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Question

CalulalicaEiplanalnolict niaccd for LhLt Nurt" cm [rraturc clavronm, 47d 4ha dethe"er ofAMLSan4l LHAU L> Lu<0 LH . 1U*0 4440A 4>0 Lll Z A L<0LG Icu Bof uMitlleric. ~H (molz Inass: 1Z8.17 gmol) 17438 duccoked 10S'echolonn Ua HmanalM74t Ernol) whu is tlc molality of tha solution? #UOX7s MY diour6 | Cac 0EaeE (H T IAT€LO-litcr solurion canlains 0.J7-qol fonnic sci (HCOOIIAMHI and 0ELmd ~dn Tcolli* What is thc pl ofthis solution? 1109 At En dizJu 214 04LIau A IorPlacetlu

calulalica Eiplanaln olict niaccd for LhLt Nurt" cm [rraturc clavronm, 47d 4ha dethe"er ofAMLSan4l LHAU L> Lu<0 LH . 1U*0 4440A 4>0 Lll Z A L<0LG Icu Bof uMitlleric. ~H (molz Inass: 1Z8.17 gmol) 17438 duccoked 10S'echolonn Ua HmanalM74t Ernol) whu is tlc molality of tha solution? #UOX7s MY diour6 | Cac 0EaeE (H T IAT€ LO-litcr solurion canlains 0.J7-qol fonnic sci (HCOOIIAMHI and 0ELmd ~dn Tcolli* What is thc pl ofthis solution? 1109 At En dizJu 214 04 LIau A Ior Plac etlunt uL' Ah-Mec onrol Wlicir colutilitt Hrom [0154 neeat eolubilny ; ethana (CHCHOH} curbon [etrachloride (CCLA butanol (CH,CH CHCH OHA CHCHOH = CHchHCHOH CCI ChCHCCHOH CHCHOH ci CHiCh €HOU CH CH-OH CC CHAHCH CH CHCICH OH - cCl 2) nonc Ol Illc abae Which Eyualion depicts dnr'e phosplalc Ion Rlarnr Hrcnsler-Lothrid HFO (aqh HO): HPO (q) OH (2q) HFO ` (aq) HO) =PO:' (aq) H,o (aq1 HFor OH-(aq)= PO;' (34) HOrt) HPO Fuaul HO) 2HFOnl H0n)=2H,0) PO-s #e" Which of tx: following subslances Ca (s) Fi(g) grcalest stanJard molxs enttony 3 3 C Brz (liq) CI: (@) se for 4ll Which of the following stalements truc [Or & rcaclion with the equilihun consizni Ke= J2x 10*? (Kpis the equilibriurn conslant) Note that 4G" the Gibbs EroE change ofthc Recer tha sndarU state condition Arld Itle rexcliom rcactant TavOlec AG > id thc naction product favored 46" and the reaclion product favored 0)46" 0 andlhc macion Tcactant Tavord Flcel of the nbote Which ofthe following compounds expecled Io have the strongest ionic bond? b) BaO c) Mgo d) Nal KBr ame fo: all Consider the reaction: 2A (g) +3 B (g) 2C ( TE(L The rezction is initiated with 0.60 Min A.0.5 Min B and 0.50 M in '(Nole 0 Min C} At cquilibrium. the value of [B]=0.1S M What is the equilibrium value of [EJ? 2) 0.95 M b) 0.90 M c) 0.80 M d) 0.60M 40soM 0 0.40 M 10. Thc pH of 0.55 M aqucous solution 0f & Weak acid HA obsenved lo b +.48 Deiennin the acid ionization constant of the acid HA )LI * 109 0 20x I08 c)33x i0S d)6.0x I0* 9) 3.0x 10' 0) none of the above.



