Newly Synthesized Azo Derived from Coumarine as Analytical Reagent and Metallic Corrosion Inhibitor

doi:10.21203/rs.3.rs-2070412/v1

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Newly Synthesized Azo Derived from Coumarine as Analytical Reagent and Metallic Corrosion Inhibitor

https://doi.org/10.21203/rs.3.rs-2070412/v1

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A new Coumarine derivatives azo dye; 8-(3-phenyl-5-pyrazolylazo)-7-Hydroxy-4-Methyl Coumarine were synthesized. The effect of pH on the spectra of the synthesized ligand, the chromogenic reaction and the stability constant of Co^+ 2, Cu^+ 2, Ni^+ 2, and Zn^+ 2 ion complexes with the synthesized ligand were studied and determined conductmetrically and spectrophotometrically. The optimum pH was determined for the complexes. 1:1and 2:1(L:M) stoichiometric complexes has been formed in solutions. The order of the stability constants of the complexes under study was; Co^+ 2<Ni^+ 2< Cu^+ 2. These metal ions were determined using the ligand as indicator. The ligand can be used as acid-base indicator. The ability of controlling corrosion of carbon steel in 1M of acidic solution of hydrochloric was electrochemically proven at room temperature. The inhibition indicated with different tests including Open circuit potential (OCP), Potentiodynamic Polarization (PP) and Electrochemical Impedance Spectroscopy (EIS) tests. The adsorption of inhibitor indicated from PP test followed Longmuir isotherm. Adsorption constant and Gibbs free energy were also calculated and explained.

Spectrophotometrically

Conductmetrically

Coumarine derivatives

Inhibition

Coumarins, (2H-1-benzapyran 2-one) are known for their physiological and fluorescent properties [1&2]. Coumarine derivatives drew the attention of many investigators due to their antifungal and antiviral activity [3&4]. 7-hydroxy Coumarine and its metal complexes with some metals show significant antitumor, antimicrobial and coagulant activities [5-9]. The Coumarine containing heterocyclic nucleus has important in organic, medicinal and physical chemistry. They are used as a food additives, perfumes, plastics [10], fluorescent brightening [1& 10], laser dyes [11]and corrosion inhibitor for some metals [12-16].

5-pyrazolone derivatives have found wide applications as cotton azo dyes [17]. Poddar et al. review the analytical applications of these compounds [18]. The complexes of 3-amino-5-phenylpyrazole with some transition metals studied by Jacimovic and Bogdanović et. al. [19& 20]. Some azo dyes of aminopyrazole were used for spectrophotometric determination of some transition metals [21, 22, 23]. Also, some arylaminopyrazole were used for spectrophotometric determination of Cu and Pd metal ions [24].

The present investigation deals with studying the conductometric and spectrophotometric properties of 8-(3- Phenyl-5-Pyrazolylazo)-7-Hydroxy-4-Methyl Coumarine for the determination of Co⁺², Ni⁺², Cu⁺² and Zn⁺². Also the work aims to study using this ligand in the micro-determination of these metal ions using EDTA titration and as acid-base indicator. The application of this ligand as a corrosion inhibitor for carbon steel in 1M hydrochloric acid solution was also discussed. Some Adsorption parameters were also reported.

2.1. Materials and solutions:

The chemicals used were all of highest available purity as shown in Table 1. Doubly distilled water was used for preparation of different solutions. The buffers used were the modified Britton and Robinson universal series (PH 2–12) [25].

