Ir Spectral Analysis Of Oxovanadium Acetylacetone Biology Essay

Ir Spectral Analysis Of Oxovanadium Acetylacetone Biology Essay Complex will have ligand that will form coordination bond to the metal center by donating lone pairs of electrons to the empty d-orbital of the metal which is similar to the Lewis acid-base reaction. In this experiment, Acetylacetone and pyridine is the ligand will act as Lewis base and will be coordinated to the metal center of Vanadium, V, which is the Lewis acid. Acetylacetone is a ÃŽ ²-diketone that contains two alpha hydrogen atoms adjacent to the two carbonyl groups. As carbonyl-group is electron withdrawing group, these two carbonyl functional group will create an inductive effect which cause the alpha hydrogen to be more acidic and be easily deprotonated. Resonance stability of delocalising the anion formed from the deprotonation under basic condition also increases the probability of the deprotonation as shown in Figure 1: Figure 1: Mechanism of the deprotonation and delocalization of the alpha hydrogen Acetylacetone exist in both keto and enol isomer form as shown in Figure 2: Figure 2: Keto-enol tautomerisation of the Acetylacetone The enolate anion is able to act as a bidentate ligand as it can chelate onto the oxovanadium metal ion with the two oxygen atoms as the binding sites to form the VO(acac)2 complexes. Two acetylacetonate ligands are able to bind to the oxovanadium metal and form a square pyramidal complex. Addition of the pyridine compound will form an octahedral geometry complex. These can be further proven using IR spectroscopy where the different strengths, lengths and nature as according to Hookes law, IR absorption spectra is able to be unique for each complex. Experimental Procedure Preparation of VO(acac)2 The preparation of VO(acac)2 started with 5ml of concentrated sulfuric acid (H2SO4) slowly added to 5 ml of deionized water in a 50 ml round-bottomed flask. Then, 18 ml of ethanol and followed by 2 g of vanadium pentaoxide (V2O5) was added into the round bottom flask. The solution was refluxed in an oil bath for an hour. The mixture was then cooled and filtered using cotton wool. Subsequently, 6 ml of Acetylacetone was added drop wise to the filtrate. The reaction mixture was carefully added portion by portion to the solution that contained 7.4g of Na2CO3 in 120 ml of deionsed water in a 500 ml conical flask. The mixture was then cooled in ice water and filtered to obtain the dark green product. Product was dried under IR lamp. The product was weighted and percentage yield was calculated. Preparation of VO (acac)2py The VO(acac)2py was prepared first by dissolving 0.5 g of the VO(acac)2 products obtained in 20 ml of ethanol in a 50ml of round bottom flask. Then, the mixture was refluxed vigorously with 2 ml of pyridine for one hour which was then concentrated using rotary evaporator. Crystal of crude VO(acac)2py formed upon cooling in ice water which was then filtered and wash with 5 ml of ether. Product was dried under IR lamp. The crude dry product was weighted and percentage yield was calculated. The IR spectrum of product was then determined. Data Treatment and Analysis Calculation of Percentage Yield of VO(acac)2 The percentage yield was calculated using the following equation: V2O5 + 4H+ Æ’Â   2(VO)2+ + 2H2O + O2 -Reaction 1 2(VO)2+ + 2 acacH Æ’Â   2H+ + VO(acac)2 Reaction 2 Mole of H2SO4 used = Amount of H+ present = 0.0938 mol x 2 = 0.1876 mol Mole of acac used = Mole of V2O5 used = (limiting agent) The ratio of V2O5 and VO2+ is 1:2, Mole of VO2+ used = 0.0111 mols x 2 = 0.0222 mols As ratio of VO2+ and VO(acac)2 is 1:1, then theoretical mole of VO(acac)2 = 0.0222 mols Theoretical mass of VO(acac)2 = mole of VO(acac)2 x molar mass of VO(acac)2 = 0.0222 mols X 265.16 g/mol = 5.890 g Percentage yield of VO(acac)2 = Calculation of Percentage Yield of VO(acac)2py Mole of pyridine used = Mole of VO(acac)2 used = (limiting agent) VO(acac)2 is the limiting agent. The ratio of VO(acac)2 and VO(acac)2py is 1:1. Mole of VO(acac)2py = 0.00194 mols Hence, theoretical mass of VO(acac)2py = mole of VO(acac)2py X molar mass of VO(acac)2py = 0.00194 mols x 344.26 g/mol = 0.667 g Percentage of VO(acac)2py yield = Infra-red Spectroscopy Table 1: Summarized Data from IR spectrum of VO(acac)2py Important peaks observed in the spectrum of VO(acac)2 /cm-1 Important peaks observed in the spectrum of VO(acac)2py /cm-1 997.7 998.04 966.04 3449.72 Discussion Geometry of VO(acac)2 and VO(acac)2py Vanadium [IV] metal exists as vanadyl, VO2+ in aqueous solution. Before the reaction of the VO2+ with the acetylacetonate, VO2+ is coordinated to five water molecules and existed as octahedral geometry. However, acetylacetonate is a stronger ligand that displaces the water molecules. Since Vanadium is bonded to oxygen with a V=O bond, only 2 