Okay tell me have you solved this question quickly what is the answer 4.69 you are getting okay the first one is correct it is 4.69 okay and how do we do that you see the number of suppose if I write down here the reaction is CS3 COOH COOH plus NaOH gives you CS3 COONA plus H2O right so 0.1 into 100 so we have actually here 10 millimoles of NaOH 10 millimoles of NaOH and for CS3 COOH we have 20 millimoles so 10 millimoles react with 10 millimoles of this right and gives what 10 millimoles of CS3 COOH so this is what this is the limiting reagent in this reaction NaOH right when 10 millimoles of this react okay yeah 4.69 is correct when 10 millimoles reacts so 10 millimoles of CS3 COONA forms now in the reaction vessel you see we have CS3 COOH present and number of moles of CS3 COOH left is what number of millimoles left that is 10 millimoles because 10 reacts with 10 so 20 minus and 10 is left right and 10 millimoles of this is formed right so whenever you have mixture of this CS3 COOH and CS3 COONA present then the solution is what solution is an acidic buffer solution acidic buffer this gives you the pH will be equals to pKa plus log of concentration of salt by concentration of acid pKa value from this you can calculate that will be 5 minus log 2 which is around 4.7 or 6 9 you can say right pKa is equals to like pH pH will write minus log of k is the formula pKa is equals to minus log of k that formula we can using here so it is 4.7 plus log of 10 by 10 is equals to 1 which is 0 answer will be 4.7 okay so this is the first case now this is easy this is a direct formula best question now the second case you see when we have added 50 millimoles 50 ml of 0.1 molar HCl second question you see 50 ml and 0.1 molar how many millimoles millimoles of HCl that will be 15 to 0.1 that is 5 millimoles of this so these this is the acid that you are adding right so since the solution is a buffer solution and in that you are adding this acid so that will try to minimize the change in pH right so what happens when you add this HCl into this the salt you have that is CS3 COO Na right it dissociates like CS3 COO minus and Na plus right and the acid that you have that is CS3 COOH it gives you CS3 COO minus plus H plus so what happens in this now you see how this buffer solution works when you add this is the iron we have because this is the salt of this the solution of this only we have buffer solution salt and weak acid and the salt right all these ions are present right so when you add HCl into this which gives H plus so this H plus combines with this CS3 COO minus this H plus is coming from HCl that's still that you are adding it combines from to this CS3 COO minus and this reaction goes backward and forms weakly dissociated or weakly ionized CS3 COOH and that is how it maintains the pH because you see it try to understand here you try to understand we are adding HCl we are giving H plus actually if this H plus will not neutralize then the pH of the solution will change but that nature buffer solution is what it minimizes the change in pH and how it minimize the extra H plus that you are getting from this acid that has to neutralize and that is neutralized by this reaction to the H plus combines with the CS3 COO minus and converts into weakly ionized or feebly ionized CS3 COOH and that is how the pH of the solution is maintained the whatever H plus is coming from acid that combines with this now what happens with this first of all 5 millimoles of H plus we have right 5 millimoles of this gives 5 millimoles of H plus same millimoles now 5 millimoles of this combines with 5 millimoles of CS3 COO minus right so in the reaction the concentration of salt that is CS3 COO minus decreases this is salt why because we assume that this ion combines with H plus and forms CS3 COOH right and the concentration of acid which is CS3 COOH it increases because this reaction goes in backward direction forms CS3 COOH number of millimoles of CS3 COOH was 10 initially and for this also it is 10 right so this gives you 10 moles of this and 10 millimoles of this now 5 millimoles of H plus combines with this forms 5 millimoles excuse me 5 millimoles of CS3 COOH so number of millimoles of CS3 COOH will be what when you add HCl 10 was initially present and 5 forms by this reaction with HCl this gives you 50 millimoles of CS3 COOH 15 COOH millimoles of CS3 COOH now the concentration of the salt will decrease so initially it was 10 and 5 reacts so it gives 5 millimoles of this is it clear tell me is it clear will calculate what is the answer is it clear or not you tell me so the point is what when you add HCl see actually one question that you can ask me over here that I was expecting but anyways you see here when I said the salt concentration is decreasing why not acid concentration is decreasing why not why this reaction is going backward why not this reaction is going backward see what I said H plus that you are coming here this H plus may react with this also and goes the session backward no see the first reaction won't go backward because this is a salt right it is weak it is it will be ionized easily it exists in the forms of this ion only because this is not the stable form in the solution it exists as this only but CS3 COOH is what it is weakly ionized right and this is what this has common ion effect also in these two equilibrium correct because of common ion effect CS3 COOH will suppress that association of this so what we assume in this mixture this NIN is mainly because of that association of this salt not because of this acid right what we say that this acid is weakly ionized so concentration of CS3 COOH minus in the solution is mainly because of dissociation of salt not because of acid so when this H plus combines then we say okay mainly because of this salt only when this H plus combines then the salt concentration will decrease because it combines with H plus and converts into weakly ionized CS3 COOH and that's why we are saying that salt concentration will decrease and acid concentration will increase salt concentration will decrease and acid concentration will increase right now you see this is the concentration of salt we have and this is the concentration of acid when we add these many moles of HCl into it now we can use the formula of pH which is again pH is equals to pKa plus log of concentration of salt divided by concentration of acid that gives you pKa is 4.7 plus log of salt by acid is log of 5 by 15 which is 1 by 3 so 4.7 minus log 3 this gives you the pH of the solution when you solve this you'll get pH of the solution log 0.3 is 0.47 or 0.48 so 4.7 minus 0.48 gives you the answer over here 4.2 something you'll get probably did you understand this did you do the same thing now that's third portion of this question is what when we add question c we add 0.150 ml of 0.1 mol of NaOH 50 ml of 0.1 mol of NaOH what is the millimole of this again it is 5 millimoles right again it is 5 millimoles now in this again you see the equilibrium exists between these two reactions which is the acid CS3 COOH it dissociates like CS3 COO minus and H plus and another one that is salt CS3 COO Na CS3 COO minus plus Na plus okay now in this solution in this solution we are adding NaOH sorry we are adding NaOH into it here NaOH we are adding so NaOH actually combines with this this OH minus that you are giving because this is base we are adding so we are giving OH minus into this so mainly dissociation of this only this is weakly ionized dissociation of this will be very less because of again common ion effect here you see common ion effect so main the concentration of Na plus will be far more than that of H plus so this OH minus combines with Na plus over here right and forms what Na plus plus OH minus and it gives NaOH in the reaction vessel right so obviously when this is combining with this so this reaction is going when you add base into it the second reaction is going into forward direction when you add acid into it the first reaction is going into backward direction that is how it neutralize the additional OH minus or H plus that we are giving in right so this is the extra OH minus we are giving in it has to neutralize to maintain the pH since it is a buffer solution right and it is neutralized by this NaOH Na plus and OH minus now when this reaction goes into forward direction obviously the concentration of CS3COO minus in the solution will increase and how it increases 5 millimoles of this combines 5 millimoles of this so extra 5 millimoles of this CS3COO minus forms so that will be again 10 plus 5 here 15 millimoles of CS3COO minus will get and and what about acid right acid concentration will decrease right so that CS3COOH will then forms 10 minus 5 is equals to 5 millimoles here so salt concentration is increasing acid concentration is decreasing so pH of the solution that will be pKa plus log of salt by acid salt is 15 acid is 5 so 4.7 plus log 3 that will be your answer here 4.7 plus 0.47 or 48 whatever you take that is the answer we will get here understood okay so you try to think on this question again at home okay this is a very good question which actually helps you to understand the question how buffer solution works okay but again if we take the class we'll take the revision class of this we'll discuss this again the working of buffer solution okay now there are some facts that you must keep in mind that for effective buffer the ratio of salt by acid should be in this this one you write down salt by acid should lie in this range for effective buffer solution okay and with this if you put you'll get the range of pKa you can find out this with the formula pKa minus 1 less than equal to pH pKa plus 1 this question they have asked many times in the exam for effective buffer the pH range should be this you can put this and this value into pH formula you'll get this one more thing here you see the log of salt by acid concentration that you have or in case of basic buffer salt by base okay this this particular portion this log part in the formula this gives you the change in pH delta pH so if they ask you what is the change in pH you have to find out effective buffer solution means what an engine that uh see we must have the ratio of the salt of concentration and acid for a solution to behave as a buffer solution like all other solutions are not buffer solution for that we should have a definite range of salt and acid concentration of salt and acid right so that ratio we must have so for effective buffer solution means for a solutions to behave for a solution to behave as a buffer solution the salt by acid ratio is found to be in this range minimum is 0.1 and maximum is 10 okay so this point this term sometimes they ask this question also and when you put this ratio 0.1 and 10 into this particular formula you'll get the range of pH on the basis of this we'll get this pH this is actually the experimental value we have okay 0.1 to 10 that's the thing right so but this this thing you keep in mind sometimes they ask you this thing directly and how do we get this formula we have here right salt by acid is nothing but this portion first you put 0.1 here and then you put 10 here you'll get pk minus 1 and then pk plus 1 the pH value understood okay naturally we'll see some concepts of general organic chemistry and we'll try to understand the concept with help of the questions okay questions itself we'll see okay we'll see now geoc see in geoc like again we cannot discuss all other things so we'll directly discuss the various electronic effects okay in organic chemistry that is various electronic effects the