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Kinetics and mechanism of oxidation of bromothymol blue by permanganate ion in acidic medium: Application to textile industrial wastewater treatment Samia M. Ibrahim a,⁎, Ahmed F. Al-Hossainy a,b aChemistry Department, Faculty of Science, New Valley University, El-Kharga 72511, New Valley, Egypt.bChemistry Department, Faculty of Science, Northern border University, Arar 1321, Saudi Arabia abstract article info Article history: Received 21 February 2020 Received in revised form 29 July 2020 Accepted 11 August 2020 Available online 16 August 2020 Oxidation of Bromothymol Blue (BTB) by oxyanion potassium permanganate as a strong oxidizing agent in acidic solutions using perchloric acid at a constant ionic strength of 1.0 mol dm −3has been studied kinetically spectro- photometrically. The order isﬁrst-order in [MnO 4 −], while a fractional-ﬁrst-order in both [H +] and [BTB]. The de- pendency on the hydrogen ion concentration of the rates shows the oxidation reaction is acid-catalyzed. Absence of either Mn IIIand/or Mn IVtransient species as involvement species in the oxidation process was conﬁrmed from Mn IIadded to the oxidation reaction. Formation of 1:1 intermediate complex formation kinetically was revealed during the rate-determining step. In the slowest step two-electron transfer processes of the inner-sphere form have been proposed. A mechanism of tentative reaction was proposed and explored with respect to kinetic pa- rameters. Identiﬁcation of the oxidation product revealed the formation of keto-BTB as derivative of bromothymol blue oxidation. The product of oxidation was isolated and identify using elemental analysis and Fourier Transform Infrared (FTIR) spectra. © 2020 Elsevier B.V. All rights reserved. Keywords: Bromothymol blue Permanganate Oxidation Kinetics Mechanisms 1. Introduction The textile industry is one of the largest water-consuming industries . They therefore refuse large amounts of wastewater. Such wastewa- ters contain toxic dyes and pigments that have a negative inﬂuence on human health and the ecosystem . The existence of dyes in wastewa- ter actually creates various hazards for living organisms, such as muta- gens and carcinogenic problems, and reduces photosynthesis; by limiting the penetration of oxygen into water . Multiple methods treat these efﬂuents . However, in the presence of toxic and non-biodegradable dyes, the biological treatments are inef- fective and produce high quantities of sludge; the physicochemical methods do have a fairly high investment cost . These limitations mean that new efﬁcient processes are developed. Bromothymol blue (BTB) is a silk dye product often used as the pH measure . It is a useful probe molecule that is not corrupted by direct oxidation and can only be chemically degraded via free-radical pathways. Potassium permanganate is a strong oxidizing agent. It has several additional advantages over other oxidizing agents: easier to handle, a readily soluble solid, and, as demonstrated for some contaminants and a higher efﬁciency in water and soil treatment . Permanganate ionis an effective oxidant in acid, neutral and basic media that is known to be a leading, environmentally friendly, and active oxidant in kinetic research . Oxidation by permanganate ion have a various mechanism so, permanganate ion is used as a multi-equivalent oxidant [8,9]. The mechanism of some redox reactions was focused on intermediate com- plexes [9–12] production, whereas free-radical mechanisms [13–15] studied other redox reactions. The suggested electron transfer form method was based on the successive electron transfers of the outer [16–18] sequence or inner [9,19–21]; simultaneous two-electron inner sphere modiﬁcations were introduced in one step [10,22–27]. It is inter- esting, in this situation, for a single phase [28–30], that a two-electron transfer type outer sphere is not veriﬁed. Methyl cellulose kinetics and oxidation mechanism , alginates , pectates , carboxymethyl cellulose [34 ], kappa-carrageenan , and chondroitin-4-sulfate  polysaccharides of permanganate ion have been recorded elsewhere in alkaline media. Again, the oxida- tion of methyl cellulose , pectates , carboxymethyl cellulose , carrageenanes , ADA  and poly (ethylene glycol) by permanganate ion in acidic solutions has been reported earlier. Pseudo-ﬁrst- order plots were shown to be reversed S-forms in these oxidation reactions and free radical interference carried out the oxida- tion reactions. The decoloration by potassium permanganate of