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THE SNAr MECHANISM: NUCLEOPHILIC AROMATIC SUBSTITUTION BY ADDITION-ELIMINATION Aromatic compounds bearing one or more strong electron-withdrawing substituents as well as a leaving group can sometimes undergo nucleophilic substitution instead of electrophilic substitution. The standard mechanisms of $\mathrm{S}_{\mathrm{N}} 2$ and $\mathrm{S}_{\mathrm{N}} 1$ reactions are not possible because of the $s p^{2}$ -hybridization at the carbons of a benzene ring, but a mechanism that involves nucleophilic addition followed by elimination, called $S_{\mathrm{N}} \mathrm{Ar}$ (nucleophilic aromatic substitution), is possible. For example chlorobenzene is not reactive toward $\mathrm{S}_{\mathrm{N}} 2$ or $\mathrm{S}_{\mathrm{N}} 1$ substitution by hydroxide. (FIGURE CANNOT COPY) However, if one or more strong electron-withdrawing groups is bonded ortho or para to the leaving group, substitution by a nucleophile is possible, as the following reactions show. (FIGURE CANNOT COPY) As the number of ortho and para electron-withdrawing groups increases, the temperature required for the reaction decreases, signifying an easier reaction. Meta groups do not produce a similar effect. $m$ -Chloronitrobenzene, for example, is unreactive. The mechanism that operates in these reactions is an addition-elimination mechanism involving the formation of a carbanion with delocalized clectrons, called a Meisenheimer intermediate. The process is called nucleophilic aromatic substitution $\left(\mathrm{S}_{\mathrm{N}} \mathrm{Ar}\right) .$ In the first step of the following example, addition of a hydroxide ion to $p$ -nitrochlorobenzene produces the carbanion; then elimination of a chloride ion yields the substitution product as the aromaticity of the ring is recovered. (FIGURE CANNOT COPY) Carbanion (Meisenheimer intermediate) Structures of the contributing resonance forms are shown further below. The carbanion is stabilized by electron-withdrawing groups in the positions ortho and para to the halogen atom. If we examine the following resonance structures for a Meisenheimer intermediate, we can see how: (FIGURE CANNOT COPY) Especially stable (Negative charges are both on oxygen atoms.) What is the product of the following reaction? (FIGURE CANNOT COPY) STRATEGY AND ANSWER: NaH is a strong base that will convert 4 -methylphenol to its phenoxide salt. $1-(p-$ Toluenesulfonyl)-2,6-dinitrobenzene contains both a good leaving group and two strong electron-withdrawing groups. Thus the likely reaction is a nucleophilic aromatic substitution $\left(S_{N} A r\right),$ leading to the following diaryl ether. 1-Fluoro-2,4-dinitrobenzene is highly reactive toward nucleophilic substitution through an S_yAr mechanism. (In Section 24.5 B we shall see how this reagent is used in the Sanger method for determining the structures of proteins.) What product would be formed when 1-fluoro-2,4-dinitrobenzene reacts with each of the following reagents? (a) EtONa (b) $\mathrm{NH}_{3}$ (c) $\mathrm{C}_{6} \mathrm{H}_{5} \mathrm{NH}_{2}$ (d) EtSNa THE CHEMISTRY OF... Bacterial Dehalogenation of a PCB Derivative Polychlorinated biphenyls (PCBs) are compounds that were once used in a variety of electrical devices, industrial applications, and polymers. Their use and production were banned in $1979,$ however, owing to the toxicity of PCBs and their tendency to accumulate in the food chain. 4-Chlorobenzoic acidis adegradation product of some PCBs. It is now known that certain bacteria are able to dehalogenate 4-chlorobenzoic acid by an enzymatic nucleophilic aromatic substitution reaction. The product is 4-hydroxybenzoic acid, and a mechanism for this enzyme-catalyzed process is shown here. The sequence begins with the thioester of 4-chlorobenzoic acid derived from coenzyme A (CoA): (FIGURE CANNOT COPY) Some key features of this enzymatic SyAr mechanism are the following. The nucleophile that attacks the chlorinated benzene ring is a carboxylate anion of the enzyme. When the carboxylate attacks, positively charged groups within the enzyme stabilize the additional electron density that develops in the thioester carbonyl group of the Meisenheimer intermediate. Collapse of the Meisenheimer intermediate, with rearomatization of the ring and loss of the chloride ion, results in an intermediate where the substrate is covalently bonded to the enzyme as an ester. Hydrolysis of this ester linkage involves a water molecule whose nucleophilicity has been enhanced by a basic site within the enzyme. Hydrolysis of the ester releases 4-hydroxybenzoic acid and leaves the enzyme ready to catalyze another reaction cycle.