acetylacetonate will only be able to form coordinate bond with the vanadium central metal ion to form the VO(acac)2 complex with a square pyramidal geometry as shown in Figure 3. Figure 3: Reaction diagram of the coordination geometry of VO(acac)2 and VO(acac)2py The geometry of this complex is in the square pyramidal geometry instead of the trigonal pyramidal geometry is due to the steric effect caused by the acetylacetonate ligands. The geometry of the square pyramidal is to reduce the steric repulsion to the minimum with the optimal distance apart of the two ligands. Also, from Figure 3, it can be seen that there is a vacant coordination site on the principle z-axis available which allow another more coordination site if there is the presence of strong ligand such as pyridine in this experiment. Therefore, complexation occurred between the pyridine molecules and the VO(acac)2 where nitrogen lone pair in the pyridine molecules act as a Ï€- donor-ligand and strong Lewis base that donate the lone pair of electron to the VO(acac)2 complexes at the vacant coordination site. With the new VO(acac)2py complex formed having a distorted octahedral geometry due to the unequal bond length between the V=O bond and the V=N bond at the axial position of the vanadium metal centre which lead to asymmetry. Also, the octahedral geometry of the VO(acac)2py is a 6-coordinate complex that is of high thermodynamic stability. Shifting of the V=O stretching band The complex of the VO(acac)2 has an oxidation complex of +4 which the vanadium(IV) ion exists as a d1. Using the Crystal Field Theory, there is electronic repulsion between the electrons of the acac ligands and the electron on the vanadium metal ion which causes the initially degenerate 5 d-orbitals of vanadium metal ion to split into two different levels. The level with the lower energy has a t2g symmetry and consists of the dxy, dxz, and dyz atomic orbitals. The level with the higher energy has eg symmetry and consists of the dx2-y2 and dx2 orbitals. The difference between the energy levels is the ligand field splitting parameter, à ¢Ã‹â€ Ã¢â‚¬  o. In the octahedral geometry, eg orbitals are on the axial direction and are the most affected by the electrostatic repulsion which destabilize the orbitals and excite them to higher energy level. The t2g orbital is not on the axial position and thus, not much affected by repulsion and thus, stabilized and move to lower energy as shown in Figure 4: eg orbital à ¢Ã‹â€ Ã¢â‚¬  0 Energy dx2-y2 dx2 dxy dxz dyz t2g orbital Figure 4: Molecular diagram illustration of Crystal Field Theory As mentioned in the previous paragraph, the pyridine is a Ï€ donor ligand that binds to the VO(acac)2 complex at the vacant site at the axial position of the vanadium(IV) ion. The addition of the pyridine to the complex reduces à ¢Ã‹â€ Ã¢â‚¬  0 which this reduction of the splitting parameter was observed using the comparison of the IR spectrum of the VO(acac)2 and VO(acac)2py. From the spectrum found in Appendix 2, the spectrum of the VO(acac)2py complex can be seen that the V=O stretching frequency of VO(acac)2py complex is 32 cm-1 lower than the VO(acac)2 complex when the V=O stretching frequency decrease from 998.04 cm-1 to 966.04 cm-1. These reduces of the stretching frequency is proportional to the stretching energy of the V=O bond of the complex. The addition of the pyridine will result in the reduction of the stretching energy of the V=O bond. This shows that the V=O bond of the VO(acac)2py is destabilized upon the addition of pyridine to VO(acac)2. This can be shown using Hookes Law as shown: where v is the stretching frequency in cm-1, k is the force constant, ÃŽ ¼ is the reduced mass. The binding of the pyridine has decrease the force constant and the lone pair of the pyridine ligand is electron-donating which increases the mass of vanadium ion that result in larger reduced mass, ÃŽ ¼, which according to the Hookes law, result in lower stretching frequency wavenumber. The wave number is proportional to the amount of energy that is needed for transition where it highly depends on the ligand field splitting parameter. The shifting of the stretching frequency indicate that the ligand field splitting parameter has decreased in magnitude which the addition of the pyridine ligand has caused destabilization of VO(acac)2py complex. Similarly, the lone pair of electrons of the nitrogen in pyridine is added onto the anti-bonding of the molecular orbitals of VO(acac)2 complex. This causes the pyridine to be trans to the V=O bond. Also, this bonding of the electrons donated will increase the electron density of the vanadiums d orbitals which will decrease the p Ï€ → d Ï€ donation from oxygen atom to the vanadium atom in the V=O bond. This result in the falls of the bond order of the complex and the lowering of the bond strength