Conversations With Henry

Henry: God gave us thermodynamics but not kinetics!

Me: What do you mean?

Henry: I mean -- we can measure differences between where we are and where we've been, and also between where we are and where we'll be. Those things never change -- they're tabulated.

Me: But you're talking about free energy differences and chemistry....

Henry: Yes, of course...that too.

Me:  ...so?

Henry: How things get from here to there is what we fight and argue about...it's the kinetics!

Conversations with Henry

Henry: I was part of the baby boom you know.

Me: Come on, weren't you too old? [Henry was born in 1915]

Henry: No I mean I helped do it.

Me: Do it?

Henry: What, aren't I "with it" enough?

Me: What are you getting at, Henry?

Henry: All those babies born after the war? That was lust, not love.

Conversations with Henry

Henry:  Did you see that business in the news about negative absolute temperatures?

Me:  You mean this?

Henry:  Yeah, that.  Good thing you know how to manipulate the Internet. I never got the hang of it. You know what that news reminded me of?

Me: No, what Henry?

Henry:  The inverted Marcus region.

Me: Remind me what the inverted Marcus region is.

[Henry moves to the white board, grumbling that people no longer use chalk & blackboards. He sketched three related figures, and then explained them in words]:

Henry: Rudy Marcus laid out three different scenarios for the reaction coordinate of a simple "downhill" reaction using intersecting parabolas to represent reactant and product. Parabolas have a long history in physics (think of pendulums, and they "track" the potential energy in molecules). In the first, notice that the "initial state" reactant parabola is slightly higher in energy than the "final state" product parabola; where they cross represents a moderately uphill barrier given by the distance, ΔG^‡.

In the second (middle) scheme, the initial state (left) parabola is higher in energy while the final state parabola stays the same—follow?  He got there by translating the left hand reactant parabola straight upwards and their intersection slides "down." The barrier to the more downhill reaction is now zero. See that?

Me: Yes!

Henry:  Here is where Marcus was an absolute genius:  if you keep on going as in the third scheme, the initial state parabola gets higher still—this is now a very downhill reaction—but notice that the barrier, ΔG^‡, goes back up because the intersect climbs up the other side!  This is the so-called "Marcus Inverted Region" and is utterly counter intuitive that a more downhill state should require more energy to reach. Boy, he really shook things up with that one!

Me: Fine, but how does that translate to the real world?

Henry: What?  Didn't you read my other stuff?

Me: Here's what I think...I've been saying all along that uphill effort requires more energy than downhill effort, for example here.  But suppose that we have something really severe like the Fiscal Cliff.  Suppose that the fall is so downhill that we will actually face a higher hurdle to get down there than if it weren't so precipitous.

Henry: Hair-brained economics!

Conversations with Henry

Jack Halpern

Henry: Jack Halpern did that beautiful mechanistic work on rhodium you mentioned.

Me: Yes I know. It was pure blind luck that Chuck Casey handed me those papers by Jack--before I even knew how to read them. That guy could write. You know, I almost went to work for him.

Henry: Did you know I helped him get that job at Chicago? I knew him from Canada...back when he was at UBC in Vancouver.  He called me up in '62, asking if I could help him find a job. I said, "why don't you apply here?"
Jack said, "there's a position at Chicago?"

Me: You hired him?

Henry: No, he replaced me!  I hadn't told anyone yet but I was moving to Stanford.

Conversations with Henry

Henry: Why'd you have to go and mention Henry Eyring?  He's a "hot button" issue in the politics of science.

Me:  Why's that?

Henry: Well, he was a Mormon you know.  He gave up his seat at Princeton to move back to Utah to run things.

Me: Does that even matter?

Henry:  Of course not. But Eyring was one of those—along with Gilbert Lewis—who should have won the Nobel Prize...but didn't.

Me:  You're not saying that his religion had something to do with why he didn't win?

Henry:  I'm not not saying that. But you do know that he's related to Mitt Romney? link

Conversations with Henry

Henry: I give you a C+ for that last effort.

Me: On ruthenium?

Henry: Yes. Don't you read anymore? I'm sorely disappointed in you this time. How could you leave out Allen and Senoff? And my stuff?  And worse, you forgot to mention ruthenium's starring role in artificial photosynthesis.

Conversations with Henry

Henry: You forgot to mention Allen and Senoff.

Me: Who? 

Henry: Allen and Senoff. They made the first dinitrogen complex from ruthenium, [Ru(NH₃)₅(N₂)]²⁺. That news caused quite a stir back in 1965. Ruthenium rhymes with iron, so you're also speculating about molybdenum. It could be iron doing the fixing in nitrogenase.  Never sell iron short.

