Can't go wrong right to the moon right diamond hands shithands, whatever they're called, right? Usually something's gonna be happen. So that's why I try to avoid Welcome to access a trader the number one community for those who are committed to taking control of their trading in order to achieve success profitability and longevity Thank you for joining us. Here's Dan Shapiro to help you find your edge master your process and own your future Hey guys, give me everybody welcome to the another weekend edition of the axis of trader calm Weekend update show up. Everybody's doing well. Cheers Let's talk about the markets, right? We're winding down summer. Okay, that's kind of been the theme now for the last week or so, right? We talked about the importance Monday and Tuesday of what happens when you have a contracting cycle Everything goes sideways the ranges are obviously getting tighter and tighter And it's more of a waiting game for your specific stocks You are specific group that you trade to kind of give you a signal to wake up and Monday and Tuesday were very Really painfully slow, you know, you had you know, you had some of these tech stocks You know moving up maybe a dollar maybe 70 cents. They were just all trading this really tight channel and the continuing point The reiteration for Monday and Tuesday session was just wait, right? Just wait distribution usually lasts about a week And if you guys remember Going back to like Wednesday of Thursday of the previous week. We already started seeing these channels Start to shrink so it's just kind of a matter of time and the key point to this was and especially to newer traders Is you don't need to trade every single day. You don't need to trade every second of the day If you don't have, you know, 38 positions on by 931 I promise you the day is not over and just relax, right? Just relax take a deep breath There shouldn't be any FOMO. There shouldn't be any, you know Mental thought of this is the last day of trading I have to put on every single position at every given time Every stock is moving. I have to be in everything Right take a deep breath slow down. It's a long-term game The more time passes the more screen time you get you're gonna start to realize very very quickly that you don't need to trade Every single day in those days that you see that channels are contracting. You just relax. You can just relax gather up data Reinforce your opinion of what's about to happen next and kind of wait for that again Like we talked about Monday and Tuesday session that underhanded pitch to wake up And the common denominator was for Monday and Tuesday. We didn't see any option flow zero Okay, there was no institutional flow in any tech stock names and we were just kind of drifting, right? Just drifting people are on vacation. We all understood that and it was just a matter of time But we just didn't know when that time was gonna come was gonna come on Wednesday Thursday Friday Next week after Labor Day, when was this finally cycle of the contracting channels gonna come to an end and start to expand? We got that answer very very quickly Come Wednesday. Okay. We saw the first sign Out-of-the-money option flow in a lot of names and not they weren't just coming for, you know 30 grand bets 60 grand bets 80 grand bets 14,000 off bets they started coming, right? They started coming you started seeing Apple they were coming for The 149 150s the 155 for the following week He started seeing even when the video is very very quiet He started seeing a really aggressive option for all again We'll get to all the individual pivots in a second but You started seeing really good option flow you started seeing repeat buyers coming in of The 820 205 calls in the video ahead of earnings a lot of aggressive buying you saw Tesla with a really long consolidation throughout the whole week Very long actually two weeks finally starting to see 730 750 short-term Exploration you started seeing Facebook, right? They were coming, you know for the 380s They were coming for short-term expiration. They were coming from Microsoft the 290s It was just a matter of time that everything was going to wake up the question was when and this is the greatest thing About being in control of your trading just understand especially if you're a new trader and I've been I've been saying this for years You don't trade because the markets open you trade because you're getting value because you have your edge because you have the Stocks that you've been trading for years and years and years or in some cases for your new traders months and months and months They finally wake up. They finally have a pulse and when the options market gets started again Again, you don't have to be an options trader to understand this well when the options market starts fueling up again They start coming in with pretty decent size And they're going out of the money really aggressively out of the money with short-term expiration Usually the underlying security is going to wake up eventually and that's exactly what we saw Wednesday Super aggressive day on Wednesday if you guys all know especially for you guys have been watching this broadcast There is no There is no video Thursday nights. I usually relax Thursday nights kind of get my center Recharge my batteries so I can be fresh in the morning. We'll show you all the continuation pivots and second from Thursday It was a very aggressive day, but Friday set up Until be a really aggressive day and we'll talk about it again in a second Really aggressive technology was the key. They all woke up not all of them But the ones that we were watching they pretty much all woke up and it's setting up to be really good prices And good potential going into next week now is everything looking great absolutely not right if you look at Amazon Again, it still hasn't recovered from its earnings. If you look at Netflix You know not really recovered I had a you know had a little bit of spark on Friday, but hasn't really recovered you look at Roku has just been getting just destroyed right especially Since you know some since those recent highs about a month ago just really really destroyed earnings didn't help You got the stay-at-home stocks not participating zoom Peloton look like you know complete, you know complete garbage You have the Chinese stocks looking, you know terrible look at Baidu right look at Baidu Look at a name like Alibaba, although it has Certain days of upper the stock is just not tradable anymore until they kind of figure out what the hell what they want to Do with listing and all that stuff is just not tradable, but there's a flip side to this There is it you know There's an aggressive nature on a lot of names that did well on earnings or actually just didn't do horrible I think that's the best way of saying it and they're doing very very well Tesla attempted to break out on Friday Got rejected again I will say this much out of all the pivots on Friday This one had the hardest probability the reason why I say that I don't know if you guys remember this You probably don't fully guys who do watch these videos religiously you kind of you kind of remember you guys remember I did a video and if Kyler or Kenny what was doing the video editing to kind of find the video I did I did a mention on a company called wish and there's nothing to do with the fact the blew up I only found out that it blew up on I only found out that it'll only blow I don't follow this stuff So I only found out this thing blew up on earnings yesterday But if you guys remember I did a video somewhere around It was somewhere around June that I felt like everybody on social media was looking at this $15 area like literally all retail Everybody and I made a joke back then I think my mother called me up and say hey What do you think about buying wish at 15 and the problem is when everybody's on the right side of the market? Usually something bad is gonna happen. So kind of fast-forward, right? So we were trading Tesla for the whole week We caught this really aggressive pivot on Thursday session from the 7-12 pivot you can see here We're right here. You see the 7-12 pivot that really set the tone for Friday But all you kept on seeing like Friday morning Thursday night over and over again watch the 727 on Tesla Watch the 727 I'm talking about you literally saw Everybody tweet that price usually when when I'm trading Tesla There's a lot of sneaky channels and nobody's really looking at and I could take advantage of but like you just Saw literally everybody 727 727 727. I sway my poodle called me downstairs. He goes Oh, it's 727 still the poodle it's still the pivot. So, you know, it took out 727 it went to 728 Got got rejected in seconds. I'm talking about got rejected in seconds went down to like 720 We actually bought it on the on the on the remount back at 727 for a push into the 730 But this is kind of what my point is on a crowded trade When you're in a crowded trade and again, there's nobody was wrong 727 was the spot on Tesla But the problem is and we've said this for years and years and years when Everybody's on the right on one side of the ledger like literally and people just waking up to never traded Tesla before just never Traded any stock before and they're all trading it on one side of the market Something is usually gonna bad gonna happen and from what I saw, you know, we tried Tesla twice on Friday I know a lot of you guys came in long. So it wasn't really that big of a deal I bought off the opening range. It ran up like two two and a half dollars in seconds and then it got stuck So I got out of it really quickly Breaking but we kind of anticipated that happening just because there was so much Social media presence on that number So I wasn't shocked but when it reclaimed it back at 727 got long again went to like 730 and change which you got rejected off the linear regression line But at least now I have a sneakier channel to kind of watch the stock into next week But that's kind of the point folks and again, you don't have to be even trading the stock But when you see people talking about the same stock at the same price and you see everybody talking about it Usually, you know, they're not wrong But there's usually a higher probability that something is gonna go wrong along the way of that entry and you know, we saw that With Tesla on Friday and you constantly see that with other names Throughout your career. So just be careful when you see everybody talking about the same stock at the same price at the same time Can't go wrong, right to the moon, right diamond hands shithands, whatever they're called, right? Usually something's gonna be happen. So that's why I try to avoid the really really aggressive Crowded trade so going into this week again lucky You have to be bullish again for all the names that I mentioned that look crappy There's a lot of names that look really really good where it's stone throws away From all time highs again on the cues. We are stone throws away I have this thing this thing's just been melting up You can see how tight it has been going and it's been really really meant melting up You guys remember we were talking about the IWM, right? Still hasn't reclaimed that 125 level on the 50 day And the ironic part about it is look how strong some of these stocks are so many names are strong and The Russell is not even participating compared to everything else. So I can just imagine right going into the fourth quarter I think we talked about this on the Tuesday and Wednesday night video Well, what do you think is gonna happen? What do you think? Well, how do you this? What do you think the probability is of a fourth quarter rally if the IWM eventually does reclaim the 50-day moving average and joins everything else? With other than that you have a lot of these asset classes doing really really well, especially the Bitcoin Crypto names have been going out of their minds. Obviously the beta names have been very very strong The banks have been on a runaway train They had that little bit of a pullback on Friday, but they've been on a runaway train Obviously that is a play on interest rates eventually going to start to rise. So you got a perfect storm, right? You got banks strong you have technology strong and if the Russell the smaller cap names Kind of reclaimed that 25 level you're gonna just see a full onslaught of a fourth quarter Bull stampede so really really aggressive week this week knock on wood I was so happy after that first two days of the week That