the BTB coloration solutions has been examined kinetically in this work. Effects of pH, Journal of Molecular Liquids 318 (2020) 114041 ⁎Corresponding author. E-mail address:[email protected](S.M. Ibrahim). https://doi.org/10.1016/j.molliq.2020.114041 0167-7322/© 2020 Elsevier B.V. All rights reserved. Contents lists available atScienceDirect Journal of Molecular Liquids journal homepage:www.elsevier.com/locate/molliq reactant concentrations and decoloration temperature have been stud- ied. The application of potassium permanganate for the treatment of real textile wastewater was also carried out. The present work seems to merit a study in order to shed more light on the mechanistic aspects of oxidation and to cover for the lack of information on the existence of both the electron transfer and the transition states in the rate- determining step. The results obtained will offer important knowledge on the chemistry of BTB dye as one of the sulfones phthalein in acidic so- lutions. Again, this study will boost the elucidation of an appropriate ox- idation reaction process in acidic solutions for these alcoholic dyes. 2. Experimental section 2.1. Materials All used products are analytical grade. Water has doubly been dis- tilled from alkaline permanganate and degassed through the atmo- spheric pressure bubbling, boiling and cooling . Through adding the reagent powder to double distilled water step through process, BTB (Aldrich Chemical Co. Ltd) solutions in stock were prepared and the solution rapidly was agitated. A stock solution of KMnO 4was prepared and standardized by the conventional methods as described elsewhere [43,44]. Then, the stock solution was stored in a dark bottle away from light to avoid photore- duction and was re-standardized spectrophotometrically before each run. By dissolving the required sample amounts in double distilled water, all other reagents were prepared. The ionic strength was kept in check by the addition of NaClO 4as non-complexing agent . In ±0.05 °C, the temperature was regulated. 2.2. Kinetic measurements The present oxidation reaction for the available spectrophotometer was relatively quick. All kinetic operations have been made under the scope of pseudo-ﬁrst-order conditions . The absorption decrease was recorded at 525 nm at permanganate ion, with the maximum ab- sorption depending on time (where [BTB]≫10 [MnO 4 −]0). During the reaction process no overlaps were found with other BTB, MnO 4 −and substances at this wavelength. AsFig. 1a indicates, an isosbestic point is found at wavelength of 274 nm. Once, a new band appear at a wave- length of around 380 nm was found to conﬁrm the presence ofintermediates and this studied occurs at the same concentration of per- manganate ion of the same concentration of the mixture (Fig. 1b). These observations may indicate the formation of some intermediate complexes. Absorbance–time plots showed that the initial part (~5–10%) was too fast to be followed by the conventional spectrophotometer used. Therefore, the cited kinetic measurements were concerned with the remained part (~90–95%) of the reaction completion. In the presence of a large quantity of BTB above [MnO 4 −] in all kinetic measurements pseudo-ﬁrst-order conditions were used. Sodium perchlorate, NaClO 4, as an inert electrolyte was used to maintain the ionic strength constant. The absorbance shift measurements on the spectrophotometer Perkin Elmer (Lambada 750) with a thermostated cell partition using a path length of cells of 1 cm is total. The estimation method was the same as elsewhere [43,44].Fig. 1(a, b) indicates the spectral variations during the redox reaction. 2.3. Polymerization test Ten percent acrylonitrile (v/v) has been used in the reaction mixture during oxidation; to test the possibility of free radical’s formation brown precipitate forming after 15 min of warmth indicates the oxidation reac- tion occurs by free-radical intervention mechanism . Again, reaction mixture between the reactants was carried out in deareated vessels at room temperature in the presence of mercuric chloride, brown precipi- tate appears after 15 min on warming. 