Interactions between Pr(III) Sm(III) Cations

Interactions between Pr(III) Sm(III) Cations pH-metric study of substituted3,5-diaryl isoxazolines complexes in 70% Dioxane solvent media . S.A.Thorat1,S.D.Thakur2 ABSTRACT:- The complex formation between Pr(III)Sm(III) metal ions and 3-(2-hydroxy-3-nitro-5-methylphenyl)-5-(2-phenylethenyl)isoxazoline[HNMP2EI]L1,3-(2-hydroxy-3-bromo-4-nitro-5-methyl)-5-(4-methoxyphenyl)isoxazoline[HBNM4MI]L2,3-(2-hydroxy-3-bromo-4-nitro-5-methyl)-5-(3-nitrophenyl)isoxazoline[HBNM3NI]L3have been studied at 0.1M Ionic Strength (26 ±0.1)oC in 70% Dioxane water mixture by Bjerrum method as adopted by Calvin Wilson .It is observed that Pr(III)Sm(III) metal ions form 1:1 1:2 complexes with ligand L1,L2L3.The data obtained were used to estimate compare the values of proton ligand stability constant (pK) metal ligand stability constant (log K).From estimated data (pK log K),the effect of substituents were studied. Key Words:-Substituted 3,5-diarylisoxazoline,Dioxane-water mixture,stability constant. 1.INTRODUCTION:- The studies in metal ligand complexes in solution of a number of metal ion with carboxylic acids, oximes, phenol etc. Would be interesting which throw light on the mode of storage and transport of metal ions in biological Kingdom.Metal with the view to understand the bioinorganic chemistry of metal ions, Banergee et al[1] have synthesized a no. of mixed ligand alkaline earth metal complexes. Bjerrums [2] dissertation has taken the initiative to develop field. Metal complexation not only brings the reacting molecules together to give activated complex [3] but also polarized electrons from the ligand towards the metal. The relation between stability and basicity of ligands is indicated by the formation constant and free energy change value Bulkier group increases the basicity of ligands as well as stability. The stability of complexes is determined by the nature of central metal atom and ligands. Poddar et al [4] investigated stability constants of some substituted pyrazolines,isoxalin e and diketone Karalmai et al [5] have studied formation constants and thermodynamic parameters of bivalent metal ion complexes with3-amino-5-ethyl isoxazole Schiff bases and N,N;N,O and O,O donar ligands in solution.Recently Tihile [6] studies on interaction between cu (II), Cr(II), Nd(II) and Pr(II) metal ions and substituted hydroxyl chalcones at 0.1 M ionic  strength pH metrically. Thakur et al [7,8] have studies the influence of dielectric constants of medium on the complex equilibrium of substituted hydroxyl-1,3- propandiones with Cr(II) metal ions and studies on interaction between Cu(II), Cr(II) and Ni(II) metal ions at 0.1M ionic strength pH metrically. Isoxazolines posses medicinal activities such as anti-inflammatory[9],antibacterial,anticonvulsant[10],antibiotic[11],antituberculer[12], antifungal[13]and anxiolytic activity[14]. In present work an attempt has been made to study the interactions between Pr(III)Sm(III) Cations At 0.1 M Ionic Strength with Ligand at 0.1 ionic strength,pH metrically in 70% Dioxane-water mixture. 2. MATERIALS AND METHODS The ligands L1,L2,L3 was synthesized in the laboratory by known literature method. The purity of these compounds exceeds 99.5% and structures were confirmed by NMR, IR and melting points. The stock solutions of the ligand was prepared by dissolving required amount of ligand in a minimum volume of dioxane subsequently diluted to final volume. Metal ion solution was prepared by dissolving metal nitrate (Sigma Aldrich) and standardized by EDTA titration method as discussed in literature . Carbonate free sodium hydroxide solution was prepared by dissolving the Analar pellets in deionised water and solution was standardized 22. The stock solution of percholric acid was prepared and used after standardization 23. 