Oxidative Decolourisation of Rosaniline Hydrochloride (RAH)

Oxidative Decolourisation of Rosaniline Hydrochloride (RAH) Kinetic, thermodynamic studies for oxidation of rosaniline hydrochloride dye by persulphate in ambient temperatures Z. M. Abou-Gamra* Abstract The kinetics of the oxidative decolourisation of rosaniline hydrochloride (RAH) by sodium persulphate was studied spectrophotometrically over pH range 3.5-9.5 at 30-45 oC. The reaction was second order with respect to dye and half order to persulphate. Increasing the pH of the medium increased the rate of decolourisation dramatically in alkaline medium. The Activation Parameters were found to be 62.11 kJ mol-1, 90.33 kJ mol-1 and -98.44J K-1 mol-1 with respect to activation energy, free energy and entropy respectively. Addition of sodium chloride and sodium sulphate had no effect on the rate of decolourisation. Key wards: Kinetics, Mechanism, Degradation, Rosaniline, Persulphate. 1. Introduction Textile dyeing process is significant source of environmental pollution. It produces large amounts of highly colored effluents, which generally toxic resistant to destruction by biological treatment methods. Many physical, chemical processes such as adsorption [1], electrochemical [2], photocatalytic [3] are used to remove the dyes from waste water. Chemical oxidative processes seem to provide an opportunity for future use in industrial wastewater. Examples of such potentially effective chemical oxidants for oxidative processes include Fenton reagent [4-5], KBrO3 [6-7] and KClO3 [8]. *corresponding author e-mail: [emailprotected] The use of persulfate has recently attention as an alternative oxidant in the chemical oxidation of contaminants [9-12]. Persulphate (KPS) is one of the strongest oxidants known in aqueous solution and has a higher potential (Eo = 2.01 V) than H2O2 (Eo = 1.76 V) [13] Table 1. It offers some advantages over other oxidants as a solid chemical at ambient temperature with ease of storage and transport, high stability, high aqueous solubility and relatively low cost. It has great capability for degrading numerous organic contaminants through free radicals ( SO4-. and HO.) generated in the persulphate system [12]. Basic dyes, such as, crystal violet, malachite green and roseaniline hydrochloride are used cotton tannin, mordant printing and dyeing in textile. Rosaniline is triphenylmethane dyes with amino group on each phenyl ring. Its structure is easily reducible where the chromophore group is destroyed and the compound loses its colour. Redox reaction of rosaniline hydrochloride by sulphite and nitrite ions are reported earlier [14-16]. This work focused on the kinetic study of oxidation of rosaniline hydrochloride with persulphate at ambient temperature spectrophotometrically. The effects of pH, dye, persulphate concentrations and temperature were studied. Also mechanism as well as rate law equation for the reaction is proposed. 2. Experimental 2.1. Reagents and materials All chemicals were of pure grade and were used without further purification. Rosaniline hydrochloride BDH (molecular weight =337.8, à ¯Ã‚ Ã‚ ¬max = 540 nm). The chemical structure of (RAH) is given in (Fig.1). NaCl and Na2SO4 were purchased from Merck. All solutions were prepared using bidistilled water. Stock solutions of dye (1 mM), K2S2O8 (100mM) were prepared. The pH is adjusted by HCl and NaOH solutions. 2.2. Kinetic experiments All kinetic measurements were carried out using a Cecil 292 spectrophotometer equipped with a water-jacketed cell holder. The reactants (dye and K2S2O8+NaOH) were thermostated for 15 min., then mixed thoroughly and quickly transferred to an absorption cell. The progress of the reaction was monitored at 540 nm. The pH of the reaction was adjusted using Griffin pH-meter fitted with a combined glass calomel electrode. 