3. Results 3.1. Stoichiometry The oxidation reaction with varying initial BTB and MnO − 4concen- trations was combined at room temperature at [H +] = 0.5 and I = 1.0 mol dm −3. The unreacted permanganate ion is expected to reach a con- stant value on a regular basis. There has been a stoichiometric average of 1.0 mol ([MnO 4 −]unreacted /[BTB] 0). The corresponding stoichiometric equation is agreed with C 27H28Br2O5SþMnO 4− þ4H þ¼C 27H24Br2O5SþMn 2þþ4H 2Oð1Þ where C 27H28Br2O5S and C 27H24Br2O5S represent the BTB and keto- derivative of BTB, respectively. The keto-derivative of BTB had been iso- lated by another approach [46,47]. Again, the product was also identi- ﬁed by the Fourier Transform Infrared (FTIR) spectral bands observed at frequency 3448 cm −1 and 3443 cm −1 that characterize the two– OH groups in BTB and these two bands converted to one band at 3443 cm −1 so, this conﬁrm the oxidation occurs at one–OH group. Again band observed at 1720 cm −1 that characterize the carbonyl group of α-ketones; strong band appear at 2962 which characterize–CH group in case of BTB but appear weak band at 2962 cm −1 in case of KBTB which characterize–CH group [10,11,17,47]. The enhancement of the absorption band of OH group at wavelength of 1720 nm in the IR spectra of the product may indicate oxidation of OH group present in BTB dye to its corresponding keto-forms as shown inFig. 2. The naked eye observation of the mixture showed that the purple color of permanganate ion in the mixture was changed to the orange color which rapidly changes to rose color indicates the completion rection of oxidation of BTB as shown inFig. 3. 3.2. Inﬂuence of reaction rate on [MnO 4 ] and [BTB] ln (absorbance) against time, plots showed that the redox reaction in [MnO 4 −]isﬁrst-order in sequence, with good straight lines for more than two half-lives of end of reaction. Not only pseudo plotting but also an independently of the oxidation rates at different initial Fig. 1.Spectral changes (200–900 nm) in the oxidation of BTB by permanganate ion in aqueous HClO 4. (a) [MnO 4 −] = 4.0 × 10 −4, [BTB] = 1.0 × 10 −3, [HClO 4] = 0.5 and I = 1.0 mol dm −3at 20 °C. (b) At the same concentrations of reactants (Reference cell: [MnO 4 −] = 4.0 × 10 −4mol dm −3at 20 °C). 2S.M. Ibrahim, A.F. Al-Hossainy / Journal of Molecular Liquids 318 (2020) 114041 permanganate concentrations ranging from 1 × 10 −4 to 5 × 10 −4 mol dm −3 have conﬁrmed this effect. A fractional-ﬁrst-order in [BTB] was obtained from the plots of lnk obs against ln [BTB] and is conﬁrmed by (lnk obs = n ln [BTB] equation). Once more, straight lines were achieved by drawings of 1/k obs in the positive intercept axis on an X axis against 1/ [BTB]. The present redox system shows the creation of 1:1 intermediate complex shown by Michaelis-Menten kinetics (Fig. 4). 3.3. Inﬂuence of reaction rate on hydrogen ion concentrations In order to explain the reaction rate and evaluate the successful reac- tion mechanism, [H +] controlled the constant ionic strength of 1.0 mol dm −3 and the constant concentrations of all other reagents. There was a rise in the acid amount to speed up the rates of oxidation. The oxidation reaction is therefore catalyzed acidically (Table 1). Dependence from [H +] was fractional-ﬁrst-order (lnk obs-ln [H +]plots). 3.4. Inﬂuence of reaction rate on ionic strength The inﬂuence of ionic strength on the oxidation rates were studied at constant [H +] and different concentrations of NaClO 4to 1.5 mol dm −3. This result was found toﬁt the extended Bronsted-Debye-Huckel equa- tion (lnk obs vs.ﬃﬃ I p =1þﬃﬃ I p plot) with positive slope as shown inFig. 5. The dependence of ionic strength is as expected in consideration of the charges, despite the ionic strength used, far from the Debye-Huckel range [48,49]. The oxidation reaction between neutral molecule of HMnO 4and positive ion or neutral molecule of BTB can therefore occur. 3.5. Reaction rate impact on salts The oxidation rate effect of Mn 2+ must be studied as it is one of the oxidation materials [50,51] is indicated that Mn 2+ is reduced to Mn III and/or Mn IVas a transient species according to the Eq.(2),byperman- ganate ions in acidic solutions. MnO 4− þ3Mn IIþ8H þ¼3Mn IIIþMn IVþ4H 2Oð2Þ When reactive oxidizing species are intermediates of Mn IIIand/or Mn IV, the addition of Mn IIwill lead in the oxidation rate accelerations. Again,ﬂuoride ions should slow down the reaction, if manganese ions are primarily the oxidation responsible species, but if permanganate ions are the primary oxidizing entities, they should not be signiﬁcantly altered . Addition of either [Mn II]or[F −] ions to the redox reaction was found to have no appreciable changes of the reaction rates under our experi- mental conditions. This negative result may interpret indicate the ab- sence of formation of either Mn III or Mn IV as transient-species intermediates throughout the oxidation reaction. 