various electronic effects are first one we have inductive effect the first effect is inductive effect second one is mesomeric effect mesomeric effect and this also will discuss one concept of resonance also hyper conjugation just a second okay so hyper conjugation electromagnetic effect electromagnetic effect so first question that they ask from this that the first three effect that we see that I have written here these are the permanent effect okay this is permanent effect and this is temporary effect permanent and temporary effect okay so what do you understand by this electronic effect suppose I have take one I have suppose if I take one molecule like c c c c and x halogen electronic effect is nothing but the displacement of electrons displacement of electrons how electron like you know displaced from one point to other point okay that's the meaning we have here electronic effects okay now like I take this example okay obviously this halogen atom attached with this carbon right that is more electronegative than the other than the carbon atom that is present okay halogen atom present over here it is more electronegative so what happened the bond pair that you have here it is slightly shifted towards this halogen atom and then it becomes del negative it will have slightly negative charge and this carbon will have slightly positive charge now when this is positive charge we have so this will also drag this electron pair to this side this becomes del 2 plus positive charge on to this and like this this positive charges is what is keep on decreasing as we go away from this x right here we will have maximum density of positive charge here we have lesser here we are even lesser and like this the positive charge density decreases and now when this positive charge density decreases with the density to withdraw electron or attract this bond pair of electron towards its side is less right and we say that this kind of effect we call it as i effect inductive effect inductive effect and why it is permanent because the molecule is halide only right it is alkyl halide and it is a molecule whenever this x is attached with this carbon this things this thing we can observe easily right that's why it is a permanent effect now the two three points that you have here you have to keep in mind that it involves only it involves only sigma electron it involves only sigma electron right now and it is what it is distance dependent also distance dependent and it is found to be the effect of this is found to be negligible after second or third carbon mainly third carbon or second carbon also sometimes we say so after second or third carbon the positive density is almost zero and then we don't observe any kind of displacement in the electron right so only sigma electrons are involved it is distance dependent also these things has been asked in the exam also right which of these are distance dependent effect like this they have asked the question okay so again you have to understand this and keep this in mind an important point it is but this thing is not true when we have resonance okay resonance we have or inductive or you know this mesomeric effect in mesomeric effect these is not true because there is pi electrons involved right there's pi electrons involved and that is not distance dependent also for that conjugation is required okay if conjugation is not there then no displacement of electron in mesomeric effect okay so there are two three characteristics of this inductive effect we have this is first thing permanent effect I have written over here sigma electrons involves okay transmission and distance dependent effect transmitted along transmitted along carbon chain right and it is represented by this arrow means the electron is displacing from this side to this side okay so if you see this one two three four and five if I write so this is chlorine right so chlorine will drag electron towards this side this also drag electron this also drag electron and like this it goes right so it is del plus delta one plus delta two plus like this so positive r density continuously decreases here right so this is the characteristics of sigma or what we say eye effect now this eye effect like I said this is the group that can withdraw electron from the carbon chain halide ions are the group or the halogen atoms are the group which can withdraw electron from the carbon chain right so this kind of group with withdraw electron from the carbon chain we call it as minus eye effect basically eye effect classified into two categories right one is plus eye and other one is minus eye minus eye group are those group which can withdraw electron or drag electron withdraw electrons plus eye are those group with releases electron releases electron so in this thing first of all you have to keep this in mind that which molecules or which atoms shows plus eye nature or which atom shows minus eye nature okay that you have to keep in mind since you see minus eye groups are the group which withdraw electron correct so they they must be electron deficient or positive charges species right so some examples I write down here that you copy down and you have to keep this in mind examples of plus eye and minus eye right so first of all you see examples of minus eye minus eye group maximum minus eye is for this nf3 plus then we have nr3 plus nh3 plus no 2 c triple bond n s o 3 h c o o h minus fluorine then chlorine then bromine iodine right c o o r o r o h then we have alkyne phenyl right these are the few examples we have actually we also take the reference of carbon and hydrogen right all those groups which has more tendency to withdraw electron then the carbon and hydrogen bond those are said to be minus eye all those groups which has more tendency to release electron then the carbon and hydrogen bond are said to be plus eye okay see this is the order that is given in any other book actually okay but if you can memorize this it is fine okay but I will also suggest to you to you know to use some logic you know common sense so that you can compare which one will have more plus eye or minus eye because these groups eventually affects the acidity and best city nature of any compound right and that is what the application part we have that we'll see okay so first of all you should know which minus eye group is dominant over which minus eye group then also you then only you can say okay this is more acidic or less acidic okay so few you know few common sense or few logic you can apply to understand okay first of all if electronegativity is more as electronegativity increases tendency to withdraw electron increases minus eye effect increases we can say this as electronegativity increases minus eye nature will be more for example you see the first one if I compare fluorine then chlorine then bromine and then iodine right obviously fluorine has maximum electronegativity order of minus eye should be this correct and that is what the order given here also okay second one you see if I ask you to compare the electronegativity of OH and SH which one will be more if I ask you to compare the electronegativity of NH2 and pH2 NH2 and pH2 fourth one suppose if I give you NH3 plus and NH2 OH2 plus and OH tell me OH and SH which one will have more minus eye okay so first one the order should be this because oxygen is more electronegative than sulfur the second one order is this nitrogen is more electronegative than phosphorus nitrogen is more electronegative than okay we have nitrogen only over here but this is the positive charge so it has more tendency to withdraw electron more minus eye oxygen positive charge more minus eye fluorine oxygen and nitrogen fluorine is most electronegative the order should be this right if you compare this one CF3, CCL3, CBR3 and CI3 the order of electronegativity should be a minus eye should be this this is the order okay so like this you can actually compare the minus eye nature of the group okay so you don't have to memorize this okay if you keep this in mind you can do many other questions okay we'll see the application of this also but we'll see we'll see few examples of plus eye okay plus eye group you see plus eye group plus eye group means what electron releasing electron releasing means what it has it must have electron present so either it has lone pair or negative charge on it okay that is the logic you can keep in mind suppose I have the first one which is CH2 lone pair, lone pair negative charge it is maximum then we have NH two lone pair negative charge oxygen lone pair negative charge C okay all alkyl group alkyl groups electron releasing so if I compare this CH3 CH3 then C CH3 H H C CH3 H CH3 and the last one we have CH3 whole thrice C what is the order of plus eye for this the plus eye will be maximum for plus eye will be maximum for this group because it contains three methyl group you see if you compare these two this has electron releasing tendency this has also electron releasing tendency this has electron releasing tendency right so here we have two electron releasing groups similarly here we have three electron releasing so maximum for this then we have this one and we have this in the last we have this yeah so this is correct right one more thing you see for if you if you have isotopes right suppose we have CT3 tritium and then deuterium right so CT3 will have maximum then we have CD3 and then we have CS3 this is also important okay for isotopes you must keep in mind bond length if they ask you bond length of carbon hydrogen bond is more than the carbon deuterium bond and is more than the carbon tritium bond so carbon tritium bond side bond bond length increases tendency to lose electron decreases okay that's the thing okay now few examples that we have already seen now we directly move to this you know some application part of it okay so eye effect eye effect also helps in you know determining the stability of intermediates like carbocation carbanion and then the acidic basic properties okay so we'll see first the stability of intermediate first question first type of question we'll see and then we'll see the acidic and basic nature okay so from 11th class who are there niranjan you're there niranjan there thus shushant is there no i don't think so anyways so we'll see this okay a few examples i'm giving okay so goc is the best way to understand goc is to solve questions okay there is theory that i have told you already okay most more application part you will see more you will understand okay so first one you see suppose if i uh take this example here we have positive sign carbocation okay one more thing is this positive charge this is fluorine and this is also fluorine first question is this we have to find out the stability of this carbocation positive charge carbon means carbocation find out the stability of this right positive charge here here we have positive charge this is methyl these two are methyl group here we have ch2 positive and then we have three positive and here we have ch2 positive here we have ch3 these two okay the first one see all like one thing you try to understand in organic chemistry if you have any charge species right so charge species is always less stable less stable than the neutral one always less stable than the neutral one okay so if you have any charge species if you are if you are able to neutralize the charge then the stability you are getting right so all these charge species you see right if it is neutralizing by these groups right and that is only possible when it releases electron right so what we can write down stability of carbocation stability of carbocation