3. Results and Discussion Kinetic study for oxidation of (RAH) by (KPS) was followed at à ¯Ã‚ Ã‚ ¬max= 540nm. Figure 2 shows the decreasing of absorbance with time. Figure 2 also shows that about 85% of rosaniline is removed in 60 minutes at temperature 25 oC. 3.1 Kinetic study In the present study, zero-, first- and second-order reaction kinetics were used to study the decolourization kinetics of (RAH) by (KPS). The individual expression were represented below Ct = Co– kot lnCt = -k1t + ln Co 1/Ct = 1/Co+ k2t where Ct is the concentration of (RAH) at reaction time t. Regression analysis based on the zero-, first- and second-order reaction kinetics for the decolourization of (RAH) by (KPS) was conducted and the results were shown in (Fig. 3). Since plotting of At versus time did not give straight line zero-order kinetics is excluded. Comparing the regression coefficients (R2) obtained from (Fig. 3b) and (Fig. c), it can be seen that R2 of the second-order reaction kinetics (Fig. 3c) was 0.9995, which was obviously much better than that based on the first-order (R2 = 0.9394) reaction kinetics. The results indicated that the decolorization kinetics of (RAH) followed the second-order kinetics well. Based on the above analysis, the second-order kinetic rate constants for the decolourization of (RAH) at different reaction conditions were shown in Table 2. 3.2. Effect of pH A thermally activated persulphate oxidation system is known to involve SO4. and HO. radicals depending on the pH of the medium. According to literature survey, SO4. is predominant oxidant radicals at pHà ¯Ã¢â€š ¬Ã‚ ¼ 7, both SO4. and HO. are present at neutral pH and HO. is predominant radical at pH à ¯Ã¢â€š ¬Ã‚ ¾ 9[9]. Keeping the concentration of (RAH), (KPS) and temperature constant and change the pH in range 3.5 to 9.5, the rate of reaction is increased by increasing the pH value, (Fig. 4). Increasing the pH in range 3.5 to 9.5 increased observed rate constant from 6.7x 10-4 to 6.8 x 10-3 mol dm3 s-1, Table 2. This is probably attributed to the effect of hydroxyl ion on (RAH) which converting it to a carbinol base with no conjugation structure. All studies have done at pH = 9 since dyeing cotton performed in alkaline medium [17]. 3.3. Effect of dye concentration The effect of initial (RAH) concentration of aqueous solution of rosaniline on oxidation process by persulphate was investigated since pollutant concentration is important parameter in wastewater treatment. The observed rate constant decreases linearly with increasing the initial concentration of rosaniline, (Fig. 5). This is attributed to relatively lower of SO4-. and HO. results from the increasing of rosaline concentration while concentration of persulphate and hydroxyl ions remains the same. The obtained results was in good agreement earlier reported [18-19]. 3.4. Effect of persulphate concentration Increasing the persulphate concentration in rang 410-3 to 2.4x 10-2 mol dm-3 increasing the rate constant from 3.1310-3 to 9.9210-3 mol-1dm3 s-1 at pH= 9 and temperature 40oC, Table 2. Plotting of log kobs versus log [K2S2O8] give straight line of slope equals 0.63 indicating the order of reaction with respect to persulphate is half, (Fig. 6). This is similar to results obtained by T. Mushinga and S. Jonnalagadda [20]. Also the fraction order ( n = 0.779) with respect to persulphate is obtained by M. Ahmadi et al[19]. 3.5. Effect of temperature The variation of the temperature in range of 303-318 K increases the rate of decolourization of rosaniline, (Fig. 7). The activation energy was calculated from Arrhenius plot and Eyring equation and was found to be 62.11 kJ mol-1. The activation energy for decolourisation of RY84 was 45.84 kJ mol-1[19] while for decolourisation of CV by persulphate was 28.9 kJ mol-1[18]. Chen-Ju Liang and Shun-Chin Huang demonstrated that the activation energy for MB with persulphate was 87 and 90 kJ mol-1 in acidic and alkaline medium respectively [9]. The other activation parameters were determined and are found to be 90.33 kJ mol-1 and -98.44 JK-1 for free energy and entropy respectively. 3.6. Effect of inorganic anions The potent effect of persulphate as oxidizing agent in destroying the organic contaminants is high redox potential of sulphate free radical. The presence of other species in waste water such as chloride, sulphate and phosphate could reduce its oxidation efficiency. It is reported earlier [21] that chloride can react with sulphate free radicals according to the following mechanism: Chloride concentrations had insignificant effect in studied range [0.008- 0.08 mol dm-3]. Also the presence of sulphate did not reduce the decolourisation rate. Similar results are observed earlier [21-23]. 