAA correspond to highest concentration can reach at the so-
lution interface per unit area. It can be extracted via the Gibbs adsorp-
tion Eq. (2) [49]:



1 δγ
Γ max ¼ − ð2Þ
2:303 nRT δ log c T
A.A. Taha, S.M. Shaban, H.A. Fetouh et al.
Scheme 1. Synthetic route of water-soluble non-ionic surfactant.
Here, n assigned to equal 1 for non-ionic SAA, (δγ/δ log c) refer to the
surface pressure, while both R & T for the gas constant & absolute tem-
perature, respectively.
The minimum surface area (Amin) of DMAC, DMAP and DMAO had
been extracted via the Gibbs adsorption equation (Eq. (3)) [50], where
Amin refer to the average occupied area via each surfactant unimer (in
square angstroms) oriented at the interface (the N resemble to the
Avogadro's number constant).
1016
Amin ¼
Γ max N
2.5. Galvanostatic measurements
The cell used in the present study consists of rectangular Plexiglass
flask with a base dimension of 10 × 5 cm with a height 10 cm equipped
with electrodes. The electrodes were constructed with a rectangular di-
mension 10 & 5 cm. A distinct cathode & anode distant of 10 cm was
fixed with a porous PVC diaphragm to prevent the evolved hydrogen
gas bubbles at the cathode. Before conducting each run, the 8 M
H3PO4 solution was filled and 2 cm height of working electrode was
rinsed, while the rest was insulated using epoxy frame.
The electrical circuit was conducted using 6 V D.C. as a power supply,
with connecting a variable resistance and a multi-range ammeter seri-
ally along with the cell. An impedance voltammeter had been connected
paralleled for potential measuring. The steady state of anodic potential
Journal of Molecular Liquids 328 (2021) 115421
had been measured versus reference electrode consisting of a small
steel sheet dipped in a Luggin tube cup that filled with inhibitor solution
(H3PO4-SAA) similar to that present in the cell. The tip of the cup was
placed at the distance of 0.5–1 mm from anode wall. Anodic tafel curves,
from which the limiting current (IL) extracted, has been plotted against
increasing the applied current stepwise and measuring the correspond-
ing steady-state anode potential. Two minutes were allowed for
reaching the steady state potential.
The anode was insulated via polystyrene lacquer except the active
surface area which polished using fine emery papers, followed by
ð3Þ degreasing with trichloroethylene, ultrasonicated in ethanol and finally
with doubly distilled before drying. The temperature was adjusted
using a bath controller ±1 °C. The preliminary experiment that con-
ducted by sparking pure nitrogen gas into the electrolyte to eliminate
the effect of dissolved oxygen during experiments, showed no effect
on the measured polarization behavior; therefore no gas sparking was
considered in our study.
2.6. Weight loss measurements
Rectangular C-steel specimens having lengths of 2 cm×2 cm×0.3 cm
were used. The specimens were polished with different emery papers
with variable grades, rinsed with double distilled water, degreased
with acetone and finally dried and weighed. The weighed specimens
were then immersed in 250 mL beaker contained 100 mL 8 M H3PO4
in absence and presence of various concentrations of the synthesized
non-ionic SAA. The immersion time ranged between 2 and 10 h. After
3
A.A. Taha, S.M. Shaban, H.A. Fetouh et al.
the specified time interval, the specimens were then removed, rinsed
with distilled water and acetone before drying at room temperature
and reweighing again. The difference in weight before and after immer-
sion was taken as weight loss. Each experiment was performed three
times and the average value was taken.
2.7. Surface studies
The morphology of C-steel surface was performed via a scanning
electron microscope (SEM) before and after immersion in H3PO4 solu-
tions without and with the optimum concentration of SAA. The atomic
force microscope (AFM) was conducted to measure the average surface
roughness factor (Ra) at two points in the center position with area of
25 × 25 μm2, with scan rate of 1 Hz and proscan 1.8 software for analyz-
ing the AFM images.
2.8. Quantum chemical calculations
Quantum chemical calculations were conducted for correlating the
relation between the corrosion inhibition efficiency and molecular
structure of DMAC, DMAP and DMAO amphiphilic inhibitors during
the electropolishing process. The thermochemical and thermodynamic
parameters; the total energy (Et), binding energy (Ebind), electronic en-
ergy, heat of formation, entropy change and free energy change of the
SAAs molecules were carried out using Hyperchem 8 software program
(https://en.freedownloadmanager.org/users-choice/Hyperchem_8.0.
html). The the geometric and the electronic structures of the DMAC,
DMAP and DMAO amphiphilic inhibitors were calculated via the
optimization of their molecular structures through density functional
theory (DFT) with Becke's three parameter exchange functional with
Lee-Yang-Parr non-local correlation B3LYP and 6-311G (d, p) basic set
confined in the Gaussian 09 program software package (https://www.
ch.cam.ac.uk/computing/software/gaussian-09) in the gas and the
aqueous phase [51,52]. The density of states (DOS) for the electrons
density occupation as well as Fermi levels were calculated by using
Gauss Sum 2.2.5 software program (https://sourceforge.net/projects/
gausssum/files/gausssum2/GaussSum%202.2.5/) at B3LYP/SDD level of
theory.
3. Results and discussion
3.1. Structure characterization of the synthesized SAA
The chemical structure of the prepared DMAC, DMAP and DMAO
non-ionic SAA has been confirmed by the FTIR and 1HNMR spectra as
outlined in the Figs. 1 and S1–S4 (supporting information).The Fig. 1a,
describe the FTIR of the DMAC non-ionic SAA, where a new amide car-
bonyl band has been formed at 1649.7 cm−1 with disappearing of
both carboxylic carbonyl at 1685–1695 cm−1 and broad -OH of the
acid (2500–3500 broad band). The bands at 2928 and 2858 cm−1
assigned to asymmetric and symmetric vibrational stretching of ali-
phatic CH group, respectively, while the bands at 3292, 1269 and
1044 cm−1 is for amide NH group C–O and C–N groups, respectively.
Fig. 1b, describe the 1HNMR of the synthesized DMAC non-ionic SAA,
which confirm its chemical structure showing the following signals at:
δ = 0.84 (t,3H,CH3 alkyl chain); δ = 1.217 (m,8H,O=CCH2CH2(CH2)
4CH3); δ = 1.4(m,2H,O=CCH2CH2(CH2)4CH3); δ = 2.0 (m,2H,O=
CNHCH2CH2CH2N(CH3)2); δ = 2.1(s,6H, O=CNHCH2CH2CH2N(CH3)
2);δ = 2.16 (t,2H, O=CCH2CH2(CH2)4CH3);δ = 2.23 (T,2H, O=
CNHCH2CH2CH2N(CH3)2); δ = 3.1 (T,2H,O=CNHCH2CH2CH2N(CH3)
2); δ = 7.68 (s, 1H, O=CNHCH2CH2CH2N(CH3)2.
Fig. S3 (supporting information), show the 1HNMR of DMAP non-
ionic surfactant showing signals at: δ = 0.842 (t,3H,CH3 alkyl chain);
δ = 1.223 (m,24H,O=CCH2CH2(CH2)12CH3); δ = 1.44 (m,2H,O=
CCH2CH2(CH2)12CH3); δ = 2.0 (m,2H,O=CNHCH2CH2CH2N(CH3)2);
δ = 2.1 (s,6H, O=CNHCH2CH2CH2N(CH3)2);δ = 2.16 (t,2H, O=
4
Journal of Molecular Liquids 328 (2021) 115421
CCH2CH2(CH2)4CH3);δ = 2.23 (T,2H, O=CNHCH2CH2CH2N(CH3)2);
δ = 3.1 (T,2H,O=CNHCH2CH2CH2N(CH3)2); δ = 7.67(s, 1H, O=
CNHCH2CH2CH2N(CH3)2.
Fig. S4 (supporting information), show the 1HNMR of DMAO non-
ionic surfactant showing signals at: δ = 0.82 (t,3H,CH3 alkyl chain);
δ = 1.219 (m,20H,O=CCH2CH2(CH2)4CH2CH=CHCH2(CH2)6CH3);
δ = 1.45 (m,2H,O=CCH2CH2CH2CH2); δ = 1.9 (m,4H,CH2CH=
CHCH2); δ = 2.0 (m,2H, O=CNHCH2CH2CH2N(CH3)2);δ = 2.1 (s,6H,
O=CNHCH2CH2CH2N(CH3)2);δ = 2.16 (t,2H, O=CCH2CH2(CH2)
4CH2CH=CH);δ = 2.24 (T,2H, O=CNHCH2CH2CH2N(CH3)2); δ = 3.08
(T,2H,O=CNHCH2CH2CH2N(perCH3)2); δ = 7.67 (s, 1H, O=C
3.2. Surface and thermodynamic study
3.2.1. Hydrophobic effect
The surface parameters of the inspected DMAC, DMAP and DMAO
non-ionic SAA as function of the hydrophobic tail variation were
determined based on the surface tension measurements at different
temperatures. The CMCs values of the prepared DMAC, DMAP and
DMAO non-ionic SAA were determined at 20, 40 & 60 °C, which corre-
spond to the intersection points in surface tension- log[C] curves as it
is inspected in the Fig. 2a–c. The experimentally determined CMCs
values (Table 1), showing the dependence of CMC performance on the
hydrophobic tail. Elongation the hydrophobic tail length of surfactant
trigger a decreasing in the measured CMCs values (Table 1 and
Fig. 2d). The decreasing of CMC is due to destroying of the water struc-
ture as function of increasing the hydrophobic tail of the dissolved sur-
factant, so the acquired system free energy is enhanced, which trigger
the aggregation of the surfactant unimers in a micelle structure or mi-
gration to the solution surface, where both cases either adsorption or
micellization, the hydrophilic head become faced with aqueous system
while as the hydrophobic tail escape from contacting with water solu-
tion. This behavior induce free energy relaxation, so decrease in CMC
values [20,53–55]. For example, the CMCs values DMAC, DMAP and
DMAO non-ionic surfactant at 20 °C, equal to 3.1, 2.1 and 1 mM respec-
tively (Table 1).
The C20 values inspected in the Table 1, refer to the dependence of
C20 on the variation of the hydrophobic tail. As the hydrocarbon tail
was elongation from 8 to 18 carbons atoms, the C20 increase. Where
with growing up the hydrophobicity, the migration rate of the DMAC,
DMAP and DMAO unimers into the surface increase and subsequently
inducing more lowering in the surface tension, so C20 increase
(Table 1) [56]. The πCMC values of DMAC, DMAP and DMAO non-ionic
SAA at 20, 40 & 60 ᴼC were determined according to Eq. (1), and the re-
sults indicated that the DMAO is the most effective non-ionic SAA that
induce more lowering in (γ) as it is outlined in the Table 1. The πCMC
values of DMAC, DMAP and DMAO non-ionic SAA at 40ᴼC were 34.17,
37.15 and 38.62 dyne/cm, respectively (Table 1). The πCMC values refer
to the degree of packing of the surfactant unimers at the interfaces,
the high value of πCMC refers to formation a compacted layer at the
phase interface, while as the lower value indicate a loosely pacing sur-
factant unimer at the interface [57,58].
The Γmax and Amin values of DMAC, DMAP and DMAO non-ionic SAA
have been determined following Gibbs adsorption Eqs. (2) and (3) re-
spectively (Table 1). The Γmax values refer to amount of accumulated
DMAC, DMAP and DMAO non-ionic SAA unimers at solution interface,
while as Amin point to the ordering density at interfaces. Elongation
the hydrocarbon tail length of non-ionic SAA lead to an increasing of
Γmax and decreasing the Amin values. The Amin values of the synthesized
DMAC, DMAP and DMAO non-ionic surfactant at 40 °C are 160.1, 149.84
and 146.69 A2 respectively, while their corresponding Γmax values equal
to 1.07, 1.11 & 1.13 (x10−10 mol.cm−2) respectively. As known with the
increasing the hydrophobic tail of surfactant, the solution hydrophobic-
ity increase that induce a migration of unimers to the interfaces, and
subsequently constructing a dense adsorption layer. This constructed
dense layer force surfactant unimers to be orient vertically at the
A.A. Taha, S.M. Shaban, H.A. Fetouh et al. Journal of Molecular Liquids 328 (2021) 115421