is directly proportional to directly proportional to plus i group and inversely proportional to minus i group okay that we can write minus i means what it withdraw withdraws electron right when suppose you have any positive charge right and when it withdraws electron then positive charge density will increase right suppose if I take this example one example I'll take here that is ch ch2 positive and here we have fluorine right another one we have ch2 positive and here we have oh ch3 just a second right these two examples I am taking right and one more example suppose if I write this okay this one you let me we'll discuss later ch two positive and ch3 this is the three examples I'm taking okay so stability of carbocation you see both are positives first of all you compare these two it will be you know easy for you to understand okay especially for those 11 plus students okay so you see this f has minus i nature right so it withdraws electron and when it withdraws electron the positive charge density on this carbon increases right this cs3 has tendency to lose electron so it releases electron so electron is going on to this carbon so positive charge density here decreases right so whenever we have increase in positive dense charge the stability will be less because we have to neutralize the charge species then only the stability will be more so if positive charge is there then electron you have to push to gain more stability if negative charge is there the electron you have to withdraw right and that's what we are saying carbocation means positive charge carbon directly proportional to plus i and inversely proportional to minus i if you take this one right this one and this one if you compare this oxygen has tendency to withdraw electron right so that will increase the positive charge density here but this tendency is less than this right so stability of this is more than this cs2 fvm so if you compare the stability of all these this is the first maximum stable then the second is this and third is this stability of this okay now only with this logic we'll try to solve this these examples that i have given you okay so now you see the first one the first one these are methyl electron releasing group right electron releasing and these are fluorine so electron withdrawing group electron withdrawing positive density here increases so stability will be less order will be this here you see oxygen has electron withdrawing nature and this methyl has electron releasing nature right so stability of this will be more because the positive charge will more linearize here cs3 electron releasing nature and f3 electron withdrawing nature stability of first is more than second this is three degree carbocation this is two degree carbocation and this is one degree carbocation three degree carbocation is most stable then two degree then one degree why because it has three alkyl group two degrees electron it has only two alkyl group and this has only one alkyl group so this is the order of i effect that we have order of stability of carbocation according to i effect o cs3 is more stable than f happen critique see o cs3 and f uh minus i nature if you see first of all the order that i've given you in that you see f has more minus i nature than o cs3 and if you know the order it's fine otherwise you can you know you can logically you can understand this fluorine is withdrawing electron oxygen is also withdrawing electron but this methyl has tendency to release electron right because of this electron releasing tendency that tendency to withdraw electron of oxygen will decrease here first case second case anyways if you if you compare fluorine and oxygen fluorine is more electronegated so that will withdraw more electron oh yeah correct critique then yeah right right so these are the few examples of stability of intermediate right like carbocation and all fine now in this if you see the stability of uh or the acid acidic and basic uh nature right acidic strength and basic strength we see some more examples we'll see into this for carbon ion okay just reverse of this carbon ion and then we'll see acidic and basic strength here we can extend this class up to uh 12 15 right do you have any other class after this can we extend this class up to 12 15 okay okay so we'll take this class then till 12 15 okay you see this uh tell me the stability order of all these first one negative charge negative charge first one is this second one is this chlorine negative charge we have here cs3 cd3 and ct3 isotopes of hydrogen tell me the answer in all this yes the first one the first one you see it is the carbon ion right negative charge we have so in this what we can apply the logic that stability of carbon ion just reverse of that carbocation carbon ion is directly proportional to directly proportional to minus i group and inversely proportional to plus i group right directly proportional to minus i inversely proportional to plus i right so here you see this is three degree carbon ion this is two degree carbon ion and this is one degree carbon ion it has three electron releasing group so stability of this will be least then we have second and then we have first in these two you see in this with the chlorine is closer to the chlorine the compound that you have over here and this chlorine has minus i nature so the electron density here will increase more than here so obviously the stability of second one is more than to that of first one oh sorry it is in the reverse order no this is a drawing correct the stability will be this okay first is more than second now you see n o2 and nf3 both has minus i nature n o2 and nf3 both has minus i nature but since we have oxygen here and we are floating here so which one will have more minus i floating right so minus i of nf3 is more than to minus i of n o2 and one positive charge also we have here this will withdraw more electron so obviously the stability of second is more than to that of first right ch3 cd3 ct3 this has maximum plus i right cs3 shows plus i effect no so both all these three will show plus i but plus i of ct3 is maximum i told you this plus i is electron releasing electron releasing so stability is minimum for this maximum for cs3 order will be this okay now next the last thing that we'll discuss today that is acid base strength acid base strength see in organic chemistry we'll consider the acidic strength it is cd3 not co3 i said it is cd3 so shouldn't the last one be opposite okay let me check last one you see what is the question that is isotopes of hydrogen right this is ch3 has plus i nature and the plus i nature of for ct3 is maximum understand swetha plus i nature of ct3 see the plus i nature of ct3 is maximum right ct3 has maximum tendency to lose electron tendency to lose electrons right this is cd3 i told you this ct3 the plus i nature of ct3 is more than to the plus i nature of cd3 and that of ch3 so more will be the plus i more will be the electron density here and less will be the stability you see stability is inversely proportional to the plus i effect that's why the third one is the least stable yeah because there is negative charge on the top and plus i nature will decrease the stability okay now you see the acid base strength you see in organic chemistry like i said the acidic strength we define by the tendency to lose h plus i and however we have two three more you know definitions of acid tendency to in with respect to the lone pair and all but in organic chemistry acids are those compound which loses h plus i and h plus iron in water h2 with respect to water we take with respect to water okay and any compound right suppose r h or any other compound right any compound if it loses h plus iron the iron that we get after losing h plus that we call it as the conjugate base okay and the strength of strength of an acid depends upon depends upon the stability of stability of conjugate base right stability of conjugate base so suppose if i take this r c o o h r c o h okay or suppose if i take this here c h 3 c o h okay c s 3 c o h and suppose we have c 2 h 5 c o o h now this is the acid and we have to compare the acid strength of this so what we'll do we'll just form the conjugate base of this minus h plus so when it loses h plus what it forms it forms c s 3 c o o minus and when this loses h plus it forms minus h plus it forms c 2 h 5 c double bond o and o minus correct now this is the conjugate base of this acid this is the conjugate base of this acid any acid you have right suppose we have h 2 o when it loses h plus it forms what o h minus and h plus so o h minus is the conjugate base of h 2 o if you have h cl so its conjugate base is cl minus we have h s of 4 minus its conjugate base is s of 4 2 minus just you release or just you remove h plus from that compound okay and now when this conjugate base is more stable it means for this molecule the tendency to lose h plus ion will be more because on losing h plus ion it is forming more stable conjugate base correct that is true for this compound also so if the conjugate base is more stable the tendency to lose h plus ion will be more and hence the acidity will be more okay c s 3 c o i am coming back to this Pratik so you see if you check the stability of these two conjugate base okay so that again depends upon the plus i nature of what plus i nature of c s 3 and c 2 h 5 so this is the both shows what both shows plus i effect this is also plus i and this is also plus i and because of plus i we know the the stability of an ion decreases this is a negative charge an ion so because of plus i the stability decreases but which which one will show more plus i c 2 h 5 larger group c 2 h 5 shows more plus i effect so that's why the stability of this compound is lesser than the this compound and hence the acidic order is this c s 3 c o h is more stable than c 2 h 5 so one more thing you can write here acidic strength is directly proportional to minus i effect and inversely proportional to plus i effect that is the same order of an ion strength yeah yeah it's relative it's relative Pratik this acidic and basic thing is obviously it is relative right basic thing if you have to compare because you compare acidity and then reverse of that will be the basic order okay that is a simple thing few examples we'll see then probably you understand yeah right c 2 h 5 is even more weaker okay that's why it is so yeah there's this acid and base thing everywhere it is relative only right you see if you take if you take h 2 s of 4 right if you take h 2 s of 4 water generally we don't see that we don't see the what acidic nature of water h 2 all right we don't see that as as nature of water but if you compare NaOH and h 2 obviously h 2 is more acidic than NaOH because NaOH is the base you understand this so acidic and basic strength is always is always relative right in any equilibrium only you have started at c l of 4 is the most most acidic compound we have see that if you see a little bit of example if i'll give you hc l of 4 is most the acidic strength of hc l of 4 is maximum okay and then we have suppose hi we have hbr we have right h 2 s of 4 also we have up to this and then we have hcl like this the strength is there so if you compare hi and hbr so obviously hi is more acidic than hbr but if you compare hbr and h2 s of 4 hbr is more acidic than h2 s of 4 and then it is true for hcl and h2 s of 4 also right so it is always relative okay few examples you see one very common type of question that they ask many times that is hf hcl hbr and hi second roh rsh h2 s and hcl rc triple bond ch rch double bond ch2 rch2 ch3 hcn hch