Me: *gulps*

Henry: I'm glad to see that you're reading and keeping up with newer stuff. Barry told me you'd be back.

Conversations with Henry

Henry: "Isoelectronic" is a perfectly fine concept. No need for you to feel it's inadequate. I'll give you an even easier example. We can play the same game with carbon, nitrogen, and oxygen:

[Henry sketches the Lewis structures for N₂ and CO]:

Henry:  Forget about the labels "C", "N", and "O" for a moment.  Don't let them color your thoughts. Think of them as the numbers 12, 14, and 16:

Me:  OK, but what does the little curved arrow 1p, 1n mean in your picture?

Henry:  That's your little Maxwell's Demon, moving a proton and a neutron from one side to the other. There's no net loss or gain, but rather just a transfer.

Me: Are you pushing electrons too?

Henry: No! The electrons haven't moved yet but they feel the polarization: suddenly there's an extra charge on the oxygen side and one less charge on the carbon side. The electrons rearrange, being drawn slightly closer to the oxygen, but not completely, and the carbon, having less positive nuclear charge, is polarized negatively by the electrons. The molecules electron's are polarized like this:

Me: Ah, that explains why carbon monoxide binds to metals like iron in hemoglobin via its carbon.

Conversations with Henry

[after a particularly tense group meeting at the start-up]

Me: Man, he about took my head off in there. I had to push back like that.

Henry: Well, don't take it too personally. He knows what he's doing. It's for the better.

Me: How so? He made me feel like crap.

Henry: When I was a grad student over at Berkeley, grown men--professors--used to curse and shout at each other over their ideas.  It was a downright mean and nasty to watch.

Me: Do you think some of that had do to G. N. Lewis?  He was still in charge then wasn't he?

Henry:  Lewis was like that, yeah. The thing is that after all that screaming and yelling over what they thought were so very important ideas--the same guys would always simmer down and go out for beers afterwards.

Conversations with Henry about another Henry

Henry: Henry Moseley really convinced everyone that atomic numbers were real. Atomic number was just Bohr's theory until Henry Moseley proved it true.

Me: Moseley's Law?

Henry: Yes. A theory becomes a law when it gets tested beyond disproof. He proved the atomic number using X-rays.

Me: How come Moseley never got the Nobel Prize like you did?

Henry: He was killed--took a Turkish bullet in the head at Gallipoli in 1915--the same year I was born.
 ___________________________
 

Henry Moseley (1887-1915)

At the link, Isaac Asimov is quoted: "In view of what he [Moseley] might still have accomplished ... his death might well have been the most costly single death of the War to mankind generally."

Conversations with Henry

Henry: Mendeleev was the best chemist the Russians ever produced.

Me:  What about Shilov?

Henry: Yeah, him too.

Conversations with Henry

Henry:  That's how you should think about things: as just protons, electrons, and neutrons---just plus, minus, and neutral. Those notions pervade material science and more.

Me: You mean like materialism?

Henry:  No, I mean atoms.

Conversations with Henry: This whole Texas thing...

Henry:  Watching Romney and Perry last night, I was reminded of the story of Al Cotton.

Me: How so?

Henry: Cotton was Geoff Wilkinson's first student -- I told you that here. Well, after graduating from Harvard, Cotton took a position at MIT which he held for many many years, building quite a group and reputation. He wrote a number of textbooks and advised quite a number of illustrious chemists. Perhaps the most famous thing he did was to identify the first quadruple bond, which was something outside the realm of organic chemistry.

Me:  Yeah, so?

Henry: The thing about Cotton was that he was arch-conservative, politically. Now, I suppose that really shouldn't matter in the physical sciences, but Al was finally so fed up that he up and left Massachusetts and went to Texas A&M.

Me:  Isn't that Rick Perry's alma mater?

Henry: Yes. Even worse, besides moving to Texas, he got Welch money.

Me: What's Welch money?

Henry: Well, some detractors thought it meant he was a Bircher. But you can google that one for yourself. All I can say is, they got the wrong Welch!  But to some, oil money is still dirty money.

Conversations with Henry: Metathesis

Henry: You should have mentioned Jim Collman.

Me: You mean for his picket fence porphyrin work?

Henry: Yes. Of course modelling work has gone out fashion, and may never come back. These days it's always better to study the real systems. But Collman deserves a medal for one thing: he went on that consulting trip and came back and shared some of it. That one single group meeting inspired two future Nobel Prizes. That's gotta speak for something.

Me: Say, how come Banks never got any recognition either?