which also lengthen the V=O bond length. Overall, there is decrease of energy need to stretch the V=O bond and thus lead to the shifting of the V=O stretching vibration to lower frequency in the spectrum. This also further proven that the VO(acac)2py has an octahedral structure. Also, there is the delocalization of the Ï€ electrons from the aromatic ring of the pyridine which able to stabilize the complex more and decrease the p Ï€ → d Ï€ donation from oxygen to vanadium in the V=O bond. This make the vanadium-pyridine complexation more feasible and stable that result in the stronger V-N stretching bond which gain partial double bond character. As a result of the inter-electron repulsion, the electron density of the V=O bond is then shifted towards the oxygen atom and cause the weakening of the V=O double bond that cause the bond to loses the characteristic of the double bond nature. Thus, lesser energy is needed to stretch the weakened and lengthened V=O bond and lead to the shifting of the frequency of the spectrum. There is also the reason of the trans influence where the trans influence is the effect of pyridine ligand that weakens the bond that is trans to itself in the complex. The electrons of the oxo-ligand in the axial position of the complex occupies the dz2 orbital that will cause new binding ligand to form coordinate bond with the vanadium ion to be trans position to the oxo ligand. Pyridine ligand have donate electrons to the VO(acac)2 complex metal center and reside in the 3dz2 orbital from the site trans to the oxygen atom which causes repulsion. Therefore, the pyridine ligand and the oxo-ligand are in the trans position to each other which uses the same orbitals on the metal vanadium ion for bonding. However, the oxygen atom cannot donate the electrons to the metal as well as the pyridine ligand which causes the V=O bond to be weaker. Therefore, both axial bonds to the vanadium are weakened and lengthened which decrease the force constant (k) and decrease the stretching frequency. The shift also helps to confirm the presence of VO(acac)2py. On the other hand, the VO(acac)2py spectrum found in Appendix 2 have showed peak of 998.04 cm-1 which has a small different to the 997.7cm-1 peak found in the VO(acac)2 spectrum. This shows that there is still presence of VO(acac)2 in the product. Also the literature value of the V=O stretching bond of the VO(acac)2 is found out to be 995 cm-1 which is close to the 997.7 cm-1 in the product spectrum. These further prove that the VO(acac)2 is present. This can explain for the relatively low yield of 58.5% of the VO(acac)2py synthesis as the reaction has not gone into completion. However, comparing the intensity of the peak of 997.7 cm-1 and 966.04 cm-1 which indicate V=O bond in VO(acac)2 and VO(acac)2py complex respectively, there is higher intensity of the 966.04cm-1 which show that more pyridine adduct is formed in product. This also shows that the reaction may be an equilibrium reaction where both product and reactant can be present. This result can also be interpreted as the reac tion is not complete and more reflux time or higher temperature for reflux is needed to carry out to ensure more products formed. Lastly, there is a broad low intensity peak at 3449.72 at the VO(acac)2py spectrum found in Appendix 2 which was due to the presence of water that may be caused by insufficient drying of the VO(acac)2py product. Observation of Color changes During the synthesis of the complex, there is a series of observation of color changing of the compound in the solution. The color changes observed during the synthesis of the VO(acac)2 is due to the change of the oxidation state of V2O5 (oxidation state of V = +5). The orange powder of V2O2 is being reacted with the H2O and H2SO4 to reduce to a dark green solution of [V(H2O)5]3+ (oxidation state of V= +3) complex during middle of the vigorous reflux. When the reflux is complete, the solution was in dark blue color which is due to the reduction of the remaining V2O5 to dark blue [VO(SO4)(H2O)5] complex (oxidation state of V = +4). During the forming of the pyridine adduct, the dark blue VO(acac)2 is changed to dark green VO(acac)2py complex. This color changing phenomenon can also be explained using the Crystal Field Theory mentioned. Electrons of the two different energy level orbitals can be excited with à ¢Ã‹â€ Ã¢â‚¬  o energy. The higher the oxidation state, there will be more different between the two splitting energy levels which therefore lead to higher à ¢Ã‹â€ Ã¢â‚¬  0. For V2O5 (oxidation state of V = +5) will have a higher à ¢Ã‹â€ Ã¢â‚¬  0 and hence will absorbs light of the electromagnetic spectrum of higher energy with higher frequency and reflect low energy light. Therefore, V2O5 will absorb the blue-green light of higher energy and reflect orange of lower energy light which