double bond nh it is acidity order acidity order you have to find out okay now you listen to me all of you see one thing for this acidic and basic strength generally you'll get two types of questions okay in one type there will be variation in size okay what i said two types of question you'll get in first type there will be variation in size variation in size and what i what we say that the acidity is directly proportional to the size of an ion because large size more uniform distribution will be there of the negative charge and that's why the stability will be more okay large size more uniform distribution of negative charge and stability will be more okay and then in the second type we have the size is not that much varying but electronegativity is there right electronegativity sizes is not that the difference in size is not that much but electronegativity difference is there so in that case acidity is directly proportional to electronegativity now you see these three questions one two and three in this there is size in there is a variation in size fluorine chlorine bromine iodine oxygen sulfur oxygen and sulfur right there is a variation in size in this you see sulfur and chlorine belongs to third period only there is not much variation but yes electronegativity difference is there right here we have carbon and carbon electronegativity difference here you see this carbon is what this carbon is sp hybridized this carbon is sp2 hybridized and this carbon is sp3 hybridized difference in electronegativity this carbon is what sp hybridized and this carbon is sp2 hybridized carbon carbon atom size is same but difference in electronegativity is there if the conjugate base is stable vashnavi you think one thing yeah how do you get conjugate base by removing h plus so if after removing h plus if you are gaining stability it means you will happily lose h plus no so that's the thing over here conjugate base we get after losing h plus so if conjugate base is stable it means the tendency to lose h plus ion will be more and that's why it is a stable more acidic compound it is more stable conjugate base more will be the acidity of that compound this is the one thumb rule you should keep in mind understood another thing you see like i said variation in size and electronegativity these two factors you have to keep in mind then you can put some logic why is the size of an ion is directly proportional to this acidity because more will be the size since the size is this negative charge and the size is this negative charge okay more will be the size more will be the distribution uniform distribution of this negative charge over this anion and that's why the stability will be more more uniform distribution means what more stability right so now you see here h f h c l h b r h i what is the conjugate base of h f f minus c l minus this is br minus and this is i minus so which which has the maximum size obviously iodine has the maximum size right so obviously the stability of iodine is maximum over here right so that's why the order of acidity is this is it clear one more thing you can think over here the bond between this h f is what it is one s and two p bond one s two p this is one s three p one s four p and one s five p okay bond length is maximum over here as bond length increases bond strength decreases right and bond strength when decreases tendency to lose h plus will be more that is also one of the way that you can think h i is most simple oxygen and sulfur you see if you lose h plus you'll get o minus and s minus so since s minus sulfur psi or sulfur is more than to that of oxygen that's why the stability of conjugate base for this compound will be more and acidity of this is more yeah predict like that also you can think oxygen being more electronegative draws more electrons and then the electron density on oxygen is more that will destabilize that iron see whenever we have the contradiction in size and charge we always give preference to charge that we always keep in mind yeah more negative see whether it is more negative charge or positive charge whenever the charge is more it is always less stable neutrally species is always more stable than the charges species so whenever you have tendency to decrease the charge you are going towards more stable state right if we have contradiction in size and electronegativity or charge we always prefer charge as a major part here right charge will always as a major factor okay so now you see the first three that I have given you it is based on the size factor oxygen sulfur both will have negative charge in its conjugate base but sulfur having more size that's why the stability of this compound is more and hence the acidity of this is more oxygen sulfur again you see both will have negative charge in its conjugate base sulfur having more size stability of this is more and hence acidity or it is this what is the confusion tell me see you listen to me one thing just one thing you listen to me there are two types of question one is when there is difference in size like the first three are given you and other one then there is difference in electronegativity no no no wait listen to me one is size difference and electronegativity difference so you don't consider this size and electronegativity see I am again explaining this okay you just listen to me don't think anything else I'll explain everything when you have both factors and what you have to keep in mind just you listen to me first first of all two types of questions are possible variation in size variation in electronegativity correct when size variation is there right so as the size of anion increases acidity increases this is the thing I have written it over here you see acidity is directly proportional to the size of anion this thing why it is actually proportional because more will be the size more uniform distribution of the charge will be there and hence the stability will be there so when you form the conjugate base of these compounds as the size of anion increases distribution of charge will be more uniform that leads towards the stability or to that the conjugate base wait wait wait wait let me explain correct so now coming back to this size factor first example you understood f minus cl minus br minus i minus i minus maximum size so most stable conjugate base and that's why the acidity order is this coming back to the second one you'll get o minus here and s minus here right so both will have negative charge size of sulphur is more so this negative charge here is more stable so acidity of this compound is more and same logic we have applied here right now if you have now if you have any contradiction if you have any contradiction in size and charge then we always prefer this charge factor into this size will not be the major factor right so for s h if you consider size or electronegativity s h is no you see Pratik like we cannot here you see here if you compare these two compounds oxygen and sulphur right so we have difference in size we have oxygen present here see I know where you have got confused you are you must have things have I don't we take electronegativity of this oxygen and electronegativity of the sulphur right that will not take when we take electronegativity here you see this kind of compound you see sulphur and chlorine both belongs to the third period right after sulphur we have chlorine right so obviously there is not much size difference here but electronegativity difference is there if you see we'll also have the size difference here so this you have to think right second example you see this carbon and this carbon do we have electronegativity difference here yes we have but do we have size difference no so we'll we'll take electronegativity here but here what we have when the elements belongs to different group or sorry different period right this is for this is for second period oxygen and this is for third period sulphur so when there is different period we have then we'll take the size factor here you see it is it is clearly understood that size is same we'll take the electronegativity factor carbon and carbon size is same we'll take the electronegativity factor right sulphur and chlorine size is very much same right very close but electronegativity difference is there right in all this example you see I have given the term which belongs to the different period when we have different period you consider you consider size in that case chlorine chlorine bromine iodine different period did you understand yeah it may be yeah Pratik correct it may be uh in some examples it may be it may be that it it won't make any difference but actual thing is this only if if you have any contradiction in size and suppose in one example in one example I have given the variation in size also and variation is electronegativity also I've given you three four examples three four molecules like that in that case we'll go with charge factor not the size factor okay so the point here is what all these things according to the size I have given you this thing the stability of what suppose this is this forms what cl minus conjugate base and s2 minus conjugate base right so chlorine is more electronegative negative charge on more electronegative is always more stable so obviously the hcl is more acidic than h2s which is more electronegative here sp hybridization is more electronegative so this is more most acidic than the second one and then the third one in these two again sp this is more electronegative is it clear now tell me okay so hello it's 12 30 now okay I'm getting late okay we'll we'll continue with some more example in the next revision classes okay fourth one which is the fourth one h2s and hcl okay h2s and hcl you see chlorine is more electronegative obviously right and we have to consider the electronegativity factor so acidity you see acidity is directly proportional to the electronegativity here you see acidity directly proportional to the electronegativity why more negative charge you always keep in one thing one thing in mind negative charge on more electronegative element negative charge on more electronegative element is always more stable is always more stable reverse of this is also true positive charge on more electro positive element is always more stable yeah chlorine is more is electronegative than sulfur that's why okay so negative charge and more electronegative positive charge on more electropositive elements are always more stable okay these two things you should keep in mind okay is it clear now if you take here H2O also if you take here H2O then this is the most acidic that's why you see it is again you see the relative thing yeah yeah right Pratik correct I know where you got confused again you are mixing these questions question number two and question number four right Pratik question number two and question number four you are mixing right okay hello Pratik we'll discuss this next class okay I know Pratik where you got confused but I'll tell you see actually depending on the question you have to think that what logic you should apply it is a bit confusing I can understand okay but then again I'll discuss this next class okay you have another class at one o'clock so I won't take much time okay yeah yeah yeah we'll discuss this next class okay Pratik I understood where you got confused but that is also I have explained but again I'll explain again okay don't worry so no bye bye take care okay we'll discuss some more examples in the next revision classes okay so bye bye take care thank you