2.1. Measurements All measurements were carried out at (26 ±0.1) 0C. Systronic microprocessor based pH meter with magnetic stirrer and combined glass and calomel electrode assembly used for pH measurements. The sensitivity of pH meter is 0.01 units. The instrument could read pH in the range 0.00 to 14.00 in the steps of 0.005. The pH meter was switched on half an hour before starting the titration for initial warm up of the instrument. It was calibrated before each titration with an aqueous standard buffer solution of pH 7.00 and 9.20 at (26 ±0.1) 0C prepared from a Qualigens buffer tablets. The hydrogen ion concentration was measured with combined glass electrode. 2.2. Procedure The experimental procedure involved the titrations of i. Free acid HClO4 (0.01 mol.dm-3) ii. Free acid HClO4 (0.01 mol.dm-3) and ligand (20 x 10-4 mol.dm-3) iii. Free acid HClO4 (0.01 mole dm-3) and ligand (20 x 10-4 mol.dm-3) and metal ion (4 x 10-4mol.dm-3) against standard carbonate free sodium hydroxide (0.15 mol.dm-3) solution using Calvin-Bjerrum and Calvin-Wilson pH titration techniques. The ionic strength of all the solutions were maintained constant by adding appropriate amount of NaClO4 solution. All titrations were carried out in 70 percentages of Dioxane-water mixtures and reading were recorded for each 0.1 ml addition. The curves of pH against volume of NaOH solution were plotted (fig 1-3). The Proton-Ligand constants were calculated from pH values obtained from the titration curves using the Irvin-Rossotti method and MATLAB computer program (Table 1) . 3. RESULTS AND DISCUSSION The extent of deviation may be the dissociation of -OH group. 3-(2-hydroxy-3-nitro-5-methylphenyl)-5-(2-phenylethenyl)isoxazoline[HNMP2EI]L1,3-(2-hydroxy-3-bromo-4-nitro-5-methyl)-5-(4-methoxyphenyl)isoxazoline[HBNM4MI]L2,3-(2-hydroxy-3-bromo-4-nitro-5-methyl)-5-(3-nitrophenyl)isoxazoline[HBNM3NI]L3 may be considered as a monobasic acid having one replaceable H+ ion from phenolic -OH group and can be represented as HL H+ + L The titration data were used to construct the curves [acid curve (A), acid + ligand curve (A+L) and acid + ligand + metal ion curve (A+L+M)] between volume of NaOH against pH.The proton-ligand formation number nA were calculated by Irving and Rossotti expression (Table1) Where ÃŽ ³ denotes the number of dissociable protons, N is the concentration of sodium hydroxide(0.15 mol.dm-3), (V2-V1) is the measure of displacement of the ligand curve relative to acid curve, where V2 and V1 are the volume of alkali added to reach the same pH reading to get accurate values of (V2-V1): the titration curves were drawn on an enlarged scale: E0 and TL0are the resultant concentration of perchloric acid and concentration of Ligand, respectively. V0 is the initial volume of reaction mixture (50 cm3). Proton-Ligand stability constant pk values of Ligand were calculated by algebraic method point wise calculation and also, estimated from formation curves nA Vs pH (Half integral method) by noting pH at which nA = 0.5[Bjerrum 1957] (Table 2). Metal-Ligand stability constants (log k) were determined by the half integral method by plotting à ¡Ã‚ ¹Ã¢â‚¬ ¦ Vs pL. The experimental à ¡Ã‚ ¹Ã¢â‚¬ ¦ values determined using expression Where N, E0, Vo and V2have same significance as in equation (1), V3 is the volume of NaOH added in the metal ion titration to attain the given pH reading and TM0 (4 x 10-4 mol dm-3) is the concentration of metal ion in reaction mixture. The stability constants for various binary complexes have been calculated ( Table 3). 