Table 1

The reg. CAS number, the supplier, the purity and the purification methods for the chemical compounds used
Compound	Reg. CAS Number	Suppliers	%Purity before purification	Purification method	%Purity before purification
CoCl₂.6H₂O	7791-13-1	Alpha hemika, USA	(99.0%)	The compounds were used without further purification	(99.0%)
NiCl₂.6H₂O	7718-54-9	Alpha chemika, USA	(98.0%)		(98.0%)
CuCl₂.6H₂O	744-39-4	Nile Co., egypt	(97.8%)		(97.8%)
ZnCl₂	7646-85-7	Techno pharmchem	(97.0%)		(97.0%)
Ethanol	64-17-5	Sigma Aldrich	(97.8%)		(97.8%)
Hydrochloric acid	7647-01-0	Merck	(37%)		(37%)

Hydrochloric acid was stocky prepared with concentration 5M then diluted using bi-distilled water to 1M used as acidic corrosive solution for C-Steel. The ligand solutions were prepared in concentration ranged from 30 to 150 µM by diluted the ligand stock solution with bi-distilled water.

2.2. Apparatus:

The IR spectra were recorded (in potassium bromide discs) with PYE unicame 1200 and UV-VIS 550 Jasco spectrophotometer was used to obtain the absorption spectra. The conductometric measurements were carried out using a conductivity bridge of a type (JENWAY).

Three fitted electrodes cell included carbon steel cylinder piece with 0.5 cm² surface area fitted in glass cover with epoxy resin as a working electrode, a platinum wire attached to copper wire and both wires fitted in glass cover used to supply current as a counter electrode and saturated calomel electrode was used as a reference electrode. Several degree of emery paper ranged from 400 to 1200 used to decrease roughness of steel surface before start any experiments, washed and degreased with water and acetone then dried.

All electrochemical tests were managed used potentiostat/galvanostat/ ZRA (Gamry Reference 3000), and Gamry Echem Analyst software 6.33 was used for correct data at room temperature. Where the working electrode started to fitting against steady-state potential for 20 minutes then the potential changed around OCP in ± 250 mV range in potentiodynamic polarization test. The current with different frequency ranged from 100 kHz to 0.2 Hz with an amplitude of 10 mV was applied at OCP in EIS test.

2.3. Preparation of ligand:

5–amino-3-phenyl pyrazole was prepared as following: The Phenathyl bromide prepared by bromination of acetophenone was changed to the cyano derivative and the latter was treated with hydrazine hydrate to give the proposed amine [26]. The azo dyes under investigation were prepared by coupling the diazotized amine with the couplers in sodium hydroxide solution [27]. The crude dyes were crystallized from ethanol. The IR spectra of the ligand is shown in Fig. 1. The elemental analysis for the ligand gives: Calculated: C 48%, H 3%, N 12.1% and found C 47.9%, H 2.9%, N12.2%. 22.4%. The band assignment of IR bands for ligand is represented in Table 2.

Table 2: The band assignment of IR bands for ligands L₁ and L₂

The confirmed structure of the prepared ligand is as in Structure 1.

8-(3- Phenyl-5-Pyrazolylazo)-7-Hydroxy-4-Methyl Coumarine

Structure 1

The 0.001M solution of ligand was prepared by dissolving the accurately weighed amounts in requisite volume of ethanol. Solutions of CuCl₂.6H₂O, CoCl₂.6H₂O, NiCl₂.6H₂O and ZnCl₂ are prepared and standardized by recommended methods [28]. The conductometric titration was done by tacking 0.025 M ligand as titrant solution and 0.0025 M metal ion as titrated solution. The potentiometric titration was done as reported in [29].

3.1. Conductometric determination of the stability constants:

The conductometric titration was carried out as explained in the experimental section and the molar conductance (Λ) was calculated. The specific conductance values were found to be generally decreased as the ligand added to the metal ion solution (Co^+ 2,Ni^+ 2, Cu^+ 2 and Zn^+ 2). This is due to the complexation of the ligand with metal ion in solution. The plots of either the measured specific conductance, κ (µs cm^− 1) or the molar conductance (Λ) (S cm² mol^− 1) versus either the ml added from titrant (metal ion or ligand solution) or the ratio of ligand to metal ion concentrations [L]/[M] gives break in the specific conductance curve at 1:1(L:M) ratio (Fig. 2–5) indicating the formation of 1:1(L:M) stoichiometric complex [30& 31].