vox recordings are in the public domain for more information or to volunteer please visit librivox.org recording by alan wayman anderson's fairy tales by hands christine anderson chapter 15 the little natch girl most terribly cold it was it snowed and was nearly quite dark and evening the last evening of the year in this cold and darkness they went along the street a poor little girl bareheaded and with naked feet when she left home she had slippers on it is true but what was the good of that they were very large slippers which her mother had hitherto worn so large were they and the poor little thing lost them as she scuttled away across the street because of two carriages that rolled by dreadfully fast one slipper was nowhere to be found the other had been laid hold off by an urchin and off he ran with it he thought it would do capitely for a cradle when he someday or other should have children himself so the little maiden walked on with her tiny naked feet that were quite red and blue from cold she carried a quantity of matches in an old apron and she held a bundle of them in her hand nobody had bought anything off her the whole live long day no one had given her a single farthing she crept along trembling with cold and hunger a very picture of sorrow the poor little thing the flakes of snow covered her long fair hair which fell in beautiful curls around her neck but of that of course she never once now thought from all the windows the candles were gleaming and it smelled so deliciously of roast goose for you know it was New Year's Eve yes of that she thought in a corner formed by two houses of which one advanced more than the other she seated herself down and cowered together her little feet she had drawn close up to her but she grew colder and colder and to go home she did not venture for she had not sold any matches and could not bring a farthing of money from her father she would certainly get blows and at home it was cold too for above her she had only the roof through which the wind whistled even though the largest cracks were stopped up with straw and rags her little hands were almost numbed with cold oh her match might afford her a world of comfort if she only dared take a single one out of the bundle draw it against the wall and warm her fingers by it she drew one out how it blazed how it burns it was a warm bright flame like a candle as she held her hands over it it was a wonderful light it seemed really to the little maiden as though she was sitting before a large iron stove with burnished brass feet and a brass ornament at top the fire burned with such blessed influence it warmed so delightfully the little girl had already stretched out her feet to warm them too but the small flame went out the stove vanished she had only the remains of the burnt out match in her hand she rubbed another against the wall it burned brightly and where the light fell on the wall there the wall became transparent like a veil so that she could see into the room on the table was spread a snow white tablecloth upon it was a splendid porcelain service and the roast goose was steaming famously with its stuffing of apple and dried plums and what was still more capital to behold was the goose hopped down from the dish reeled about on the floor with knife and fork in its breast till it came up to the poor little girl when the match went out and nothing but the thick cold damn wall was left behind she knighted another match now there she was sitting under the most magnificent Christmas tree it was still larger and more decorated than the one which she had seen through the glass door in the rich merchant's house thousands of lights were burning on the green branches and gaily colored pictures such as she had seen in the shop windows looked down upon her the little maiden stretched out her hands towards them when the match went out the lights of the Christmas tree rose higher and higher she saw them now as stars in heaven one fell down and formed a long trail of fire someone is just dead said the little girl for her old grandmother the only person who had loved her and who was now no more had told her that when a star falls a soul ascends to god she drew another match against the wall it was again light and in the luster there stood the old grandmother so bright and radiant so mild and with such an expression of love grandmother cried the little one oh take me with you you go away when the match burns out you vanish like the warm stove like the delicious roast goose and like the magnificent Christmas tree and she rubbed the whole bundle of matches quickly against the wall for she wanted to be quite sure of keeping her grandmother near her and the matches gave such a brilliant light that it was brighter than at noonday never formally had the grandmother been so beautiful and so tall she took the little maiden on her arm and both flew in brightness and enjoy so high so very high and then above was neither cold nor hunger nor anxiety they were with god but in the corner at the cold hour of dawn sat the poor girl with rosy cheeks and with a smiling mouth leaning against the wall frozen to death on the last evening of the old year stiff and stark sat the child there with her matches of which one bundle had been burnt she wanted to warm herself people said no one had the slightest suspicion of what beautiful things she had seen no one even dreamed of the splendor in which with her grandmother she had entered on the joys of a new year end of chapter 15 chapter 16 of anderson's fairy tales this is a libra vox recording all libra vox recordings are in the public domain for more information or to volunteer please visit libra vox.org recording by inna schumacher the dream of little tuck ah yes that was little tuck in reality his name was not tuck but that was what he called himself before he could speak plain he meant it for charles and it is all well enough if one does but know it he had now to take care of his little sister augusta who was much younger than himself and he was besides to learn his lesson at the same time but these two things would not do together at all they sat the poor little fellow with his sister on his lap and he sang to her all the songs he knew and he glanced the while from time to time into the geography book that lay open before him by the next morning he was to have learned all the towns in zealand by heart and to know about them all that is possible to be known his mother now came home for she had been out and took little augusta on her arm tuck ran quickly to the window and read so eagerly that he pretty nearly read his eyes out before it got darker and darker but his mother had no money to buy candle there goes the old washerwoman over the way said his mother she looked up the window the poor woman can hardly drag herself along and she must now drag the pale home from the fountain be a good boy tacky and run across and help the old woman won't you so tack ran over quickly and helped her but when he came back again into the room it was quite dark and as to a light there was no thought of such a thing he was now to go to bed there was an old turn up beds dead in a delay and thought about his geography lesson and of zealand and of all that his master had told him he ought to be sure to have read over his lesson again but that you know he could not do he therefore put his geography book under his pillow because he had heard that was a very good thing to do when one wants to learn one's lesson but one cannot however rely upon it entirely well there he lay and thought and thought and thought and ordered once it was just as if someone kissed his eyes and mouth he slept and yet he did not sleep it was as though the old washerwoman gazed on him with her mild eyes and said it were a great sin if you were not to know your lessons tomorrow morning you have aided me i therefore will now help you and the loving god will do so at all times and all of a sudden the book and a text pillow began scraping and scratching click click that was an old hen who came creeping along and she was from koji i'm a koja hen note koji a town in the bay of koji to see the koji hens is an expression similar to showing a child london which is said to be done by taking his head in both hands and so lifting him off the ground at the invasion of the english in 1807 an encounter of a no very glorious nature took place between the british troops and the undisciplined danish militia end note said she and then she related how many inhabitants they were there and about the battle that had taken place and which after all was hardly worth talking about gobbledygravity plump down fell somebody it was a wooden bird the pop and j used at the shooting matches at prasto now he said that there were just as many inhabitants as he had nails in his body and he was very proud the waltzin lived almost next door to me note prasto is still smaller town than koji some hundred paces from it lies the manor house niso where for waltzin the famed sculpture generally sojourned during his stay in denmark and where he called many of his immortal works into existence end note plump here i lie capitally but this attack was no longer that lying down all at once he was on horseback on he went at full gallop still galloping on and on a night with a gleaming plume and most magnificently dressed held him before him on the horse and thus they rode through the wood to the old town of bordenborg and that was a large and very lively town high towers rose from the castle of the king and the brightness of many candles streamed from all the windows within was dancin song and king wildmer and the young richly attired maids of honor danced together the morn now came and as soon as the sun appeared the whole town and the king's palace crumbled together and one tower after the other and at last only a single one remained standing where the castle had been before note bordenborg in the reign of king wildmer a considerable place now an unimportant little town one solitary tower only and some remains of a wall show where the castle once stood end note and the town was so small and poor and the schoolboys came along with their books under their arms and said two thousand inhabitants but that was not true for there were not so many and little tucky laying his bed it seemed to him as if he dreamed and yet as if he were not dreaming however somebody was close beside him little tucky little tucky cried somewhere near it was a seaman quite a little personage so little as if he were a midshipman but a midshipman he was not many remembrances from corso note corso on the great belt called formally before the introduction of steam vessels when travelers were often obliged to wait a long time for a favorable wind the most tiresome of towns the poet baggason was born here end note that is a town that is just rising into importance a lively town that has steamboats and stage coaches formally people called it ugly but that is no longer true i lie on the sea said corso i have high roads and gardens and i've given birth to a poet who was witty and amusing which all poets are not i once intended to equip a ship that was to sail all around the earth but i did not do it although i could have done so and then too i smell so deliciously for close before the gate bloom the most beautiful roses little tuck looked and all was red and green before his eyes but as soon as the confusion of colors was somewhat over all of a sudden they appeared a wooded slope close to the bay and high above stood a magnificent old church with two high pointed towers from out the hillside spouted fountains and thick streams of water so that there was a continual splashing