is shown off as orange with naked eyes. When there is a reduction of the compound to VO(acac)2 or VO(acac)2py compound, the light absorbed was at lower frequency and light reflected was of higher frequency such as blue-green and thus, there is the change of orange powder to blue-green product. Therefore, VO(acac)2 and VO(acac)2py appe ared as blue-green compounds. Possible Limitations and Sources of Errors in Experiment There are several limitations of the experiment that result in not having 100% yield of the product of both VO(acac)2 and VO(acac)2py complexes. Firstly, there may be loss of product due to the cotton wool filtration that causes some of the filtrate to be trapped in the cotton wool and unable to pass through. Secondly, according to the Le-Chateliers principle, for the Reaction 2, if there is an increase in the H+ concentration, reaction will shift the concentration of the reaction to the left which result in lesser product produce. When the reaction mixture is added slowly to the alkaline sodium carbonate solution, incomplete neutralization may occur where not all H+ are removed, and hence lesser product is produced. Therefore, longer cooling time will be needed for re-crystallization so as to allow more crystallization of VO(acac)2 and push the reaction to the right. Another limitation is of using of the sulphuric acid, H2SO4 may result in the reduction of the VO2+ ions to V3+ ions which decrease VO2+ ions available for product of VO(acac)2 formations. The lower percentage yield of the VO(acac)2py may be due to incomplete refluxing and thus lead to low yield obtained. Also, impurities may be present in the VO(acac)2 product produced that observed at the bottom of the flaks which lead to false weight measured and inaccurate percentage calculated. The round bottom flask should be swirled every fifteen minutes during the reflux which can prevent the settling of the V2O5 solid at the bottom of the flask and identifying impurities. The yield of the VO(acac)2py can be improved with addition of excess pyridine and increase the reflux time. Possible Precaution in Experiment For the synthesis of the VO(acac)2 complexes, there is a step of the adding of ethanol into the mixture of solution for reflux. Ethanol was used as solvent. The metal vanadium atom is surrounded by non-polar ligands of acetylacetonate or pyridine in second part of the experiment. Ethanol is more non-polar than water and will form solvent-solute interactions with the complexes and dissolve those ligands for better interaction in the solution. The use of the ethanol also helps to separate the VO(acac)2 from the insoluble V2O5 residue that will be filtered and remain in the cotton wool during filtration. Also, ethanol was used to prevent side reaction that will arise so as to increase the yield of the product. From reaction 1, there is the reaction of the V2O5 and the H2SO4 to produce the intermediate VO2+ ion that besides reacting with the acetylacetonate in reaction 2, VO2+ can react with the water and oxygen molecules by-product formed from reaction 1. It is as shown in Reaction 3. The side reaction will decrease the amount of VO2+ available for reaction with the acetylacetonate in reaction 3 to form product of VO(acac)2. This will decrease the amount of yield of the product produced. 4VO2+ + 2H2O + O2  ® 4VO2+ + 4H+ Reaction 3 However, this side reaction can be reduced with the addition of ethanol where ethanol will react with oxygen and produce acetaldehyde as shown: C2H5OH +  ½O2  ® CH3CHO + H2O Reaction 4 Also, using vacuum to remove the oxygen and water formed can be a good way to reduce problem of side reaction with VO2+. Another precaution taken was adding drop wise of the acetylacetonate to ensure sufficient reaction time and prevent influx of the H+ concentration and shift the equilibrium to the left and decrease the yield of the product formed. Anhydrous sodium carbonate, Na2CO3, was dissolved in water so as to form alkaline solution to neutralise H+ ions so as to shift the acetylacetonate toward the enol form. This will increase the formation of the VO(acac)2 products. Also, the mixture solution was added slowly to the sodium carbonate solution so as to prevent the rapid foaming caused by the product of CO2 and lose of product due to overflowing. Also, slowly adjusting the pH with more alkaline environment and less mixture solution allows the reaction to react at steady pace and reduce any side reaction to occur. Conclusion The percentage yield of the product of VO(acac)2 and VO(acac)2py complex were 77.8% and 58.5% respectively. From the IR spectrum of VO(acac)2py, it is shown that the V=O bond have shifted from 9998.04 cm-1 to 966.04 cm-1. This shifting of the peak indicate the formation of the pyridine adduct, VO(acac)2py, with the decrease in the wavenumber of the V=O stretching band.

