Comparative Study Between TBP and Dibutylalkyl Phosphonates

Comparative Study Between TBP and Dibutylalkyl Phosphonates CHAPTER 7 PHOSPHONATES AS ALTERNATIVE TO TBP FOR ACTINIDES AND FISSION PRODUCTS Solvent extraction studies of U (VI), Th (IV), Eu (III) and Tc (VII) in dibutylalkyl phosphonates have been carried out in present study. Uptake of these metal ion and formation of metal-ligand bond is a direct consequence of phosphorus-carbon bond and to understand the influence of these changes in the bond was the main objective for the present study. Thus synthesis and solvent extraction studies of Dibutyl Propyl Phosphonate (DBPrP) and Dibutyl Pentyl Phosphonate (DBPeP) were carried and were compared with those available for Tributyl Phosphate (TBP). Thus this study will represent a comparative study between TBP and dibutylalkyl phosphonates. 7.1 Introduction Spent nuclear fuel (SNF) is a complex system with large number of elements and there isotopes which are produced during the nuclear fission of U and Pu. These spent fuel rods containing activation products along with fission products needs to be dealt while reprocessing and waste management of SNF which is carried out at reprocessing plant. TBP a triester of phosphoric acid is a major extractant used for nuclear fuel reprocessing that is Plutonium Uranium Extraction PUREX processes worldwide for the separation of uranium and plutonium from the dissolver solution [1]. Even though it has been a workhorse in nuclear industry since long period there are major drawbacks like its significant solubility in aqueous phase, third phase formation during macro level extraction of tetravalent actinides in nitric acid medium, low selectivity of U and Pu over Zr and Ru and presence of chemical and radiolytic degradation products of TBP viz. monobutyl and dibutyl phosphoric acid are responsible for lowering the decontamination factor (DF) [2-6]. Significant research in the scientific community using higher homologs of TBP has shown that they are more resistant to third phase formation and aqueous solubility. Basicity of the phosphoryl oxygen and the nature of substituents attached to the P atom are key factor responsible for the extraction ability of any organophosphorus extractant. Enhancement of the basicity on the phosphoryl group may be achieved by replacement of C-O-P group directly by C-P group. Neutral organophosphorus extractants show the variation in the basicity of the phosphoryl oxygen as phosphine oxide > phosphinates > phosphonates > phosphates [7]. Studies in the past have reported that phosphonates are better extractants for the extraction of uranium and thorium as compared to that with corresponding phosphates [8, 9]. In the nuclear reprocessing industry dibutylalkyl phosphonate was found to be one of the promising candidates as a replacement for TBP. Lower D values than that of corresponding phosphinates and phosphorus oxide makes stripping easier in case of phosphonates. The main objective of this study was to focus on the potential extraction capabilities of U (VI), Th (IV), Eu (III) and Tc (VII) which are relevant from nuclear fuel cycle view point by the phosphonates DBPrP and DBPeP. 7.2 Synthesis of Dibutylalkyl Phosphonates Phosphonates used in the present study was synthesized using Michaelis Becker reaction [10]. In this reaction equimolar amount of sodium is allowed to react with dialkylhydrogen phosphonate and dialkylsodium phosphonate thus obtained is further allowed to react with alkyl halides and final product with P-C bond is obtained. Figure 7.1 Michaelis-Becker Reaction Preset reaction involves nucleophilic substitution of phosphorus on alkyl halide to yield phosphonate as shown in the figure below. Figure 7.2 Mechanism for Michaelis-Becker Reaction The preparation of these phosphonates were carried out in a refluxation unit by drop wise addition of dibutylhydrogen phosphate over a period of 30 minutes to the reaction mixture i.e. sodium (1.15g, 0.05 mol) + hexane (100 mL). The addition of dibutylhydrogen phosphate was continued until the dissolution of sodium was complete. After this complete reaction mixture was stirred under gentle refluxation for about 4 hours during which 1-bromoalkane was added over a period of half-an-hour. This reaction mixture was then washed with water after cooling it at room temperature after which the product was distilled using reduced pressure to get rid of impurities. 7.3 Mechanism of Extraction in Dibutylalkyl Phosphonates Uptake of metal ions from the aqueous phase using dibutylalkyl phosphonates is by formation of neutral complex formation. Solvation of metal ion takes place by nitrate ion which is the aqueous phase used in the present studies. Then the solvation of these neutral metal nitrate species takes place with the help of dibutylalkyl phosphonate which gets extracted be the organic phase. MX+aq + X NO3 + nDBAPorg M(NO3)X.nDBAPorg Following equation gives the equilibrium constant for the above reaction Keq = [M(NO3)X.nDBAP]org / [MX+aq] [NO3]X[DBAPorg]n Distribution ratio (D) is the ratio of activity of metal ion in organic phase to that in the aqueous phase at equilibrium, which can be rearranged and represented in the following way. D = Keq [NO3] X[DBAPorg]n Distribution ratio depends on the concentration of nitrate ions and concentration of extractant. There is always a rise in the D value as the nitrate ion concentration increases while the fall at higher acidity indicates the extraction of nitric acid. 7.4 Solvent Extraction Studies Extraction of U (VI), Th (IV), Eu (III) and Tc (VII) with were carried out in a plastic tube with preequliberated organic phase that comprised of 1.1 M DBPrP and DBPeP in n-dodecane. 