Fig. 1. (a) FTIR, (b) 1HNMR spectrum of the synthesized DMAC non-ionic SAA.

interfaces. Hence decreasing the Amin, consequently enhancing the ac- ΔH ads −ΔGoads
ΔSads ¼ ð7Þ
cumulated amount of the amphiphilic unimers at the interface T
[20,24,59–62]. 0 ΔGo 1
The thermodynamic behavior of the synthesized DMAC, DMAP and ∂ Tmic
DMAO non-ionic SAA at 20, 40 & 60 ᴼC, were calculated according to ΔHmic ¼ −T 2 @ Ap ð8Þ
∂T
the Gibbs Eqs. (4)–(9) [63–67], and the determined thermodynamic pa-
rameters were depicted in the Table 2. 0 ΔGo 1
∂ Tads
ΔGomic ¼ RTlnðX CMC Þ ð4Þ 2@ Ap
ΔHads ¼ −T ð9Þ
∂T
 
ΔGoads ¼ ΔGomic −6:023X10−2 π CMC=ᴦ
Max
ð5Þ
The, XCMC is the CMC molar fraction that calculated based on surface
ΔHmic −ΔGomic tension. The calculated both change in micellization free energy
ΔSmic ¼ ð6Þ
T (ΔG°mic) and adsorption (ΔG°ads) of the DMAC, DMAP and DMAO, are

5
A.A. Taha, S.M. Shaban, H.A. Fetouh et al. Journal of Molecular Liquids 328 (2021) 115421

Fig. 2. (a-c) The relationship between surface tension and log concentration of DMAC, DMAP and DMAO non-ionic surfactant, respectively, at various temperatures; (d) Temperatures and
hydrophobic tail length effect of the synthesized DMAC, DMAP and DMAO non-ionic SAA.

negative, implying that the two adsorption & micellization process are
spontaneous, in a way to minimize the gained solution energy from
the dissolved SAA compounds in the aqueous system [68]. The data
inspected in Table 2, disclose that, the ΔG°ads for all synthesized surfac-
tants at the different temperatures are more negative than that corre-
sponding ΔG°mic, implying that the predicted behavior of the
surfactants DMAC, DMAP and DMAO in aqueous solution is adsorption
at solution interface first till maximum saturation, then aggregation
and constructing a micelle structure.
As the hydrophobic tail length of surfactant increase, both ΔG°ads
and ΔG°mic are increased negatively, referring to enhancing the surfac-
tant ability to adsorption and micellization as it is clarified in the
Table 2. With increasing the chain length of hydrocarbon tail of non-
ionic surfactant, it enhance the solution hydrophobicity so destroying
water structure and promote increasing the system free energy; conse-
quently orienting the surfactant unimers tend to move toward the solu-
tion surface and/or aggregation in micelle structure to make a relaxation
for the acquired higher free energy. In the adsorption process, the hy-
drophilic head become contacted with the polar solution, while the hy-
drophobic tail be oriented away from the solution to avoid unfavorable
energically contact with the polar aqueous phase. In micelle formation,
the hydrophilic head become directly faced with the polar medium,
while the hydrophobic tail be trapped inside the micelle to avoid unfa-
vorable energically contact with polar medium [68,69].
The change in the entropy of micellization (ΔSmic) & adsorption
(ΔSads) have been determined from the Eqs. (6) and (7) respectively,
and the results were inspected in the Table 2. The ΔSmic & ΔSads values
are positive predicting enhancing the amphiphilic ordering throughout

Table 1 Table 2
The surface properties of synthesized nonionic surfactant at various temperatures. Micellization and adsorption thermodynamic parameters of the prepared nonionic
surfactants.
Comp. Temp. °C CMC/ C20 *10−5 πCMC/ Гmax *10−10 Amin/A2
(mM.L−1) (mol.L−1) (mN m−1) (mol.cm−2) Comp Temp. ΔG°mic ΔHmic ΔSmic kJ. ΔG°ads ΔHads ΔSads kJ.
°C kJ mol−1 kJ.mol−1 mol−1.K−1 kJ.mol−1 kJ.mol−1 mol−1.K−1
DMAC 20 3.108 2.39 34.87 1.16 128.41
40 1.874 1.75 34.17 1.07 160.1 DMAC 20 −23.86 19.33 0.147 −26.53 20.38 0.160
60 1.036 1.07 30.59 0.98 173.20 40 −26.78 22.06 0.156 −30.07 23.26 0.170
DMAPt 20 2.106 0.71 38.17 1.24 124.20 60 −30.11 24.96 0.165 −33.31 26.32 0.179
40 1.000 0.48 37.15 1.11 149.84 DMAP 20 −24.81 19.43 0.151 −27.66 20.26 0.163
60 0.698 0.33 35.00 1.02 160.00 40 −28.42 22.17 0.162 −31.77 23.12 0.175
DMAO 20 1.000 0.22 40.50 1.30 119.70 60 −31.20 25.09 0.169 −34.58 26.16 0.182
40 0.713 0.13 38.62 1.13 146.69 DMAO 20 −26.62 11.98 0.132 −29.54 12.37 0.143
60 0.503 0.09 36.11 1.04 155.30 40 −29.30 13.67 0.137 −32.71 14.11 0.149
60 −32.11 15.47 0.143 −35.49 15.97 0.154