The Twilight Saga 4: Breaking Dawn 26. Shiny

â€Å"I don't know how much we should tell Renee about this,† Charlie said, hesitating with one foot out the door. He stretched, and then his stomach growled. I nodded. â€Å"I know, i don't want to freak her out. Better to protect her. This stuff isn't for the fainthearted.† His lips twisted up to the side ruefully. â€Å"I would have tried to protect you, too, if I'd known how. But I guess you've never fit into the fainthearted category, have you?† I smiled back, pulling a blazing breath in through my teeth. Charlie patted his stomach absently. â€Å"I'll think of something. We've got time to discuss this, right?† â€Å"Right,† I promised him. It had been a long day in some ways, and so short in others. Charlie was late for dinner – Sue Clearwater was cooking for him and Billy. That was going to be an awkward evening, but at least he'd be eating real food; I was glad someone was trying to keep him from starving due to his lack of cooking ability. All day the tension had made the minutes pass slowly; Charlie had never relaxed the stiff set of his shoulders. But he'd been in no hurry to leave, either. He'd watched two whole games – thankfully so absorbed in his thoughts that he was totally oblivious to Emmett's suggestive jokes that got more pointed and less football-related with each aside – and the after-game commentaries, and then the news, not moving until Seth had reminded him of the time. â€Å"You gonna stand Billy and my mom up, Charlie? C'mon. Bella and Nessie'll be here tomorrow. Let's get some grub, eh?† It had been clear in Charlie's eyes that he hadn't trusted Seth's assessment, but he'd let Seth lead the way out. The doubt was still there as he paused now. The clouds were thinning, the rain gone. The sun might even make an appearance just in time to set. â€Å"Jake says you guys were going to take off on me,† he muttered to me now. â€Å"I didn't want to do that if there was any way at all around it. That's why we're still here.† â€Å"He said you could stay for a while, but only if I'm tough enough, and if I can keep my mouth shut.† â€Å"Yes†¦ but I can't promise that we'll never leave, Dad. It's pretty complicated___† â€Å"Need to know,† he reminded me. â€Å"Right.† â€Å"You'll visit, though, if you have to go?† â€Å"I promise, Dad. Now that you know/usf enough, I think this can work. I'll keep as close as you want.† He chewed on his lip for half a second, then leaned slowly toward me with his arms cautiously extended. I shifted Renesmee – napping now – to my left arm, locked my teeth, held my breath, and wrapped my right arm very lightly around his warm, soft waist. â€Å"Keep real close, Bells,† he mumbled. â€Å"Real close.† â€Å"Love you, Dad,† I whispered through my teeth. He shivered and pulled away. I dropped my arm. â€Å"Love you, too, kid. Whatever else has changed, that hasn't.† He touched one finger to Renesmee's pink cheek. â€Å"She sure looks a lot like you.† I kept my expression casual, though I felt anything but. â€Å"More like Edward, I think.† I hesitated, and then added, â€Å"She has your curls.† Charlie started, then snorted. â€Å"Huh. Guess she does. Huh. Grandpa.† He shook his head doubtfully. â€Å"Do I ever get to hold her?† I blinked in shock and then composed myself. After considering for a half second and judging Renesmee's appearance – she looked completely out – I decided that I might as well push my luck to the limit, since things were going so well today___ â€Å"Here,† I said, holding her out to him. He automatically made an awkward cradle with his arms, and I tucked Renesmee into it. His skin wasn't quite as hot as hers, but it made my throat tickle to feel the warmth flowing under the thin membrane. Where my white skin brushed him it left goose bumps. I wasn't sure if this was a reaction to my new temperature or totally psychological. Charlie grunted quietly as he felt her weight. â€Å"She's†¦ sturdy.† I frowned. She felt feather-light to me. Maybe my measure was off. â€Å"Sturdy is good,† Charlie said, seeing my expression. Then he muttered to himself, â€Å"She'll need to be tough, surrounded by all this craziness.† He bounced his arms gently, swaying a little from side to side. â€Å"Prettiest baby I ever saw, including you, kid. Sorry, but it's true.† â€Å"I know it is.† â€Å"Pretty baby,† he said again, but it was closer to a coo this time. I could see it in his face – I could watch it growing there. Charlie was just as helpless against her magic as the rest of us. Two seconds in his arms, and already she owned him. â€Å"Can I come back tomorrow?† â€Å"Sure, Dad. Of course. We'll be here.† â€Å"You'd better be,† he said sternly, but his face was soft, still gazing at Renesmee. â€Å"See you tomorrow, Nessie.† â€Å"Not you, too!† â€Å"Huh?† â€Å"Her name is Renesmee. Like Renee and Esme, put together. No variations.† I struggled to calm myself without the deep breath this time. â€Å"Do you want to hear her middle name?† â€Å"Sure.