3.1. Metal Ligand Stability Constant (Log K) It is observed that (Table3 a-c ) sufficiently large difference between log K1 logK2Values of Sm(III)for ligand L1 L2Pr(III) for ligand L3 indicates the stepwise formation of complex between metal ion and ligand except Pr(III)for ligand –L1;L2 Sm(III)for ligand L3. It showed that less difference between log K1 log K2 values indicates complexes are occurring simultaneously. The higher value of ratio(Log K1/ Log K2) forPr(III)- Ligand- L1 L3 Sm(III)-ligand-L2 complex indicates the more stable stepwise complex formation as compare to Sm(III) –Ligand-L1 L3 Pr(III)-Ligand L2 complexes. 3.2. Proton-Ligand stability constant (pK):- It is observed from titration curve in (fig.1,2,3)shows that the ligand curves starts deviating from free acid (HClO4) curves at pH > 2.12,2.0,2.14 respectively. The extent of deviation s may be the dissociation of –OH group completely. 4. CONCLUSION From the titration curve, it is observed that the departure between (Acid + Ligand) curve (Acid+Ligand +Metal) Curve for all system of L1,L2,L3 started from pH=2.12 to 3.38, this indicate the commencement of complex formation. Also change in color from yellow to brown in pH range from 3.35 to 10.07 during the titration showed the complex formation between Metal Ligand. Table no.1 :Proton Ligand Formation number (à ¡Ã‚ ¹Ã¢â‚¬ ¦A) at (26 ±0.1)0C and at ionic strength  µ=0.1 moldm-3 NaClO4 in 70%Dioxane-Water mixture. a) System : HBMP2EI(L1) PH V1 V2 V2 – V1 à ¡Ã‚ ¹Ã¢â‚¬ ¦A 4.42 4.70 5.07 5.14 5.21 5.42 5.63 6.00 6.14 6.21 6.28 6.35 6.37 6.42 6.49 6.70 6.84 7.00 7.35 7.42 7.56 7.70 8.00 8.35 8.42 8.56 8.70 9.00 9.35 9.70 3.2518 3.2519 3.2743 3.2743 3.2743 3.3000 3.3330 3.3330 3.3330 3.3413 3.3413 3.3572 3.3589 3.3660 3.3661 3.3662 3.4496 3.4582 3.4662 3.4662 3.4867 3.4867 3.5000 3.5000 3.5330 3.5332 3.5660 3.6330 3.6660 3.7661 3.4117 3.4501 3.5030 3.5039 3.5060 3.5327 3.5659 3.5660 3.5660 3.6083 3.6293 3.6568 3.6589 3.6807 3.6889 3.6977 3.7824 3.7912 3.8159 3.8159 3.8464 3.8509 3.8670 3.8670 3.9112 3.9119 3.9502 4.0330 4.1227 4.2487 0.1599 0.1982 0.2287 0.2296 0.2317 0.2327 0.2329 0.2330 0.2330 0.2670 0.2880 0.2996 0.3000 0.3147 0.3228 0.3315 0.3328 0.3330 0.3497 0.3497 0.3597 0.3642 0.3670 0.3670 0.3782 0.3787 0.3842 0.4000 0.4567 0.4826 0.7597 0.7023 0.6566 0.6552 0.6520 0.6507 0.6504 0.6503 0.6503 0.5996 0.5681 0.5506 0.5502 0.5282 0.5608 0.5030 0.5018 0.5016 0.4767 0.4767 0.4619 0.4552 0.4512 0.4512 0.4349 0.4342 0.4260 0.4037 0.3192 0.2805 b) System : HBNM4MI(L2) PH V1 V2 V2 – V1 à ¡Ã‚ ¹Ã¢â‚¬ ¦A 3.35 3.37 3.56 3.70 4.00 4.35 4.37 4.42 4.49 5.07 5.14 5.21 5.42 5.63 6.00 6.14 6.21 6.28 6.35 6.37 6.42 6.49 6.63 6.84 7.00 7.35 7.42 7.56 7.70 8.00 8.35 8.42 8.56 8.70 9.00 9.35 9.49 9.63 9.70 9.84 9.98 10.00 3.2021 3.2024 3.2038 3.2042 3.2083 3.2475 3.2482 3.2518 3.2519 3.2743 3.2743 3.2743 3.3000 3.3330 3.3330 3.3330 3.3413 3.3413 3.3572 3.3589 3.3660 3.3661 3.3662 3.4496 3.4582 3.4662 3.4662 3.4867 3.4867 3.5000 3.5000 3.5330 3.5332 3.5660 3.6330 3.6660 3.6661 3.6662 3.6663 3.7003 3.7660 3.8000 3.2834 3.2962 3.3205 3.3215 3.3267 3.3671 3.3758 3.3848 3.3849 3.4332 3.4333 3.4333 3.4659 3.4995 3.4996 3.4997 3.5083 3.5086 3.5250 3.5295 3.5370 3.5371 3.5374 3.6213 3.6299 3.6474 3.6534 3.6742 3.6824 3.6974 3.6987 3.7328 3.7588 3.7927 3.8826 3.9660 3.9999 4.0240 4.0333 4.0830 4.1660 4.2330 0.0813 0.0938 0.1167 0.1173 0.1184 0.1196 0.1276 0.1330 0.1330 0.1589 0.1590 0.1590 0.1659 0.1665 0.1666 0.1667 0.1670 0.1673 0.1678 0.17060 0.1710 0.1710 0.1712 0.1717 0.1717 0.1812 0.1872 0.1875 0.1957 0.1974 0.1987 0.1998 0.2256 0.2267 0.2496 0.3000 0.3338 0.3578 0.3670 0.3827 0.4000 0.4330 0.8777 0.8559 0.8245 0.8231 0.8219 0.8203 0.8083 0.8002 0.8002 0.7614 0.7613 0.7613 0.7509 0.7503 0.7501 0.7499 0.7495 0.7490 0.7484 0.7442 0.7436 0.7435 0.7434 0.7430 0.7430 0.7288 0.7199 0.7196 0.7045 0.7043 0.7028 0.7014 0.6629 0.6614 0.6277 0.5527 0.5023 0.4666 0.4470 0.4451 0.4170 0.3723 c) System : HBNM3NI(L3) PH V1 V2 V2 – V1 à ¡Ã‚ ¹Ã¢â‚¬ ¦A 3.35 3.37 3.56 3.70 4.00 4.35 4.37 4.42 4.49 5.07 5.14 5.21 5.42 5.63 6.00 6.14 6.21 6.28 6.35 6.37 