A Creeping, Fitful Progress

So, I spend two hours every Monday morning and Thursday evening on the road between the M-R-D Metropolitan area and Cathedral City. I happen to like the trip but it cuts into my day and driving with tourists on the road drives me nuts.









I also happen to love Cathedral City where I grew up and went to University. The place just can't have a bad picture taken of it even with a cellphone camera in bad light. On the other hand the city has no reason to exist other than that it is a provincial capital and has a university. It means that it is a largely white collar city where no one really works for a living.











Now, the reason why I am doing this is to get some publishable research done. That means that I have to get something done that a) no one has thought of before b) if they did think of it they failed and c) succeed. Which requires creative thinking, discipline, keen observation and old-fashioned luck.

This summer my focus has been on the physical chemistry problem of what happens when a well known industrial reducing agent [which everyone uses in huge excess because it is a) typically impure b) short lived in solution and c) has the solubility of beach sand (are you still with me on this sentence, we had a digression there that was almost humanities style writing in length, I am going to have to fix that before I try to write a scientific paper ... Subject -Verb - Object, keep it simple and stay away from weird tenses ... anyhoo back to our regularly scheduled sentence)] becomes a soluble species. In my hands, it has pulled a Luther on me. When Luther was in the tight grip of the Catholic Church they were able to minimize his eccentricities. However, when he was "free" of the confines of the church he went mad (so to speak) and started chewing the furniture (check out R. C. Sproul and "The Madness of Luther"). That is what happened to my compound when I was able to get it to dissolve ... it started chewing one whatever was around (solvent, container and spectrometers).

The problem is that I need pure compounds to characterize and with this material I am already starting at 85% purity on the best commercial samples. So my only hope is the formation of crystals that I can separate from the impurities and chewed on bits of furniture.

I thought I had the problem licked when massive well formed crystals formed from one of my oils. For a week I gloried in my crystals, there they were so close, just on the other side of the glass, so close. But I needed to isolate them and that meant work-up. Then things did not go so well, the crystals survived filtration and back distillation of the solvent but the real test is when you evacuate the reaction chamber to remove the solvent so you can handle the sample in the drybox. In less than a minute, while I watched, the massive crystals lost all structural integrity and became something that looked like Playdough if Campbell Soups made a tomato soup play dough.

What I have done once I can do again. But this time the path will be much longer and technically difficult to avoid the decomposition of the solvated crystals. I still do not know why some German or Russian did not do this chemistry 50 years ago and so in my spare time I am scouring the old literature for secondary research stories to make sure that I am not re-inventing the wheel. But that is research.

It is good to be back at the bench. The glassblowing is coming back to me and I like the people I am working with. I feel blessed and I will feel even more blessed when in two weeks the science courses will be taught at ABU without my name listed as professor. Then I will know what a sabbatical feels like.

Research and Ghosts

So ... it's been a long time. Research at the bench is what it always has been. Sometimes it is a visceral delight as the reagents cook up into something new. Sometimes it is a grind to get through routine housekeeping necessary to keep a lab working. Sometimes bench research erodes the soul with countless small stumbling blocks that can stop a research program in its tracks. I have known them all in the last month or so.

The car has worked well. The driving has been fine since the trip from home to here is in my opinion a great little drive. The weather has been "tourist weather" (hot and sunny). So I leave the unplanned garish squat of a community by an unloved river and drive to an urbane and quiet small city with a wide beautiful river. Why did I ever leave here?

Ghosts.

The research has gone pretty much as I expected. Slow and at times frustrating. I was fortunate to stumble into a discovery that will allow me to look at some interesting and relevant chemical aspects of battery chemistry. I am currently up to my eyeballs in various forms of oils that refuse to form solids. It's the colour changes that jazz up my day. I have discovered a chemical reaction between two compound that have been known for decades and one of which is an industrial reagent. Not only that the reaction features the combination of two white crystalline solids with a secret solvent and I get the brightest most interesting colours and colour changes. If I can determine what the chemical species are that are responsible for the colour changes I may just get into the inorganic textbooks after all. It looks like I will be spending the balance of my sabbatical doing ESR and Raman and hopefully X-ray crystallography. Why did I ever leave here?

Ghosts.

We had a water main break in the the basement of our Chemistry building two days ago. The water filled a room so that the water was about a meter deep and the doors into the room could not be opened (genius designer had then all swing INTO the room). Not only that the only access to a shut-off valve was behind a wall in the room filled with water. Needless to say the lower floor (which includes the chemical storeroom) was inundated and they had to turn off the electricity to the whole building. We suddenly discovered that the fumehoods have an important role in making it possible to breathe the air and we all bolted for the nearest exit like a bad Mexican burrito.