It will be known that the conductometric titration was used to evaluate the end point (neutralization point) in many acid-base neutralization reaction and precipitation ones. On the bases of the obtained results of the conductometric titration, we can conclude that the conductometric titration can be considered one of the important methods for standardization of transition metal cations using the investigated ligand and vice-versa. The conductometric standardization method was preferred than others because it need not special conditions such as (buffer solution, ionic strength and suitable indicator). It should be noticed that the concentration of the titrant solution (0.001) molar and the concentration of the titrated solution (0.0001) molar are the suitable concentrations which results in the proper values of specific conductance (not low value), hence decrease the error in the conductance measurements.

The formation constants (K_f) for 1:1 Ligand-metal ion stoichiometric complexes, was calculated as reported earlier [32& 33]. The values of the formation or stability constants calculated by conductance measurements are presented in Table 3.

Table 3

The formation constant of the formed complexes in solution from conductometric and potentiometric measurements
Method	CoCl₂	NiCl₂	CuCl₂	ZnCl₂
Conductometric	7762	8128	9120	8710
Potentiometric	8165	8450	9533	8593

For ions of similar electronic configuration, the stability constants of complexes metal ions of the same charge should be inversely proportional to the metal ions radii. The order of the stability constants of the complexes under study was; Cu^+ 2 > Ni^+ 2 > Co^+ 2 [34].

3.2. Potentiometric determination of the stability constants:

The potentiometric titration was carried out as explained in the experimental section. The pH values were found to be generally decreased as the ligand added to the metal ion solution (Co^+ 2,Ni^+ 2, Cu^+ 2 and Zn^+ 2). This is due to the deprotonation of the ligand as a result of the complexation of the ligand with metal ion in solution and so consumes more NaOH solution (Fig. 6).

The values of the formation or stability constants from potentiometric measurements are represented in Table 3. The values of the formation or stability constants calculated by both methods (conductance and potentiometric measurements) are in agreement as represented in Table 3.

3.3. Acid–base equilibrium and ligand ionization constant:

Ligand is red–orange powder which soluble in water and its solution yellow in acidic medium and red- orange in alkaline one. The absorption spectra of ligand at different pH show in Fig. 7. The equilibrium of the dissociation for ligand can be shown as in Scheme 1.

The dissociation constants pK₂were evaluated spectrophotometrically by half height method and the values was found to be 10.50 for ligand. The change in color for this ligand occur in alkaline medium, so these reagents can be used as indicators in acid–base titration similar to phenolphthalein and cresol red indicators and give the same accuracy and precision. Examples for titrations using the ligand as indicators for some strong and weak acids with NaOH are shown in Table (4). The result indicate that the ligand give the same accuracy and precision for Phenolphthalein and cresol Red indicators.

Table 4

Examples for titrations using the ligand as indicator for some weak acids with 0.2 N NaOH comparing to phenolphthalein (Phph) and cresol red (C.R.) indicators
Acid indicator	Malonic acid 0.2 N			Oxalic acid 0.2 N			Acetic acid 0.2 N
Acid indicator	ligand	Phph	C.R.	ligand	Phph	C.R.	ligand	Phph	C.R.
x ± t_0.95. s_x	19.70 ± 0.014	19.59 ± 0.097	19.64 ± 0053	20.15 ± 0.014	20.07 ± 0.033	20.10 ± 0.044	20.90 ± 0.014	20.88 ± 0.069	20.87 ± 0.033
S	0.011	0.080	0.042	0.011	0.027	0.035	0.011	0.057	0.027
av. deviation	--	0.072	0.032	--	0.024	0.020	--	0.044	0.024
Maximum deviation	--	0.110	0.060	--	0.030	0.050	--	0.080	0.030
Acid indicator	benzoic acid 0.2 N			O-Phthalic acid 0.2 N			Tartaric acid 0.2 N
Acid indicator	ligand	Phph	C.R.	ligand	Phph	C.R.	ligand	Phph	C.R.
x ± t_0.95. s_x	19.94 ± 0.053	19.89 ± 0.053	19.91 ± 0069	21.25 ± 0.016	21.21 ± 0.053	21.18 ± 0.033	20.69 ± 0.033	20.61 ± 0.053	20.65 ± 0.016
S	0.042	0.042	0.055	0.006	0.019	0.009	0.027	0.042	0.011
av. deviation	0.024	0.032	0.048	--	0.032	0.024	0.024	0.032	--
Maximum deviation	0.060	0.060	0.060	--	0.060	0.030	0.030	0.060	--