6.42 6.49 6.70 6.84 7.00 7.35 7.42 7.56 7.70 8.00 8.35 8.42 8.56 8.70 9.00 9.35 9.70 9.84 10.00 10.35 10.70 3.2021 3.2024 3.2038 3.2042 3.2083 3.2475 3.2482 3.2518 3.2519 3.2743 3.2743 3.2743 3.3000 3.3330 3.3330 3.3330 3.3413 3.3413 3.3572 3.3589 3.3660 3.3661 3.3662 3.4496 3.4582 3.4662 3.4662 3.4867 3.4867 3.5000 3.5000 3.5330 3.5332 3.5660 3.6330 3.6660 3.7661 3.7907 3.8000 3.9000 4.0330 3.2608 3.2638 3.2708 3.3042 3.3250 3.3755 3.3780 3.3818 3.3819 3.4321 3.4332 3.4333 3.4641 3.4982 3.4982 3.4991 3.5077 3.5082 3.5242 3.5259 3.5330 3.5332 3.5333 3.6333 3.6569 3.6665 3.6828 3.7033 3.7034 3.7503 3.7506 3.7922 3.7930 3.8328 3.8998 3.9329 4.0661 4.1248 4.1660 4.2988 4.5316 0.0587 0.0614 0.0670 0.1000 0.1167 0.1280 0.1298 0.1300 0.1300 0.1578 0.1589 0.1590 0.1641 0.1652 0.1652 0.1661 0.1664 0.1669 0.1670 0.1670 0.1670 0.1671 0.1671 0.1837 0.1987 0.2003 0.2166 0.2166 0.2167 0.2503 0.2506 0.2592 0.2598 0.2668 0.2668 0.2669 0.3000 0.3340 0.3660 0.3988 0.4986 0.9117 0.9078 0.8994 0.8499 0.8248 0.8061 0.8048 0.8047 0.8047 0.7630 0.7614 0.7612 0.7537 0.7522 0.7522 0.7520 0.7517 0.7507 0.7496 0.7496 0.7496 0.7493 0.7493 0.7243 0.7010 0.7003 0.6755 0.6757 0.6759 0.6256 0.6253 0.6126 0.6117 0.6039 0.6039 0.6037 0.5534 0.5024 0.4557 0.4081 0.2617 Table 2: Proton Ligand Stability Constant pK System pK Half integral method Pointwise calculation method HNMP2EI (L1) HBNM4MI(L2) HBNM3NI(L3) 7.0027 9.4939 9.8442 7.3487 9.2643 9.2987 Table 3: Metal Ligand Stability Constant(Log K) a) HNMP2EI (L1) System Log K1 Log K2 Log K1-LogK2 LogK1/LogK2 Pr(III) Sm(III) 6.5807 6.7926 3.8465 3.9788 2.7342 2.8138 1.7108 1.7071 b) HBNM4MI(L2) System Log K1 Log K2 LogK1-LogK2 LogK1/LogK2 Pr(III) Sm(III) 9.4786 9.5747 7.7377 6.6563 1.7409 2.9184 1.2249 1.4384 c) HBNM3NI(L3) System Log K1 Log K2 Log K1 LogK2 LogK1/LogK2 Pr(III) Sm(III) 9.9990 9.7658 7.4911 7.4891 2.5079 2.2767 1.3347 1.3040

Development of Tools Throughout Time Essay -- essays papers

Development of Tools Throughout Time Our world today has many different kinds of tools. I realized this when I was walking through The Home Depot a few weeks ago. On one isle are nails, and screws, the next isle there are power drills to go along with power saws and power sanders. Now imagine the world with no tools, no nails or screws. It would be pretty difficult to do most anything. We would have no houses to live in, no cars to travel to work in, and we would have no place of employment in which to work. Without tools our world would be nothing. This is the world our ancestors faced, and they had nothing but rocks and sticks. Homo Habilis had the challenge of being the first hominid with a larger brain, which allowed him to have the ability to do more things. With early hominids lacking size and strength to kill large animals they used certain objects to kill and devour these animals. This ultimately led to the development of tools. By 2.5 million years ago, a new human evolutionary trend had begun. The change to a upright bipedal posture, and existing flexibility at the shoulder, arms, and hands allowed hominids to carry and manipulate objects much more readily. Early hominids began to manipulate the physical world, inventing solutions to the problems of human existence. Instead of foraging, as do most primates, on a more or less individualistic basis for food sources, early hominids invented stone tools with which they could slay larger animals. This began a switch from scavenging to hunting as the main means by which meat was acquired. The earliest known tools yet discovered were found by Louis and Mary Leakey at Olduvai Gorge dating back to about two million years ago. They originally thought that these tools were made by the Australopithecus, but later determined that they were made by the Homo Habilis . The first tools found were classified as