4. Reaction Mechanism and Rate Law The probable mechanism of reaction involves the break of conjugation of roseaniline hydrochloride. Since the fraction order of persulphate is observed, It likely that the initial reaction is thermal decomposition of persulphate, Applying equilibrium approximation and assuming an equilibrium between the reactant and product of (eq. 1) From (eqs.5 6) If the proposed mechanism and rate low are probable, so plotting of kobs versus [S2O82-]1/2 should yielded straight line passing by origin and the slope should be equals k x K1/2. Using the data in Table 3 and the plot gave straight line passing by the origin with slope =0.065 (R2 = 0.9557) which support the proposed mechanism. Conclusion In this study, (RAH) was successfully degraded in aqueous solutions by the persulphate and it was found that the reaction of (RAH) degradation follows the second-order kinetic model with respect to (RAH) and half order to persulphate. The activation energy for (RAH) degradation with the persulphate was determined to be 62.11 kJ mol-1.The presence of inorganic ions such as NaCl and Na2SO4 had no effects on the (RAH) degradation. References 1- Z. M. A bou-Gamra, H. A. Medien, Kinetic, thermodynamic and equilibrium studies of Rhodamine B adsorption by low cost of biosorbent sugar cane bagasse Eur. Chem. Bull., 2(7) (2013) 417-422. 2-M. JoviĆ¡, D. StankoviĆ¡, D. ManojloviĆ¡, I. AnÄ‘elkoviĆ¡, A. MiliĆ¡, B. DojÄ inoviĆ¡1, G. RogliĆ¡, Study of the electrochemical oxidation of reactive textile dyes using platinum electrode, Int. J. Electrochem. Sci., 8 (2013) 168-183. 3-J. Ã…  Ãƒ ­ma, P. Hasal, Photocatalytic degradation of textile dyes in aTiO2/UV system chemical engineering transaction 32 (2013) 79-84. 4- Z. M. Abou-Gamra, Kinetic of decoloration of alizarine red S in aqueous media by Fenton like mechanism, Eur. Chem. Bull., 3(1) (2014) 108-112. 5- H. A. Medien, S. M. E. Khalil, Kinetics of the oxidative decolorization of some organic dyes utilizing Fenton-like reaction in water J. King Saud Univ. (Science), 22 (2010) 147-153. 6-A.H. Gemeay, G.R. El-Ghrabawy, A.B. Zaki, Kinetics of the oxidative decolorization of Reactive Blue-19 by acidic bromate in homogeneous and heterogeneous media Dyes Pigments 73 (2007) 90-97. 7-M. Nasiruddin Khan, Z. Siddiqui, F. Uddin, Kinetic and mechanism study of the oxidative decolorization of neutral Red by bromate in micellar Medium, J. Iran. Chem. Soc., 6(3) (2009), 533-541. 8- Y. Mohammed, A.C. Etonihu, V.A. Tsa, Hexamethylpararosaniline chloride (crystal violet) oxidation by chlorate ions in aqueous acidic medium: approach to the mechanism of reaction, Trakia J. Sci. 9 (2011) 1-7. 9-C. Liang, S. Huang, Kinetic model for sulfate/hydroxyl radical oxidation of methylene blue in a thermally-activated persulfate system at various pH and temperatures, Sustain Environ. Res., 22(4) (2012) 199-208. 10-C. Liang, Z. Wang, C. J. Bruell, Influence of pH on persulfate oxidation of TCE at ambient temperatures, Chemosphere 66 (2007) 106-113. 11-X. Xu, X. Li, Degradation of azo dye Orange G in aqueous solutions by persulfate with ferrous ion, Separation and Purification Technology 72 (2010) 105-111. 12-X. Xu, S. Li, J. Liu, Y. Yu, H. Li, Activation of persulfate and Its environmental application, International J. of Environment and Bioenergy, 1(1) (2012) 60-81. 13- D.C. Harris, Quantitative Chemical Analysis, 4th Edition, W.H. Freeman and Company, New York, 1995. 14- J.F. Iyun,. H.M. Lawal, Non- metal redox kinetics; the reduction of pararosaniline chloride by sulphite ions acidic solutions, J. Chem. Soc. Nigeria 22(1997)155-159. 15- O.A. Babatunde, Kinetics and mechanism of reduction of parafuchsin by nitrite Ions in aqueous Acid Medium, World Journal of Chemistry 4 (1) (2009) 39-44. 16- J.F. Iyun, O.D. Onu, Nigerian J. Chem. Research, 3 (1998), 24. 17- A. Walters, D. Santillo, P. Johnston, â€Å"An Overview of Textiles Processing and Related Environmental Concerns†. Greenpeace Research Laboratories, Department of Biological Sciences, University of Exeter, Exeter EX4 4PS, UK, 2005, p.16. 18-L.M.A. Fayoumi, M.A. Ezzedine, H.H. Akel, M.M. El Jamal, Kinetic study of the degradation of crystal violet by K2S2O8 comparison with malachite green, Portugaliae Electrochimica Acta 30(2) (2012) 121-133. 19- M. Ahmadi, J. Behin, A. R. Mahnam, Kinetics and thermodynamics of peroxydisulfate oxidation of reactive yellow 84, Journal of Saudi Chemical Society (2013), in press. 20- T. Mushinga, S. B. Jonnalagadda, A kinetic approach for the mechanism of malachite green-peroxydisulphate reaction in aqueous solution, International Journal of Chemical Kinetics, 24 (1992), 41-49. 21-Y. Lee, S. Lo, J. Kuo, C. Hsieh, Decomposition of perfluorooctanoic acid by microwave activated persulfate: Effects of temperature, pH, and chloride ions, Frontiers Environ. Sci. Engin., 6(1) (2012), 17-25. 22-B. E. T. Soares, M. A. Lansarin, C. C. Moro, A study of process variables for catalytic degradation, Braz. J. Chem. Eng., 24(1) (2007) 29- 36. 23-A. H. Mcheik, M. M. El Jamal, Kinetic study of the decolorization of rhodamine B with persulphate, iron activation, Journal of Chemical Technology and Metallurgy, 48(4) (2013) 357-365. 1