3.4. Chromogenic reaction with metals ions:

3.4.1. Optimum pH and wavelengths:

The absorption spectra of all studies complexes were investigated at different pH values and (Figs. 8& 9 as examples). The optimum pH for developing the color of the complexes of ligand with Co^+ 2, Ni^+ 2, Cu^+ 2 and Zn^+ 2 ions and the maximum wavelengths are given in Table 5.

Table 5

The characteristic properties for 2:1 L-M complexes by molar ratio method
Metal ion	Optimum pH	Maximum λ	log β	εx10⁴ (L. mole^− 1 cm^− 1)	a (mL. g^− 1 cm^− 1)	sx10³ µg. cm^− 2
Co^+ 2	9	600	9.22	1.71	0.290	3.45
Ni^+ 2	5	550	8.75	1.74	0.296	3.38
Cu^+ 2	8	575	8.95	1.79	0.280	3.57
Zn^+ 2	7	550	8.94	0.67	0.100	10.00
S: Sandell sensitivity, a: Specific absorptivity, and ε: Molar absorptivity.

3.4.2. Beer's law:

Beer's law was verified and found to be satisfactory obeyed when the concentration up to 5.89, 2.95, 2.92, 5.88, ppm, for Co^+ 2, Ni^+ 2, Cu^+ 2 and Zn^+ 2 for ligand. Example for verification of Beer's law for the ligand was shown in Figs. 10&11.

3.4.3. Composition of the complexes:

The composition and apparent stability constant were evaluated by continuous variation [35] and molar ratio methods [36]. Both methods indicated the formation of 1:1 and 2:1(L:M) complexes. The stability constant for these complexes, log B was calculated [37& 38] from the molar ration (M.R.) and the continuous variation (C.V.) methods. The characteristic properties for complexes are given in Table 5 and shown in Figs. 12& 13.

The suggested structure of the formed stoichiometric complexes was represented in Scheme 2:

3.4.4. Applications as acid-base indicator:

In the alkaline range of pH, excluding some indicators such as Alizarine yellow, Nitramine and Tropacline, no excellent indicator substances have been found. The ligand has a great stability of red color, a charp change of transition interval of color and a remarkable shift of maximum wavelength. Change from pH 10 to pH 11, the color change from yellow to red.

Some examples for titrations of some weak acids with NaOH are shown previously in Table 4 which indicate that the ligand give the same accuracy and precision for Phenolphthalein and cresol Red indicators.

Recommended procedure for determinations of metal:

In 25-ml volumetric flask transfer a suitable aliquot solution containing up 20–30 mg of metal ions and add 1 m of 10^− 3M of dyes and 5ml of universal buffer of the recommended pH for each metal ions and completing the measuring flask with bi-distilled water. Measure the absorbance of the complex at λ_max for each metal against the reagent blank. Determine the concentration of the metal from the standard calibration curve obtained under the same conditions. The purposed methods has been successfully applied to the micro-determination of some metals such as Ni in some kind of alloys Ni chrome (III), Nickel and Cu in Coebronze using Spectrophotometric determination of the metals Co, Ni, Cu and Zn using the ligand as indicators. The method examined and was found to be accurate and highly reproducible as indicated by low standard deviations values calculated for 80 mg metal ions / 10 ml (10 determinations) amounting to 0.003. The method is useful for determination of Co (II) over a range 0.0-2.5ppm, Ni (II) over a range 0.0-2.5ppm, Cu (II) over a range 0.0-3.5ppm and Zn (II) over a range 0.0-2.5ppm.