† â€Å"Carlie. With a C. Like Carlisle and Charlie put together.† Charlie's eye-creasing grin lit up his face, taking me off guard. â€Å"Thanks, Bells.† â€Å"Thank you, Dad. So much has changed so quickly. My head hasn't stopped spinning. If I didn't have you now, I don't know how I'd keep my grip on – on reality.† I'd been about to say my grip on who I was. That was probably more than he needed. Charlie's stomach growled. â€Å"Go eat, Dad. We will be here.† I remembered how it felt, that first uncomfortable immersion in fantasy – the sensation that everything would disappear in the light of the rising sun. Charlie nodded and then reluctantly returned Renesmee to me. He glanced past me into the house; his eyes were a little wild for a minute as he stared around the big bright room. Everyone was still there, besides Jacob, who I could hear raiding the refrigerator in the kitchen; Alice was lounging on the bottom step of the staircase with Jasper's head in her lap; Carlisle had his head bent over a fat book in his lap; Esme was humming to herself, sketching on a notepad, while Rosalie and Emmett laid out the foundation for a monumental house of cards under the stairs; Edward had drifted to his piano and was playing very softly to himself. There was no evidence that the day was coming to a close, that it might be time to eat or shift activities in preparation for evening. Something intangible had changed in the atmosphere. The Cullens weren't trying as hard as they usually did – the human charade had slipped ever so slightly, enough for Charlie to feel the difference. He shuddered, shook his head, and sighed. â€Å"See you tomorrow, Bella.† He frowned and then added, â€Å"I mean, it's not like you don't look†¦ good. I'll get used to it.† â€Å"Thanks, Dad.† Charlie nodded and walked thoughtfully toward his car. I watched him drive away; it wasn't until I heard his tires hit the freeway that I realized I'd done it. I'd actually made it through the whole day without hurting Charlie. All by myself. I must have a superpower! It seemed too good to be true. Could I really have both my new family and some of my old as well? And I'd thought that yesterday had been perfect. â€Å"Wow,† I whispered. I blinked and felt the third set of contact lenses disintegrate. The sound of the piano cut off, and Edward's arms were around my waist, his chin resting on my shoulder. â€Å"You took the word right out of my mouth.† â€Å"Edward, i did it!† â€Å"You did. You were unbelievable. All that worrying over being a newborn, and then you skip it altogether.'7He laughed quietly. â€Å"I'm not even sure she's really a vampire, let alone a newborn,† Emmett called from under the stairs. â€Å"She's too tame.† All the embarrassing comments he'd made in front of my father sounded in my ears again, and it was probably a good thing I was holding Renesmee. Unable to help my reaction entirely, I snarled under my breath. â€Å"Oooo, scary,† Emmett laughed. I hissed, and Renesmee stirred in my arms. She blinked a few times, then looked around, her expression confused. She sniffed, then reached for my face. â€Å"Charlie will be back tomorrow,† I assured her. â€Å"Excellent,† Emmett said. Rosalie laughed with him this time. â€Å"Not brilliant, Emmett,† Edward said scornfully, holding out his hands to take Renesmee from me. He winked when I hesitated, and so, a little confused, I gave her to him. â€Å"What do you mean?† Emmett demanded. â€Å"It's a little dense, don't you think, to antagonize the strongest vampire in the house?† Emmett threw his head back and snorted. â€Å"Please!† â€Å"Bella,† Edward murmured to me while Emmett listened closely, â€Å"do you remember a few months ago, I asked you to do me a favor once you were immortal?† That rang a dim bell. I sifted through the blurry human conversations. After a moment, I remembered and I gasped, â€Å"Oh!† Alice trilled a long, pealing laugh. Jacob poked his head around the corner, his mouth stuffed with food. â€Å"What?† Emmett growled. â€Å"Really?† I asked Edward. â€Å"Trust me,† he said. I took a deep breath. â€Å"Emmett, how do you feel about a little bet?† He was on his feet at once. â€Å"Awesome. Bring it.† I bit my lip for a second. He was just so huge. â€Å"Unless you're too afraid†¦ ?† Emmett suggested. I squared my shoulders. â€Å"You. Me. Arm-wrestling. Dining room table. Now.† Emmett's grin stretched across his face. â€Å"Er, Bella,† Alice said quickly, â€Å"I think Esme is fairly fond of that table. It's an antique.† â€Å"Thanks,† Esme mouthed at her. â€Å"No problem,† Emmett said with a gleaming smile. â€Å"Right this way, Bella.