So between the lithium night treat, the nickel to night tree and the strong team nitrate, the one that we should actually used to precipitate the maximum out of the carbonate ions from the solution should be the strong team nitrate. And the reason for this is has the lowest ks beef value asking here. And so they gave us a case be table with the lithium carbonate, nickel to carbon and the strontium carbonate. And so adding strong human nitrate trying him carbonate is actually what we'd be making. So it would make sense for look at these case p values. And so when a case be value is closer to one, that means that the, um substance dissolves very readily and be squeak. It's only ions and it doesn't like to stay in the forms of for instance, lithium carbonate. The case be was one then what we would have is only the theme ions and only the carbonate ions. We would actually have the lithium carbonate, but here so lithium carbonate has the value closest Thorne and strong from carbonate has value closest zero, which means that it likes the state s surround him carbonate and so once we put the strontium nitrate into the solution and it reacts with the carbon e ions, we get the strong carbonate and have a lot of precipitated. Then for one beer, what we're looking at is for the carbon compound that contains the cattle on chosen in part a, which we chose as strontium nitrate, giving us drunken carbonate determine the concentration of each eye on of that compounded solution equilibrium. So this is the equilibrium, expression or equation. And so what? We have your strong him carbonate solid, solid in equal air be in, which is what these double arrows are with strong team two. Plus, it's the cat eye on and it's a quest. And then the carbon, eh? I unders and own. And that's also Equus. So then, um, what we need now is chaos P is actually just an equation, like it's just a formula that you follow. So they gave us the KSB and Cass be equals the concentration of whatever is a quest on the right side of your equation. So we have the strong tea, um, cat eye on multiplied by the concentration of the carbon A an eye on. So now since they gave us our case, P value, which is just 5.60 times 10 to the negative 10th. We're setting that equal to basically just the concentration of the strong Thiam times, the concentration of the carbonate and what we can do there is that's just x Times X giving us X squared. So now if we just take the square to both sides and we saw for eggs X equals the concentration of the strontium I on which is also equal. So the concentration of the carbonate ion, which overall is equal to 2.37 times 10 to the negative fifth Moeller. And so that's the concentration off each eye on in solution. So now moving on part C one mixing the solution should the student ensure the carbonate solution or the nitrate solution is an access. So for this, what we have to think about it, Which one of these ions would actually help us more? So we are Actual precipitated is strong team carbonated, which is as our CEO three. So we don't need more carbon ian solution because it doesn't matter how much carbonate we have, because that's just gonna stay as an eye on but for the strong tea Um, the way that we got the strong team is from the strong tea of nitrate, which is this So if we don't have enough strontium, then we can't make the strong him carbonate. So the nitrate solution should be an access because in order to create the maximum amount of precipitate, you need enough strong team I owns to react with all of the carbonate ions and having the access strontium ions in the solution doesn't affect the master of the carbonate in the virginal example. So we have a fixed amount of carbonate, but we I don't know, having more having the access won't give us the precipitate but having the excess of strong here Mayan means that we can react all off the carbon e into precipitously and then having the extras drawn to him doesn't affect anything. So then moving on to part dear after titrate and sufficient solution to precipitate out all of the carbonate ions, the student filters the solution before placing in the crucible and heating it to drive off the water after several beatings. The final mass of the precipitate it remains constant is determined be 2.2 grams. So the first thing we wanted to do is determine the number of moles of Pacific it. So what we d'oh is we take our 2.2 grams of our strong team carbonate, and we multiply that by the molar mass, which is basically just a ratio that allows us to go from grand symbols or moral stra graham. So 1 47.63 grams Uh, s or C 03 her one more and overall, that gives us okay after I put it into my calculator one point 37 times tend to the negative seven Negative, second more. And now, um, moving on determining the mass of the carbonate present in the precipitate. What we do is we take these moves that we just got and then we multiply that bye. You have one more of, um, you have one mole of the carbon e ion her one more of the strong him carbonate substance. So then, since it's just a wonder one we end up with 1.37 times tend to the negative second more of the