3.5. Corrosion Inhibition Study (Electrochemical Techniques):

3.5.1. Open circuit potential test:

The following recordation simulates the Open Circuit potential of the steel electrode against time with and without different concentrations of the ligand (Fig. 14). The open-circuit potential at all concentrations of ligand ranged between 0 to 150 µM was reached the steady-state potential before starting any of the following tests. The electrode potential shifted into more negative potential with increasing in the addition of ligand concentration compared with electrode potential in blank solution. The electrode potential at blank solution equal − 369 mV while in ligand solutions ranged between − 370 and − 423 mV where the cathodic reaction controlled. This shifting can be explained according to the formation of protective film on the steel surface by adsorption of the ligand [39& 40].

3.5.2. Potentiodynamic Polarization test:

The effect of increasing the concentration of the ligand on the kinetics of the reaction at electrode/electrolyte interface was indicated in both cathodic and anodic directions. From the analysis of experimental data, the corrosion current density (i_corr), corrosion potential (E_corr), cathodic and anodic current density (β_a and β_c), inhibition efficiency (ⴄ), and surface coverage of ligand (θ) are summarized in Table 6. Tafel fit of PP curves (Fig. 15) indicated a decrease in the current density of corrosion as compared with a blank solution which proved a decrease in the rate of the kinetic reaction of corrosion. The adsorption of the ligand on a steel surface may block the active sites on steel and cause a decrease in the reaction between steel and corrosive medium. The Coumarine ligand ensures a mixed worked inhibitor which is indicated by comparison of corrosion potential at different concentrations of the ligand with corrosion potential of blank solution which is shifting in a small range located between 3 to 40 mV [41]. The mixed Working effect of inhibitors was indicated from changing in both slopes of both anodic and cathodic curves.

Table 6

**Data from PP test for corrosion of C-Steel in 1M HCL at different concentrations of Coumarine at 298 K**
comp. Name	Conc. µM	${{I}}_{{c}{o}{r}{r}}$ ${\mu }\mathbf{A} {\mathbf{C}\mathbf{m}}^{-2}$	$- {{E}}_{{c}{o}{r}{r}}$ ${\mu }\mathbf{V}$	${{\beta }}_{{a}}$ ${\mu }\mathbf{V}/{d}{e}{c}$ V/dec	${{\beta }}_{{c} }$ ${\mu }\mathbf{V}/{d}{e}{c}$ V/dec	$\%{\eta }$	${\theta }$
Blank	0.0	207	389.0	0.0990	0.2228	--	--
	30	50.2	383.0	0.0882	0.1961	75.75	0.76
	50	44.0	297.0	0.0952	0.1861	78.74	0.79
	70	42.9	426.0	0.1258	0.1684	79.28	0.79
	90	42.2	430.0	0.1390	0.1592	79.61	0.80
	150	38.8	392.0	0.0794	0.1890	81.26	0.81

3.5.3. Electrochemical Impedance Spectroscopy:

EIS test was carried out for CS corrosion in 1 M HCl in the presence and absence of ligand. Through the Nyquist plot (Fig. 16) and Bode plot (Fig. 17), the relationship between impedance of electrode and concentration of ligand are directly proportional. While reversibly proportional with capacitance of double layer, values of charge transfer resistance were found to be increased as the concentration of ligand increased. This proves the increase of adsorption of ligand on the surface of steel leading to an increase in diameter of resistance charge transfer through electrode and decrease in electrode capacitance. Fitting and analysis of impedance data was done by using CPE equivalent circuit. The efficiency of inhibition found to increase as increasing in concentration of ligand through increasing in thickness of electrode and resistance of charge transfer and decreasing in capacitance of double layer [42]. Charge transfer resistance, Capacitance of double layer, surface coverage and efficiency inhibition of ligand represented in Table 7.