That meant that yesterday I ended up in the Engineering Library doing some long delayed literature work. After a long day of somewhat fruitful reading I headed out of the library and wandered around looking for a bathroom.

Ghosts.

In a random corner of a random corridor I ran into this picture ...

And this picture had this small detail ...

Kevin was a friend, a good friend. We went to school together, we worked together and we enjoyed each others company. He was bright and devoted to sports. We were both raised in a community where feelings were mostly repressed but I knew him as a sensitive and curious brother. We sort of drifted apart in University I went into science and he went into engineering but it was a measure of his ability that in a program where the "four year degree" took everyone five years to complete ... he finished in four. I remember meeting him in the hallway of the Chemistry building ... we walked by each other and simultaneously turned and realized who the other person was. For fifteen minutes it was like old times ... but time had moved on and Kevin was anxious for work so he had decided to go into the Armed Forces. We talked about wives and babies and then the tide took us apart.

About a year later we heard that Kevin and some other students were down in a hole in British Columbia learning how to wire explosives. One of those can't ever happen accidents happened and some people died including Kevin. I went to his funeral where a doddering old pastor who didn't know him said some stuff that had no meaning to a young wife and daughter. We all cried at the outright wrongness of his early death. And then our lives moved on.

So here I am in this random corner of a random building crying again. That is why I left this place ... there are too many ghosts that can bubble up from my past and rob the precious moment of the present from me while I remember old wounds, words or loves. I have gotta go home and kiss my family and live in the precious gift of the present.

As long as I live, I will carry the memory of that last conversation with me. It is precious to me and, in reality, symbolized all the friends left behind while I was off chasing electrons. Rest in peace brother ... you are not forgotten.

A link to an appropriate piece of music for my mood.

Dealing With Unstable Compounds: Part 5

Well, this series was not intended to be a current file but a nostalgic recollection of events when I wore a younger mans clothes ... then this happened.

About ten years ago I had an undergraduate student make up a batch of S3N3Cl3 (trithiazyl trichloride, about 10 grams in three separate sealed glass tubes). My intention at the time was that I would use the compound in a simple synthetic sequence that I helped discover.

S3N3Cl3 + 3 AgAsF6 --> 3 AgCl (s) + SNAsF6
8 SNAsF6 + S8 --> 8 SNSAsF6

This was the summer that I was going to bring the plan to fruition and I started the process by getting the sample tubes out of the old storage lockers. In my research group air sensitive compounds such as S3N3Cl3 were stored in sealed glass tubes, wrapped in paper towel and then packed in sturdy cardboard tubes.

Now, these glass tubes were placed in a blue plastic case and moved from ABU to UNB in my car and then kept in my office while I considered when and how I should do some chemistry with them. Late last week I got a call from a graduate student (in the research group that I am now working with) and he said that there had been an explosion in my office. I arrived about 10 minutes later and the top two floors of the chemistry building smelled strongly of sulphur-chlorides (a distinctive smell somewhere between skunk (thiols: LINK) and chlorine. The office itself was filled with a choking fume to the point where I could not enter the office while still winded from running up the stairs. Once we got the windows open and the ventilation fans working this is what I found:


It would appear that over the years a significant amount of the S3N3Cl3 had decomposed.

8 S3N3Cl3 (s) --> 3 S8 (s) + 12 Cl2 (g) + 12 N2 (g)

That kind of decomposition lead to a build-up of pressure in the glass tubes and it is possible that in moving the tubes microcracks in the tubes started to propagate to the point where the glass tubes failed in a spectacular manner. It is true that it is unfortunate that the explosion occurred at all but my oh my, I might have been stunned if I had have been in the office when the tubes exploded and I might have been in worse shape if they had have exploded in my car during transport. There is also the point that I had a tube of S4N4 in the same case (see below). I think that all in all I was lucky.

It all reminded me of 25 years ago when the senior graduate student in the research group that I had joined had a disagreement with me over the nature of my glass tube seal off. I favoured a secure heavy glass seal-off while he favoured a more fragile "elf's cap" seal-off. His comment was that if for any reason the pressure was to build up in the glass tube it would fail at a low pressure. I guess he was right.

I am unaware of any published account of an explosion resulting from S3N3Cl3 decomposition in sealed tubes with time (or for that matter even heat). Makes me wonder about all the other Main group chemists out there that might have similar tubes of similar vintage.