2 mL of preequliberated extractant was agitated with 2 mL of nitric acid in a shaking incubator at 25 0C for 1 hour. After the equilibration the two phases were allowed to separate and were analysed for the metal ion content using suitable technique. 7.4.1 Extraction studies of nitric acid Around 2 mL of various concentrations of nitric acid (0.1-6M) were taken in an equilibration tube and equilibrated with 1.1 M DBPrP/DBPeP, n-dodecane at room temperature for an hour. The nitric acid concentration in both the phases was determined by acid-base titration. Figure below depicts the uptake of nitric acid in DBPrP and DBPeP compared with the available literature values of TBP. As observed from the plot it is clear that D values in case of phosphonates are higher as compared with that of TBP which is the direct consequence of the higher basicity of the phosphonates. Prasanna et al. have reported that the changes in alkyl group structure do not have significant affect on extraction of nitric acid [11]. 7.4.2 Extraction Studies of U (VI) After the equilibration the two phases were separated and analysed for U (VI) content spectrophotometrically using Arsenazo-III as chromogenic agent [12]. Organic phase concentration was estimated by subtracting concentration of U (VI) in equilibrated aqueous phase from the initial feed concentration. Below figure shows the comparative data for the uptake of U (VI) in TBP, DBPeP and DBPrP in the complete nitric acid range (0.1-6 M). There was a constant increase in the uptake of U (VI) metal ion with the increase in nitric acid concentration. Also the observed increase in the uptake of U (VI) as TBP Figure 7.3 Variation of DU(VI) as the function of acid concentration for Dibutylalkyl phosphonates at 25 0C 7.4.3 Extraction Studies of Th (IV) Figure 7.4 depicts the variation of extraction behavior of Th (IV) by 1.1 M of TBP, DBPrP and DBPeP extraction in n-dodecane under identical conditions. As expected there is a constant rise in the D values as the concentration of nitric acid goes on increasing. Also higher analogs of neutral organophosphorus extractant shows the higher uptake which is again a direct conciquence of the increased bascicity on phophoryl oxygen the highest uptake of Th (IV) is Figure 7.4 Variation of DTh(IV) as the function of acid concentration for Dibutylalkyl phosphonates at 25 0C 7.4.4 Extraction Studies of Europium (III) Figure 7.5 Variation of DEu(III) as the function of acid concentration for Dibutylalkyl phosphonates at 25 0C 7.4.5 Extraction Studies of Technetium (VII) Figure 7.3 Variation of DTc(VII) as the function of acid concentration for Dibutylalkyl phosphonates at 25 0C References Schulz, W.W.; Berger, L.L.; Navratil, J.D. Eds.; Science and Technology of TBP; RC Press: Boca Raton, FL, 1990; Vol. 3. Crouse, D.J.; Arnold, W.D.; Hurst, F.J. Proceedings of the International Solvent Extraction Conference (ISEC’83), Denver, Colorado, 1983; pp 90–96. Marcus, Y.; Kertes, A.S. Ion Exchange and Solvent Extraction of Metal Complexes; Wiley- Interscience, New York, 1969; p 953–954. Kolarik, Z. Proc. International Solvent Extraction Conference, Toronto, Canada; Lucas, B. H., Ritcey, G. M., Smith, H. N., Eds.; 1977; Vol. 1. Kertes, A. S. Solvent Extraction Chemistry of Metals; McKay, H. A. C., Healy, T.V., Jenkins, I. L., Naylor. A, Eds.; Macmillan: NY, 1965; p. 377–379. Srinivasan, T. G.; Ahmed, M. K.; Shakila, A.M.; Damodaran, R.; Vasudeva Rao, P. R.;Mathews, C. K. Third phase formation in the extraction of Pu by TBP. Radiochim. Acta. 1986, 40, 151–154. Berger, L. L. Uranium and plutonium extraction by organophosphorus compounds. J. Phys. Chem. 1958, 62, 590–593. Siddall,T.H., III. Trialkylphosphates and dialkylalkylphoshonates in uranium and thorium extraction. Ind. Eng. Chem. 1959, 51(1), 41–44. Madigan, D.C.; Cattrall, R.W. The extraction of thorium from nitrate solution by dibutylbutyl phosphonate. J. Inorg. Nuclear Chem. 1961, 21, 334–338. Kosalapoff, G.M. Isomerisation of alkylphosphites. III. The synthesis of n-alkylphosphonic acids. J. Am. Chem. Soc. 1945, 67, 1180–1182. R. Prasanna, A. Suresh, T.G. Srinivasan, P.R. Vasudeva Rao, Extraction of nitric acid by some trialkyl phosphates, J. Radioanal. Nucl. Chem., 222 (1-2) (1997) 231-234. Perez-Bustamante, J. A.; Palomares Delgado, F. The extraction and spectrophotometric determination of sexavalent uranium with Arsenazo III in aqueous-organic media. Analyst 1971, 96, 407–422. Kalina, D.G.; Mason, G.W; Horwitz, E.P. The thermodynamics of extraction of U(VI) and Th(IV) from nitric acid by neutral phosphorus based organic compounds, J Inorg. Nucl. Chem. 1981, 43, 159–163.