was so damn painfully slow that everything eventually woke up and that's exactly what happened So let's talk about let's talk about Friday's pivots, and then we'll talk about some names that I like for this week Again, you could you could just see this so here was the pivot remember there's no video on Thursday night, so Thursday there was a really sneaky pivot on Tesla 712 for experienced traders only if it can build it Could finally wake up remember there's a bunch of other areas that needs to clear obviously cleared out everything So it kind of led to Friday's big number of fantastic move yesterday took out five days worth of selling 727 continues to be a big number it needs to confirm and that's when kind of everybody was looking at the stock and only went up a few points Before it got rejected on Thursday night apple Thursday session, excuse me apple 148 huge level rejected three times a daily needs to build You know it's still sitting around that 149 levels So I'm about a buck buck and change but that 150 level on apple is gonna be really really big Going into this week. You see it got rejected here several times So this one definitely definitely keep an eye on look guys. I know some of you guys Are still long from Thursday off that 148 level. This looks really really good just a matter of time Thursday again Thursday, you can see how big that Thursday session was 286 big level right this is Thursday session 286 big level needs to build they're coming for the 290 weeklies even the end of the month 300 calls and then obviously for Friday's notes nice casual pop on Wednesday 289 289 needs to build for expanded move here with snow Right here with snow so it on Thursday it took out this 86 took out the 89 went to 92 this thing looks higher. This thing looks like it wants to press that 300 levels. So really good name there Etsy right we talked about this on Thursday session 194 50 195 needs to build the 50-day supplies around 97 the macro trade starts above 97 and my notes a gun for Friday that exactly we discussed now needs that 197 base for macro and here is Etsy right here is Etsy you can see why exactly this 97 right so took out the 94 and a half 95 trader right to supply right which is the 97 area guys for this week keep an eye on Etsy This thing can just get above and close above 97 You got a you got a gap fill only at 210 maybe even the 220 so keep an eye on Etsy for for this week Facebook again, you can see how beta reacted really really well Especially the last couple of days Facebook rejected 363 twice needs to build here was Facebook, right? So it took out the 363 level you can see here on the 60 minute chart took out this whole 363 level the only reason why it stopped Right at supply is because well there's supply usually happens. So you have a bigger macro level approaching approaching Facebook for this week Put up about a $2 move on Friday But you have this big macro level that's ahead on Facebook's if everybody everything gets strong social Facebook Microsoft 290 needs to build again these guys one by one. They're waking up folks one by one So here is Microsoft took out this 290 traded to 293 this thing looks like it's gonna test the 300 level in the next couple of weeks Microchips stopped exactly at 52 a little bit thin of a thin of a name. I'm not really feeling this one Amazon never got the 3316 Pen I still like guys watch pen for this week. I get it. You got football season starting. You have the MLB Down the stretch you have college football starting watch pen look at this channel here on pen right off the bottom Right if pen and again, it's nowhere near it yet But seven alert this thing can get above 75 and again, it's still $4 away, but if pen can reclaim 75 I think it's gonna wake up. So watch that as well Dog dog went absolutely nuts 131 50 132 Needs to build here was dog DDOG So it took out the 31 50 32 and traded all the way up to 37 and a half I still like it this thing gets above 38 you should get another move up So again, you can see big big moves really really strong moves thing and take on the way 135 38 next stop it went to 37 and a half Microsoft looking strong put up a $3 up $3 candle Destroyed that with 291 55 went to 293 Andy again, this is the power of option flow. This is my point You don't need to be an options trader to understand that there's a significance of option flow A block comes in for 5000 5000 calls traded For next week's 117 any close over 110 is huge. It needs to reclaim here was AMD Right off that aggressive call buying on a oops not amc big difference AMD so here's the 110 it took out the 110 Went to nearly 112 over 112 this thing is gone So keep an eye on that but big big moves one after another after another Facebook 365 on deck here comes the 310 calls coming in on November. Remember option flow Really does dictate on the line security movements. Here comes the 130 for january is on amd Sparking it up one by one 112 on deck Good stuff, you know excellent moves excellent moves Just a friendly reminder again for all you guys who are planning to join us Over the weekend, please watch the workshops. This is not a basic A basic strategy you could just find on youtube. There's a lot of moving parts, you know, we're we're It's so consistent. You have to be very very specific and what you're doing So please please just watch the workshops before you come in on monday on the video 201 needs to build Again repeat 205 call buyers coming in one by one by one.  You could get a push ahead of earnings Let me give you guys a couple of names. I I like Going into this week. Keep an eye on this open Again, not usually a name that I would look at but it had a really really big move on earnings Rested it might go sideways for a couple of days, but if this thing could just take out these earnings highs You got it. You know, you have a nice channel to fill what I like about it I had this monster move on huge expansion volume And you had a nice rest area here with about a third of the size Keep an eye on this thing to attack the top of the range here Look at nvax right nvax looks very very strong. If you look at what You know what this delta variant is doing all these, you know, all these stocks are really starting to pop modern I have this magical Run bntx have this magical run, you know, keep an eye on this thing This thing starts taking out this whole channel here nvax could explode as well Um, let me see what else I want to talk about. Look at victoria secrets. How you doing? Right victoria secrets. Yeah, it looks looks like they they got spun spun off I think I think they were owned by limited brands. They got spun off again You know a nice tight channel on victoria secret. That's what I said, right? This thing confirms this channel Who knows maybe this thing could expand as well Not everything to the long side, right? You have zoom looks like it wants to break down. You have peloton Looks like it wants to break down. You got Baidu looks like an inch away from falling off the end of the earth So there is value on both sides For me, at least the value is on the long side But again, it's very very quickly to shift gears and all that good stuff comes with it guys I'm a blessed remainder of your weekend. God bless. Enjoy the weather Especially for all of us in the northeast. We know what there's coming. So let's soak up the sun and enjoy


The FW Fitch Company presents Dick Powell as Private Investigator Richard Rogue in Rogue's Gallery.   The FW Fitch Company makers of Fitch's saponified coconut oil shampoo and Fitch's shaving creams presents Dick Powell as Private Investigator Richard Rogue in Rogue's Gallery. Rogue speaking, I guess it wouldn't be polite for me to make the statement that Judge Colin Baker was a snake. I'll just say I think there was some truth in the rumor that he did shed his skin three times a year. The judge, who isn't a judge anymore, was a big barrel-chested guy with a dramatic mop of wavy white hair worn in a sort of a modified wind-blown bob, the better to impress the juries with. He'd made himself for reputation back east as a far-eating VA, and then later as a hanging judge. He'd been out here about five years and had built a statewide reputation as a brilliant criminal lawyer on a set-of-thief-to-catch-of-thief basis. He had just won a big case and he was having a cocktail party at his penthouse apartment on top of the building which housed his plush offices. Betty Callahan had covered the trial, and now she and a photographer from her paper were covering the party. I tagged along. Oh, there was a dandy crowd there. Pasty-faced politicians, tired-faced women, and the old two-faced judge in all of his glory. Oh, Richard, isn't this a lovely place. Clear up here on top of this building. Just like living on a mountain. Yeah, only you can't lock the bottom entrance of a mountain. You see anybody here you would really like to know.   I don't like these people any better than you do. It's over as soon as you can. Let's go someplace where I can take my hand off my pocketbook. Well, well, my dear Miss Callahan, I'm sorry I couldn't get over to you before. Indeed I am. I saw you come in, but Richard Rowe, I'm so glad you could come, sir. Thanks. And now, my dear, I suppose you like some pictures. I see you have a photographer with you. How thoughtful of you. Yes. Could I get a group around the fireplace? Just you and the people connected with the trial, the defendant and the witnesses. Of course, I'll round them up for you immediately. Oh, thank you, Jack. Yes. Mike. Yeah? You ready to go? Hey, they're sure serving good luck here here. Real scotch. None of that nearscotch I get at the bar. Good. Now, here's what I want, Mike. Get me some shots of the group that's forming over by the fireplace. Right. We'll put the judge in the middle and have everybody congratulating him and the man he saved from the gas chamber. I can think of a few captions for that picture. Richard. You can't call a prominent guy like the judge a crook and you can't call a murderer a murderer after a court jury says he's not. You get the idea, Mike. Come on, Mike. You stay right here, Richard. I'll be back as soon as we've covered the odd angle on the story. And then we leave, right? Yeah. Just as soon as I can, dear. I wandered around in the crowd and listened in to scraps of conversations. Jim Gorseth, an oily politician on the judge's payroll, was talking with the, with the Mary Miller. Mary is a self-made wealthy widow whom the judge had defended after she'd poisoned her husband. She was glaring hate at the judge like a death ray and I moved within earshot of them. Well, Mary, you enjoying yourself at this testimonial to our friend's genius? I'd rather be at his wake. I'd enjoy my cocktails more. You can count me in on that, too. I'm surprised that you don't marry. He got you out of a pretty bad spot, didn't he? Yes, for exactly half the money Fred left me. I didn't kill Fred, you know. I was innocent. Oh, sure, sure. Well, here's to meeting you again soon at his wake. Happy little gathering.  But everybody was getting along with the judge. He was a big man. He had lots of money, lots of power. In a way, I couldn't help admiring the old boy, posing over by the immense fireplace, tossing that snowy mane of his about, and filling the rooms with his deep-throated laughter. Betty finally got all of the pictures she wanted and came glaring over to me. I got a little lump in my throat like I always do when I see Betty. Oh, if Mark Anthony could have seen her, Cleopatra would have been in the second barge, rowing. We'll leave in just a moment, Richard. We have to stay and bring one toast to the judge. He's going to be hurt if we don't. Well, I wouldn't want to cause him pain. Oh, he's getting our cocktails now. He's going to bring them over. Okay. Did you get some pretty pictures of the old windbag? He's charming. I like him. Hmm. Here he comes. How could you like a guy like that? Well, here we are. Hope they're not too strong. Miss Callahan, I wonder if you would forgive me if I borrowed Mr. Rogue for just a moment. I have something I wish to ask his advice on privately. Why, sir? Couldn't we make it tomorrow, Judge Betty? Tomorrow will be too late. I'm afraid, Mr. Rogue. This will only take a few minutes.  