Cultural Impacts Essay

â€Å"Culture (from the Latin cultura stemming from colere, meaning â€Å"to cultivate,†) generally refers to patterns of human activity and the symbolic structures that give such activity significance. Different definitions of â€Å"culture† reflect different theoretical bases for understanding, or criteria for evaluating, human activity. In general, the term culture denotes the whole product of an individual, group or society of intelligent beings. It includes technology, art, science, as well as moral systems and the characteristic behaviors and habits of the selected intelligent entities. †(Wikipedia) Any culture can be viewed as a blend of values, norms, institutions and artifacts of a civilization that has been passed on from generations through learning alone. The ideological perspective of life and the significance of things in it form the values of a society. Norms, are the expected collective behavior of the people where as the institutions are the structures within the society that transmit theses values and norms. Also, artifacts are the relics or the materialistic representation of a culture, derived from within it. Thus, cultures basically evolve and thrive on the basis of religion, historical background, environment and the social structure. Religious beliefs are typically the central themes of different cultures and more often than not the basic values are a derivative of them. For example, the 10 Commandments of Christianity or the five precepts of Buddhism are guidelines that transform the behavior of their followers. Similarly, religion occasionally is also implicated with government, as in a theocracy. The European and the New World cultures have been profoundly influenced by Christianity for at least the last 500 to 1700 years. Likewise Islam’s influence has fashioned a great deal of the North African, Middle and Far East regions for more than a 1000 years. Historical incidents also add new dimensions to any culture. For instance, most of the Commonwealth countries and the Europe celebrate a public holiday on the Boxing Day. On this day, the people organize feasts, festivals and certain sports in order to celebrate and also to share these rejoicing moments with the poor and the needy. There is no precise basis of this cultural carnival but only some theories that stem out from some historical happenings. Some believe that it was a day when people presented gifts to those who had worked throughout the year for them. Others argue that it was an annual gathering of extended families in the feudal times in which the lord of the estate handed out stipends to the serfs. Another group disputes that it was basically the day of the year when the church would distribute its donation money to the poor. Whatever may be the explanation, the Boxing Day is now an integral part of the western culture. (Wikipedia) The influence of different cultures on trade and commerce is profoundly instrumental and therefore it is not surprising that business tactics have diversely evolved in different regions of the world. In fact, the technological developments of the late 1990’s, in the arena of electronic media have added new dimensions to the concept. Consequently, the global giants of the corporate sector have been lavishly investing in examination of the cultural influences on the regional economies in order to maximize profits. â€Å"In China, for example, the foundation of Chinese respect for hierarchy and the family social collective is based upon the relational norms expounded by the Confucius and legal codes such as those developed during the Tang Dynasty. This institutionalized relational logic has shaped a society whose transactional order rests on social obligation to higher authority and to the family rather than on rules oriented to protecting the individual. Chinese capitalism is seen to be intrinsically different from the Western capitalism because of this contrast in institutional framing over a long period of time. † (Warner 2003) These and other brands of cultural