Motivation Theory: Explaining Tourist Behavior

Motivation theory â€Å"Crompton (1979) notes it is possible to describe the who, when, where, and how of tourism, together with the social and economic characteristics of tourist, but not to answer the question â€Å"why,† the most interesting question of all tourist behaviour. † (Fodness 1994, p. 556) While motivation is only one of many variables in explaining tourist behaviour, it is nonetheless   a very critical one, as it constitutes the driving force behind all behaviour (Fodness 1994).Motivation sets the stage for forming people's goals (Mansfeld 2000) and is reflected in both travel choice and behaviour; as such it influences people's expectations, which in turn determine the perception of experiences. Motivation is therefore a factor in satisfaction formation (Gnoth 1997). Basic motivation theory suggests a dynamic process of internal psychological factors (needs, wants and goals), causing an uncomfortable level of tension within individuals’ minds an d bodies, resulting in actions aimed at releasing that tension and satisfying these needs (Fodness 1994).Motives, implying such an action, require the awareness of needs, as well as objectives, promising to satisfy these now conscious needs in order to create wants and move people to buy (Goosens 2000). Objectives or goals are presented in the form of products and services, it is therefore the role of marketing to create awareness of needs and suggest appropriate objectives, promising the satisfaction of these (Mill and Morrison 1985). Several authors suggest (Dumazedier 1967, Krippendorf 1987, Parker 1983) that in the Western World free time and holidays are connected to the concept of self-actualisation or self-realisation.The latter defined by Grunow-Lutter (1983. p. 76) as â€Å"a person's dynamic relationship between the real and the ideal self, constituting a process of decreasing the distance between these two cognitive systems, themselves subject to continuous change. † It is the individual's aim to achieve a state of stability, or homeostasis (Goosens 2000), which is disrupted when the person becomes aware of the gap between real and ideal self, or as Goosens calls it a need deficiency. The resulting need to self-actualise represents the motive, which under the constraints of the situation sets the stage for the process of motivation (Gnoth 1997).But to what extent does tourism satisfy the intrinsic need for self-actualisation? Tinsley and Eldredge (1995) summarise 15 years of research into psychological needs, satisfied by leisure activities, and proposed leisure activities clusters such as novelty, sensual enjoyment, cognitive stimulation, self-expression, creativity, vicarious competition, relaxation, agency, belongingness and service. It is questioned however; whether these superficial needs are intrinsically motivated (Goosens 2000, p. 303), suggesting that these motivations are merely culturally learned stereotypes or explanations for lei sure behaviour.As Fodness (1994) states, a widely accepted integrated theory for needs and goals behind motivation is lacking. The question is of course why this is the case. Research into motivation can be distinguished into two categories, the behaviourist and the cognivist approach (Gnoth 1997). The discussion has therefore traditionally revolved around either push or pull factors influencing tourist behaviour (Crompton 1979). Push factors represent lasting dispositions, as they are internally generated drives. The individual, energised by such drives, will then search objects for the promise of drive reduction and develop a motive (Gnoth 1997).The behaviourist view thus emphasises the emotional parameter of decision-making, while the cognivist approach focuses on situational parameters in which motives are expressed, consequently encompassing a certain knowledge which the tourist holds about goal attributes as well as a rational weighing up of situational constraints (Gnoth 1997 ). This cognitive process results in motivations, which are more object specific than motives, as these only imply a class of objects and may result in a range of different behaviours, depending on the situation.This unidimensional approach has been criticised however (Pearce 1993, Parinello 1993), as push and pull factors influence the consumer simultaneously (Hirschman and Holbrook 1986), integrated by the concept of involvement, an unobservable state of motivation, arousal, or interest (Goosens 2000), which is evoked by stimulus or situations. This is the case, since pull factors such as marketing stimuli as well as the destination's and service's attributes respond to and reinforce push factors.Consequently research increasingly seeks to integrate emotions and cognition in the individual's decision-making process (Hartmann 1982, Pearce and Caltabiano 1983, Braun 1989, Gnoth 1997), indicating a more holistic approach. As a result it became evident that people's intrinsic needs ar e influenced