No, of course not. Okay. All right, Judge. Where did we go? My study, right through here. Congratulations, Judge. You showed it a fine job. Now, I received a rather alarming note tonight, Mr. Rogue. Yes? When? It was under my glass when I returned to the serving table after those pictures were taken. Here it is. Hmm. Paper and envelope from the dime store, huh? Well, I can't trace them. Hmm. Well, let's have a see here. Hmm. Have a good time, you murderer. You won't be alive at this time tomorrow night. You're going to celebrate an anniversary.  Printed in block letters with no skill. Anybody could have written that. And anybody could have left it there on the serving table. That's right. There have been a hundred people drifting in and out of here. You, uh, take the note seriously? Rogue, I've had threatening letters before, of course, but this one will... I have a hunch about it. A premonition. We'll return to our story in just a moment. First, when it comes to good grooming, your mirror can't tell you everything. It can't tell you how much clean, fragrant hair adds to that indefinable something called charm. Don't take chances on detracting from your loveliness. Keep your hair fresh and clean smelling at all times by using Fitch's saponified coconut oil shampoo regularly. This clear golden liquid shampoo lathers magnificently and washes away dust, dirt, perspiration, and unpleasant odors from your hair. Fitch's saponified shampoo is made from mild coconut and pure vegetable oils. It never leaves the hair dry or harsh feeling. Thus, you can use it as often as you like and be sure that your hair is shining clean and free from offending odors. Have a professional application of Fitch's saponified coconut oil shampoo the next time you're at your barber or beauty shop or buy a bottle at your drug or toilet goods counter. Ask for the economical large size, 16 ounces for $1. Now back to Dick Powell as private investigator Richard Rogue in Rogue's Gallery. I didn't want to go to the party in the first place, but I wanted to be with Betty Callahan and she had to be there. It was a victory cocktail party which Judge Colin Baker was throwing to celebrate the fact that he'd cleared another guilty murderer. I wasn't particularly happy when the judge took me in his study and showed me a note threatening him with death within the next 24 hours. In fact, I didn't pay much attention until I looked at the judge's face. He was scared. Rogue, I've had threatening letters before, but this one, well, I have a hunch about it, a premonition. What are you going to do about it? The safest place in the world for me to stay is right here in this penthouse, and I want you to stay with me, Rogue. Me? I'll pay you well for your time, and what's well? I'll give you $500 if you'll stay with me for the next 24 hours, Mr. Rogue. Oh, 500 clams, huh? Well, Judge, that makes it very interesting. You'll accept the assignment then? Like a flash. Just let me explain it to Betty Callahan. I was supposed to take her out tonight. Very well. I'm sure Miss Callahan will understand when you tell her about the fee. I need you, Mr. Rogue. So, you're so busy you have to break your date with me. That's a habit of yours, isn't it, Richard? Oh, I will. Well, you won't ever have to do it again. You'll never have another chance. Oh, but Betty, maybe you'll listen. The judge figures someone is going to try to kill him tonight. You don't want to be a party to a murder, do you? You're not worried a bit about the judge, and you know it, Richard. You're thinking of that $500. Well, is that bad? Five bills will buy a lot of entertainment. You can have a lot of joy on $500. Don't knock it. Don't sneer at it. Well, I suppose I might just as well get Mike to take me home. I should have known that you'd get a better offer. You always do. Mike? Miss Callahan? Miss Callahan, I'm afraid I owe you an apology. Oh, no, Judge, I can't very well blame you. If my friend Richard is so crazy about that money... Judge, I got word for you. I can't take the assignment. But I have your word, Mr. Robe. Well, I wouldn't want you to break your word with anybody else, Richard. Oh, no. Are you ready, Mike? You can shove off, Mike, and I'm taking Miss Callahan home. Huh? Okay by me? I'm really sorry, Judge, but... Now, look, you two youngsters. There's no point in having a disagreement over this.  They're beginning to leave now. Then, Mr. Robe, you can take Miss Callahan home and come back. Ah, that would leave you alone for about an hour. There's only one entrance to this place. That's my private elevator. I'll give you the key. You can lock it as you leave. No one can possibly get up here. Oh, I don't want to cause all that trouble. Oh, it'll only be a little while, baby. I hope you'll do this favor for me, Miss Callahan. I need Mr. Robe's moral support tonight. Even at my age, I feel that I'm... too young to die. Bailey and I hung around for another hour until all the guests either walked or were helped from the cocktail party. Then the judge and I went through the penthouse like as it goes through Cotton. We looked under everything that was raised from the floor and behind everything that stood a foot high. Then we turned on the floodlights and searched the area surrounding the penthouse and the roof. There was nobody there. The judge was alone when Betty and I rode his private elevator and locked it with a foolproof lock before we got into my car and headed for her place. Betty was annoyed and that ride home was as romantic as a tub full of wet wash. But she'd been annoyed before and I wasn't worried. I left her at her apartment and fiddlefooted out to my car. I opened the car door, bent to get in. Lightning struck behind my ear. I heard the thunderbolts rocketing past and latched on to one for a while ride through the firmament. Stars kept exploding in my face but I hung on until I saw my home away from home. Good old cloud eight. I let go, dropped a neon or two and landed a softly smokering. I didn't open my eyes for a moment. Hello, Eugor. I didn't think you were ever going to get here, Rocky. I was worried. Where have I been? My centuries ago. I saw you way upstairs knocking at the pernigate. But they wouldn't let you in. Eugor, this isn't... Oh, tell me that this isn't... I'm glad to know that. What happened? Oh, I gotta get out of here. All right, Eugor. Give me a shove. What are you doing? I'm trying to get these handcuffs off you. Oh, where are we? We're in the hills above Mulholland Drive. Somebody brought you up here, chloroforms you and handcuffed you to this tree with your own handcuffs. You need a bodyguard, Rocky. How did you find me? I got a phone call telling me where you were to bring a file. Stand still or I'll leave you here. Oh, okay. Who did it? I'm waiting for you to tell me that. I don't get it. Somebody wanted you out of the way for a while, Rocky. How do you want to tell me what you're mixed up in? I wasn't on a case. Ooh. There. I don't have to get a new chain for your bracelets, but anywhere you're unharnessed from that tree. Look, Urban, I was supposed to be bodyguarding Judge Colin Baker last night. Bodyguarding that crook? Why? Well, he got a death threat. A note found on the serving table during a cocktail party. Go on. Somebody promised to kill him within 24 hours. What did you leave him for? I took Betty Callahan home. Somebody must have followed me when I left the judge's penthouse. He knocked me out as I left Betty. Maybe we'd better check on the judge's health. Maybe that note wasn't kidding. How do you feel? Uh, oozy. You can hang your head out the window in the way back. We'd better see whether your client needs a bodyguard or an undertaker.  My mouth was lined with brown, blotting paper and my shoes were full of lead. I wasn't feeling very well as I got in Urban's official sedan and headed for the penthouse where I'd left Judge Colin Baker. My head ached like a broken heart until I took a couple of pills from Urban's first aid kit. And by the time we pulled up in front of the office building, I felt like I had a chance at living if I wanted to and I decided I wanted to. The private penthouse elevator was still locked just as I'd left it and that made me glad. We entered it. Maybe we should have called before we took this trip. Oh, I want to see the old boy. I owe him an apology if he's still alive. How could he be dead unless somebody else had a key to this elevator? Well, they didn't. The only other key is on the judge's key ring. He told me that. And what are you worried about? I'm not worried. I just hate to give him back those nice, crisp C-notes. I saw him. I hope he's up. Well, this is it. Oh, good lord. Well, the judge will never be any debtor. Blow in the face. He's been strangled, Robbie. We'll continue our story in just a moment. First, a word to the ladies. It's long been acknowledged that fragrance and charm go hand in hand. But unpleasant hair and scalp odors can banish charm in a hurry. By using Fitch's saponified coconut oil shampoo regularly, you can keep your hair flower-fresh and fragrant. That's because Fitch's saponified shampoo makes billows of fragrant lather, lather that floats away dirt, oily film, and displeasing odors from the hair. Then the lather rinses away easily and completely. You see, Fitch's saponified coconut oil shampoo contains its own special patented rinsing agent. This rinsing agent works right with the plain rinse water to assure you that your hair will be sparkling, radiant with all its natural color highlights. And there's no danger that your hair can offend others with unpleasant scalp odors. Or Fitch's saponified shampoo leaves it dewy-fresh and fragrant. Next time, ask for Fitch F-I-T-C-H Fitch's saponified coconut oil shampoo. Now back to Dick Powell as private investigator Richard Rogue in Rogue's gallery. Maybe I was surprised when I saw Judge Colin Baker looking up at me from the floor of his living room. I'm not sure. I had a hunch. Don't ask me why. I just had a hunch that he was dead when Urban brought me out of that stupor up there above Mulholland Drive.  Urban and I walked over to him. He's been strangled, Rogue. Yeah, yeah, looks like it. Any marks on his throat? No, no marks. Looks like there was a struggle, though. Table kicked over. How could anybody get in here? There was locked. There's no other entrance. What are you trying to do? Tell me this guy's not dead? No, he's dead all right. But how could he be strangled? Cigarette, Urban. No, thanks, Rogue. So he was murdered, wasn't he? Yeah. That calls for the medical examiner. I don't get it. There was nobody here when I left. There's been nobody here since. There's a peculiar odor in here. Smell it? No, no, no. Sit down, Rogue. He won't look around. There's been a murder. You're mixed up in it and I want to talk with you. Oh, you think I killed him? I didn't know him that well. I wasn't even mad at him. Hey, what's that? A check. A check for $2,500 made out to the victim and signed by Mary Miller. Was she here last night? Yeah, she was here. But I never heard of a dame her age doing a human fly act. Maybe she had a key to the joint. She didn't believe me, she didn't. Where's the phone? It's in the bedroom. I'm going to use it. Wait here, Rogue. There was a peculiar odor in that room. A faintly familiar odor, but I couldn't place it. My poor old beat-up mind was whirling a million revolutions a minute and getting no place. Then I remembered the note the judge received. It had mentioned an anniversary. So I decided not to wait instead. I took that long elevator ride and grabbed a cab for the library. May I help you? Oh, yes, I, uh, I want to see the files on the Gotham City newspapers for the last 10 years. All right, sir. It's going to take me some time to get them out of the storeroom. Any specific dates? Yes, I, uh, I would like to see copies of the additions 5, 6, 7, 8, 9 and 10 years ago today. All right, sir, if you'll just have a chair. You sure you feel all right? You look ill. Oh, I, uh, I always look like this, thank you. Just get me the papers, please. They're mighty important. Confidentially, I think they're going to solve a murder. The librarian got me the papers. I went to work on them. Gotham City was the city where judge Colin Baker had made his reputation as a hanging judge. My hunch was as strong as a brides coffee and it paid off. In the issue for seven years ago that day, I found the name of Judge Colin Baker on the front page. A man he had sent to the chair for murder had been executed screaming his innocence. Within an hour after the electricity had torn through the body of this man, Harold Michaels, the real killer had confessed. And this was the anniversary of that legal murder. I called Betty Callahan at her paper. She wasn't there. She was covering the police investigation in Baker's murder. I took a cab back to the judge's penthouse. Isn't this terrible, Richard? It hadn't been for me insisting on you taking me home. The judge would have been alive. Or I would have been dead. Where have you been, Rogie? I told you to stay here.  