Table 7

EIS parameter values of C-steel corrosion in 1M HCL without and with different concentrations of Coumarine at 298.15 K
comp. Name	Conc. ppm	${{R}}_{{p}}$ Ω cm²	${{C}}_{{d}{l}}$ µF cm^− 2	$\%{\eta }$	θ
Blank	0.0	69	70	--	--
	30	179.8	44.8	61.62	0.62
	50	247.2	45.5	72.09	0.72
	70	396.0	37.9	82.58	0.83
	90	408.6	33.4	83.11	0.83
	150	431.9	34.3	84.02	0.84

3.5.4. Adsorption Isotherm:

The mechanism of adsorption of inhibitor on the surface of steel depends on the replacement of water molecules away from the surface of steel [43] as shown in the following equation.

ligand(sol) + xH₂O(ads) → ligand(ads) + xH₂O(sol) …………….. (1)

Through the fitting of the mechanism of adsorption through several adsorption isotherms [44], Langmuir adsorption isotherm (Fig. 18), was found to have the best correction coefficient (Fig. 18) [45]. The inhibitor predicted to form a monolayer on the surface of the steel. The adsorption isotherm was fitted according to the following equation.

$\frac{C}{{\theta }}$ = $\frac{1}{{K}_{ads}}$ + $C$ ………………….. (2)

Where, the surfactant concentration is C, the part of the covered surface is θ, the adsorption equilibrium constant is K_ads, the universal gas constant is R and temperature is T.

Gibbs free energy of adsorption of ligand on steel calculated at room temperature from the following equation.

$${K}_{ads}=\frac{1}{55.5} \text{e}\text{x}\text{p}\left[\frac{{-\varDelta G}_{ads}^{^\circ }}{RT}\right]$$

………………

Where, ${\varDelta G}_{ads}^{^\circ }$ free energy of adsorption, 55.5 is the concentration of water in acid solution, T is absolute temperature (Kelvin) and R is universal gas constant (J mol^− 1 K ^− 1).

The value of Gibbs free energy of ligand found to be -6.6 kJ mol^− 1 which be below − 20 kJ mol^− 1 which is the ideal value of physical adsorption while − 40 kJ mol^− 1 is ideal one for chemical adsorption [45]. The previous explanation proved physically adsorbed layer of ligand on surface of electrode. Negative charge of Gibbs free energy indicates spontaneous adsorption mechanism of steel surface [46].

-Ethics approval and consent to participate: Not applicable.

-Consent for publication: Not applicable.

-Availability of data and materials: All data generated or analyzed during this study are included in this published article.

-Competing interests: Authors declare no competing financial interest.

-Funding: No funding is present.

-Authors' contributions;

F. I. El-Dossoki,wrote the main manuscript text.

F.A. El-Seify, make part of the experimental part and wrote part of the manuscript text.

M.M. Goda, make part of the experimental part.

All authors read and approved the final manuscript.

All authors reviewed the manuscript.

-Acknowledgements: Authors acknowledgement the faculty of science and engineering collage for their contributions in finishing the experimental part of this work.

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No competing interests reported.

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Scheme 1
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Scheme 2

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Newly Synthesized Azo Derived from Coumarine as Analytical Reagent and Metallic Corrosion Inhibitor

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Abstract

Figures

1. Introduction

2. Experimental

2.1. Materials and solutions:

2.2. Apparatus:

2.3. Preparation of ligand:

3. Results And Discussion

3.1. Conductometric determination of the stability constants:

3.2. Potentiometric determination of the stability constants:

3.3. Acid–base equilibrium and ligand ionization constant:

3.4. Chromogenic reaction with metals ions:

3.4.1. Optimum pH and wavelengths:

3.4.2. Beer's law:

3.4.3. Composition of the complexes:

3.4.4. Applications as acid-base indicator:

3.5. Corrosion Inhibition Study (Electrochemical Techniques):

3.5.1. Open circuit potential test:

3.5.2. Potentiodynamic Polarization test:

3.5.3. Electrochemical Impedance Spectroscopy:

3.5.4. Adsorption Isotherm:

Declarations

References

Additional Declarations

Supplementary Files

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