4. Discussion Although there have been substantial research on the kinetics of ox- idation by permanganate ion of organic and inorganic substrates and of alcoholic macromolecules in acidic solutions as multi-equivalent oxi- dants, several unanswered questions concerning the mechanisms of ox- idation in terms of electron transfer and the intermediate states in the rate-determining processes have been recorded . Therefore, there may be a problem of fundamental importance, whether the transition, in a series or in the simultaneous two-electron transitions, of electrons, takes place through a sequential one-electron transfer procedure: Mn VII Fig. 2.FTIR spectra of BTB and its keto-derivative. Fig. 3.Naked eye observation for changing of color during the reaction progression at room temperature. (a): [BTB] in 0.5 M HClO 4;(b):[MnO 4 −] in 0.5 M HClO 4; (c): during progression (d): after completion of reaction. Fig. 4.Chart 1/k obsagainst 1/[BTB] in perchlorate solutions to oxidize BTB through permanganate ion. [MnO 4 −] = 4.0 × 10 −4,[H+] = 0.5 and I = 1.0 mol dm −3at 35 °C.3 S.M. Ibrahim, A.F. Al-Hossainy / Journal of Molecular Liquids 318 (2020) 114041 to Mn VIto Mn Vin a sequence or Mn VIIto Mn Vto Mn IIIin a single step. Therefore, it is important to know whether the pathways for the elec- tron transfer process are outer-sphere or inner-sphere type. The reactions complexity in relation to the formation of unstable in- termediates through the transition of manganese ion from heptavalent to divalent state into acidic solutions can cause these difﬁculties. Conse- quently, this oxidant has proposed different reaction pathways for oxi- dation of various substrates. Many redox reactions tend to take place by free-radical  or free-radical interventions through creating ion-pairs , and intermediate complexes of the inner-sphere nature . In the absence of free-radical intervention certain reactions of oxidation were carried out via outer-sphere mechanisms . Under our discrepancies of the kinetic results the speculated mech- anism for the oxidation of BTB by permanganate ion involves the pro- tonation of both permanganate ion and BTB to give the more reactive permanganic acid (HMnO 4) and alkoxnium ion (BTBH +), respectively. BTBþH þK1⇌BTBH þ ð3Þ MnO 4þH þK2⇌HMnO 4 ð4Þ The BTBH + substrate, with proton release before the rate- determining stage, were followed by a HMnO 4attack at the center of a 1:1 intermediate complex (C 1). HMnO 4þBTBH þK3⇌C 1þH þ ð5ÞInstead, in a rate determining stage, the slow decomposition of the formed intermediate complex to give radical (C 1•) substrate and re- duced (Red) shape (as Mn III/Mn IV) of the permanganate ion, throughout the slowﬁrst stage oxidation products as follows. C 1→kC∙ 1þRedð6Þ The following equation provides a rate rule for changing the rate constants by changing the concentrations of hydrogen ion and substrate as shown in the following equation. Rate¼− dMnO − 4 dt¼ kK1K2K3Hþ BTB ½ TMnO − 4 1þK 1Hþ þK 1K2K3Hþ MnO − 4 ð7Þ where [BTB] Tis the analytical total concentration of the BTB substrate. The term rate-law is usually written as Rate¼− dMnO − 4 dt¼k obs MnO − 4 ð8Þ Comparing Eqs.(7) and (8)and rearrangement, ones concludes that 1 k obs ¼ 1 kK 1K2K3Hþ þ 1 kK 2K3 ! 1 BTB ½ þ K 0 ð9Þ where *K′=[MnO 4 −]/k[BTB]. With the use of Eq.(9)where either the expressions of (1/k obs) vs. (1/[BTB]) were given straight lines with positive intercepts on (1/k obs) axes at constant [H +]or(1/k obs) vs. (1/[H +]). In the Michaelis-Menten plot the tiny intercept (Fig. 4) could be overlooked and thus Eq.(9) the following formula may be limited, BTB ½ k obs ¼1 k n¼ Hþ −1 k0 þ1 k″ ! ð10Þ wherek nis the second-order rate constant,k′=kK 1K2K3andk″= kK 2K3, respectively. In compliance with Eq.(10)[BTB]/k obs versus [H +]−1 has given good straight lines with positive intercept on [BTB]/ k obs axes, as shown onFig. 6; the values of the apparent rate constants k’,k″and the protonation constantK 1can be determined on their slopes and intercepts. These values calculated by using the least-squares Fig. 5.Ionic strength dependency of the rate constants in the oxidation of bromthymol blue by permanganate ion in aqueous perchlorate solutions. [MnO 4 −]=4.0×10 −4, [BTB] = 1.0 × 10 −3,[H+] = 0.5 mol dm −3at 35 °C. Table 1 Dependence of pseudo-ﬁrst order of the rate constants (k obs)on[H +] and [BTB] reactants in the oxidation of bromothymol blue by permanganate ion in aqueous perchlorate solu- tions. [MnO 4 −] = 4.0 × 10 −4and I = 1.0 mol dm −3at 35 °C. [H +]amol dm −3 103kobs,s−1 103[BTB] b mol dm −3 103kobs,s−1 0.5 0.58 1.0 0.58 1.0 1.51 3.0 1.47 Experimental error ± 4%. a[BTB] = 1 × 10 −3mol dm −3. b[H+] = 0.5 mol dm −3. Fig. 6.Plots of [BTB]/k obsvs 1/[H +] in the oxidation of bromothymol blue by permanganate ion in aqueous perchlorate solutions. [MnO 4 −] = 4.0 × 10 −4, [BTB] = 1.0 × 10 −3,I=1.0 mol dm −3at various temperatures. 