by external factors. Rojek (1990) asserts that in post-modern society the superstructure of advertising, television, fashion, lifestyle magazines and designer values increasingly take the role of forming knowledge and beliefs.People's needs are neutral (Heckhausen 1989), as motives however, they require an object towards which the need is directed, and when linked to actual situations, cultural and social impacts are also applied (Gnoth 1997). Situations raise motives to the level of values, as such they are evaluations based on learned behaviour and perception (Lewin 1942, Vroom 1964). If a drive is reduced satisfactorily the individual is likely to remember the behaviour and employ the same behaviour again, thus acquiring habits (Hull 1943).Tourism experiences may therefore become learned behaviour and acquire the role of habit enforcers. Cognivists argue that knowledge and beliefs in future rewards, anticipatory in nature (Vroom 1964), are equally a product of former ly encountered situations (Murray 1938), and external formation. It may be concluded that motives merely represent learned behaviour, which are influenced by offered objects or tourism activities, while motivations represent knowledge and beliefs formed by society and culture or tourism marketers.The psychogenic need for self-actualisation, abstract in nature, is therefore operationalised in a learned and practical manner and expressed in values, which are learned strategies to either adapt one's environment to one's needs or adapt one's self to a given environment (Kahle 1983). Such values equally include effects of enculturation and socialisation (Fodness 1994). Furthermore the perceived gap between real and ideal self, may indicate both externally and internally controlled evaluations (Gnoth 1997).McCabe therefore asks what researchers can expect to know about individuals' drives, by asking them about their motivations and needs as these may not be available to individuals as par t of their consciousness (2000a, p. 215). Iso-Ahola (1982) states that â€Å"people do not walk around with numerous leisure needs in their minds and do not rationalise specific causes of participation if their involvement is intrinsically motivated† (cited in Goosens 2000, p. 303). Hence it may be assumed that needs are suggested by mmediate social peers, and the wider context of particular social realities as well as the influence of the media (McCabe 2000a). Yet as Weissinger and Bandalos (1995) stress, intrinsic leisure motivation, which is a global disposition and describes a tendency to seek intrinsic rewards, is characterised by self-determination, an awareness of internal needs and a strong desire to make free choices based on these needs. While self-actualisation may be accepted as a need intrinsic to all individuals, society exercises a great deal of influence on the formation of the ideal self and thus perceived needs.However the notion of authentic or true self, d etermined by way of experience, offers a solution to the predicament. According to Waterman (1984), individualism symbolises four psychological qualities, the first one is a sense of individual identity, based on the knowledge of who one is and what one's goals and values are, as such it is related to the philosophical concept of true self, which indicates what an individual reckons personally expressive and what it is to be actualised (p. 30).The second is Maslow's self-actualisation, which is the driving to be one's true self. The third quality is Rotter's (1966) internal locus of control, which reflects a willingness to accept personal responsibility for one’s life, and finally prinicipled (postconventional), moral reasoning (Kohlberg 1969), which involves consistency with general abstract principles (cited in Kim and Lee 2000, p. 156). Consequently, only if   tourists become more autonomous and thus aware of intrinsic needs and motives are they able to self-actualise.As McIntosh and Goeldner (1990) explained, order is becoming less important in Western society and a desire for disorder in the tourism experience is becoming more important. Kim and Lee point out that â€Å"opportunities for unplanned action and freedom from institutionalised regulations are distinctive of Western tourists† (2000, p. 157). This indicates that tourists exhibit a certain desire to liberate their identities. According to Krippendorf (1984), in order for tourists to cease being just users of holidays, they must come to know themselves, their motives and other cultures.It may therefore be assumed that self-actualisation is an intrinsic need, characteristic of any tourist, but must be understood in terms of true self as opposed to ideal self and as such is independent of societal pressures and involves the transcendence of habitual behaviours and mindstates. This proposition requires further elaboration and must be viewed in the context of modernity, which hinders t his process but at the same time brought about its awareness.