and close beside them sat an old king with a golden crown upon his white head for that was king hoa near the fountains close to the town of rose guild as it is now called and up the slope into the old church went all the kings and queens of danmark hand in hand all with their golden crowns and the organ played in the fountains rustle little tucks saw all heard all do not forget the diet said king crore note rose guild once the capital of danmark the town takes its name from king crore and the many fountains in the neighborhood in the beautiful cathedral the greater number of the kings and queens of danmark are interred in rosegill too the members of the danish diet assemble end note again all disappeared yes and whether it seemed to him just as if one turned over a leaf in a book and now stood there an old peasant woman who came from sorb note sorb a very quiet little town beautifully situated surrounded by woods and lakes whole book danmark's molier founded here an academy for the sons of the nobles the poets hoa and ingerman were appointed professors here the latter lives there still end note where grass grows in the marketplace she had an old gray linen hanging over her head and back it was so wet it certainly must have been raining yes that it has said she and she now related many pretty things out of whole book's comedies and about wildmer and absalon but all at once she cowered together and her head began shaking backwards and forwards and she looked as if she were going to make a spring croak croak said she it is wet it is wet there is such a pleasant deathlike stillness and salt she was now suddenly a frog croak and now she was an old woman one must dress according to the weather said she it is wet it is wet my town is just like a bottle and one gets in by the neck and by the neck one must get out again in former times i had the finest fish and now i have fresh rosy cheek boys at the bottom of the bottle who learn wisdom hebrew greek croak when she spoke it sounded just like the noise of frogs or as if one walked with great boots over more or is the same tone so uniform and so tiring that little tuck fell into a good sound sleep which by the by could not do him any harm but even in the sleep there came a dream or whatever else it was his little sister augusta she with the blue eyes and the fair curling hair was suddenly a tall beautiful girl and without having wings was yet able to fly and she now flew over zealand over the green woods and blue lakes do you hear the cockro cockadoodle the cocks are flying up from koji you will have a farm yard so large oh so very large you will suffer neither hunger nor thirst you will get on in the world you will be a rich and happy man your house will exalt itself like king Voldemort's tower and will be richly decorated with marble statues like that at prasto you understand what i mean your name shall circulate with renown all around the earth like unto the ship that was to have sailed from course all and in rose skill do not forget the diet said king raw then you will speak well and wisely little tucky and when at last you sink into your grave you shall sleep as quietly as if a land saw said tuck awaking it was bright day and he was now quite unable to call to mind his dream that however was not at all necessary for one may not know what the future will bring and out of bed he jumped and read his book and now all at once he knew his whole lesson and the old washerwoman popped her head in at the door nodded to him friendly and said thanks many thanks my good child for your help may the good ever-loving god fulfill your loveliest dream little tucky did not know at all what he had dreamed but the loving god knew it at the end of chapter 16 chapter 17 of anderson's fairy tales this is a levy vox recording all levy vox recordings are in the public domain for more information or to volunteer please visit levy vox dot org recording by kathleen larberg anderson's fairy tales by hands christian anderson chapter 17 the naughty boy a long time ago there lived an old poet a thoroughly kind old poet as he was sitting one evening in his room a dreadful storm arose without and the rain streamed down from heaven but the old poets that warm and comfortable in his chimney corner where the fire blazed and the roasting apple hissed those who have not a roof over their heads would be wetted to the skin said the good old poet oh let me in let me in i am cold and i'm so wet exclaimed suddenly a child that stood crying at the door and knocking for admittance while the rain poured down and the wind made all the windows rattle poor thing said the old poet as he went to open the door there stood a little boy quite naked and the water ran down from his long golden hair he trembled with cold and had he not come into a warm room he would most certainly have perished in the frightful tempest poor child said the old poet as he took the boy by the hand come in come in and i will soon restore thee thou should have wine and roasted apples for thou art fairly a charming child and the boy was so really his eyes were like two bright stars and although the water trickled down his hair it waved in beautiful curls he looked exactly like a little angel but he was so pale and his whole body trembled with cold he had a nice little bonus hand but it was quite spoiled by the rain and the tints of his many colored arrows ran one into the other the old poet seated himself beside his hearth and took the little fellow on his lap he squeezed the water out of his dripping hair warmed his hands between his own and boiled for him some sweet wine then the boy recovered his cheeks again grew rosy he jumped down from the lap where he was sitting and danced around the kind old poet you are a merry fellow said the old man what's your name my name is cute but answered the boy don't you know me there lies my bow it shoots well i can assure you look the weather is now clearing up and the moon is shining clear again through the window while your bow is quite spoiled said the old poet that were sad indeed said the boy and he took the bow in his hand and examined it on every side oh it is dry again and it's not hurt at all the string is quite tight i will try it directly and he bent his bow took aim and shot an arrow at the old poet right into his heart you see now that my bow is not spoiled said he laughing and away he ran the naughty boy to shoot the old poet in that way he who had taken him into his warm room who had treated him so kindly and who had given him warm wine and the very best apples the poor poet lay on the earth and wept for the arrow had really flown into his heart five said he how naughty a boy Cupid is i will tell all children about him that they may take care and not play with him for he will only cause him sorrow and many a heartache and all good children to whom he related the story took great heat of this naughty Cupid but he made fools of them still for he is astonishingly cunning when the university students come from the lectures he runs beside them in a black coat and with the book under his arm it is quite impossible for them to know him and they walk along with him arm in arm as if he too were a student like themselves and then on perceived he thrusts an arrow to their bosom when the young maidens come from being examined by the clergyman or go to church to be confirmed there he is again close behind them yes he is forever following people at the play he sits in the great chandelier and burns in bright flames so that people think it really is a flame but they soon discover it is something else he rose about in the garden of the palace and upon the ramparts yes once he even shot your father and mother right in the heart ask them only and you will hear what they'll tell you oh he is a naughty boy that Cupid you must never have anything to do with him he is forever running after everybody only think he shot an arrow once at your old grandmother but that is a long time ago and it is all past now however a thing of that sort she never forgets fine naughty Cupid but now you know him and you know too how ill behaved he is end of chapter 17 recording by Kathleen Larbert chapter 18 of Anderson's fairy tales this is a LibriVox recording all LibriVox recordings are in the public domain for more information or to volunteer please visit LibriVox.org recording by Catalina Watt Anderson's fairy tales by Hans Christian Anderson chapter 18 the red shoes there was once a little girl who was very pretty and delicate but in summer she was forced to run about with bare feet she was so poor and in winter were very large wooden shoes which made her little insteps quite red and that looked so dangerous in the middle of the village lived old dame shoemaker she sat and sewed together as well as she could a little pair of shoes out of old red strips of cloth they were very clumsy but it was a kind thought they were meant for the little girl the little girl was called Karen on the very day her mother was buried Karen received the red shoes and wore them for the first time they were certainly not intended for mourning but she had no others and with stocking the speed she followed the poor straw coffin in them suddenly a large old carriage drove up and a large old lady sat in it she looked at the little girl felt compassion for her and then said to the clergyman here give me the little girl I will adopt her and Karen believed all this happened on account of the red shoes but the old lady thought they were horrible and they were burnt but Karen herself was cleanly and nicely dressed she must learn to read and so and people said she was a nice little thing but the looking glass said thou art more than nice thou art beautiful now the queen once traveled through the land and she had her little daughter with her and this little daughter was a princess and people streamed to the castle and Karen was there also and the little princess stood in her fine white dress in a window and let herself be stared at she had neither a train nor a golden crown but splendid red Morocco shoes they were certainly far handsomer than those dame shoemaker had made for little Karen nothing in the world can be compared with red shoes now Karen was old enough to be confirmed she had new clothes and was to have new shoes also the rich shoemaker in the city took the measure of her little foot this took place at his house in his room where stood large glass cases filled with elegant shoes and brilliant boots all this looked charming but the old lady could not see well and so had no pleasure in them in the midst of the shoes stood a pair of red ones just like those the princess had worn how beautiful they were the shoemaker said also they had been made for the child of account but had not fitted that must be patent leather said the old lady they shined so yes they shine said Karen and they fitted and were bought but the old lady knew nothing about their being red else she would never have allowed Karen to have gone in red shoes to be confirmed yet such was the case everybody looked at her feet and when she sat through the chancell door on the church pavement it seemed to her as if the old figures on the tombs those portraits of old preachers and preachers wives with stiff ruffs and long black dresses fixed their eyes on her red shoes and she thought only of them as the clergyman laid his hand upon her head and spoke of the holy baptism of the covenant with god and how she should be now a matured christian and the organ peeled so solemnly the sweet children's voices sang and the old music director sang but Karen only thought of