6
A.A. Taha, S.M. Shaban, H.A. Fetouh et al.
micellization and adsorption process respectively. Increasing the hydro-
phobic tail, both ΔSmic & ΔSads values increase indicating more ordering
induced. The ΔSads values higher than ΔSmic, referring more freedom of
hydrophobic tail throughout the adsorption adaptation compared to
micellization process [57,70]. The changes in micellization enthalpy
(ΔHmic) & adsorption enthalpy (ΔHads) were determined using
Eqs. (8) and (9) respectively and the results pointed to positive value
of ΔHmic and ΔHads, (Table 2), referring that micelliztion and adsorption
processes controlled by the entropy change, where methylene group
transferring either from the micelle interior or transferring from surface
into inside solution due adsorption at, induce a decreasing in the en-
tropy so less ordering [71–73].
3.2.2. Effect of temperature
The solution temperature showed a great influence on the deter-
mined CMCs values of the DMAC, DMAP and DMAO aqueous solution.
Raising the solution temperature, it induce a decreasing in CMCs
(Table 1 & Fig. 2d). This is due to elevating the solution temperature, it
leads to a decrease in the water hydration surrounding the hydrophilic
head, so increasing the micellization tendency (CMC values decrease).
However, increasing the solution temperature, induces a destroying
the water structure around the hydrophobic tail moiety of DMAC,
DMAP and DMAO, which disfavor micellization process and increasing
the CMC values. Finally, the net magnitude of the two opposing-
temperature effect on water hydration determine the final CMC trend
[74–77]. Based on the results in Table 1, the CMCs values decreases as
function of temperature increasing. For example, the CMCs values of
DMAC at 20, 40 and 60 °C, are 3.1, 1.87 and 1.036 mM respectively
(Table 1).
The C20 values (Table 1), indicates that the solution temperature is
directly proportionally to the C20. The effect of water hydration disrup-
tion around the hydrophobic tail as a results of increasing the solution
temperature is dominant than that induced around hydrophilic head,
as it is concluded from the CMC behavior with temperature (Table 1).
So raising the solution temperature, enhance the movement of the
unimers toward the interfaces, consequently more reduction in the
(γ) is attained as it is depicted in the Table 1.
Elevating the temperature, the Γmax decrease while Amin increase.
The Amin values of the DMAC non-ionic SAA at 20, 40 and 60 °C equal
to 128.41, 160.1 and 173.2 A2 respectively, while their corresponding
Γmax values equal to 1.16, 1.07 and 0.98 (x10−10 mol.cm−2) respec-
tively. Elevating the temperature lead to increasing the solution activa-
tion energy so enhancing the repulsion force between the hydrocarbon
tails and polar aqueous solution, subsequently orienting unimers hori-
zontally at the air/solution interface so Amin increased and subsequently
the amount of the Γmax decreased.
The calculated change in ΔG°mic and ΔG°ads of the prepared DMAC,
DMAP and DMAO non-ionic surfactant are found to increase negatively
as function of increasing of solution temperature as it is outlined in the
Table 2, whereas the surfactant ability toward adsorption and micelliza-
tion are enhanced as it is clarified in the Table 2. Increasing the temper-
ature, induce destroying the water hydration surrounding the
amphiphilic unimer head, so activation energy is predicted to increase,
which promote the unimers to migrate to surface and/or constructing
micelle [68,69].
3.3. Galvanostatic polarization measurements
Fig. 3a–c, display the anodic dissolution polarization curves for of
carbon steel in the aggressive solution 8 M H3PO4 containing various
concentrations of the synthesized DMAC, DMAP and DMAO non-ionic
SAA inhibitors and that without at 15 °C.
Anodic dissolution of C-steel in the aggressive H3PO4 (Fig. 3a–c,
blank) shows a limiting current (IL) because of the dissolution is
under mass transport control, where the reaction products diffusion is
limited. At IL, the second part of the curve, a thin film of salt with a
7
Journal of Molecular Liquids 328 (2021) 115421
saturated metallic cations concentration is developed on the anodic sur-
face which restrict the rate of metal ions departure from the surface. In
first part of the curve, below IL, etching take place and C-steel dissolu-
tion implicates simultaneous formation of Fe2+ and Fe3+, where the
amount of the formed Fe3+ becomes important at higher potential
and in the third part, where C-steel dissolution is accompanied by O2
evolution at anode with some localized pitting occurs [15,78].
An Applied potential against the current was graphically plotted and
the (IL) was obtained by the extrapolation of the linear portion of the
dissolution potential and the obtained data was confined in the Table 3.
Appearance of IL plateau in the presence of the different concentra-
tions of the synthesized DMAC, DMAP and DMAO compounds, shows
that these SAA do not induce change in the diffusion-controlled mecha-
nism of iron dissolution to a charge transfer mechanism. Nevertheless,
the synthesized DMAC, DMAP and DMAO effect the IL by different de-
grees indicating that their inhibitive effect depends on their type.
The inhibition efficiency IE (%) of the synthesized SAA (DMAC, DMAP
and DMAO) can be calculated via Eq. (10), where the IL(SAA) is the limit-
ing current of the aggressive solution containing various concentration
of the synthesized SAA, while the IL(blank) is in the absence of SAA.
!
ILðBlankÞ –I LðSAAÞ
IE ð%Þ ¼  100 ¼ θ  100 ð10Þ
ILðBlankÞ
The obtained IL and IE (%) values of the studied SAA (Table 3 and
Fig. 3a–c), showing an increase of the IE (%) as functional of increasing
the dose of the as-prepared non-ionic SAA as well as temperature de-
creasing. The IE of investigated inhibitors could be arranged in the
order: DMAO > DMAP > DMAC. This order of the inhibition efficiency
reflects the important role of the hydrophobic chain length confined
in the synthesized non-ionic SAA as well as the possible active number
of the adsorption centers (and their basicity) in the inhibition processes.
The IE (%) of the studied SAA was found to increase as function of
concentration increasing from 0.01 mM to 5 mM. A maximum IE of
SAA has been exhibited at 5 mM. The increase in IE (%) is ascribed to en-
hancing the amount of the adsorbed DMAC, DMAP and DMAO non-ionic
inhibitors on C-steel surface, hence increasing the surface coverage (θ)
that act as insulator between the corrosive H3PO4 medium and C-steel
surface [79–81]. As depicted in the Scheme 1, the molecular structure
of the studied non-ionic SAA contain the same number of nitrogen
atoms (2 atoms attached to the molecule) and C_O group with varia-
tion in the hydrophobic chain length. Therefore, they are able to adsorb
on C-steel surface via the lone pair of electrons of N- and O- atoms be-
sides the п- electrons of C_O group, while the hydrophobic tail act as
more covering layer on the steel surface. The surfactant DMAO has addi-
tional п- electrons of C_C in the unsaturated hydrophobic tail which
provide a strong adsorption center rather than other two surfactant
with saturated hydrophobic tail [82–84].
Results in Table 3, exploit enhancing the IE as functional of increas-
ing the hydrophobic tail length of the synthesized non-ionic SAA,
where IE of DMAC, DMAP and DMAO at 15 °C are equal to 76.19,
85.72 and 90.48 at concentration 5 mM. As clearly outlined from
Tables 1 and 2, the hydrophobic character of the synthesized SAA in-
creasing from DMAC to DMAO, it induce increasing the adsorption ten-
dency as well as increasing the Γmax. The DMAO surfactant has higher
Γmax (Table 1) and ΔGoads (Table 2), which promote it to be more effec-
tive surfactant as corrosion inhibitors as confined from the inhibition ef-
ficiencies in the Table 3 [85].
The inspected results in Table 3, provide information regarding to
solution temperature (15–45 °C) and the corresponding inhibition effi-
ciency, where the IE of the synthesized DMAC, DMAP and DMAO com-
pounds was found to decreases as their solution temperature increase.
This could be interpreted as a results of physical adsorption induced
by the inhibitors on the C-steel surface via high electronic cloud func-
tional groups like oxygen, nitrogen and double bond.
A.A. Taha, S.M. Shaban, H.A. Fetouh et al. Journal of Molecular Liquids 328 (2021) 115421

Fig. 3. (a-c) Typical anodic polarization curve for electropolishing of vertical C-steel plate in 8 M H3PO4 in presence of different concentrations of DMAC, DMAP and DMAO at 15 °C.
(d) Langmuir adsorption isotherm for C-steel in 8 M H3PO4 solution at 15 °C for studied SAA.

Different adsorption isotherms (Langmiur, Flory-Huggins, Frumkin

and Temkin) based on the calculated electrochemical surface coverage
area (θ) were conducted for describing the adsorption of the non-ionic
DMAC, DMAP and DMAO inhibitors. The Langmuir isotherm through
Table 3 Eq. (11) was best fitted isotherms with highest R2 (Table S1), with
Values of Limiting current and % inhibition for dissolution of steel in 8 M H3PO4 acid in ab- slope 1.29,1.15 and 1.09 for DMAC, DMAP and DMAO at 15 °C, respec-
sence and presence of SAA at different temperatures.
tively as outlined in the Fig. 3d and Table S2 (supporting information).
SAA 15 °C 25 °C 35 °C 45 °C The slight shift in the slope than unity, refer to presence interaction
Conc (M) IL (A) %IE IL (A) %IE IL (A) %IE IL (A) %IE forces between the adsorbed molecules [86].
DMAC Blank 0.42 0.00 0.48 0.00 0.52 0.00 0.58 0.00

C 1
1 × 10−5 0.33 21.43 0.39 18.75 0.43 17.31 0.49 15.52 ¼ þC ð11Þ
5 × 10−5 0.27 35.71 0.36 25.00 0.41 21.15 0.46 20.69 θ K ads
1 × 10−4 0.19 54.76 0.32 33.33 0.39 25.00 0.44 24.14
5 × 10−4 0.17 59.52 0.26 45.83 0.35 32.69 0.41 29.31 Where C is the concentration of the synthesized non-ionic SAA, and
1 × 10−3 0.12 71.43 0.18 62.50 0.28 46.15 0.37 36.21
5 × 10−3 0.10 76.19 0.15 68.75 0.23 55.77 0.31 46.55
Kads is the adsorption equilibrium constant. The extracted Kads values
DMAP 1 × 10−5 0.25 40.48 0.30 37.50 0.35 32.69 0.34 41.38 were depicted in Table S2 (supporting information), revealing the
5 × 10−5 0.21 50.00 0.26 45.83 0.31 40.38 0.30 48.28 strong adsorption of DMAO on the steel surface. The standard free en-
1 × 10−4 0.17 59.52 0.22 54.17 0.29 44.23 0.28 51.72 ergy of adsorption (ΔG°ads) regarding to the non-ionic surfactants
5 × 10−4 0.11 73.81 0.18 62.50 0.24 53.85 0.23 60.34
DMAC, DMAP and DMAO was extracted according to Eq. (12) based
1 × 10−3 0.08 80.95 0.15 68.75 0.20 61.54 0.20 65.52
5 × 10−3 0.06 85.71 0.12 75.00 0.17 67.31 0.09 84.48 on the adsorption equilibrium constant [87,88]:
DMAO 1 × 10−5 0.21 50.00 0.26 45.83 0.34 34.61 0.42 27.59

5 × 10−5 0.19 54.76 0.22 54.17 0.30 42.31 0.36 37.93 ΔGads ¼ −RT ln ð55:5K ads Þ ð12Þ
1 × 10−4 0.12 71.43 0.20 58.33 0.26 50.00 0.33 43.10
5 × 10−4 0.08 80.95 0.15 68.75 0.22 57.69 0.26 55.17
1 × 10−3 0.06 85.71 0.13 72.92 0.19 63.46 0.23 60.34 Where R refer to the universal gas constant (8.314 J.mol−1.K−1), T to
5 × 10−3 0.04 90.48 0.11 77.08 0.16 69.23 0.22 62.07 absolute temperature while the 55.5 value represent the water molar
concentration (mol./L).