carbonate and then what we need to do is take the Moler Mass off the carbon e ion and multiply that by the moles. And so once the molar mass of carbon e is so carbon is 12 plus the 40 the 48 from the three oxygen. So it's 60. So then once we take 60 times so 0.137 times succeed, which gives us zero point e to two grams of this carbon ee eye on. So then, um, poor E. What we need to do is determine the percent by massive carbonate in the original sample. So the 0.822 grams of the carbonate weakness around that 20.82 grams and just carry the 26 eggs and then you divide that by don't know why I did that. Um, so it's the zero point 82 grams divided by the one point 39 grams from the original sample. And then if you multiply it by 100 that's how you're gonna percent and we end up with 43.4 percent of the carbon E who of the, um carbon e i aunt in the original solution so that moving on too. Oh, you know, I did that. So then moving on to part, as is the original compound most likely lithium carbonate, which is ally to Theo. Three, um, sodium carbonate ing any to Theo three or potassium carbonate, which is you if you go through here. So what we do now is so it's the, um 60.1 for all three, um, on the numerator because what we're looking at for all of them is the carbonate. But then the only difference is the total math. So we're either dividing it by 73.89 because you had the mass of the carbonate plus the mass of dilithium or 16.1 divided by one of 5.99 or 60.1 divided by 1 38.21 Oh, and so you multiply all these by 100 and you enough with anyone 0.2% for that 56.6% for this and 45 0.4% for the pizza, potassium carbonate and

So just drop of some contextual information. I'll just draw up on the screen. The equations of interest to have log he started the bay for pressure is equal to a minus. B over T f C ABC The coefficients t is all temperature we have pieced are a since Y a multiplied by P. P start is a partial pressure. Why is the mole fraction of Pete is the total pressure? So the full form of L. F Ellis, the lower flammability limit. So what we have is a flashpoint of us over a 15 flashpoint Brussels based 75 degrees Celsius and in the ambient temperature of our lab is 20 to 25 degrees Celsius. So the temperature of solving a is 15 degrees Celsius, which is lower than the ambient temperature in the lab so soften a can ignite easily have exposed exposed to a flame. However, if we take a look at solving B, it's 75 degrees Celsius, which is higher than the ambient temperature in the lab. To solve and be cannot ignite is easily if exposed to a flame, so solvent be is safer to keep in the lab two. Therefore, it must be monitored the temperature of the solvent. They does not rise above 15 degrees Celsius streets, which it must be refrigerated. However, there is no need to put solvent be in the fridge. It's moving on, Susie next part here. So the LF l of methanol in air is about six miles to sound, and the total pressure is one atmosphere. So one atmosphere we know is equal to 100 and 1.3 to 5. Killer Paschal's more fraction of methanol is equals the ratio one component in the total mixture. So why, for methanol is equal to 9.6 fried by 100 we get not quite, not six to the mole. Fraction of math does not point North. Six. We can calculate the partial pressure of methanol. You start. Um, it's equal to not point not six. We'll swap by one a 1.3 to 5. That gives us 6.795 kill of our skulls. So the part of pressure methane is 6.0 76 95 Killer pass girls. I was just written on the screen there. So now that we know the partial pressure of methanol, methanol coefficients. We have listed as a B and C weaken. Substitute them in on solve our equation. Hands we have logged 6.795 seek to 16.5785 Take away 3638.27 Divided by T. R. 239.5 We sold the T. We got a value of 6.768 degrees Celsius, so the flashpoint of methanol and the temperature are closer to each other. Therefore, the values of flashpoint were taken around 7 to 8 degrees Celsius. Eso, the flashpoint of methanol, is a lot less than the ambient temperature of the environment. So if methanol is exposed to an open flame, it will easily evaporate. Entertain? LF l and if it's exposed to ignition source, it can easily catch fire. So the common ignition sources we have our sparks heart plates, Bunsen burners in the lab

Hey, guys, lets troll Problem 41. The first question is wife was Gene is an effective weapon on low spots. We know that the density off for spring is 98 19 to Grandpa Mall and the density off air is 29 g per mole. Therefore, we see that fortune is a lot heavier than air and the Russian off the DNC disease 3.41 we stay. This pressure is higher. More than one. Andi Wasin is a lot heavier than air and it will displace the air near the ground, such as in the trenches on the ground. Let's try to this town. It is a written here and in this place, Yeah, near the ground. And for this reason, it is an effective weapon. Okay, Next we need to calculate how many Grandma's off. Austin. He's in the feet sample. We know that volume off Cylindrical Tubize. It is my our square age. And now it is given that the outside diameter of the do