I've got the motive for this murder. You have, Richard? What did the medical examiner have to say, Urban? You know the doc. He won't give any official opinion until he's had a chance to analyze the contents of the body. What's your theory on the motive? Well, I... Hey, Betty, where are you going? I'm with the working press. Mike and I are going to get some pictures.  And I recognize that far away look in your eyes. Now, what goes?  If you've got any theories, let me in on them. Signed, huh? Look, Urban, this place is air-conditioned, isn't it? The penthouse is. The building isn't. Yeah? I'll be back in a minute. Hey, where are you going? I'll be back in a minute. I want to check that theory of mine. Cyanide. That word brought back that dainty smell I'd noticed in the apartment when Urban and I had discovered the judge's body. Cyanide. The odor of cyanide is brought out by cigarette smoke. I had been smoking when I detected it. Ah, the pieces of this murder were falling in place like a well-trained chorus. I found the ladder that led to the top of the penthouse where the air-conditioning machinery was located. Ran up the ladder, gun in hand. And there he was. The murderer. Just lifting an earthenware crock from inside the housing of the intake fan on the air-conditioning system. Put it down, Mike. Take another move toward me, Rogie. I'll let you have this coffee. I'll be back in a minute. Hey, Rogie.  What good luck do you, Mike? You can't get away. Another five minutes and I would have been home. Free. How'd you figure me, Rogie? Why did you have to horn in? I looked up the Gotham newspapers for seven years ago today. The day Judge Baker executed a man named Harold Michaels, an innocent man. Was he your brother? Your name's Michaels, isn't it? He was my father. And I executed the man who executed him. In his own private gas chamber. Just like they do it at Quentin. I waited a long time for the chance. Look, Mike, I'm not arguing right or wrong with you.  And I'm going to take you in. Put that crock down. Oh, I don't think so, Rogie. I'll just stand here. I have to think. Just for my information, Mike, how did you delay the action of the gas until you knew the judge would be alone? I thought of everything. I didn't want to hurt anybody but Baker.  I tested it half a dozen times. You know, it took a drop of acid three hours to eat through the cord. I'm glad I killed him, Rogie. I'm coming after you, Mike. I'm not waiting, Rogie. I don't like the gas chamber. Mike. Mike. Don't come back here. I'm not sorry for anything. Tell him that was my payoff line. Will you, Rogie? So long? No. Don't, Mike. Don't jump. Mike's plan for murdering the man who had caused his father's execution was as near perfect as any murder will ever be. While the guests were having whoopie at the cocktail party, he put that jar of acid in the air conditioning intake, hung the sign I had pellet over it and was back at the party leaving that note before anybody missed it. When he found that I was going to return to spend the night with the judge, he had to knock me out and get me out of the way for at least five hours. Three hours before the cyanide fell into its acid bath and two more hours which it took for the air conditioning system to completely change the air in the penthouse. That was clever. I thought that, yes, it looks like I did it again. Had a narrow escape, though, but that didn't bother me. I drive every day in the Los Angeles traffic. You know what I mean? This is Dick Powell again, ladies and gentlemen. Hope you enjoyed our story tonight. Ray Buffham wrote it. Leith Stevens composed and conducted the music in D. Engelbach produced and directed. Be with us again next week, will you? We have a story for you about a black-eyed senior reader from Argentina, a Latin-type corpse and a mysterious gold piece. We call it Latin-type. Thanks for listening and now here's Jim Doyle. Be sure to tune in again next week. Same time, same station. When you will again hear Dick Powell as private investigator Richard Rogue in Rogue's gallery.  Fitch's Ideal Hair Tonic is not sticky or greasy, yet it gives your hair that well-groomed look.


Good morning. In the last lecture, we looked at how to derive or synthesize a rate law for heterogeneous catalyst, when the reaction is taking place on the surface. There are different steps occurring, while the reaction is taking place on the surface of the catalyst. We already looked at these steps. First is of course, the external mass transfer, then the internal mass transfer or diffusion through the pores and actual catalytic site is present on the surface, which is nothing but the wall of the pore and on this side, the reaction would take place. So, after the diffusion that is the second step, we have adsorption of the reactant on the catalytic site, then the adsorption species or the adsorption component, we will undergo the reaction. We looked at isomerization, dehydrogenation reactions, there are many possible reactions and this transformation will occur on the surface that is nothing but a surface chemical reaction. Then the product, which is possibly in the adsorbed state will get desorbed the fourth step and then again the back diffusion through the pores of the product and then the external mass transfer of the product. So, these are the different steps, we have already looked at them, but while deriving the rate law, we looked at only three steps that is adsorption, surface reaction and desorption. Only three steps we looked at and we synthesize the rate law and then I told you how to determine or how to validate this rate law on the sense how to know whether the rate law that we have synthesized is correct or not. That is through the experimental data, performing experiments in laboratory under different conditions and seeing the effect of partial pressures of the reactant, sometimes the products and see whether the rate equation that we have derived fits well in the experimental data that we have got. So, I gave you an example last time of cyclohexane dehydrogenation and I told you how it fits well for the rate equation derived based on the assumption that the chemical reaction controls, but sometimes it is quite possible that adsorption or desorption would control. So, it all we have to check that through the experiments. Now, today we are going to look at the other steps, which we had ignored before and these are external mass transfer and internal mass transfer that is diffusion.  So, on a catalyst particle we have a reactant going first to the external surface then inside and somewhere you have a catalytic side where the adsorption reaction and desorption would occur and then the diffusion back diffusion and then back mass transfer to the bulk of the product. So, these are the steps we are now going to concentrate more next 3-4 lectures on this particular step that is pore diffusion. A very important step I told you that the catalysts are porous in nature and there are different or there are many or several pores inside the catalyst. In fact, that is the main reason the catalysts would have very large surface area. So, even if the main active catalytic components say for example, palladium or platinum or Nikkei or Rudenium these metals may not have very large surface area what we do is we put them on supports. Supports have very large surface area we disperse this catalyst on the supports so that we get very large surface area and nice dispersion maximum number of atoms of the catalytic component will be available for the reaction and I need very less catalyst loading that is the idea. So, we are going to look at the porous catalysts now as I told you before the first lecture on catalysis like there are different types of catalysts sometimes you may have to deal with non porous catalysts where the reaction takes place only on the external surface like for example, gauze say platinum gauze, silver gauze and all that. In that case we do not need to worry about this pore diffusion effect, but there are many catalysts which are porous in nature for them we need to consider the effect of pore diffusion. The rate equation that we have derived will further get modified because of the pore diffusion effects and we are going to look at the effect of pore diffusion in this particular lecture. Now, I have told you that we have a catalyst I will redraw the picture of the catalyst again. So, we have this catalyst in which you have different pores remember I had done this before as well and then I have this particular space which may be considered as solid continuous solid actually there are micro pores inside, but then for our analysis purpose let us say that I have these spaces where only solid is present and these are the empty spaces which are nothing but pores which are nothing but pores. And the actual catalytic site will be present somewhere on these surfaces or the walls of the pores and in order to access these sites a molecule has to diffuse. So, it will enter the pore from various locations there will be several such locations through which it will go inside and will get diffuse. So, if the catalyst particle has a radius capital R overall movement of the reactant molecule will be inside a catalyst particle towards the center though it will not directly go to the center because there is hurdle here, constriction here it will go this way. Why I am explaining all this in detail because later on you are going to introduce a concept called effective diffusivity and I am going to relate it to the normal diffusivity then with the molecule is moving without any constriction hurdles and so on. Now, imagine a situation where I have a molecule which is sitting at a center of this classroom and for some reasons there is a concentration gradient and this molecule has to diffuse. Diffusion takes place when you have a concentration gradient or other chemical potential gradient and this has to diffuse now this molecule does not know where the walls are walls are far away from the molecule and this molecule will flow assuming or other will get transferred rather there will be flux because of its movement assuming that there are no walls at all because they are far away from the molecule. Now, what is this particular motion molecule like how do we characterize it is a fixed law and then there is a constant called as diffusivity. This diffusivity has nothing to do with the walls it is a free molecule present in the bulk and it is moving because of the concentration gradient. Now, this is not going to experience any resistance otherwise from the walls, but there will be some resistance and because of its molecular weight because of the medium and all that and that is why we have called we have a parameter called diffusivity and this diffusivity will decide how fast the molecule will move now compare this situation as against a molecule which is present inside the pores inside the pores here now if molecule is moving here it is going to experience some resistance from the walls why because look at the pores what is the typical size of the pore the pore size is very small and that is the reason we get such a large surface area. So, this size is of the order of few nanometers or it can be angstroms the different types of pores micropores, macropores, mesopores the very small and the order of magnitude of this diameter of the pore is comparable with the size of the molecule what is the typical size of a molecule say benzene it is close to 6 angstroms. So, 6 angstroms molecule size and suppose you have a pore of say 15 or 20 angstroms then it is going to definitely face some resistance look at a mean free path of the molecule definitely it will experience the existence of the wall around it and the diffusivity will go down. So, this wall effect this wall effect what else there is for example, this molecule is moving from the external surface inside if I look at the actual distance travelled by the molecule it is this distance but the molecule is going to go this way. So, it has to follow a torches path and the diffusivity the effective diffusivity if I consider the actual moment this then the diffusivity will further go down because of this path that it has