lower paleolithic tools. These tools belong to the Oldowan tool tradition. These tools which were opportunist in nature were characterized by an all-purpose generalized chopping tool. These were produced by removing a few flakes from a stone either by using another stone as a hammer or by striking a pebble against a large rock. Manufacturing tools this way is called the percussion method. Many of these tools were made out of quartz or lava; which were not the most common st... ...hominids we would have no understanding of any prehistoric life. Their technological advances helped us to create more efficient tools which allow us to research these ancient cultures. As one can see, we are presently expanding our modern tool kits every decade; so who is to say what technological advances will be made in the next several millennia's. Tools have evolved to influence, if not determine, human history. Bibliography Burenholt, Dr. Govan. The First Humans - Human Origins and History to 10,000 B.C. New York; Harper Collins Publishes. 1993 Haviland, William A. Anthropology - Ninth Edition Orlando ,Florida; Harcourt College Publishers. 2000 Johanson, Donald and Lenora. Ancestors New York; Villard Books. 1994 Leaky, Richard. Origin of Humankind New York; Harper Collins Publishers. 1994 Rowlett, Ralph M., Michael G. Davis, and Robert B. Grabe. Friendly Fire http://anthropology.about.com/gi/dynamic/offsite.htm?site=http%3A%2F%2Fwww.discoveringarchaeology.com%2F0599toc%2F5feature3-fire.shtml Time-Life Books. The Human Dawn New Jersey; Time-Life Books. 1990 Wallbank, T. Walter. Civilization Past and Present New York; Harper Collins Publishers. 1992

Starbucks Analysis Based on Ansoff’s Matrix

Growth Analysis on Starbucks Ansoff Matrix Market Penetration| Product Development| Market Development| Diversification| Starbucks have achieved market penetration by promoting its products in many ways. Their promotion allows Starbucks product to be known all around the US. They are constantly improving their products and making new coffee flavors to give the consumers different choices at he moment of ordering. Their USP, which is quality, makes the costumer’s loyalty to the brand to increase therefore Starbucks has a constant demand from the costumers.Starbucks has developed new products for the existing coffee houses to attract a new market. Some new products that Starbucks has established are: breakfast and pastry products. With these products consumers have a different option when going to the coffee house, as well, as new consumers that are searching for breakfasts. Starbucks has established coffee houses all over the world. They are constantly trying to enter new count ries to offer their worldwide known products. An example of this can be the recent opening of the first Starbuck in Ecuador.This is a way to analyze Ecuador’s market and make further decisions for implementing more coffee houses in Ecuador. Starbucks has developed diversification by implementing their new products in the new market. These products are usually based on the country’s culture and demand, which are different form Starbuck’s original products. We think that Starbuck is going to growth because based on an article in which it stated that Starbucks’s profit was better than predicted.This is a clue to infer that Starbuck’s is gaining its lost consumers and loyalty to the brand. By being constantly trying to enter new countries and offering their products, is also a way that Starbucks is trying to expand its market. All these factors and much more are essential for the growth of Starbucks in the US as in other counties. Bibliography: http:// www. reuters. com/article/2010/07/20/us-starbucks-idUSTRE66J5DT20100720

Prejudice And Prejudice By Maya Angelou - 1824 Words

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