Back From the Land of the Bluenosers

So I take a used car that I have owned for three weeks down the student conference and the wucka-wucka-wucka noise just gets louder the further I get from home. And the weather just gets worse and worse (heavy rain and wind). So I'm driving along singing "Nearer My God to Thee" as I drive through some awful weather and I do not have a clue what I will do if the car breaks down. But I get to the land of the Bluenosers and the student conference. The attendance numbers were pretty good with over a 100 students attending but my focus as a judge were the oral presentations. I was expected to take notes on all the 15 minute long student presentations and be ready to assess them in six categories with first , second and third prizes in each. The Powerpoint presentations are all pretty good but they keep coming every 15 minutes from 9 AM until 4 PM. To my eyes the biggest problem is trying to determine what work was done by the student and what work was "group work". The end of the conference and of course there would have to be a 2 hour meeting for an interprovincial / interuniversity organization that I am on the executive. Then and only then me and the car beat it home.

So I go to the car dealership and complain bitterly about the car and we work out a deal to get the car fixed and since I have to go to Cathedral City they lend me a car. It was this stylish number with an air scoop and and big wing on the back. And all that on a 2004 Rio that has a top highway speed of 120 km/hr. Oh, it's a headturner, everyone watches me drive by like I am some sort of idiot from the backwoods. At least it was free I keep telling myself. It got me there and back and that was all I needed.

Cathedral City is really looking better now that spring has finally made an appearance and the leaves are filling out. Kind of surprising considering it was just three weeks ago I made the first run. But now with the National Conference starting this weekend it has got to be about the research.

So I am pushing together a presentation on the calculations that we have been doing. On one end of things the fact that we can do the study using simple calculations means that I can participate without access to any fancy cop equipment like they have on CSI but to me it seems like a sterile non-chemistry project. I guess you have to ride the horse that brought you. I will make my presentation and after the seminar the job will have to be to get the paper written and submitted. This first paper of my sabbatical probably does not deserve publication in the first rank journals but we think it will get into one of the second rank journals. It really doesn't matter since no one actually read s the journals any more and for the most part all journals are deposited with the majour online search engines so that any search of the journals online will result with a hit.


This first project is really quite simple. All first year students are taught about Born-Haber cycles to use to evaluate the thermodynamic aspects of chemical reactions. Our group was part of a new simplified calculation of a key component of the cycle called the lattice energy(essentially the force that holds a solid together). It was in fact my academic grandfather Neil Bartlett that had the insight first and then my academic father developed it with a British chemist so that the calculations were more general. It fell to me to find a way to use the calculations on an experimental problem and it worked out pretty good. Our calculations both explained what the pat term of reactivity that we observed in out system and also were predictive concerning what reactions would or would not work. But first, I have to get this presentation out of the way, so as much as I have been tortured by Powerpoint presentations in recent days here I am putting one together. I am trying to tell myself that I need to keep the slides simple, use colour sparingly and cut as much out as possible.

These Made Me Laugh

Brilliant contribution from the chemistry blog Everyday Scientist at :

http://blog.everydayscientist.com/

It seems that the creators of the Demotivators posters have posted a program for creating your own poster. Some of these are excellent.

Chemistry and Cars

So a week later and back in Cathedral City for more discussions and beginning the assembly of the presentation. But the whole process is mired in discussions about the significance of certain seemingly small differences in patterns of reactivity. That means that while research discussions are important and necessary they sometimes really slow down progress on what needs to get done immediately.

And then there is the car. The big gamble that I took on this sabbatical is that I went out on a limb and bought a five year old car driven by a little old lady. It was clear that I was going to have to make a lot of trips to Cathedral City so I had to make a choice between rental cars every time I needed a car and a purchase. I bought a five year old car with 64,000 km on it. Worked fine for two weeks and then it went past 66,666 kms.

And started to fall apart. Getting the beast fixed has cost me precious time that I did not have and the front end is still making a speed dependant wukka-wukka-wukka noise. That means more time, more money and more distraction. This has got to end soon.

Anyway this weekend I have to go to a student conference as a judge which means I will have to pay attention to about thirty 15 minute powerpoint presentations. I hope to find some time to work on my own presentation with weekend.

Getting Started

Spent a day in Cathedral City trying to sort out some details of what I might be able to do on my sabbatical. There is a tension between trying to do something that I would like to do and something that is helpful to the research group that I am joining. It is clear that the lab will be busy this summer which will be good for developing a research culture but will also strain resources and restrict availability of materials and equipment. Dr. J says that there will be room at the bench for me (what I want to do) as long as writing papers is the number one priority (what I need to do). I am still entangled with The University in the Wildwood but that is quickly resolving. The focus right now is "combat literature reading" to get myself back into some level of research literature engagement for preparation of the paper at Winterpeg later this month.

The drive back and forth was peaceful and this morning the River was so high it was close to the bank edge but so quiet and peaceful that it looked still even though it was ripping along. The trees are just starting to bud, the farmers are working the higher sandy fields that have drained in the hope that the spring flood has crested. I miss the cycle of planting with hope, working with determination and harvesting with joy (the best way to mark time). Another day and a lifetime ago.

This must be what a student feels like.