to follow. So, for the same displacement or the movement or distance it has to go this way. So, this is another effect we are going to put all these effects in one parameter later then the pores these pores there is no guarantee that they should be of uniform size there are very few catalysts especially zeolites and all that where the pore size is well defined. But, take example of say ion exchange resin you cannot define the pore size it is in the range there is a pore size distribution that you will see. So, if you take a single pore the pore itself will have something like this the wall is not straight and then there is a possibility that the area of cross section will vary as the molecule moves ahead. So, there is again some constriction that it is going to experience and because of that further the diffusivity will go down. So, now the effective diffusivity if I want to determine the effective diffusivity that diffusivity is nothing but the normal diffusivity and the effect of all these factors. So, let us define a term called effective diffusivity. So, we call this as DE effective diffusivity the effective diffusivity is equal to Knudsen diffusivity DA which is a diffusivity inside a pores that means it considers the resistance offered by the fluid inside a pore and the walls of the pores. Now, how do I relate these two? This is definitely going to be larger than this because this is smaller right. So, there will be some effect because there is a space constraint. So, some effect will come because of phi p which is nothing but porosity because some space is occupied by solid that is not available for the movement of the molecule. So, it has to be multiplied by the porosity it will further reduce. So, porosity is always less than 1 then I was telling you about the constriction this is called as constriction factor because the variable area and there is another factor called as tortuosity alright. Sometimes people club these two and they call as tortuosity factor. So, in some books you will see sigma not present there and you have a tau f or whatever less tortuosity factor, but what needs to be understood from this is that this is a normal Knudsen diffusivity that we define for a molecule right. You have phi here taking effect of considering the effect of porosity presence of solid constriction and then the tortuosity ok. This considers the effect of wall anyway right, but these three factors are the factors which are dependent on the solid that we have ok. It is a morphology it is porous structure and so on right. So, these are the factors which will change from particle to particles right solid to solid catalyst right. So, this is the effect to diffusivity. Now, this diffusivity once I have this I have this diffusivity in terms of other factors I can write a normal fixed law type of equation for a solid porous solid ok. So, what this allows me to do is to write mass balance flux equation based on fixed law ok. Only difference is instead of normal diffusivity we have a we have an effect to diffusivity here ok.  Now, the tau that we have defined is as I said like the molecule has to follow a path this way because of the porous structure, but actual distance that it travels is only this much ok. So, I am at the external surface and I am going inside, but then it has to follow this path. So, the extra path that it has to follow will result in reduction in a diffusivity ok. Now, the tortuosity is defined as actual distance travelled divided by shortest possible distance between these two points. Suppose this is point a this is point b the shortest possible distance between a and b right. So, it is very easy to define or even easy to calculate the value of tau suppose I know the angle here ok. So, let us say I have I just approximate it like this and this is same 90 degrees is the angle ok. Can I calculate the value of tortuosity? You can do this exercise tortuosity is the actual distance travelled. So, let me say that this is L this is L. So, the actual distance travelled is 2 L if this is 90 then I can calculate this distance this is going to be 2 L divided by root 2 right 2 L divided by root 2. So, the value of tortuosity comes out to be root 2 which is say 1.41 tortuosity is greater than 1. So, always greater than 1 we cannot we cannot expect to have straight pores very difficult. So, at. So, in extreme situation would be tortuosity is 1, but not quite unlikely sometimes the tortuosity can be of the order of 5 6 7 10 it can be that high it all depends on the material ok. And of course, people have control over making a material also like this is separate all together different area where we design catalyst as per our requirement, but then for our analysis let us take this tortuosity as a material property and that will come when the or that can be evaluated when the material is design or it is available. And then we go ahead and get a value of effective diffusivity beds based on the known value of Knudsen diffusivity alright. Now, once we know the value of diffusivity as I said before we can write the fixed law for the solid. So, let us assume that I have a spherical particle I have a spherical particle and then the molecule is going inside ok. Now, this is a center and let us take a differential element and write fixed law around this. So, this is r plus delta r and this is r and the radius is capital R ok. Now, this is a diffusion taking place as I told you this particle you go to have pores inside, but now I am going to assume that the diffusion is taking place straight along the radial direction actual movement is like this, but then now that I have considered that effect of tortuous movement in my effective diffusivity I am free to write equation something similar to what I do normally for diffusion or flux writing mass balance when there is a concentration gradient alright. Now, look at this particle again there is catalysis happening in sense there is a reaction taking place. So, as n when the molecule goes inside it is going to meet catalytic species and reaction is going to take place. So, it is something happening in parallel. So, reaction and diffusion they are taking place simultaneously. So, as n when there is a movement is a reaction also taking place. Now, the overall rate of the reaction will depend not only on the actual rate of reaction actually in a sense the one that we derived yesterday considering the effect of adsorption desorption and chemical reaction whichever is the controlling whatever ok. So, that particular rate and now the rate of diffusion will also matter you can imagine the situation where the reaction is instantaneous very fast. Even if adsorption controls or desorption controls or even the reaction chemical surface reaction controls all these steps are happening very fast. But then diffusion becomes very slow that particles molecules are not able to diffuse inside then the overall rate will go down right. So, diffusion is playing an important role here. If the diffusion is very fast the pores are wide enough diffusivity is very large then it is the chemical reaction or whatever adsorption desorption at the site that will probably control the overall rate. So, try to understand the importance of diffusion now internal diffusion we are not yet talked about external diffusion or mass transfer fine. So, we are going to write the law sorry the mass balance for this the flux balance there is no convection here there is only diffusion that is taking place. So, the flux at r is W a r this is the way I am defining the flux W is the flux of component a that is reactant in radial direction into 4 pi r square what is it the area right at r at r minus W a r at r minus W a r minus W a r sorry a r 4 pi r square at r plus delta r here the flux here minus the flux here can I write this equal to 0 no right this is this is another term that we need to consider here that we need to consider here what is that term that term is reaction if there was no reaction then this would be equal to 0 right, but there is reaction taking place. So, look at this as a CSTR so material coming in going out and plus reacted is equal to 0 right. So, I need to add the reaction term so plus reaction rate r a into let me explain all this later first let me write it into rho C which is nothing but a density of the particle mass per unit volume into 4 pi r m square into delta r. So, this is a reaction term I will explain this detail is equal to 0. So, material at r is going out minus coming in plus generation term right. Now, r a will have its own sign depending on whether we have reactant or product if a is a reactant it will have a negative sign what is this this is volume this is volume 4 pi r m square into delta r then rho C is a density. So, this is volume this is density then density into volume is nothing but mass. So, rate is expressed per unit mass of the catalyst I told you in the last lecture most of times in solid catalyst reactions the rate is expressed per unit mass of the catalyst. So, r a is per unit weight of the catalyst you have to multiply it by the weight. So, this is to be this has to be the weight of the catalyst. So, density into volume right. So, this is the mass balance this is the mass balance.  As I said we can use a fixed law for this with in spherical coordinates to write the flux equation for W a r. So, W a r is nothing but minus d e that is effective diffusivity into d c a by d r. So, this is a flux.  Then just play with the equation assume delta r approaching 0 I can convert that difference equation to the differential equation.  So, I have just substituted for W and converted the difference equation to the differential equation and I get this particular equation right. Now, if I want to write the expression for r a dash what is r a dash? r a dash is the rate of reaction, intrinsic rate of reaction when the molecule is present near the catalytic site. So, if r a we can obtain it by rate law then r a can be k into c raise to n. So, if I expand it further what I get is d to c a by d r square just expand this further plus 2 by r d c a by d r square plus 2 by r d c by d r. Let me explain it later, but let me write it first k n into s a into rho c divided by d e look at this d e this d e is coming here I am just dividing both the terms by d e right that is effective diffusivity into c a raise to n is equal to 0. Now, this you would be able to guess what I have done here I have divided both the sides by r square right. So, what is happening is you have d d 2 c a by d r square second order equation d c a by d r 2 by r. Now, I have written expression for r a dash that is the rate of reaction at the catalytic site in terms of these constants. So, let us try understand these constants k n is going to be the rate constant we will see the units then s a is a surface area is a surface area rho c I have already told you it is the density mass for it volume c a is a concentration raise to n this n is nothing, but order of the reaction with respect to a the intrinsic kinetics here has been assumed to be nth order reaction that means the kinetics is a power law model rather than the commonly used models like Langmuir-Hinshelwood and so on for heterogeneous catalysis right. I have a reaction let us say that I have only an isomerization reaction a going to b only single reactant present n. So, k into c a raise to n right and this is nothing, but a diffusivity all right. Now, can you guess the unit of k n I have multiplied it by surface area now.  