her red shoes in the afternoon the old lady heard from everyone that the shoes had been red and she said that it was very wrong of Karen that it was not at all becoming and that her future Karen should only go in black shoes to church even when she should be older the next Sunday there was the sacrament and Karen looked at the black shoes looked at the red ones looked at them again and put on the red shoes the sun shone gloriously Karen and the old lady walked along the path through the corn it was rather dusty there at the church door stood an old soldier with a crutch and with a wonderfully long beard which was more red than white and he bowed to the ground and asked the old lady whether he might dust her shoes and Karen stretched out her little foot see what beautiful dancing shoes said the soldier sit firm when you dance and he put his hand out towards the soles and the old lady gave the old soldier arms and went into the church with Karen and all the people in the church looked at Karen's red shoes and all the pictures and as Karen knelt before the altar and raised the cup to her lips she only thought of the red shoes and they seemed to swim in it and she forgot to sing her psalm and she forgot to pray our father in heaven now all the people went out of church and the old lady got into her carriage Karen raised her foot to get in after her when the old soldier said look what beautiful dancing shoes and Karen could not help dancing a step or two and when she began her feet continued to dance it was just as though the shoes had power over them she danced around the church corner she could not leave off the coachman was obliged to run after and catch hold of her and he lifted her in the carriage but her feet continued to dance so that she trod on the old lady dreadfully at length she took the shoes off and then her legs had peace the shoes were placed in a closet at home but Karen could not avoid looking at them now the old lady was sick and it was said she could not recover she must be nursed and waited upon and there was no one whose duty it was so much as Karen's but there was a great ball in the city to which Karen was invited she looked at the old lady who could not recover she looked at the red shoes and she thought there could be no sin in it she put on the red shoes she might do that also she thought but then she went to the ball and began to dance when she wanted to dance to the right the shoes were danced to the left and when she wanted to dance up the room the shoes danced back again down the steps into the street and out of the city gate she danced and was forced to dance straight out into the gloomy wood then it was suddenly light up among the trees and she fancied it must be the moon for there was a face but it was the old soldier with the red beard he sat there nodded his head and said look what beautiful dancing shoes then she was terrified and wanted to fling off the red shoes but they clung fast and she pulled down her stockings but the shoes seemed to have grown to her feet and she danced and must dance over fields and meadows in rain and sunshine by night and day but at night it was the most fearful she danced over the church yard but the dead did not dance they had something better to do than to dance she wished to seat herself on a poor man's grave where the bitter tansy grew but for her there was neither peace nor rest and when she danced towards the open church door she saw an angel standing there he wore long white garments he had wings which reached from his shoulders up to the earth his countenance was severe in grave and in his hand he held a sword broad and glittering dance shout thou he said dance and I read shoes till thou art pale and cold till thy skin shrivels up and thou art a skeleton dance shout thou from door to door and where proud vain children dwell thou shalt knock that they may hear thee and tremble dance shout thou mercy cried Karen but she did not hear the angel's reply for the shoes carried her through the gate and to the fields across roads and bridges and she must keep ever dancing one morning she danced past a door which she knew well within sounded a psalm a coffin decked with flowers was born forth then she knew that the old lady was dead and felt that she was abandoned by all and condemned by the angel of god she danced and she was forced to dance through the gloomy night the shoes carried her over stack and stone she was torn till she bled she danced over the heath till she came to a little house here she knew dwelt the executioner and she tapped with her fingers at the window and said come out come out I cannot come in for I am forced to dance and the executioner said thou dost not know who I am I fancy I strike bad people's heads off and I hear that my axe rings don't strike my head off said Karen then I can't repent of my sins but strike off my feet in the red shoes and then she confessed her entire sin and the executioner struck off her feet with the red shoes but the shoes danced away with the little feet across the field into the deep wood and he carved out little wooden feet for her and crutches taught to the psalm criminals always sing and she kissed the hand which had wielded the axe and went over the heath now I have suffered enough for the red shoes said she now I will go into church that people may see me and she hastened towards the church door but when she was near it the red shoes danced before her and she was terrified and turned around the whole week she was unhappy and wept many bitter tears but when sunday returned she said well now I have suffered and struggled enough I really believe I am as good as many a one who sits in the church and holds her head so high and away she went boldly but she had got no farther than the church yard gate before she saw the red shoes dancing before her and she was frightened and turned back and repented of her sin from her heart and she went to the parsonage and begged that they would take her into service she would be very industrious she said and would do everything she could she did not care about the wages only she wished to have a home and be with good people and the clergyman's wife was sorry for her and took her into service and she was industrious and thoughtful she sat still and listened when the clergyman read the bible in the evenings all the children thought a great deal of her but when they spoke of dress and grandeur and beauty she shook her head the following sunday when the family was going to church they asked her whether she would not go with them but she glanced sorrowfully with tears in her eyes at her crutches the family went to hear the word of god but she went alone into her little chamber there was only room for a bed and chair to stand in it and here she sat down with her prayer book and while she read with a pious mind the wind bore the strains of the organ towards her and she raised her tearful counsels and said oh god help me and the sun shone so clearly and straight before her stood the angel of god in white garments the same she had seen that night at the church door but he no longer carried the sharp sword but in it stared a splendid green spray full of roses and he touched the ceiling with the spray and the ceiling rose so high and where he had touched it they gleamed a golden star and he touched the walls and they widened out and she saw the organ which was playing she saw the old pictures of the preachers and the preacher's wives the congregation sat in cushion seats and sang out of their prayer books for the church itself had come to the poor girl in her narrow chamber or else she had come into the church she sat in the pew with the clergyman's family and when they had ended the psalm and looked up they nodded and said it is right that thou art come it was through mercy she said and the organ pealed and the children's voices in the choir sounded so sweet and soft that clear sunshine streamed so warmly through the window into the pew where Karen sat her heart was so full of sunshine peace and joy that it broke her soul flew on the sunshine to god and there no one asked after the red shoes end of chapter 18 recording by Kathleen a what london please visit seen the future dot blog spot dot co dot uk end of anderson's fairy tales by hands christian anderson


Well, everyone, welcome back to the chat GPT video. In this one, we're going to talk about the chat GPT is at capacity now error. And a few of the ways you can possibly fix it. There's no guarantees. Generally, what's happening is their servers are basically overloaded. Traffic is massive. It's overloaded. And well, what can you do, right? You're kind of getting cue and you wait and see what happens. That said, there are some potential fixes. And I'm going to go through about eight or 10 of them. And they're going to increase in complexity from super simple, captain obvious stuff all the way through to the more complicated ones. So the first one, and I don't even really need to say this, is wait a little, all right? Here's the thing, if you're getting that error, chances are it's because their servers are at capacity. It's also possible you got logged out and a few other things. But if you're not in a rush, wait 15 minutes, come back, try again. Captain obvious checking out. The second one is refreshing the page. Again, pretty simple stuff if you've worked in IT or if you ever talked to somebody in the IT world, they'll always tell you to refresh the page. This though, here's the thing, refreshing the browser not only reloads the page, but it makes a separate request for the page. So it's sending in another request. So it's not coming from cash. So keep that in mind, refreshing the page often works. The next one I like to try is the log out login method. Again, captain obvious here, checking in for the third time, but this works. A lot of the time, if you've been logged in for a while and you've been inactive, it doesn't know if you're logged in or you're logged out and it will just assume you're out. So just log back in and try again if that doesn't work. That said, if none of these are working, there are a few other options. The first one is you can try the incognito mode. Go to Google browser or create an incognito browser, I don't know, use Google Chrome or whatever you wanna use but use it on incognito browser. And what this means is none of your browsing history, cookies, site data or information you've entered in is saved on your device. So you're basically kind of not anonymously browsing, but kind of does that matter to chat GPT? It's hard to say, but chat GPT seems to know everything. So it might know. So you might wanna give that one a crack. That one might be the fix. If that doesn't work, let's continue the escalation.  Basically you wanna go in and get rid of all of that.  That might be the next best option for you. Other than that, the only other things I can suggest is you can create a second account. Right now you can actually, it looks like you can have two accounts set up to the same phone number. So if you have a Google account and a Yahoo account or a Facebook account or whatever it is, log out of one, log in to the other if you have two accounts. If you don't have two accounts, make a second account, give that a crack. And if none of these things work, work part of me, you can always try a VPN. Don't know if that's gonna work, but it does work for some things and it might be worth a crack. Those are some of the fixes, guys. Let me know if you have a fix that's working for you and what's your experience. Thanks for watching, ton more stuff coming up, stay tuned.