values of a society are carefully considered when industries are being setup or when corporations are being established. This facilitates in determining the managerial skills required in the executive professionals who are responsible for communicating and representing their companies within the local industries. A working paper series issued from the George Washington University, discusses the U. S. /Mexican business alliances negotiations and the impact of their respective cultures on them. Mexico’s mestizo culture with its strong collectivist touch has embedded the people with the capacity to share power or authority equitably and the gift to accept and tolerate uncertainty and ambiguity in situations. However, they have also inherited the aptitude for individualism and tend to get involved in a loosely held social structure with little or no care for others. This is contrary to the culture in the United States, where people long for absolute power, are highly skeptical of ambiguous scenarios and more often than not downplay relationships. All, this along with the socio-political history of the two nations-which has been marred by discords and suspicion- is significantly determining in their mutual business alliances. (Teegen and Doh 2002) Moreover, the cultural heritage of a region characterize the production and sale of several products that otherwise do not correspond to the world wide demand. For instance, the annual Basant euphoria in the Punjabi region of the Indo-Pakistan, in which people fly kites and festivals are organized, much business is spawned. It becomes the very attraction for the tourists who converge here from all parts of the world, and the economic activity generated only in the city of Lahore has been estimated to be around PK Rupees 1. 5 to 2 billion annually. The proceeds of the events are shared by almost every one including the people belonging to the seasonal cottage industries and even the local vendors. Thus, the big corporations plunge into the scene and grab at every opportunity to escalate sales. The competitive environment forces them to inspect the cultural characteristics of the event and then to employ this knowledge in launching innovative products in the market as well as in transforming their already existing marketing techniques. (The News 2007) For a progressive business structuring in a region or country, political culture-which itself is a subsidiary of the social culture-can be of immense significance. An illustration can be vividly observed in the political history of Pakistan and the revolutionary rule of its Premier Mr. Zulfiqar Ali Bhutto (1973-77), which was influenced by the socialism philosophy of the Soviet Union. He aggressively followed these policies and nationalized most of the Pakistan’s industries. (Wikipedia) Consequently, the foreign investors and the big multinationals lost faith in the country and capital were taken out of the country. Locally, twenty two families in Pakistan had owned most of these nationalized banks, companies and industrial units. Sadly, this resulted into a deindustrialization in Pakistan, as none of the families have ventured in to even a single industrial project since the last 28 years. (Pakistan link) â€Å"In the fall of 1991, in the midst of the NAFTA negotiations, Vitro Sociedad Anonima (Vitro), the $3 billion Mexican glass maker, had signed a tentative $800 million joint venture with Corning Inc. †¦Ã¢â‚¬ ¦Just two years later, the joint venture was dissolved. According to company officials and external analysts, cultural differences were a principal cause of the alliance’s failure. † (Teegen and Doh 2002) Investigations showed that the Mexicans believed that Corning was a bit impulsive in their decision making; the Americans felt Vitro had a very time-consuming approach. Vitro management despised the frankness of the Americans, while polite Vitro executives, sometimes gave Americans the impression that they were reluctant to admit concerns and errors. (Teegen and Doh 2002) Thus, when businesses are being setup in different regions of the world, there is a need to develop a correlation between the corporate and the social cultures. References Babar Sattar. Immorality of Basant http://www. thenews. com. pk/daily_detail. asp? id=45221 Accessed: June 9, 2007 Boxing Day – Wikipedia, the free encyclopedia http://en. wikipedia. org/wiki/Boxing_Day Accessed: June 9, 2007 Culture – Wikipedia, the free encyclopedia http://en. wikipedia. org/wiki/Culture Accessed: June 9, 2007 Hildy J. Teegen (The George Washington University) and Jonathan P. Doh (Villanova University)-April 2002. â€Å"U. S. /Mexican Business Alliance Negotiations: Impact of Culture on Authority, Trust and Performance†. White Paper (The George Washington University). Malcom Warner . Culture and Management in Asia. Routledge, 2003 Who Owns Pakistan http://www. pakistanlink. com/hussaini/09-10-99. html#top Accessed: June 9, 2007 Zulfikar Ali Bhutto – Wikipedia, the free encyclopedia http://en. wikipedia. org/wiki/Zulfiqar_Ali_Bhutto Accessed: June 9, 2007