† I followed him out the back, toward the garage; I could hear all the others trailing behind. There was a largish granite boulder standing up out of a tumble of rocks near the river, obviously Emmett's goal. Though the big rock was a little rounded and irregular, it would do the job. Emmett placed his elbow on the rock and waved me forward. I was nervous again as I watched the thick muscles in Emmett's arm roll, but I kept my face smooth. Edward had promised I would be stronger than anyone for a while. He seemed very confident about this, and I felt strong. That strong? I wondered, looking at Emmett's biceps. I wasn't even two days old, though, and that ought to count for something. Unless nothing was normal about me. Maybe I wasn't as strong as a normal newborn. Maybe that's why control was so easy for me. I tried to look unconcerned as I set my elbow against the stone. â€Å"Okay, Emmett. I win, and you cannot say one more word about my sex life to anyone, not even Rose. No allusions, no innuendos – no nothing.† His eyes narrowed. â€Å"Deal. I win, and it's going to get a lot worse.† He heard my breath stop and grinned evilly. There was no hint of bluff in his eyes. â€Å"You gonna back down so easy, little sister?† Emmett taunted. â€Å"Not much wild about you, is there? I bet that cottage doesn't have a scratch.† He laughed. â€Å"Did Edward tell you how many houses Rose and I smashed?† I gritted my teeth and grabbed his big hand. â€Å"One, two – â€Å" â€Å"Three,† he grunted, and shoved against my hand. Nothing happened. Oh, I could feel the force he was exerting. My new mind seemed pretty good at all kinds of calculations, and so I could tell that if he wasn't meeting any resistance, his hand would have pounded right through the rock without difficulty. The pressure increased, and I wondered randomly if a cement truck doing forty miles an hour down a sharp decline would have similar power. Fifty miles an hour? Sixty? Probably more. It wasn't enough to move me. His hand shoved against mine with crushing force, but it wasn't unpleasant. It felt kind of good in a weird way. I'd been so very careful since the last time I woke up, trying so hard not to break things. It was a strange relief to use my muscles. To let the strength flow rather than struggling to restrain it. Emmett grunted; his forehead creased and his whole body strained in one rigid line toward the obstacle of my unmoving hand. I let him sweat – figuratively – for a moment while I enjoyed the sensation of the crazy force running through my arm. A few seconds, though, and I was a little bored with it. I flexed; Emmett lost an inch. I laughed. Emmett snarled harshly through his teeth. â€Å"Just keep your mouth shut,† I reminded him, and then I smashed his hand into the boulder. A deafening crack echoed off the trees. The rock shuddered, and a piece – about an eighth of the mass – broke off at an invisible fault line and crashed to the ground. It fell on Emmett's foot, and I snickered. I could hear Jacob's and Edward's muffled laughter. Emmett kicked the rock fragment across the river. It sliced a young maple in half before thudding into the base of a big fir, which swayed and then fell into another tree. â€Å"Rematch. Tomorrow.† â€Å"It's not going to wear off that fast,† I told him. â€Å"Maybe you ought to give it a month.† Emmett growled, flashing his teeth. â€Å"Tomorrow.† â€Å"Hey, whatever makes you happy, big brother.† As he turned to stalk away, Emmett punched the granite, shattering off an avalanche of shards and powder. It was kind of neat, in a childish way. Fascinated by the undeniable proof that I was stronger than the strongest vampire I'd ever known, I placed my hand, fingers spread wide, against the rock. Then I dug my fingers slowly into the stone, crushing rather than digging; the consistency reminded me of hard cheese. I ended up with a handful of gravel. â€Å"Cool,† I mumbled. With a grin stretching my face, I whirled in a sudden circle and karate-chopped the rock with the side of my hand. The stone shrieked and groaned and – with a big poof of dust – split in two. I started giggling. I didn't pay much attention to the chuckles behind me while I punched and kicked the rest of the boulder into fragments. I was having too much fun, snickering away the whole time. It wasn't until I heard a new little giggle, a high-pitched peal of bells, that I turned away from my silly game. â€Å"Did she just laugh?† Everyone was staring at Renesmee with the same dumbstruck expression that must have been on my face. â€Å"Yes,† Edward said. â€Å"Who wasnt laughing?† Jake muttered, rolling his eyes. â€Å"Tell me you didn't let go a bit on your first run, dog,† Edward teased, no antagonism in his voice at all. â€Å"That's different,† Jacob said, and I watched in surprise as he mock-punched Edward's shoulder. â€Å"Bella's supposed to be a grown-up. Married and a mom and all that. Shouldn't there be more dignity?† Renesmee frowned, and touched Edward's face. â€Å"What does she want?† I asked. â€Å"Less dignity,† Edward said with a grin. â€Å"She was having almost as much fun watching you enjoy yourself as I was.† â€Å"Am I funny?† I asked Renesmee, darting back and reaching for her at the same time that she reached for me. I took her out of Edward's arms and offered her the shard of rock in my hand. â€Å"You want to try?