4S.M. Ibrahim, A.F. Al-Hossainy / Journal of Molecular Liquids 318 (2020) 114041 method and found to be 0.91, 0.79, 0.57 and 0.55 at 20, 30, 40 and 50 °C, respectively. The calculated values of protonation constants (K 1)were found to be in good agreement. The negative entropies of activation (ΔS ≠) values inTable 2show the compactness of the intermediates rather than the reactants. Again, the positive values forΔG ≠indicated that the intermediate complexes pro- duced were non-spontaneity as suggested by the proposed mechanism. As shown by the ionic strength dependency of rate constant, the strong propensity of the reaction between the neutral molecule and the posi- tive ion would aid in this phase the observed low energy activation value of E ≠(Table 2). It implies that the reactants need little energy to interact and create the intermediate states of the complexes developed. However, entropy of activation has been previously reported [55–59] as being more negative for inner-sphere reactions, with reac- tions with negative values of theΔS ≠being conducted of one- and two-electron transfer of inner-sphere mechanism. Considering the values found for the entropy of activation (Table 2), it is better to use permanganate ion to oxidize BTB by means of two-electron shifts within the sphere rather than by the outside-sphere method. It should beremembered in this context that the mechanism of outer-sphere two- electron transition does not seem to be experimentally conﬁrmed . The disturbance of the alteration in spectra (Fig. 1) can suggest that the original quick portion of the reaction to oxidation is not the true phase of electron transfer. Therefore, the initial rapid part of oxidation may be attributed to a fast formation of an intermediate between the re- actants. The appearance of an isosbestic point indicate the existence of equilibrium state between the permanganate ion and the intermediate complex formed. Again, some trials have been performed in order to de- tect the formation of hypomanganate (V) intermediate as transient spe- cies. Unfortunately, all attempts were unsuccessful. This failure may be attributed to the lower absorptivity of formed Mn(V) under our exper- imental conditions of lower reactants concentrations or the fast reaction between the formed Mn Vand C 1 .(Eq.(6)) to give rise to theﬁnal oxida- tion products. In view of the above-mentioned kinetic deﬁnitions and study results, as outlined inScheme I, a tentative reaction process can be proposed for oxidation of bromothymol blue by acidic permanganate. 5. Conclusions The kinetics and mechanism of oxidation of BTB in acid perchlorate solutions with a constant ionic strength of 1.0 mol dm −3 as sulfonphthalein dyes by permanganate ion oxidizer have been analyzed spectrophotometrically. The experimental results revealed that oxida- tion displays a single pathway reaction; the order with respect to [MnO − 4]isﬁrst-order, fractional-ﬁrst-order with respect to both [BTB] and [H+]. Dependence on acidity in reaction levels suggested acid- catalyzed reaction. The addition of Mn IIto the reaction mixtures con- ﬁrmed the absence of either Mn IIIand/or Mn IVtransient species as in- volvement species in the oxidation phase. Formation of 1:1 intermediate complex prior to the rate-determining step was revealed, kinetically. A tentative reaction mechanism was speculated and discussed with respect to the kinetic data and measured the kinetic parameters. Table 2 The thermodynamic parameters of the protonation constant (K 1) and the activation pa- rameters of the apparent rate constants (k′andk″) in the oxidation of bromothymol blue by permanganate ion in aqueous perchlorate solutions. Constants Parameters ΔH ≠ kJ mol −1 ΔS≠ J mol −1K−1 ΔG≠ 293 kJ mol −1 Ea ≠kJ mol −1 k′43.66−391.09 114.63 50.36 k″18.14−305.96 89.66 26.96 k′ na 21.35−181.25 53.13 23.95 ΔH° kJ mol −1 ΔS° 293 J mol −1K−1 ΔG° 293 kJ mol −1 K1 −12.49−0.0433 +0.219 Experimental errors ±4%. aThesecond-orderrateconstantat[H +] = 0.5 mol dm −3. Scheme I.Mechanism of oxidation of bromothymol blue by permanganate ion in aqueous perchlorate solutions.5 S.M. Ibrahim, A.F. Al-Hossainy / Journal of Molecular Liquids 318 (2020) 114041 CRediT authorship contribution statement Samia M. 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