8
A.A. Taha, S.M. Shaban, H.A. Fetouh et al. Journal of Molecular Liquids 328 (2021) 115421

Table 4 Table 5
Thermodynamic parameters extracted from Langmuir adsorption isotherm. Values of thermodynamic activated parameters for dissolution of C-steel in 8 M H3PO4 in
absence and presence of SAA.
SAA Temp. °C ΔGads kJ mol−1 ΔH°ads kJ mol−1 ΔS°ads J mol−1 K−1
Conc (M) SAA Ea KJ.mol−1 ΔH⁎ KJ.mol−1 -ΔS⁎ J.mol−1.K−1
DMAC 15 −31.95 −33.38 −32.06
25 −31.42 0.0 DMAC 7.99 5.48 232.76
35 −31.1 1× 10−5 9.79 7.27 228.51
45 −31.84 5× 10−5 13.24 10.73 217.90
DMAP 15 −33.09 −22.70 −33.16 1× 10−4 20.88 18.36 193.83
25 −33.55 5× 10−4 22.49 19.98 189.53
35 −34.02 1× 10−3 29.12 26.61 169.76
45 −34.13 5× 10−3 29.13 26.62 171.29
DMAO 15 −33.81 −13.23 −33.85 1× 10−5 DMAP 13.38 10.87 219.59
25 −34.66 5× 10−5 13.12 10.61 221.51
35 −34.49 1× 10−4 14.31 11.80 218.29
45 −36.28 5× 10−4 20.59 18.07 199.86
1× 10−3 24.44 21.92 188.77
5× 10−3 11.61 9.10 234.49
1× 10−5 DMAO 13.02 10.50 219.70
5× 10−5 13.41 10.89 219.71
The heat of adsorption (ΔH°ads) and entropy of adsorption (ΔS°ads)
1× 10−4 24.55 22.04 184.87.
were determined via Van't Hoff Eq. (13) [89]: 5× 10−4 28.76 26.24 173.06

! 1× 10−3 33.26 30.74 159.63
−ΔH ads 5× 10−3 41.50 38.99 134.25
ln K ads ¼ þ Constant ð13Þ
RT

To obtain ΔH°ads, plotting ln Kads vs 1/T, yielded a straight lines with The transition state theory had been conducted to detect the change
slope equal to -ΔH°ads/R and intercept equal ΔS°ads/R. in the entropy activation (ΔS*) and Enthalpy (ΔH*), as configured in
The standard adsorption entropy (ΔS°ads) was determined via the Eq. (16) [94], Where, k & NA correspond to the metal dissolution rate
Eq. (6) [90]: and Avogadro's number, respectively, while h to Planck's constant.
 
ΔGads ¼ ΔHads −TΔSads

ð14Þ



⁎ 
IL R ΔS ΔH ⁎
ln ¼ ln þ − ð16Þ
T NA h R RT
The extracted thermodynamic parameters via Eqs. (12)–(14), re-
garding to the adsorption the non-ionic inhibitors DMAC, DMAP and With plotting the log (k/T) vs. (1/T), promote straight line with an in-
DMAO on the carbon steel in 8.0 M H3PO4 acid were confined in the    ⁎  ⁎
tercept of log R
þ ΔSR with a slope of ΔH R . The extracted ΔH*
Table 4. The depicted ΔG°ads values in the Table 4, are around −31 to NA h

−36 kJ.mol−1 predicting that the adsorption mechanism of the synthe-
sized DMAC, DMAP and DMAO involves both physical and chemisorp-
tion adsorption via electrostatic electron sharing of unpaired electrons
on N-atoms to the vacant d-orbital of C-steel [91]. In the present
study, the negative sign of ΔH°ads. indicates that the adsorption of the in-
vestigated SAA on C-steel surface is exothermic [92].The negative value
of ΔS°ads indicating more ordering takes place in going from the freely
move SAA in the bulk to the more orderly inhibitor molecules on
C-steel surface.
The performance of inhibitor and the dissolution rate of C-steel are
greatly affected by temperature. The Arrhenius-type plot (Eq. (15))
was conducted for determining the apparent activation energy (Ea) re-
garding to the corrosion process, where the variable k correspond to IL
(limiting current), A to frequency factor [93], R to gas constant, while
T to absolute temperature.
Ea
LnI L ¼ LnA−
RT
The apparent activation energy of the dissolution reaction in a solu-
tion containing different concentrations of the non-ionic inhibitors
DMAC, DMAP and DMAO and that without could be determined via
plotting Ln IL Vs. 1/T, with a straight lines having a regression coefficient
nearly equal 1, as an indication for obeying the Arrhenius equation. The
Ea values were extracted from straight line slope, while the intercept
gave the pre-exponential factor (Table 5). From the extracted data in
Table 5, it is clear that the Ea values increased as functional of increasing
the concentration of the injected SAA inhibitors in comparison with 8 M
H3PO4 (SAA- free solution) [10]. The increase in Ea is due to increasing
energy barrier of dissolution reaction. When the inhibition efficiency
drops with increasing temperature and the Ea in presence of SAA is
higher than the Ea in the absence of SAA, then the adsorptive film
formed on the metal surface is believed to be due to physical adsorption.
values were depicted in Table 5, revealing the positive signs of ΔH#
reflected the endothermic behavior of the tested C-steel dissolution in
8 M H3PO4 acid and indicated that the C-steel dissolution is difficult.
The entropy of activation (ΔS⁎) in of the steel rinsed in the 8 M H3PO4
without and that containing the synthesized non-ionic SAA was large
and negative. This indicate that the activated complex in the rate deter-
mining step represents an association rather than dissociation, meaning
that, decrease in disordering takes place on going from reactants to the
activated complex. The ΔS⁎ values are less negative for the aggressive
solution containing the synthesized non-ionic SAA than that for the
without SAA. This could be attributed to the departure of large fraction
of more disordered H2O molecules that adsorbed on the surface of C-
steel metal and replace with less disordered SAA molecules as follows:
[95].
SAA ðsolÞ þ x H2OðadsÞ ⇋ SAAðadsÞ þ x H2OðsolÞ
ð15Þ
where x is the size ratio that is no of water molecules replaced by one
surfactant molecule.
3.4. Weight loss measurements
The corrosion inhibition efficiency (IEwt) and surface coverage (θ) of
studied non-ionic surfactants DMAC, DMAP and DMAO have been de-
termined via weight loss technique by using the Eq. (17) [96,97]:


ΔW SAA
IEwt ¼ 1−  100 ¼ θ  100 ð17Þ
ΔW Blank
Where the ΔW and ΔWblank are the weight losses (g) in the presence
and absence of the studied non-ionic SAA. The inhibition efficiency of C-
steel in 8 M H3PO4 acid containing different concentration of the synthe-
sized non-ionic surfactant DMAC, DMAP and DMAO and that without