To Kill a Mockingbird Quote Analysis

Reading Log: To Kill a Mockingbird, Chapters 5-7 â€Å"Then I saw the shadow†¦the shadow of a man with a hat on†¦the shadow, crisp and toast moved across the porch towards Jem.. When it crossed Jem†¦ he went rigid. † (53) The context of this quote is during their sneaky trip to Boo Radley’s house. This was the last day Dill was going to stay in Maycomb for this year, so they decided to take a quick peek at Radley Place by creeping around the house and looking through the side windows. As they are take a quick peek, the see the shadow of what they think is Boo with a hat on. They go numb with fear, and run for it.As they are leaving the area from under a fence, they hear a shotgun go off from Radley Place. The quote of narration from Scout accurately describes the kind of fear that the neighborhood legends give to the kids. The description, â€Å" He (Jem) put his arms over his head and went rigid† (53), shows how bloated up of a character Boo Radle y is. They do not even know if this shadow is Boo, however they are frozen with fear. However, after this event occurs, the little gifts that begin to appear in the tree leads the reader to make an educated guess that it is Boo Radley who is constantly giving these gifts.Since they used deductive reasoning to believe that it couldn’t have been Miss Maudie or any other person in Maycomb, they only other person in their neighborhood that came to mind was Boo Radley. Also, to enforce their conclusion that it was Boo Radley who was giving the gifts was when Nathan Radley cemented the hole in the tree. The series of gifts ending up in the tree molded Boo’s character into a more human-like personality. Miss. Maudie also told Scout that Boo used to be a nice boy who only became supposedly â€Å"insane† because of his family.She stated that Boo’s family was extremely religious and drove Boo insane when his father was constantly obsessed with â€Å"sin†. Sc out now has more sympathy for Boo, who is now a poor man who was abused as child, rather than a freak of nature who eats squirrels. Boo symbolizes the growth of Scout more mature perspective of the world. The quote represents Scouts (as well as Jem’s and Dill’s) childish mentality, and sets the framework for Scouts growth of maturity. I have a story that is eerily similar to this one. Several blocks down, we had a lady who never came out of the house.The legend in our townhome complex was that two of the kids only saw her face once, and she yelled at them the moment she saw them. She also supposedly looked like a witch, which was definitely a credible description for us 8 year-olds. Soon enough, we set out to see her face once more. The whole pack of us, about 6 people, stood in front of her house while one of us rang the doorbell several times consecutively to bait her out of her house. As we starting sprinting for our lives, we heard the loudest yelling we had ever h eard.Our fear of her had spiked up exponentially. But obviously, we needed to this again tomorrow. Same plan, same time, and we went underway. However, this time, we decided to hide behind some bushes adjacent to her house. Fifteen seconds later, she came out in a wheelchair with an oxygen tank beneath her. Our fear had turned to shame and sympathy immediately. The lie of her looking like a witch represents the legends of Boo having fangs and eating cats, and the sympathy we had for this lady in her wheelchair represents Boo having an abusive family as a child.

Organizational Cultural Inventory (OCI) Essays - 1224 Words

OCI Paper I applied the Organizational Cultural Inventory (OCI) with the intention that it is a fictional company, J Enterprises. It will be assumed that it is one of the largest financial services companies in the world. The main emphasis of the responses comes from the department in which I work. However, the results could be indicative of the entire company. The OCI Circumplex showed that the company has a culture with moderately strong Oppositional and Humanistic-Encouraging styles. It also significantly displays Avoidance and Self-Actualizing styles. The two least prominent styles are Perfectionistic and Approval. At first glance, the organization may seem to be working against itself, since the styles are on opposite sides of the†¦show more content†¦The company has a strong terminal value of supporting a long-term investment philosophy. Two of the instrumental values used to achieve this are being courageous, and exercising self-discipline. One instance that showed both of these values was during the late 1990s. At that time, investments in technology companies, and the technology sector of the financial markets had been increasing at a high rate of return. This organization did not spend disproportionate resources creating or maintaining products to â€Å"chase† the returns on technology investments. That would be co nsidered contrary to the company value of long-term investing. This showed both courage and self-discipline. A strong strategy is another factor that is prevalent in this organization. One of the strategies, directed towards institutional investors, is to position the company as the total retirement provider. This concept is a part of everyday dealings with the clients. For example, when there are discussions with a company about that client’s main retirement plan, the presentation is made to service other retirement vehicles that the company may have. 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