Resolving Family Conflict - 1608 Words

Families provide people with an atmosphere in which to live, grow, and develop. A family culture is established by the parents and instilled in the children during their upbringing. A healthy family is a family which follows a set of strong morals, stays loyal to one another, cooperates, and works together to avoid conflict. An environment where there is openness amongst family members is ideal because minds that are open are more susceptible to avoiding conflict than minds that are closed. If conflict gets the best of a family, it has the potential to increase hostility and create remoteness between family members, however, if a family resolves conflict, it can strengthen and enforce the family relationships. A family must establish†¦show more content†¦Willy was unwilling to talk with Biff about the affair incident that Willy created his own reasons for why Biff did not get along with him. Willy insisted that Biff was spiting him, but in reality, Biff had already come to accept the fact that his father was not perfect and that spiting him had worn off as a motive for retribution. It was not until the end of the play that Willy and Biff reconciled after they finally talked about their differences and their love for each other. It turned out, all they needed to do was just talk to each other, instead of fighting and refusing to confront one another. A family should be willing to take risks and confront problems that pose as conflicts. Confronting every single issue is not healthy, but confronting those issues that significantly bother family members should be considered. Linda was an emotionally weak character who was unable to confront Willy about his thoughts of committing suicide. She was afraid of what might happen if he found out that she knew that he was emotionally unstable. 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Essay about Making the St. Louis Connection - 2591 Words

Adolf Hitler spent much of his life wanting to be a painter and when he was eighteen years old he fled with two other young men to Vienna. He and the two other men wanted to attend the Academy of Fine Arts in Vienna. The two other men were accepted but Adolf Hitler was not. He blamed his non-acceptance on the fact that the art academy had been run by the Jewish and were discriminating against him. After years of failing in the art industry, Hitler’s political ambitions rose to the surface and he brought the Nazi Party to power in Germany. The Rape of Europa investigates Hitler and other leading advisors, and how they looted numerous of the great museums and private art collections of Europe during the duration of World War II in order to†¦show more content†¦When the museums are brought the paintings Jewish people will try to fight for the painting because it was part of the heritage. 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Unfortunately, not all of them really help, therefore, the question is there something that can really maintain or improve our cognitiveRead MoreEconomic History of St. Louis1845 Words   |  8 PagesDavey Oetting 12/1/06 History of St. Louis St. Louis was acquired from France by the United States under President Thomas Jefferson in 1803, as part of the Louisiana Purchase. It was founded by the French in 1764 when Auguste Chouteau established a fur-trading post and Pierre Laclà ¨de Liguest, a New Orleans merchant, founded a town at the present site. They named it after King Louis XV of France and his patron saint, Louis IX. From 1770 to 1803, St. Louis was a Spanish possession, but it was cededRead MoreBiography Of Dr. Imogene M. King Essay1185 Words   |  5 PagesWhere she never thought, would lead her to become one of the Pioneers and most sought Nurse Theorist. 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