Now, what is the unit of s a s a is say meter square per gram of the catalyst or k g of the catalyst whatever. So, this is a unit of s a right. Why I have defined this particular parameter here because normally k n would be available in the unit of or unit on the basis of area that is per unit area. See now the different type of rate constants in a normal reaction without catalysis or rather without heterogeneous catalysis rather normally we have the rate constant per unit volume that is why we multiply rate by volume in many design equations. In the last lecture I told you that for solid catalyzed reactions or heterogeneous catalysis the rate is expressed per unit weight of the catalyst. So, that is why we multiply normally to the rate by w that is the weight of the catalyst right. Now, I am defining another rate constant here which is expressed per unit area of the catalyst which area it is a area present in the pore can be very high very large ok. So, per unit area of the catalyst. So, if you have a rate constant per unit area of the catalyst it has to be multiplied by the surface area per unit weight of the catalyst. So, this gives me k n into s a gives me the rate constant per unit weight of the catalyst because k n is per unit area s a is area per unit weight. So, this becomes per unit weight of the catalyst right and rho c if I multiplied by rho c then it becomes my normal rate constant that is per unit volume of the catalyst. So, this is nothing but the rate constant expressed per unit volume of the catalyst. It may be noted that k n in some standard reaction engineering text books like for example, J N Smith. So, this is the constant of the catalyst. The k n is taken to be per unit mass of the catalyst. So, in that case k n that they are using in their book is equivalent to k n into s a that is surface area that we are using in our notations. I hope it is clear. So, this together like all these parameters together is nothing but my normal rate constant per unit volume of the catalyst. Now, what is the actual unit of the rate constant? So, for a first order reaction r a is equal to minus k c a right and if I want to get a unit of k r a is expressed this is a per unit volume of the rate that is moles per second is equal to minus k moles per meter cube. So, what is the unit of k for a first order reaction? It is second inverse. So, this is a k this is a k small k normally. This is per unit volume because I am expressing rate per unit volume, but for a first order reaction the unit is second inverse second inverse that is the unit of first order rate constant when the rate is expressed per unit volume. Now, if I express rate for a first order reaction per unit weight of the catalyst. So, what is the what is the unit of the rate constant? Just look at this. Now, this is for the volume per unit volume. Now, I am going to look at weight of the catalyst. Now, r a is expressed per kg of the catalyst right moles per second moles per meter cube right. So, what is the unit of k here? Unit of k is meter cube per kg second. This is for the volume this is for the per unit weight this is per unit volume this is per unit weight right. Now, what about the unit when I express my rate per unit area per unit area area of the catalyst. 1 upon meter square moles per second minus k moles per meter cube this is for area basis is area of the catalyst. So, what is the unit of k here? Unit of k is meters per second and this is nothing, but our k m that we have just written our balance along the spherical particle the k m right. So, let me summarize I have 3 types of rate constants 3 types of rate constants expressed per unit volume for a first order reaction k has a unit second inverse second per unit mass of the catalyst right. First order reaction k has a unit meter cube per kg second and third surface area of the catalyst first order reaction k has a unit meter per second. So, these are the 3 different units that we probably going to deal with as and when we solve the problems later. So, in our rate equation k m is this right k n is this then k n into s a is this and k n into s a into rho c that is the density of the catalyst particle then it is nothing, but the rate constant per unit volume right. So, let us get back to the equation the original equation that we have derived you have this equation in this you have the entire k n s a into rho c is nothing, but the rate constant per unit volume. Now, why we doing all this we are doing all this to get the concentration profile inside a particle we need to get we need to know how the concentration changes as we go from the external surface to the interior of the catalyst. And why do we want all that because later on I am going to determine how much is the reduction in the concentration and because of which how much is the reduction in the rate overall rate right when the diffusion is important. So, that is the purpose now we have this differential equation all I need to know is the boundary condition first to solve this differential equation and get the concentration profile inside a catalyst. So, what is the boundary condition here I have a particle I have a particle I have it is a second order differential equation I need two boundary conditions. So, at r is equal to capital R I have c a is equal to c a bulk or 0 whatever outside concentration right. Since external mass transfer effects are not present we are assuming that c a s is equal to c a b which is something that I am going to see which is something that I am going to measure I cannot go inside a pore and get a concentration or measure the concentration. I will see the concentration only in the bulk why the concentration inside a particle is lower than what you have outside it has to be lower why because there is a resistance face by the molecules while diffusing from the external surface to the interior. And since there is a concentration gradient there is a flow there is a flux diffusion that is taking place if this diffusion is significant then the concentration gradient is significant even if you have a very active catalyst present inside it is not going to see the concentration outside a particle it is going to see the concentration which is smaller than outside right. And because of which the rate will go down and our aim is to rather characterize the quantifier rather these particular resistance and reduction in the rate because of the inter particle diffusion alright. So, r is equal to capital R c a is equal to c a b and there is another boundary condition that I need is equal to r is equal to 0 since there is a symmetry you have c a is equal to finite or d c a by d r is equal to 0. So, with these two boundary conditions I need to solve this equation alright I need to solve this equation and get a concentration profile once I get a concentration profile my job would be easier I would be able to know the local rates at every point inside a particle and from that I can calculate the overall rate which is going to be the actual rate rather and it is going to be less than what it would be when there is no inter particle diffusion resistance fine. So, I have this equation and I need to further modify this to get some dimensionless parameters which are going to give me some idea about the importance of diffusion. So, let us de-dimensionalize this equation by defining certain dimensionless variables. So, let us say I have I express concentration as psi equal to c a divided by c a s or c a b rather that is what I have used c a b what is c a b is a bulk concentration is at the external surface that is the external surface you can even call this as c a s. So, some books you may see a notation c a s c a b right and then there is another dimensionless variable that I define is lambda and something to do the radial distance r divided by capital R. If I have these two variables defined dimensionless variables dimensionless concentration this is dimensionless radial distance. If I have that then my differential equation gets reduced to a form. So, this is a differential equation that I have I am going to substitute for dimensionless concentrations and dimensionless radial distance what I get is this I am directly writing this you can try it on your own. So, d 2 psi by d lambda square plus 2 by lambda d psi by d lambda minus k n s a rho c r square c a b raise to n minus 1 divided by d e that is diffusivity into psi raise to n minus 1 divided by m equal to 0 equal to 0. So, this becomes my non-dimensional form of the equation psi is a dimensionless concentration lambda is dimensionless radial distance. Now look at what I have got here now this is a term that is going to tell me something. So, let me write that term separately and denote it as phi m. So, this phi is different from porosity this is not phi s this is phi n, but then I will say at phi n square is equal to k n s a rho c r square c a b n minus 1 this term I am just writing it here again. Y square will be clear later to you it makes the solution easier. So, this is a term now look at this term carefully what do you have in this term in the numerator you have the parameters related to reaction what do you mean the rate constant is more the rate of reaction is more surface area rho c all these parameters have something to do the reaction of course, this r is a it is common for all I will just manipulate this equation further let us not consider r square at this moment, but otherwise rest the parameters are showing the dependence or the they are influencing the reaction what about the denominator d e d is something that will affect the diffusion. Now let me just manipulate this other other just play with this equation further phi n square is equal to k m s a rho c r c a b n b divided by d e into c a b see earlier I had c a b c a b raise to n minus 1 now what I am doing is I am writing c a b raise to n and I am taking c a b here minus 0 divided by r. So, what do I see here I see that this is nothing, but the diffusion rate see that concentration gradient distance diffusivity something if you have a linear gradient then this becomes the flux due to diffusion. Whereas in numerator you have something that will affect the reaction actual reaction. So, the 2 rates that I am comparing here, so this particular parameter phi n square is going to give me the relative importance of actual reaction taking place at a site which may have adsorption desorption surface chemical reaction and all and diffusion. So, relative importance of these 2 processes if phi n is very large what does it mean? It means that diffusion is slow diffusion is important if phi n is very small diffusion very fast or not important at all that means it is like an open catalyst there are no pores right or pores are very large. So, this value is going to tell me everything. So, for a given reaction for a given catalyst if I can determine the value of phi n or phi n square the magnitude of this particular parameter is going to tell me whether reaction is important or diffusion is important. If this value is very large then diffusion is important sense is slow and it is going to control the rate and if it is very small then I do not need to worry about it I will just take it as if like there is no diffusion problem. So, this phi n is called as Thiele modulus it is a very important term in heterogeneous catalysis that tells you the importance of pore diffusion this term is called as or this particular number is called as Thiele modulus. So, phi m is Thiele modulus I can write it for different types of reactions first order reaction second order reaction and so on. So, the equation that I have is for a spherical particle because I am talking in terms of the radius of the particle if I have cylinder if I have something else some other shape then I will have a corresponding characteristic dimension of that particular shape we will look at that separately like suppose I have a cylindrical pore how do I write expression for how do I derive expression for Thiele modulus. But, right now I am doing it for a spherical particle and I have the expression given by this that is phi n is equal to k m rho C s a C a b n rho c s a raise to n minus 1 r square divided by d e and suppose n is equal to 1 the first order reaction because very easy k 1 rho c s a r square divided by d e sorry this is phi n square now phi 1 would be r root of k 1 rho c s a b n rho c s a b n rho c s a b n rho c s a divided by d e. If I give a rate constant per unit volume I do not need to write all this it would be r k v d e why k v because it is expressed in terms of per unit volume because this has a unit per unit volume. First order reaction it will be second inverse this is a dimensionless number look at a units r meter r square divided by d e. k second inverse d e meter square per second right. So, if you look at this no units this is dimensionless number everything will get cancelled here. So, remember phi is the dimensionless number called as Thiele modulus which gives you the importance of tells you the importance of pore diffusion effects. If the value of phi is large then the pore diffusion effects are significant I cannot ignore them and if the value of phi is relatively small say 0.01 or whatever then I can safely ignore pore diffusion and treat the reaction as if there are no pore diffusion effects and the reactions taking place on the catalytic surface which is wide open for me. We will go further and try and simplify this and understand pore diffusion effects in detail get some more insight in next lecture. Thanks.