Henry: Well, you know those Swedes--they don't like dirty industries. Especially oil companies.

Conversations with Henry: I'm Your Hapten

[This post is a continuation-in-part of the previous post]

Henry: What Wilkinson first gave the world now goes by a name. It's called hapticity.

Me: I know what hapticity is, but I didn't realize the word was Cotton's idea.

Henry: Yep.  Cotton was Geoff Wilkinson's first student.

Me: Did you know him?

Henry: Of course! Both of them.

[pause]

Henry:  I suppose the notion was there all along, sort of half-baked.

Me: What was?

Henry: Hapticity-the notion that a metal could latch onto several carbons simultaneously.  I mean, there was Zeise's salt, known since the 1820's, yet nobody knew its structure. That sure changed quickly.  Then along came Dewar and Chatt, your heroes, to explain it all! [Henry laughs]

Me:  They're not my heroes! Well maybe Dewar was.

Henry: And then there was Reihlen's iron butadiene complex. That was like an open-faced sandwich! [Henry laughs again]. Geoff knew all his work too--even though the war hid some of it. It still does.

Me: You make it all sound so obvious!

Henry:  No, Geoff just proved Pasteur's old dictum that chance favors the prepared mind.

Conversations with Henry

Henry:  I once gave an exam by passing out a blank Periodic Table and asked students to fill in the blanks from memory:

Me: Yikes! Did anybody pass?

Henry: A few. But everyone got vanadium right!

Time For Cocktails: Conversations With Henry

Me: Remember that time you took me to the faculty club?

Henry: Yeah?

Me: What were you drinking? I didn't really like cocktails then.

Henry: Martini. Extra dry

Me: Gin or vodka?

Henry: That's like asking me: English or Western?

Me: I'll never forget when you said 'look, over there! -- that's Milton Friedman!'

Conversations with Henry: That man was a genius

Henry: Linus Pauling had an answer for that little orbital problem you mentioned here.

Me: Pauling had answer for everything. The greatest chemist ever.

Henry: He was an interesting guy. You knew he was up here with me for a while? He had a falling out with Cal Tech.  I remember he used to come to seminars and always sat in the first row. He was well past retirement age then. Anyways, he tended to nod off when the lights went down during talks. Especially if the speaker showed too many dahls of slides.

Me: What are dahls?

Henry: A dahl is a unit of boring slides. Named after a famous crystallographer who used to put people to sleep at his talks. A "dahl" is approximately 10 boring slides. You do remember what slides are?

Me: Yeah. They were considered an improvement on overheads.

Henry: Linus Pauling was first and foremost a crystallographer. One time (I remember this clearly) he woke up when the lights went back up and asked the speaker a devastating question about a structure -- I mean the man could demolish arguments in his sleep. It was like he threw an intellectual dart at the speaker and hit him right in the forehead.

Me: Heh, I heard people used to say that about you too...

[Henry smiles]

Conversations with Henry: More Nodes for Nerds

[This post is a continuation-in-part of this one: link]


Henry: So after helium comes lithium with three electrons. That third electron must go into a new and different orbital called the 2s orbital.

Me:  The 2s orbital is like the 1s orbital except it's bigger, right?

Henry:  Not exactly. It's not like those Russian matrushka dolls where the next bigger shell simply encompasses the previous one. The 2s orbital interleaves the 1s orbital so that its electrons can stay closer to the core without getting in the way of the others. Likewise the 3s orbital interleaves the 2s and the 1s. Look at these cross-sections:

original

Me:  Why are you even showing me this stuff?  Trooper York says he hates chemistry.

Henry:  I'm just trying to explain why the toy metals like lithium, sodium, and potassium are so boring -- not the whole of chemistry.

Conversations with Henry: Nodal Theory

Henry: The electrons in hydrogen and helium are easiest to depict -- they stay in simple spherical orbitals surrounding the kernel. There are no nodes.

Me: What are nodes?

Henry: In physics, a node is a point of minimum displacement in a periodic system, for example in a vibrating string:

The first harmonic (fundamental) has no nodes, except for the stationary ends. The second harmonic has one additional node in the middle. Nodes correlate with higher energy-- the more nodes, the higher the energy.

Me: How does this relate to electrons?

Henry: Well look at these pictures of how electrons surround a nucleus: Which shape has more nodes?

Me: An s-orbital has no node, a p-orbital has one node, a d-orbital has two nodes, and an f has three?

Henry: Exactly! And that's how electrons order themselves in atoms. It's almost self-assembly. If there's one thing we've learned about electrons it's that they don't flow uphill.

Me: There's got to be exceptions for every rule.