9
A.A. Taha, S.M. Shaban, H.A. Fetouh et al. Journal of Molecular Liquids 328 (2021) 115421

Table 6 condensed layer that isolate the action of the corrosive solution especially
Weight loss measurements for C-steel in 8 M H3PO4 solution in absence and presence of with presence the interactions between hydrophobic tails via Vander
different concentrations of SAA at an immersion time range (2h− 10h) at 15 °C.
Waals force [98,99]. A high IE exhibited by the prepared surfactant over
Conc., (M) Time, (hrs) Inhibition efficiency, %IE a long exposure time confirming their stability in 8 M H3PO4 acid.
2 4 6 8 10
−5 3.5. Surface parameters-inhibition efficiency relationship
1 × 10 DMAC 14.33 15.08 15.42 17.00 19.26
5 × 10−5 21.83 22.54 23.33 24.14 26.41
1 × 10−4 40.00 40.63 42.50 43.82 45.67 Surfactants that give the greatest lowering in surface tension for
5 × 10−4 45.83 46.43 47.92 49.52 52.01 CMC, and πCMC is the most effective surfactant. According to results in
1 × 10−3 56.33 56.90 58.33 60.00 62.21 Table 2, DMAO achieves the maximum reduction of γ at CMC (reach
5 × 10−3 60.50 61.43 63.12 64.91 67.01
1 × 10−5 DMAP 41.00 41.51 43.33 45.09 46.75
40.50 mN.m−1) compared with that obtained by DMAC and DMAP.
5 × 10−5 50.00 50.71 52.12 53.61 54.97 This is in good agreement with the maximum IE results obtained by
1 × 10−4 55.33 55.87 56.92 58.01 59.22 DMAO (Table 3).
5 × 10−4 59.50 59.92 61.25 62.52 64.00 According to the data in Table 2, it is found that Гmax. of DMAO is
1 × 10−3 64.83 65.15 66.50 67.90 69.31
higher than that of both DMAC and DMAP. On the other hand the
5 × 10−3 71.50 73.01 75.83 75.86 77.92
1 × 10−5 DMAO 35.83 36.43 38.00 39.52 40.41 value of Amin. for DMAO is lower than that of both DMAC and DMAP.
5 × 10−5 49.83 50.32 51.62 52.92 54.00 The high value of Гmax of DMAO gives information regarding to the ac-
1 × 10−4 56.67 57.06 58.50 60.11 61.90 cumulation of the DMAO unimers at the interfaces with a close packing
5 × 10−4 64.50 64.92 66.21 67.37 68.61 accompanied with a less occupied area for each unimer unit on the C-
1 × 10−3 72.33 72.78 74.00 75.41 76.10
5 × 10−3 78.83 79.13 79.92 81.01 82.51
steel surface than DMAC and DMAP. This behavior leads to enhancing
the electrostatic interaction of the well packed adsorbed molecules, in-
crease surface coverage area and more homogenous adsorbed film. At
the same line the ΔG°ads, of the surfactant DMAO is more negative
with different immersion periods are given in Table 6. The outlined re- than DMAP than DMAC, which give the surfactant higher tendency to
sults in Table 6 and Fig. 4a; disclose an increase in the IE with incremen- be adsorbed on the interfaces. Finally we can conclude that all the pro-
tal addition of the prepared non-ionic surfactants DMAC, DMAP and vided surface parameters of the studied non-ionic surfactant predict
DMAO to the aggressive solution (8 M H3PO4) because of increasing that the surfactant DMAO could be most active one as regarding to
the adsorption coverage area on steel surface induced by these inhibi- protecting the steel from corrosion which is confirmed experimentally
tors as discussed previously considering the surface performance. In- based on the IE values inspected in the Tables 3 and 6. The relation be-
creasing the hydrophobic chain length of the prepared non-ionic tween surface activity and IE had been conducted in previous studies
inhibitor DMAC, DMAP and DMAO, enhance the IE, where the metal dis- [100–103]. As the hydrophobic chain length of the inhibitors increase,
solution decrease. This behavior is due to the fact that increasing the so- both of surface activity and adsorption ability toward the interfaces be-
lution hydrophobicity enhance the adsorption tendency on the steel came enhanced [104]. Thus, increasing the adsorption increases the
interfaces, therefore more protection for C-steel. amount of adsorbed molecules onto metal surface which increases sur-
The inhibition efficiency of the studied non-ionic surfactant DMAC, face coverage value (θ) [104,105]. Consequently, the surface of the
DMAP and DMAO at different immersion time have been studied as metal is protected from the aggressiveness of acid attack. Also, increas-
outlined in the Table 6. The Fig. 4b, showing the effect of exposure time ing the surface activity of surfactant inhibitor considerably decreases
(in hours) on the IE of DMAC, DMAP and DMAO for C-steel corrosion in their CMC values.
8 M H3PO4 acid, (concentration 5 mM) at 15 °C and the results revealed
an enhancement in the IE with increasing immersion time for all the syn- 3.6. Quantum chemical calculations
thesized non-ionic surfactants. This behavior suggests more adsorption
on the C-steel surface has been occurred. As the adsorption became en- Quantum semi-empirical calculation methods (which use simple
hanced, the surfactant density becomes sufficiently high forming a approximation to solve the time dependent (TD) Schrӧdinger equation)

Fig. 4. (a) Inhibition efficiency percentage – concentration dependence curves for C-steel in 8 M H3PO4 solution contaning different SAA at 15 °C and 10 h. (b) Inhibition efficiency
percentage – immersion time dependence curves for C-steel in 8 M H3PO4 solution contaning different SAA at 15 °C.

10
A.A. Taha, S.M. Shaban, H.A. Fetouh et al.
Table 7
Quantum semi-empirical calculations.
SAA DMAC DMAP DMAO
Total Energy (Et)(au) −56,338.62 −83,927.21 −90,090.63
Binding energy (Ebind) −3777.34 −6021.71 −6452.03
Electronic energy −360,046.19 −630,955.91 −687,818.86
Heat of formation −86.45 −130.07 −114.40
Entropy(ΔS) 0.01 0.18 0.02
Free energy(ΔG) −56,338.5 −83,536.7 −90,090.5
Total energy (at 373 °C) −83,530 −83,927.215 −89,671.70
Entropy(ΔS) 0.17 0.21 0.25
Free energy(ΔG) −56,154.9 −83,608.4 −89,764.3
were performed to inform about the energy of the large synthesized
non-ionic surfactants molecules: DMAC, DMAP and DMAO. It is rela-
tively rapid method and applied to the very large molecules. However,
the limitation of this method is that it does not perform well with hy-
drogen bonding and the transition structures [106]. Table 7, lists the
quantum thermochemical and thermodynamic parameters for the
DMAC, DMAP and DMAO molecules: The total energy (Et), binding en-
ergy (Ebind), electronic energy, heat of formation, entropy change and
the free energy change of formation.
From Table 7, it can note that DMAO have the most stable structure
among the synthesized SAA molecules due to the lowest total energy
and binding energy. The theoretical calculations exploited that the
DMAO has the more negative Et, showing its high stability over the
DMAC and DMAP SAA. This finding is in a good agreement with the ex-
perimental findings from Tables 3 and 6, that DMAO showed the highest
inhibition efficiency of corrosion of C-steel during electropolishing.
[107,108]. The calculated binding energy (Ebind.) and the electronic en-
ergy of the studied SAAs follows the same order as the total energy:
DMAO < DMAP < DMAC (Table 7). This trend correspond to the trends
of the molecular size and the inhibition efficiency of these molecules for
corrosion of C-steel during the electropolishing. The larger molecules
are more strongly adsorbed on the metal surface.
The calculated negative value of the heat of formation indicating that
the exothermic bond formation follows the order: DMAP < DMAO <
DMAC. This means that the formation of DMAP is more exothermic pro-
cess than DMAC. This difference may be attributed to the presence of the
double bond in DMAO. The entropy of formation increases in the order:
DMAC< DMAO < DMAP. The latter surfactant (DMAC) has the lowest
value of entropy of formation due to its smallest size among the pre-
pared SAAs. Although DMAO contains 18 C, its entropy is lower than
that of DMAP (16 C) due to the presence of double bond that cause
some restricted movement of the SAA molecule. The free energy of for-
mation of all studied SAAs has negative value indicating the spontane-
ous formation of these SAAs. The DMAO has the most negative value
of (ΔGformation) indicating that, it is the most spontaneously formed
SAA. Also, it was shown from the calculations that thermodynamic pa-
rameters at any temperature (for example 100 °C) followed the same
as order as that obtained at zero Kelvin degree (Table 7).
The highest occupied molecular energy (HOMO) and the lowest un-
occupied molecular orbital energy (LUMO) were visualized from the
chk files while Mulliken charge population analysis (atomic charge cen-
ters) obtained from the LOG files of the optimized structures of SAAs
molecules using Gaussian 09 software program. The wave functions of
the frontier molecular orbitals (HOMO and LUMO) orbitals (of the opti-
mized geometries) and Mulliken charges are given in Figs. 5 and 6.
All the bond lengths, dihedral angles and the bond angles (Appendix
I) confirmed the suggested molecular chemical structures of the SAA
molecules. These suggested chemical structures were further confirmed
by simulation of the theoretical IR spectra (Fig. 7A) of the SAA using Td-
DFT theory in the vibrational mode [109].
On comparison of these simulated theoretical FTIR spectra of the sur-
factant molecules with their experimental FTIR spectra (Figs. 1a and S1–
11
Journal of Molecular Liquids 328 (2021) 115421
S2 (supporting information)). The former spectra nearly showed the
same characteristic bands at approximately the same wave numbers
(ν, cm−1) looks like the experimental FTIR spectra. This finding reflects
the correct suggested chemical structure of the surfactant molecules
based on the experimental spectroscopic methods (FTIR and 1HNMR).
To determine the possible adsorption sites of these SAA, the related
wave functions of the (HOMO) and (LUMO) orbitals were analyzed. As
shown in Fig. 5b, the HOMO wave function is mainly located on the ter-
minal nitrogen atoms of the three SAAs molecules; however, it becomes
more localized around the terminal nitrogen on going from DMAC to
DMAO SAA. While the wave function of LUMO located mainly around
the amide group in all SAAs molecules, its localization follows the
same order of HOMO, but it is populated around the double bond in
DMAO. The Mulliken population analysis (Fig. 6) is conducted mostly
for calculating the charge distribution over the whole molecule skeleton
[109,110]. Fig. 6, showed that the heteroatoms (O, N (amide) and N ter-
minal have the highest values of the atomic charges suggesting that the
adsorption center in each surfactant molecules is mainly located among
these atoms. It is clear that the terminal nitrogen is the most probable
adsorption center in each SAA molecule. Mulliken charges on this nitro-
gen atom are mainly synergistically enhanced by the presence of double
bond in DMAO.
Fig. 7B, shows the energy level diagrams of the electronic occupation
to the molecular energy levels of the SAA molecules obtained by solving
the time independent Schrodinger equation for a particle in one-
dimension box.
Some of the global reactivity indicators are directly extracted from
the output files of Gaussian energy calculation such as: EHOMO, ELUMO
and μ, while other parameters were extracted mathematical using the
following equations [111,112].
Ionization energy : IE ¼ −EHOMO ð18Þ
Electron affinity : EA ¼ −ELUMO ð19Þ
Energy gap : ΔE ¼ ELUMO −EHOMO ð20Þ
−1
Electronegativity : χ ¼ ðEHOMO þ ELUMO Þ ð21Þ
2
−1
Hardness : η ¼ ðEHOMO −ELUMO Þ ð22Þ
2
−2
Softness : σ ¼ ð23Þ
EHOMO −ELUMO
Pi 2
Electrophilicity : ω ¼ ð24Þ
2η
The quantum chemical parameters (Table 8), provide the expecta-
tion about the performance of the synthesized non-ionic surfactants
DMAC, DMAP and DMAO molecules. The EHOMO is associated with the
electron donating ability, where the HOMO level is the regions of the
highest electron density at which electrophiles attack and represent
the active centers with highest ability to form a bond with the metal
surface, and the greater high level offering ability of free electrons to
the unoccupied d-orbital of steel and consequently the higher inhibition
efficiency of steel corrosion. The unfilled 3d-orbital of Fe atoms could
bind with HOMO of the DMAC, DMAP and DMAO [113], while the 4 s-
orbital of steel surface could donate the electrons to LUMO energy
level of the DMAC, DMAP and DMAO. So, the adsorption of DMAC,
DMAP and DMAO on the C-steel surface may be due to the interaction
between 3d,4 s orbitals of Fe and the frontier molecular orbitals of
SAA molecule [114]. The lower the value of ELUMO, the more probability
of the surfactant molecules to accept electrons from C-steel surface, as
the energy gap (ΔELUMO-HOMO) decreased, and the inhibition efficiency
of steel corrosion increased.
A.A. Taha, S.M. Shaban, H.A. Fetouh et al.
Fig. 5. (A) The optimized molecular structures of (a) DMAC (b) DMAP (c) DMAO. (B) HOMO and LUMO wave functions of studied SAA (a) DMAC, (b) DMAP, (c) DMAO.
Based on the parameters summarized in Table 8, the calculated
EHOMO values of DMAO, DMAP and DMAC are −5.85, −5.86
and − 5.87 eV. The quite difference among the calculated values for
the three studied SAA revealed that the charge (electron) donation abil-
ity of these SAA cannot be used for explaining why the DMAO could ef-
fectively inhibit the steel dissolution more than DMAP and DMAC.
DMAO has the lowest LUMO energy revealing its higher ability to get
electrons via the anti-bonding orbital of Fe surface. Moreover, DMAO
12
Journal of Molecular Liquids 328 (2021) 115421
has the lowest ΔE values which correspond to higher stability of [Fe-
DMAO] charge transfer complex.
The HOMO and LUMO energy level diagram regarding to the tested
DMAO, DMAP and DMAC (Fig. 5B), reflect the orbital electron densities
were distributed homogenously throughout the molecules. Hence Mulli-
ken atomic charges (Fig. 6) had conducted to describe the inhibition ap-
proach induced via the synthesized SAA. There are a satisfactory
correlation between the inhibition efficiency of DMAO, DMAP and DMAC
A.A. Taha, S.M. Shaban, H.A. Fetouh et al. Journal of Molecular Liquids 328 (2021) 115421