is there 135 centimeter. The one thickness given is 0.559 centimeter, 0.559 centimeter. Therefore, the insect damage in or the two wins. 01 635 minus the wall thickness. Want to play the brain to which gives the inside diameter off that your best 0.5 to 32 centimeter different? The volume that you bees, The height even is 15 centimeter and the volume of the day break it is 3.22 Sentimentally square centimeter cube. The volume of the Cube. Now, if the plant had warned, then the amount off Gina would have been introducing the guest. Photography's the amount off or swim. Let's get a new page then they want a phosgene introduced into the gas chromatograph. Um, he's the mess we know message can to volume multiplied. Viridian City Before we can write, we know density is a little pressure multiplied by Muller mess divided by Opti. Now we can insight on the gallows here the volume off the two with 3.22 centimeter cube. Let's come back to Leader, my dividing by 1000 centimeters. The pressure given here is one in him. The Mueller mess so far Genius. 98 point 92 grand Permal. That's constantly 010821 liter a team morning, your son Kevin Anderson and the temperature even. Here is 23 Calvin Ex con wanted to 2032 centuries that's converted to kill them by adding to 73. And when we do this calculation, we get the Grandma law for swimming in the fifth Central on to promote the Grammys. 0.1313 Graham. This is down Grandma's off Austin in the fifth sample. Mhm in the first sample. The next problem is or to the safe concentration off Jean exceed. If all the question evaporated into the room, we need to do some calculation. Transferred this question. No Dumb Moon's off oxygen in the air the number of months and is built to massive aided by Mueller Mess. The mess we just calculated is 3.22 Sentimental Cube. Let's converted program. We want to play in 1.37 and the Mueller mess is 98.92 Grandpa on one. And when we do this calculation, we get the most off US win in the area. 00446 moments. Now the most off air we can can collect the months affair we can use the item gets the question and is going to be V by rt The pressure given use one. It was very Christian. The volume ease given us 2200 Fit cube that's converted to leader by multiplying 28.317 Leader Yes. Constant is 0.0 8 to 1 leader. Administrative pressure. Mullen, your son Calvin in your son, the temperature is 23 d uses, she s and we get to 563 mol affair. Now we can calculate parts more million off oxygen in the air, parts per million off phosgene in There is a question number of months off Austin in the air and number off most off Yes, which gives 17.4 months ago by 10 in over six or we can say 17.4 p p. M. Now the parts per million off question in the air is more than the safe level, off 0.1 ppm. Therefore, question would have exited the 67 However, even in the question where below the self level, there would still be an answer. Live in the end, the floor because fortune is denser than air and will displace it. The next Russian is that things we did that made the experiment unnecessary has under what of the things that he would have done. So the things we did which made the experiment has a disease. The first thing we did not follow the proper safety protocol district in the material safety data sheet and fortune it needs for adequate personal protective equipment such as Gas Mosque and the experiment would have been done in a film head. As a precaution, he should have followed thumb safety protocols and product have used. He should have used from the productivity movement so he could have done these things to make the experimentalists hazard us.

Explanation for part A a style Cohen design A derivatives. Are he used then free 50 acids. Sins. The former his style is a tile. Coenzyme a can be transport it in the mitochondria and the later is we will ever in the cytoplasm. And the experiment. The researchers? Yeah, he used to read Oh, God Lever Michael Corn Andrea Yeah. Explanation for part B. None half lower. Molecular weight. A style coins. I'm a very great use. Were found with Ciccio Troy. Oh, I said I'll coenzyme Since this David use he is the first conversion can Virgin toe is a dial. All right. Coenzyme air. Y yeah. Vita oxidation. Yeah. Explanation for part C Both meet to roames off bitta oxidation explanation for party. They get him off drones is higher, then cease derivatives. Do you do the difference and configuration and shape off the and Zain Substrate complex explanation for part e The substrate for l C Eddie are we and C A. D is different friends here. Kinetic parameters oh, are used for different show processing off to explanation for a party. The kinetic her majors detective that says all right, I zumer is a better substrate in L C early and we we l see Eddie, do you to this? It came can be concluded there. There are fewer since I Zomer eyes Omar's after in cu patient off red liver. My took on Rhea Yeah. Answer! What part edge the Trans Faked can be Take a melodic in the body They okay can be broken Dawn by the cells How able in a slower read compare to see spate


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