Hey, you guys welcome back to my channel So I decided to film a whole house clean with me for you guys and to be honest I was just ready to have my entire house clean at once So this gave me a lot of motivation to film it for you And I just started in the dining room by cleaning off the table. I really like to start here This is my favorite place in the house to start when I'm gonna clean a bunch of it I just feel like I can put the dishes in the sink and get everything ready to load the dishwasher and of course wiping down The height chair is very important these days All right before I go too much further.  So everything that you see in this video will be from Grove I get personal care products. Well, I'm just gonna go ahead and show you what all I ordered I can't totally remember everything I ordered from them. So we'll see. Oh, yes I'm super excited to try this out. I'm actually gonna probably use this on my countertops Well, I'm cleaning in the kitchen today and it's seventh generation the scent is morning meadow I also grabbed just some apple cider vinegar. I drink this in water sometimes. I'm really excited to try these out So they are a thin to thick shampoo and conditioner They have all kinds of vitamins for kids to you guys I just had my Grove anniversary where I have been a member with them for a year and I'm telling you they still Consistently send you free products in your orders. So this is what I got for free It's this hand pump. I'll open that in a second and then this is from their new skincare line It's called rooted and I'm excited to try these as well. Here is the hand pump So cute it's gonna match my dish soap pump at my sink I'll show you guys in a second and I'm gonna fill it up and put it over there I absolutely love it So like I said, if you guys have never tried out Grove and you want some awesome free cleaning products Check out the link below. So I went ahead and filled up my hand soap dispenser and also refilled my dish soap dispenser I really love using these and having a pump on them It's just a lot handier when you're working at the sink. Plus that soap smells so good Then I just worked on emptying the dishwasher and getting it refilled I Have a good question to make this all-purpose cleaner is my new favorite The smell is to die for plus. I mean you guys can see how big that bottle is. It's really a great buy I scrubbed out my sink and then hand washed a couple things and I decided to try out using the Grove Concentrate cleaner. This is actually the tub and tile I just decided to scrub it down with a Mr. Clean Eraser and that It made a really good combination actually and I think I'll be doing it again The glass cleaner is my absolute favorite and I've actually tried most of the ones on Grove's website And I still go back to this one every time. It just leaves everything super street-free I'm gonna get comments about this But how funny are the cows with everything being sped up? At one set of sheets, I needed to put on one of my girls' beds That morning they had had an accident So I cleaned their sheets and just needed to put them back on Kylie is a great little helper I've tried to get the girls more involved in chores And so I had her pick up all of their laundry off the floor The bathroom was next and I just wiped down the Mirror and the sink and then also cleaned the toilet as well This is a newer brand to Grove. It's called real simple They have dish soap and other things as well and the scents that they have are so Good, they just have a really really good smell to them actually down and I just made the bed I need to get a king-size Down comforter for this bed, but I just haven't yet and haven't found the right deal for the one that I want You guys know if you watch me often that this room is generally the biggest monster to tackle But you know what? I would rather see messes like this because I know that they're having fun and playing and being kids and Life is not about having a perfect house. Just keeping sanity alive Funny how the story goes little hope up a good dreams I'm singing louder than the crowd for watching today. You guys don't forget to check the links out in the description box If you're new to my channel hit the subscribe button Give this video a like and I'll see you in tomorrow's video Sit me up like lemonade. We both know it's


Income tax 2021-2022. Payments. Get ready to get refunds to the MACS diving into income tax 2021-2022. Most of this information can be found in the Form 1040 Instructions Tax Year 2021 on the IRS website at irs.gov, irs.gov, income tax formula. We're focused down here on the payments area. Quick recap of the formula. Everything down to this taxable income. You can imagine basically kind of like a modified income statement where we have income minus different types of deductions. Then we get to the taxable income. Then we apply the tax calculation, which is confusing because it's not a flat tax, but we finally get to the tax and you would think then that you would be comparing the tax then to what we paid because we have to pay during the year, which would be the withholdings typically for a W-2 employee.


Mindy is an associate professor of clinical surgery at Albert Einstein College of Medicine and was appointed to serve on the American Academy of Pediatrics Committee on Bioethics this year. She graduated from the Emory School of Medicine, completed the general surgery residency at the University of Illinois in Chicago and fellowship training in pediatric surgery at the University of Michigan in Ann Arbor. In 1992, she joined the section of pediatric surgery at the University of Chicago and later joined the McLean Center faculty after completing her surgical ethics fellowship at the McLean Center in 2009. In 2011, she joined the Division of Pediatric Surgery at Montefiore and she asked me to pronounce it correctly in Dubronx and is the program director of the general surgery residency at Montefiore in Dubronx. She's currently in the Einstein Cardoza Masters of Science and Bioethics program and the title for her talk today is, quote, can we talk about sex? Mindy? Thank you, thank you for the invitation and the privilege of participating in this conference and my only disclosure is I have no relation to Dr. Ruth. So I'm gonna tell you a story. In 1993, early in my career as a pediatric surgeon, I was performing an elective inguinal hernia repair on a three-year-old girl. She had a right-sided inguinal hernia and the operative plan was to repair the right side and then explore the left side because of the high instance of bilaterality in females less than five years of age. And the other point that was emphasized during my training was to open the hernia sac and deliver up either a fallopian tube or an ovary to confirm that the patient was a genotypic female, XX. When I opened the right hernia sac, I withdrew a testis, not a fallopian tube or an ovary and when I explored the other side and opened the left hernia sac, I retrieved the other testis. I then passed an instrument through the hymen and determined that the patient had a shortened blind end in a vagina. This confirmed clinically the diagnosis of a non-veralized male with androgen insensitivity syndrome, a cause of male pseudo-homaphroditism. I then planned to perform bilateral orcheectomy to avoid the future development of malignancy in these intra-abdominal testis. Prior to proceeding with that procedure, I consulted a pediatric endocrinologist with decades of experience. He agreed with my diagnosis of my operative plan and then asked me what I planned to tell the patient's mother. I explained that I would not refer to the gonads as testis, simply gonads. I planned to tell her that her daughter's gonads were abnormal and would not produce eggs and then planned to obtain informed consent for the gonadectomy. Then after the procedure, I planned to explain that her daughter did not have a uterus and would not be able to have children. When comfortable, her daughter would be taught how to insert a vaginal dilator to lengthen her vagina and that she would be able to have intercourse and be sexually active. He agreed with these points and then he made the following recommendation.  Mothers and daughters fight and you would not want this information revealed in a moment of rage. He also planned to see the child in his clinic. The mother agreed to gonadectomy and after the procedure we discussed her daughter's inability to have children due to the fact that she lacked gametes and a uterus and her future sexual functioning. We also discussed the referral of the pediatric endocrinology clinic. I did not discuss the fact that her daughter was a genotypic male with an XY karyotype. This child was assigned female gender of birth because she had female external genitalia and was being raised female. There was no indication for any surgical intervention that would convert her to a male phenotype. There are three types of differentiation required for sexual reproduction. Gonadal for the production of gametes, genital for the conveyance of gametes to a point of fertilization and behavioral for the urge to behave sexually. Gender or sexual identity, a person's self-representation as a male or female is essentially established in all children by three years of age. And sexual identity is separate from sexuality which occurs later. Sexual ambiguity and gender uncertainty are unsettling for parents and physicians. The baby born with ambiguity regarding its sex or as in this case, the child that is found to have a discrepancy between their presumed sex and their genotype raises many ethical issues for parents and physicians. In reviewing and analyzing this case in my mind over the past 20 years, the ethical issue remains the issue of disclosure of the genotype to the patient's mother. The ethical guidelines at stake include beneficence, autonomy, and non-maleficence. In 1993, I thought I was being beneficent by following the recommendation of my consultant. For this parent and outpatient inguinal hernia pair had become complicated by the necessity for gonadectomy and being confronted by the fact that her daughter had no reproductive potential. I thought I was acting in the best interest of both the patient and her mother by limiting the amount of information and hopefully allowing for the comprehension of the difficult message delivered. I knew that the pediatric endocrinologist and a support group would be additional resources for further explanation, clarification, alleviation of fears, and reassurance. This may have been a rationalization, alleviating me of the burden of delivering information that I was unprepared to deliver, specifically her daughter's male genotype. I had never encountered this type of case during my fellowship and I felt very much unprepared to deal with the mother's reaction to this information. In following my consultant's recommendation, I was complying with his paternalistic approach to this case. There was an imbalance in power in the doctor-patient-parent relationship. I had information to disclose and I determined what was disclosed. And having knowledge of the karyotype would not have resulted in a change in this child's gender assignment. She'd been raised as a girl under the