Fig. 6. Mulliken Population analysis (a) DMAC (b) DMAP (c) DMAO.

Fig. 7. (A) The theoretical vibration spectra of the SAA. (B) The energy level diagrams for the electronic distribution in the SAA molecules DMAC, DMAP & DMAO.

13
A.A. Taha, S.M. Shaban, H.A. Fetouh et al. Journal of Molecular Liquids 328 (2021) 115421

Table 8 The electronegativity (χ) of the synthesized non-ionic surfactant

Quantum chemical parameters of synthesized SAA. SAA is observed in the order: DMAO > DMAP ≈ DMAC, where the
SAA DMAC DMAP DMAO low χ of SAAs molecules reflect the corresponding high inhibition effi-
Total Energy (ev) −56,338.62 −83,927.21 −90,090.63
ciency of steel corrosion.
E HOMO (ev) −5.87 −5.868 −5.85 The absolute hardness (η) refer to the resistance toward the defor-
ELUMO (ev) 0.80 0.79 0.77 mation or polarization of the electron cloud of the SAA inhibitor mole-
ΔE (ev) 6.67 6.65 6.63 cules, while the softness (σ), is a property of these synthesized
TNC −4.53 −6.56 −6.879
inhibitors that measures the molecular reactivity extent. The hardness
χ (Electronegativity)(ev) 2.538 2.538 2.54
Pi(Chemical potential) (ev) −2.539 −2.5385 −2.544 and softness are connected with Lewis theory of acids and bases and
η (Hardness) (ev) 3.34 3.33 3.31 Pearson's hard and soft acids and bases [115]; a hard molecule charac-
σ (Softness) (ev−1) 0.29 0.30 0.31 terized with large ΔELUMO-HOMO, while the soft one is that has a smaller
ω (Electrophilicity) (ev) 0.96 0.97 0.98 ΔE. Based on the simplicity of donating electron by soft molecules to
μ (Dipole moment) (debye) 3.36 3.157 3.272
an acceptor partner, a greater interaction with soft C-steel surface
than does the hard one. EP process involve dissolution of C-steel surface
in the acidic medium, the inhibitor and the metal act as Lewis base
and the total negative charge (TNC) of SAA molecule, where the more neg- and Lewis acid respectively. Since C-steel surface is soft acids therefore
ative the atomic charges of the adsorbed inhibitors, the higher is TNC, soft inhibitors are most effective for corrosion of those metals in the
which promote the adsorption process induced by SAA and enhancing acidic medium. The order of the studied SAA according softness was
the inhibition efficiency to steel corrosion during electropolishing. The found to be: DMAO > DMAP > DMAC. This trend supports the inhibition
calculations showed that the TNC values increase in the order: DMAC < efficiencies obtained from the employed electrochemical method
DMAP < DMAO, which supports the sequence of the increase of the inhi- (Table 3).
bition efficiencies obtained from galvanostatic method (Table 3). These re- The softness is closely related to the polarizability of SAA molecule;
sults clarify the strong dependence of the inhibition efficiency on TNC of DMAO (softer inhibitor) has the smaller ΔE which promotes easier po-
the studied SAAs. larization and thus more reactivity. The electrophilicity index (ω)

Fig. 8. Densities of states (DOS) of studied DMAC, DMAP and DMAO.