For the deeper play this week I'm pretty intrigued by Blake Bortles. Tennessee has allowed four passing scores to Ryan Tannenhill and to Sean Watson to start the year, and they've allowed the highest average depth of target in football. That's why we've seen big plays against the Titans. And part of that reason is Malcolm Butler. According to Pro Football Focus, Butler has allowed the most yards in the league to start the year and only nine players have faced more targets. Meanwhile, Bortles has thrown it deep on 19% of his passes this year, which is about league average, but it's well above his career average. Bortles has the matchup and is a decent streamer here in week three.


Happy Thursday everybody. I'm Joe for JaspysCaseBrace.com. This sapphire has been flying off the shelves Here's the second half of the case from that case. We popped up a little bit earlier this evening This is it. This is our last our last five bucks of bowman sapphire for for a little bit, but keep your eye out You never know when we're gonna get some more all teams in all car chip and if you're one of the first 16 spots You get a chance at an extra spot so big. Thanks to this group right here chant at a buy one get one scenario Thanks, Joe for finishing this one off Let's give away that extra spot. That's our first dice rule second ice will be for names and teams one and a five six times one two three four five and Once more six than final time fingers crossed extra spot for Tristan. There you go Tristan Thanks for being an early bird. You got a little buy one get one scenario for you Now let's assign everybody to randomize everybody a team Let's roll it randomize it six and a five eleven times for names and teams one two three and 11th and final time After 11 got Joe down to mark six and a five eleven times for the teams one two three Three Four and 11th and final time after 11. We got the Royals Down to the Diamondbacks All right, Joe with the Royals and Cardinals Matt with the Pirates Tristan with the Cubs Joe with the Yankee Steve with the Blue Jays Joe with The Twins Tristan with the Astros mark with the Tigers Joe with the Giants Chad with the Marlins Tristan with the Brew Crew Darren with the Guardians Joe with the Orioles mark with the Rangers Tristan with the A's Chad with the Phillies Joe with the Reds and Braves Chad You got my Dodgers Joe with the Angels Tristan with your early bird spot the Red Sox Joe with the Padres and Nationals Tristan with the Mets Kevin with the White Sox Mark with the Rockies Joe with the Mariners and Diamond or Mariners and Rays Mark you have the Diamondbacks Let's alphabetize by team and we're in a positive video when we come back We're gonna see if there's any trades and then we'll have the break and we'll see you on the other side All right, welcome back ladies and gentlemen No deals done during the trade window. So the list remains the same break number four And there's the second half right there James. How many boxes is the number vlog? It's for picker team 18 So if you look right Above it, you can don't notice that picker team 18 is sold out and it's a two box break Rexaw great meme from a Of Bruce was from signs Now you mean sixth sense Signs with a a Phoenix There's a Phoenix a Joaquin Phoenix a River Phoenix a walking Phoenix walking Phoenix The Rexaw great meme of Bruce wills from sixth sense Come on Rex that says if you think you're having a bad day. This guy found out he was dead and still went to work not exactly a Not exactly resting in peace There right our first parallel Green green Jose Ramos 18 out of 50 and then behind the red is a tiger 13 out of 15 Jase young I say is he Josh Young's brother Rangers Josh young that goes to mark and the Tigers Tiger uppercut its older brother is Josh young all card ship. Of course a lot of nice stuff here especially the Bowman firsts I was box one Rex says when he dies he wants his casket filled with Reese's pieces so he can rest in pieces That's a good idea You think Reese's the Reese's pieces company. I don't know who they're owned by Mars. You think they'll If you requested that do you think they'll donate Reese's pieces? Speaking of signs by the way, I went to a Many moons ago went to a buddy's house and he had a you know glasses of water laying around in various You know fill levels It's just like what are you in signs got zero zero laughs? apparently Apparently the people there Not see the movie. I thought it was clever There's William Bergola 34 out of 99 for the Phillies tried to trade couldn't trade mojo for a Chad dog Nice Jill you want you want one of one engraved on your gravestone It's five out of 20 jet Williams jet That goes to Tristan and the Metropolitan's Here lies Jilo underscore 810 One of one. Oh Jilo you'd put a link to Jaspie's on your on your gravestone Well, we'll we'll we'll definitely give the surviving members of your family a little bit of break credit for that That'd be awesome Here lies Jilo underscore 810 a one of one www.jaspiescasebreaks.com What a guy? What a guy Here's Jose Salas 46 out of 99 for the fish Chad Cromwell the other Chad this time with the Marlins Could we engrave like a QR code? Into the grave so does that work will engrave a QR code in there and they could just people just use their phones or Their mobile device go straight to Jaspie's all right. There's JR Richie 50 Five out of 50 that is out of 50 Joe and the braves Joe looks in the rapes Two more to go. Do I need to watch the first round of the Genesis open again? Probably not guardies Already saw it's Thursday. So it must be some Thursday night basketball on TNT. Yes Clippers Oh Clippers sons a good game. Oh and a purple Jordan Lawler three out of ten Nice low number on that one mark was set With the Arizona Diamondbacks. He's a cold-hearted snake look into his eyes And I thought he's from it's Carrollton Tex. I thought it's at Camarillo, California. I kicked it over there I told you that's the speech bubble. I kicked it over there. And then we got Trey Sweeney 66 out of 99 Yankees Joe look is with the Yankees with the Bronx bombers That's the 2021s 20th overall pick first rounder Got an Elijah green Nice Elijah green for that's for Joe and the Nationals You're a fifth overall pick moment first All right final box fifth and final as I mentioned before We're sold out of this Bowman draft sapphire edition even personal breaks are sold out too It went fast So big thanks everybody For making this happen appreciate it. We might get some more. So just checking on the website Often and good luck everybody holiday If we took a holiday Joe locus with the Orioles, this is a nice one This is your number one overall pick Matt holidays kid Jackson holiday and we got some orange behind Ellie Della Cruz orange Christian Hernandez six 25 for Tristan and the Cubs Got a yellow parallel coming up Behind blaze Jordan. It is 26 out of 99 Jackson Job Tiger uppercut that goes to Mark and the Tigers Tiger 2021s third overall pick and that my friends Is that I'm Joe for Jaspy's case breaks calm Thanks everyone for filling up all that Bowman draft sapphire. I'm Joe and I'll see you next time for the next one