assumption that she was XX. Inspection of birth revealed unequivocal female external genitalia. It was simply full disclosure. This mother had a right to know this information. I thought that my actions were benefiting or preventing or mitigating harm to the mom and the patient. In retrospect, I'm concerned that I was maleficent in feeling to disclose the child's karyotype to the mother because I was compromising the parent's autonomy in the decision-making process. The surgical management of intersex conditions raises questions as to whether intersex is a disease or a malfunction about the basis for treatment decisions and the authority of parents and others, such as religious authorities, to make irrevocable decisions for children. These questions remain incompletely answered and have highlighted the need for evidence-based outcome studies and have contributed to the shift from paternalistic physician-centered decision-making to patient-centered decision-making. In 1953, Dr. John Morris, a gynecologist, published a seminal paper describing the clinical anatomic and histologic features of 82 cases of the syndrome of testicular feminization. He stated, quote, from the psychosexual aspect, these patients are definitely female. He argued against the disclosure of the genotype. It goes without saying that it would be unwise to inform the patient of the true state of affairs. It seems only necessary to state that childbearing is impossible. Morris's paper and recommendation of non-disclosure of the genotype set the tone for decades in the management of patients with complete androgen insensitive syndrome. And I'm gonna use the acronym CAIS from this point on. In 1988, the ethical debate of whether to disclose the genotype to the parents and patient with CAIS was reviewed. The arguments explore issues of paternalism and deception. The question of whether disclosure to the parent of the patient's genotype could result in potential unnecessary harm to the patient was raised with the concern that the genotype could be disclosed in a moment of anger. This concern was shared by the pediatric endocrinology consultant, in my case. This argument was countered with the concern of the potential consequences should the patient learn her genotype in an inappropriate and uncontrolled fashion. The parents and patient may feel deceived by their physician's non-disclosure of the patient's genotype. It was concluded at that debate that physicians must stress the fact that being a female doesn't depend on gonads or chromosomes, but rather her feminine self-image with respect to social roles and sexuality. In 1992, in a 24-year retrospective review from a single children's hospital of 21 patients with testicular feminization, the authors, pediatric surgeons, stated that the results of the chromosomal analysis were given only if the parents asked for the information. A review by the American Academy of Pediatrics and Committee on Genetics in 2000 illustrated the paternalistic concealment-centered model. Intersex was viewed as a rare anatomical abnormality requiring immediate medical attention. The urgency was rationalized to minimize medical, psychological, and social complications. However, the evidence substantiating that surgery performed for cosmetic reasons during infancy relieves parental distress and improves the parental child bond is lacking. In contrast, patient-centered care includes expeditious assessment, decision-making, and gender assignment without the urgency for cosmetic surgical intervention. The current emphasis of surgical management is functional outcome rather than cosmesis. It's now established practice in 2013 to disclose the genotype at the time of diagnosis of CAIS. Failure to disclose the genotype as it relates to the diagnosis may result in the patient learning about her diagnosis in an unsupported setting. For example, via the internet, the possibility of the patient discovering her genotype in an inappropriate matter is not a theoretical concern. In 2012, the US Olympic team had more female athletes than male athletes. Despite this advance, a masculine-appearing female athlete may face investigation for hyperangogenism and have her eligibility to compete as a woman challenged. In 2009, Caster Semenya, a runner whose physical appearance associated with fast-finishing times in attaining the gold medal in the 800-meters 2009 World Championships, prompted gender examination to determine if she had an unfair competitive advantage. After significant public scrutiny, she was cleared to resume international competition in 2010. The results of the gender tests were not revealed for privacy reasons. The International Olympic Committee's sex verification policy, in attempt to determine who is eligible to compete as a female to avoid unfair competitive advantage, may publicly challenge a female athlete's femininity, sexuality, gender role, and role in society. Imagine an athlete being told that she cannot compete as a woman, even though she's been raised as a woman, views herself as a woman, and until this event has had a female role in society. The necessity of gonadectomy in CIS is accepted, however, the timing remains controversial. The testes are normal and not dysgenetic and malignant degeneration prior to puberty is rare. The current recommendation is to allow for the natural progression of puberty, performing gonadectomy once final height and breast development have been attained. Performing gonadectomy in the post-puberty minor will require disclosure in order to obtain informed consent from the parents and ascent from the teenager. The Intersex Society of North America recommends the following patient-centered model. Following diagnostic workup, newborns with intersex should be given a gender assignment as boy or girl. Gender assignment is simply assigning a label and does not involve surgery. Procedures necessary to sustain the health of the child should be performed. Genital normalizing surgery should not be performed until the child can make an informed decision. The surgery can result in the excision of tissue that may be needed for subsequent reconstruction. This patient-centered paradigm highlights that the person with an intersex condition has the right to self-determination regarding their body, particularly since the surgical procedures are not reversible and the risks are substantial. Newborn gender assignment is preliminary. The child may decide later in life to change their gender assignment. As a matter of fact, a law went into effect last month, allowing German parents to register their newborn babies as neither male nor female if they were born with ambiguous genitalia. The German Ethics Council urged the change to alleviate hasty parental decision-making and possible premature commitment to surgery immediately after birth. Judith Butler, in Doing Justice for Someone, notes that the intersex movement challenges the societal ideal of gender dysmorphism. When a continuum exists between male and female, she asks her readers to consider being less rigid in the classification of gender. But one difficulty with the establishment of a continuum of gender is the practicality of gender assignment. When a baby's born, the first questions that asked is, is it a boy or a girl? Societal rigidity in viewing gender as male or female is reflected in the current International Olympic Committee's sex verification policy. And it's interesting that one of our former fellows, Hillel Gray, made this statement. Besides sports, religion is another domain that is permitted to treat people differently because of their sexual identity. Think about it. In the orthodox community, you have to know the sex.  Prior to the acceptance of a continuum between male and female, society must have the vocabulary to have the conversation about gender. The term intersex implies somewhere between male and female. Although my patient was defined as intersex, there was no ambiguity in terms of her gender assignment. She was assigned female gender birth based on the female features of her external genitalia and was raised female. Terms such as intersex, pseudomathrodite and sex reversal are perceived as potentially pejorative by patients and can be confusing to both physicians and parents. The AAP Consensus Statement in 2006 on the management of intersex disorders proposes the term disorders of sexual development defined as congenital conditions in which development of chromosomal, gonadal or anatomic sex is atypical. The focus must be on how to disclose the information, not whether to disclose the information. Surgical education is a process that leads to the acquisition of a fund of knowledge, the clinical integration and application of this knowledge, technical skills and the development of surgical judgment. The pediatric surgical trainee expands their surgical repertoire, attaining the expertise to manage congenital anomalies, tumors and other conditions specific to infants and children. Although the perioperative and surgical management may be mastered, the delivery of information regarding congenital anomalies, tumors or unexpected findings at operation may be challenging to the trainee that's not had the exposure to these cases or the opportunity to shadow in attending. This aspect of training, the acquisition of templates to disclose information is highly variable. I had no previous exposure to the manage of a child with an intersex disorder during my fellowship. This case necessitated informing a parent of unexpected findings at operation and raised an ethical conflict for me regarding complete disclosure of the diagnosis to the parent. As we equip our pediatric surgical trainees with the knowledge and technical skills to care for infants and children, we must also enable them with the templates for effective communication with patients and their families. As physicians, we must be equipped with a vocabulary to not only disclose the medical information to our patients and families, but to impart reassurance and convey certainty. The conversation about gender will require the evolution of our vocabulary regarding gender. Thank you. We have time for a question or comment or two. Just a question. I wanna thank you for addressing this incredibly important issue that really gets very little time, I think, in medical ethics discussions.  I mean, I know some of the change that's happened in the treatment of patients with intersex conditions has it been because of activists within the intersex community or individuals who suffer from this? And I wonder how that's informed your work or if there's any formal research or writing or anything from individuals with this condition. Thank you for your question. I think there's been a tremendous awareness created by the New England Journal article that came out several years ago regarding children that had ambiguous genitalia. And it was amazing when they became teenagers that several of them had ambiguity about their assigned gender and sexual identity. And it created an awareness that we really need to have a form of self-determination for these children. In terms of my own practice, I think just open disclosure and the consensus within my division of pediatric surgery, everyone's in agreement. Thank you very much, Wendy.