14
A.A. Taha, S.M. Shaban, H.A. Fetouh et al.
introduced by Parr [116] outline the SAA inhibitors ability toward ac-
ceptance of the electrons from the metal surface and reflecting the sta-
bilization in energy when the system acquires an additional electronic
charge from the environment. It provides insight about the nucleophilic
or electrophilic nature of the tested SAA inhibitors. A good electrophilic
is recognized by high value of chemical potential and the electrphilicity,
while a good nucleophilic has low value of both parameters. In this
study DMAO is the strongest electrophile.
The low dipole moment (μ) indicating the more ability toward accu-
mulation of the inhibitor molecules on the metal surface. The parameter
μ is the first derivative of the energy regarding to an applied electric
field. There is a lack of agreement in the literature studies on the corre-
lation between the dipole moment and the inhibition efficiency [117].
The results recorded in Table 8 indicate that no significant relationship
Fig. 9. SEM of the surface morphology before and after EP at 288 °K in the absence and presence of SAA.
15
Journal of Molecular Liquids 328 (2021) 115421
was recorded between the inhibition efficiency of the studied SAA and
the dipole moment values.
The densities of states (DOS) as well as Fermi levels of the SAA
molecules were calculated by applying Gauss Sum 2.2.5 program to
the optimized molecular of the SAA [118] at B3LYP/SDD level of theory.
Fig. 8 showed the DOS of surfactant DMAC, DMAP and DMAO as the
numbers of states per interval of energy at each energy level, which
are available to be occupied by the electrons. DMAO is the most favor-
able electron donor molecule. A high DOS at a specific energy level
means that there are many states available for occupation by the elec-
trons, hence scales of DOS varies linearly with the electron donation
ability of SAA molecules. The DOS becomes more abundant near Fermi
levels on going from DMAC to DMAO i.e. the trend of increasing DOS fol-
lows the order: DMAO >DMAP >DMAC.
A.A. Taha, S.M. Shaban, H.A. Fetouh et al.
The extra deep values of DOS observed in DMAO reflect the more
confined the electron density and the lower ΔELUMO-HOMO appears
from DOS is strong confirmation of the greater inhibition efficiency to-
ward the corrosion of C-steel during electropolishing.
3.7. Surface characterization
3.7.1. SEM
The surface morphology of the C-steel specimens before and after EP
at 15 °C for 10 min in the absence and presence of the synthesized non-
ionic SAA is shown in the Fig. 9. Fig. 9a shows C-steel surface before EP at
magnification of 5000, which show the badly damaged and rough sur-
face for raw C-steel surface, because of severe damage, clear pits and
cavities. The surface heterogeneity is markedly observed. Inspections
of the polished C-steel sample in 8 M H3PO4 solution (Fig. 9b), the sur-
face morphology improved markedly; with little pits and cracks
Fig. 10. AFM images before and after EP at 288 °K in the absence and presence of SAA.
16
Journal of Molecular Liquids 328 (2021) 115421
observed in the polished surface. Fig. 9c, reveals the surface on C-steel
after EP in 8 M H3PO4 solution containing 5 mM DMAC, outlining a grad-
ual surface enhancement with more a uniform structure morphology
than blank as confined via absence of pits, cracks as well as grooves.
As represented in Fig. 9d, the surface morphology was markedly get bet-
ter via addition of 5 mM from the DMAP inhibitors, where the grooves
and grain boundaries are filling up with eliminating the etching effect.
Finally the Fig. 9e, provide a well-polished surface as a result of adding
of 50 mM from the DMAO inhibitor, where the grain boundaries are
clearly disappeared with a smooth and bright surface is attained. The
improving the surface morphology as a results of addition the synthe-
sized SAA inhibitors onto the steel surface is attributed the well adsorp-
tion induced on the surface. This behavior confirms the highest IE
recorded for DMAO using electrochemical and chemical techniques.
By comparing the effect of the three SAA, it is noticed that, the well-
polished and uniform C-steel surface are obtained by addition of
A.A. Taha, S.M. Shaban, H.A. Fetouh et al.
Fig. 11. Reflectance diagram of electropolished specimens in the absence and presence of 5х10−3M concentration of the synthesized SAA.
5 × 10−3 M where completely smooth, even and uniform surface are ob-
tained and this behavior confirmed the data obtained from polarization
and weight loss method.
3.7.2. AFM
The microstructure characterization of the C-steel surface has been
conducted via two-dimensional and three-dimensional images AFM,
before and after electropolishing without and with SAA are given in
Fig. 10., as outlined from the extracted data in Table S3 (supporting in-
formation), the addition of the synthesized DMAC, DMAP and DMAO
into the aggressive solution, induce a decreasing the surface roughness
of the immersed steel. On inspection the Table S3 (supporting informa-
tion), it show highest surface roughness (Ra) of 177.9 for raw steel, and
electropolished C-steel has 8 M H3PO4 solution has Ra of 154.7 nm. The
addition of the synthesized SAA inhibitor induce markedly reduction Ra
as outlined in Table S3 (supporting information), with best reduction in-
duced by the DMAO inhibitor as confined in the Fig. 10.
3.7.3. Gloss value (brightness)
It is seen that the brightness and reflectance of the carbon steel be-
came enhanced upon treating with DMAC, DMAP and DMAO as
outlined in the Table S3 (supporting information).
The addition of the synthesized non-ionic SAA, lead to controlling
the corrosion of C-steel in H3PO4 acid. It is notable that the adsorption
of the three studied SAA, enhance the action of the normal anodic film
in improving the microstructure of the surface. The UV–Vis spectra of
untreated C-steel specimen that EP in 8 M H3PO4 (blank) and C-steel
that EP in 8 M H3PO4 electrolyte containing 5 mM of different SAA is
shown in Fig. 11, where the reflectance of the specimen that
electropolished at 8 M H3PO4 became enhanced compared with that
treated with the synthesized SAA inhibitors, so the reflectance of treated
specimens is relevant to the adsorption of SAA of the surface of steel.
The value of the specular reflectance is 6.126 before EP, while 19.187
is after EP. The addition of 5 mM of DMAC, DMAP and DMAO enhance
the degree of surface reflectance into 24.145, 33.399 and 36.735
respectively.
The inhibitory effect of the synthesized non-ionic surfactants for C-
steel dissolution in 8 M H3PO4 solution was comparatively and even bet-
ter than those of previously reported inhibitors at the same condition
[13–15] (Table S4, supporting information). That may be due to SAA
properties, SAA are bifunctional molecules, they will diffuse out of the
bulk H2O phase and adsorb at the interfaces between steel and H3PO4
corrosion medium. Also, they have the ability to orient themselves at
the interfaces; therefore can give better corrosion inhibition efficiencies.
The highest inhibition was achieved by SAA compared to that obtained
by lawsonia plant extract; tri-ethanol amine and valsartan drug
(Table S4, supporting information).
17
Journal of Molecular Liquids 328 (2021) 115421
4. Conclusions
Three non-ionic surfactants were synthesized via one click
amidation chemistry and their chemical structure was confirmed via
FTIR and 1HNMR spectroscopy. The surface and thermodynamic param-
eters of the synthesized SAA were determined from the surface tension
measurement. The affinity of the prepared SAA toward adsorption and
micellization process were enhanced as functional of increasing the so-
lution temperature and increasing the hydrophobic character of surfac-
tant. Galvanostatic polarization and weight loss measurements show
that synthesized SAA surfactants have good inhibition properties for
the dissolution of steel in 8 M H3PO4 acid, revealing high adsorption ten-
dency of the steel surface that follow Langmuir isotherm. The hydro-
phobic tail of the synthesized non-ionic surfactant are controlling in
their performance as effective corrosion inhibitors, where the order of
IE is: DMAO > DMAP > DMAC. SEM analysis, UV–Vis spectra and surface
roughness measurements revealed that; addition of 5×10−3 M of
DMAC, DMAP and DMAO to the electropolishing electrolyte is effective
to enhance the surface quality. In the presence of the prepared non-
ionic SAA, the solution appeared promising and a distinguished im-
provement in the finish was observed. The addition of the three synthe-
sized non-ionic surfactants induced a decreasing in the steel corrosion
rate and affected the quality of the electropolished steel.
CRediT authorship contribution statement
Asia A. Taha: Project administration, Funding acquisition, Investiga-
tion, Methodology, Writing - original draft, Writing - review & editing.
Samy M. Shaban: Data curation, Formal analysis, Investigation, Meth-
odology, Project administration, Funding acquisition, Resources, Writ-
ing - original draft, Writing - review & editing. H.A. Fetouh: Software,
Writing - original draft, Writing - review & editing. Salma T. Taha:
Data curation, Funding acquisition, Methodology, Software, Writing -
original draft. Dong-Hwan Kim: Project administration, Resources,
Writing - review & editing, Data curation, Funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
This work was supported by the National Research Foundation
of Korea (NRF) grant funded by the Korea government (MSIT)
A.A. Taha, S.M. Shaban, H.A. Fetouh et al. Journal of Molecular Liquids 328 (2021) 115421

(2020R1A5A1018052) and the Ministry of Education, Science and Tech- the support from the Egyptian petroleum research institute and Alexan-
nology (NRF-2018R1D1A1B07041584). We would like to acknowledge dria university.

Appendix A. Supplementary data

Supplementary data to this article can be found online at https://doi.org/10.1016/j.molliq.2021.115421.

Appendix I

DMAC

Row Tag Symbol NA NB NC Bond Angle Dihedral

1 1 C
2 2 C 1 1.532357
3 3 H 1 2 1.097194 111.1391
4 4 H 1 2 3 1.097155 111.1136 119.7174
5 5 C 2 1 4 1.534094 113.2015 59.87719
6 6 H 2 1 5 1.099417 109.4229 −122.048
7 7 H 2 1 5 1.09938 109.4496 122.0906
8 8 C 5 2 1 1.534108 113.6228 −179.726
9 9 H 5 2 1 1.100377 109.188 58.00342
10 10 H 5 2 1 1.100331 109.1715 −57.5256
11 11 C 8 5 2 1.534155 113.4091 179.8914
12 12 H 8 5 2 1.100184 109.2343 57.78312
13 13 H 8 5 2 1.100082 109.3124 −57.9142
14 14 C 11 8 5 1.533247 113.3239 −179.69
15 15 H 11 8 5 1.100166 109.3285 58.20747
16 16 H 11 8 5 1.099983 109.2294 −57.4909
17 17 C 14 11 8 1.535655 112.7695 179.8184
18 18 H 14 11 8 1.099117 109.4805 57.97992
19 19 H 14 11 8 1.09646 110.0475 −58.7291
20 20 C 17 14 11 1.525213 112.4274 176.1607
21 21 H 17 14 11 1.099122 109.2867 57.53585
22 22 H 17 14 11 1.096692 110.3221 −59.4061
23 23 O 20 17 14 1.234945 121.8097 −46.3208
24 24 N 20 17 14 1.360756 115.4926 133.773
25 25 C 24 20 17 1.455668 123.5791 176.2948
26 26 H 24 20 17 1.011035 118.3554 1.953096
27 27 C 25 24 20 1.537331 111.9052 −102.911
28 28 H 25 24 20 1.095504 109.3425 135.9135
29 29 H 25 24 20 1.0913 106.4871 19.13201
30 30 N 27 25 24 1.462944 112.5321 −174.772
31 31 H 27 25 24 1.10796 109.1292 59.96885
32 32 H 27 25 24 1.096629 108.1397 −55.8215
33 33 C 30 27 25 1.461397 112.3539 −72.7594
34 34 H 33 30 27 1.093728 110.694 59.3619
35 35 H 33 30 27 1.10747 112.7561 −61.8034
36 36 H 33 30 27 1.095148 109.4478 177.9555
37 37 C 30 27 25 1.460664 111.1917 162.9262
38 38 H 37 30 27 1.095185 109.8728 −58.0639
39 39 H 37 30 27 1.095487 109.551 −176.83
40 40 H 37 30 27 1.107236 113.1463 62.81511
41 41 H 1 2 5 1.09623 111.4443 −179.985
DMAP