† She smiled her glittering smile and took the stone in both hands. She squeezed, a little dent forming between her eyebrows as she concentrated. There was a tiny grinding sound, and a bit of dust. She frowned, and held the chunk up to me. Til get it,† I said, pinching the stone into sand. She clapped and laughed; the delicious sound of it made us all join in. The sun suddenly burst through the clouds, shooting long beams of ruby and gold across the ten of us, and I was immediately lost in the beauty of my skin in the light of the sunset. Dazed by it. Renesmee stroked the smooth diamond-bright facets, then laid her arm next to mine. Her skin had just a faint luminosity, subtle and mysterious. Nothing that would keep her inside on a sunny day like my glowing sparkle. She touched my face, thinking of the difference and feeling disgruntled. â€Å"You're the prettiest,† I assured her. Tm not sure I can agree to that,† Edward said, and when I turned to answer him, the sunlight on his face stunned me into silence. Jacob had his hand in front of his face, pretending to shield his eyes from the glare. â€Å"Freaky Bella,† he commented. â€Å"What an amazing creature she is,† Edward murmured, almost in agreement, as if Jacob's comment was meant as a compliment. He was both dazzling and dazzled. It was a strange feeling – not surprising, I supposed, since everything felt strange now – this being a natural at something. As a human, I'd never been best at anything. I was okay at dealing with Renee, but probably lots of people could have done better; Phil seemed to be holding his own. I was a good student, but never the top of the class. Obviously, I could be counted out of anything athletic. Not artistic or musical, no particular talents to brag of. Nobody ever gave away a trophy for reading books. After eighteen years of mediocrity, I was pretty used to being average. I realized now that I'd long ago given up any aspirations of shining at anything. I just did the best with what I had, never quite fitting into my world. So this was really different. I was amazing now – to them and to myself. It was like I had been born to be a vampire. The idea made me want to laugh, but it also made me want to sing. I had found my true place in the world, the place I fit, the place I shined.

Cation Definition and Examples

A cation is an ionic species with a positive charge. The word cation comes from the Greek word kato, which means down. A cation has more protons than electrons, giving it a net positive charge. Cations with multiple charges may be given special names. For example, a cation with a 2 charge is a dication. One with a 3 charge is a trication. A zwitterion has both positive and negative charges at different regions of the molecule, yet an overall neutral charge. The symbol for a cation is the element symbol or molecular formula, followed by a superscript of the charge. The number of the charge is given first, followed by a plus symbol. If the charge is one, the numeral is omitted. Examples of Cations Cations may be either ions of atoms or of molecules. Examples include: AgAl3Ba2Ca2HH3OLiMg2NH4

The Study of the Relationship (Satire) Essay - 1024 Words

The Study of the Relationship Introduction A relationship? Something meaningful? Forever? HA! All ploys and devious schemes devised by horifically cruel creatures, in order to have their every wish granted for all of eternity. These terms were created to destroy our lives, they were created by the most evil and demented of all creatures, The Female. Ask any boyfriend, or should I say slave, and they will tell you that the Female is a very mean creature that gets her every way without any questions. They turn us into their servants and force us into a permanent relationship, or a permanent slavery, as I prefer to call it. Step One: Scouting Their Prey The First thing you need to remember about these...things, is that they†¦show more content†¦Asking you too get something for her at any time in the night, picking her friend up for her from somewhere exactly opposite of where you are, and the list goes on. But this is the moment where a small part of you may wish to be single again, but its not a loud enough voice to hear yet. Step Three: Stuck Between A Rock And A Bigger Rock You got this far in? Your stuck now, how does it feel? By this time you cannot get out of it until she breaks it off with you, which is highly unlikely at this step. You are completely and utterlly whipped, and under her control. Her will shall be done, and believe me, it is. This is the point where that voice got louder, its almost yelling...but heres where she gets more devious again. Lets say for example, that she is depressive, and extremely self-consious(as are most women), and you just cant deal with it anymore. But she says that she Loves you...theres a toughy. You say it back, because 1. You May Truly Love Her 2. You Know Your Supposed To Say It or 3. Your Afriad of What Will Hapen If You Dont. 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