Row Tag Symbol NA NB NC Bond Angle Dihedral

1 1 C
2 2 C 1 1.532322
3 3 H 1 2 1.097232 111.1259
4 4 H 1 2 3 1.097209 111.145 −119.715
5 5 H 1 2 3 1.096252 111.4511 120.1326
6 6 C 2 1 5 1.534145 113.2486 −179.986
7 7 H 2 1 6 1.099435 109.4231 −122.071
8 8 H 2 1 6 1.099402 109.4427 122.0828
9 9 C 6 2 1 1.53411 113.6246 −179.936
10 10 H 6 2 1 1.100414 109.1711 57.82122
11 11 H 6 2 1 1.100444 109.1614 −57.6744
12 12 C 9 6 2 1.53424 113.5747 −179.827
13 13 H 9 6 2 1.100318 109.2296 57.94164
14 14 H 9 6 2 1.100331 109.2343 −57.6449
15 15 C 12 9 6 1.534295 113.6158 179.9834
16 16 H 12 9 6 1.100304 109.2181 57.79319
17 17 H 12 9 6 1.100307 109.2326 −57.7766
18 18 C 15 12 9 1.534251 113.5459 −179.695
19 19 H 15 12 9 1.100293 109.2452 58.06731
20 20 H 15 12 9 1.100313 109.2405 −57.5328
21 21 C 18 15 12 1.534301 113.6297 179.9863
22 22 H 18 15 12 1.100312 109.209 57.79972

18
A.A. Taha, S.M. Shaban, H.A. Fetouh et al. Journal of Molecular Liquids 328 (2021) 115421

(continued)

DMAP

Row Tag Symbol NA NB NC Bond Angle Dihedral

23 23 H 18 15 12 1.10031 109.2362 −57.765

24 24 C 21 18 15 1.534253 113.5307 −179.589
25 25 H 21 18 15 1.100287 109.2502 58.17003
26 26 H 21 18 15 1.10031 109.2439 −57.438
27 27 C 24 21 18 1.534292 113.6331 −179.947
28 28 H 24 21 18 1.100304 109.2049 57.86559
29 29 H 24 21 18 1.100299 109.2389 −57.7006
30 30 C 27 24 21 1.534238 113.5059 −179.496
31 31 H 27 24 21 1.10026 109.2537 58.27166
32 32 H 27 24 21 1.100283 109.2543 −57.3538
33 33 C 30 27 24 1.534235 113.6004 −179.801
34 34 H 30 27 24 1.100251 109.2126 58.01658
35 35 H 30 27 24 1.100237 109.2491 −57.5788
36 36 C 33 30 27 1.534226 113.4292 −179.383
37 37 H 33 30 27 1.100106 109.2888 58.43686
38 38 H 33 30 27 1.100147 109.2821 −57.2683
39 39 C 36 33 30 1.533155 113.2608 −179.396
40 40 H 36 33 30 1.099999 109.2361 58.33884
41 41 H 36 33 30 1.100147 109.3304 −57.376
42 42 C 39 36 33 1.5359 112.9066 −179.452
43 43 H 39 36 33 1.096534 109.9756 59.21645
44 44 H 39 36 33 1.099176 109.5297 −57.5113
45 45 C 42 39 36 1.52503 112.252 −174.602
46 46 H 42 39 36 1.096602 110.4371 60.85308
47 47 H 42 39 36 1.099017 109.2488 −56.2032
48 48 O 45 42 39 1.235208 121.716 47.96862
49 49 N 45 42 39 1.360185 115.6797 −133.258
50 50 C 49 45 42 1.45573 123.334 −179.469
51 51 H 49 45 42 1.010802 118.568 3.90297
52 52 C 50 49 45 1.537372 112.1063 −99.8975
53 53 H 50 49 45 1.095165 109.1396 138.8756
54 54 H 50 49 45 1.091452 106.6185 22.11351
55 55 N 52 50 49 1.463213 112.4747 −175.37
56 56 H 52 50 49 1.10778 109.0706 59.47325
57 57 H 52 50 49 1.096512 108.1835 −56.3658
58 58 C 55 52 50 1.461369 112.3702 −72.3821
59 59 H 58 55 52 1.093696 110.7376 59.87404
60 60 H 58 55 52 1.107522 112.7655 −61.3364
61 61 H 58 55 52 1.0951 109.397 178.4442
62 62 C 55 52 50 1.460729 111.1716 163.3609
63 63 H 62 55 52 1.095207 109.8787 −58.0543
64 64 H 62 55 52 1.095522 109.5542 −176.823
65 65 H 62 55 52 1.107254 113.1354 62.83635
DMAO

Row Tag Symbol NA NB NC Bond Angle Dihedral

1 1 C
2 2 C 1 1.541424
3 3 C 2 1 1.533773 113.4624
4 4 H 2 1 3 1.099159 108.8807 −122.161
5 5 H 2 1 3 1.099824 109.1827 122.3273
6 6 C 3 2 1 1.534281 113.2051 −179.881
7 7 H 3 2 1 1.100169 109.3899 57.88058
8 8 H 3 2 1 1.100141 109.231 −57.8808
9 9 C 6 3 2 1.534191 113.638 178.6479
10 10 H 6 3 2 1.100088 109.2004 56.57577
11 11 H 6 3 2 1.100082 109.2413 −59.036
12 12 C 9 6 3 1.533201 113.0141 −179.777
13 13 H 9 6 3 1.099954 109.3785 57.94373
14 14 H 9 6 3 1.10012 109.3152 −57.8733
15 15 C 12 9 6 1.535543 113.0702 179.2078
16 16 H 12 9 6 1.096448 109.9421 57.87554
17 17 H 12 9 6 1.099104 109.4847 −58.7214
18 18 C 15 12 9 1.525518 112.1346 −175.153
19 19 H 15 12 9 1.096633 110.5232 60.52264
20 20 H 15 12 9 1.099114 109.2663 −56.5906
21 21 O 18 15 12 1.235368 121.9342 45.4615
22 22 N 18 15 12 1.359463 115.7635 −134.404
23 23 C 22 18 15 1.457189 122.8287 −177.483
24 24 H 22 18 15 1.010496 118.6678 −3.20001
25 25 C 23 22 18 1.537478 112.2786 85.66629
26 26 H 23 22 18 1.092759 108.0777 −34.7499
27 27 H 23 22 18 1.093375 107.5868 −151.333
28 28 N 25 23 22 1.463706 112.5388 −177.125

(continued on next page)

19
A.A. Taha, S.M. Shaban, H.A. Fetouh et al. Journal of Molecular Liquids 328 (2021) 115421

(continued)

DMAO

Row Tag Symbol NA NB NC Bond Angle Dihedral

29 29 H 25 23 22 1.108111 109.5381 57.5297

30 30 H 25 23 22 1.095217 107.3973 −58.3371
31 31 C 28 25 23 1.461086 112.4398 −73.8434
32 32 H 31 28 25 1.093699 110.74 59.25423
33 33 H 31 28 25 1.107664 112.7869 −61.9389
34 34 H 31 28 25 1.095189 109.429 177.8244
35 35 C 28 25 23 1.460627 111.1819 161.8554
36 36 H 35 28 25 1.095147 109.8955 −58.0743
37 37 H 35 28 25 1.095573 109.5516 −176.88
38 38 H 35 28 25 1.107347 113.1362 62.80913
39 39 C 1 2 3 1.505603 112.7279 179.9946
40 40 H 1 39 2 1.098488 109.6953 122.3094
41 41 H 1 39 2 1.101221 109.7557 −120.946
42 42 C 39 1 2 1.337087 125.3595 −117.082
43 43 H 39 1 2 1.09311 115.8596 61.4146
44 44 C 42 39 1 1.505527 125.6221 177.2179
45 45 H 42 39 1 1.093149 118.6518 −1.10032
46 46 C 44 42 39 1.541162 112.5287 −116.544
47 47 H 44 42 39 1.101192 109.6895 122.6702
48 48 H 44 42 39 1.098418 109.8487 5.84251
49 49 C 46 44 42 1.534172 113.6316 −178.009
50 50 H 46 44 42 1.099168 108.8539 59.64481
51 51 H 46 44 42 1.099856 109.0991 −55.7803
52 52 C 49 46 44 1.534037 113.1313 −179.736
53 53 H 49 46 44 1.100194 109.3153 58.13326
54 54 H 49 46 44 1.100157 109.3434 −57.655
55 55 C 52 49 46 1.534533 113.7706 179.8852
56 56 H 52 49 46 1.100227 109.1649 57.65473
57 57 H 52 49 46 1.100233 109.1685 −57.8481
58 58 C 55 52 49 1.533958 113.3845 −179.938
59 59 H 55 52 49 1.10028 109.2987 57.89242
60 60 H 55 52 49 1.100263 109.2883 −57.801
61 61 C 58 55 52 1.534378 113.6783 179.9267
62 62 H 58 55 52 1.100426 109.2494 57.72522
63 63 H 58 55 52 1.100406 109.2486 −57.8623
64 64 C 61 58 55 1.532246 113.2009 179.9801
65 65 H 61 58 55 1.099435 109.2086 57.77948
66 66 H 61 58 55 1.099395 109.2113 −57.8308
67 67 H 64 61 58 1.097204 111.1227 −59.8529
68 68 H 64 61 58 1.096226 111.4514 179.9954
69 69 H 64 61 58 1.097196 111.1255 59.84922

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