Wednesday, September 12, 2012
Chain Folding in Alkanes Both Great and Small
The length between folds can be altered with the crystallization temperature - longer folds occurring at higher temperatures:
83 repeat units is longer, a lot longer than what a new report expects for alkanes. Reading the paper requires a subscription/pay-per-view, but the Computation Organic Chemistry Blog has a nice review of it. In this case, the researchers found that 17 repeat units is the longest alkane that is still expected to be linear. Any longer than that, and the folded configuration is more stable.
Now this is not exactly an apple-to-apples comparison. Most obviously, the small-molecule alkane work is not about its crystallization. The research is computational and is supported by gas phase IR data, which means that there are minimal or no interactions with other molecules, only those interactions of the molecule with itself. But still, 18 vs. 83 is a very large difference. Obviously the neighboring segments in the 3-D structure of the crystal supports the longer fold length, regardless of whether the segments are from different molecules or a distant portion of the same molecule. The more serious question that I have is what is the longest alkane that doesn't show chain folding upon crystallization - i.e., how what is the longest alkane that crystallizes as "spaghetti in a box"?
 All illustrations are from "Principles of Polymer Morphology" by D.C. Bassett
 Update: A reader has pointed out that that a C-C bond is actually 1.54 Å long, not 1.54 nm long. However, since I misread the fold length off the chart as 120 nm and not 120 Å , 83 C-C bonds was still correctly calculated.
A C - C bond is 1.54 nm long. In the trans configuration, the bond is at a 19.5 angle from the backbone, so each bond adds 1.54 nm * cos(19.5o) = 1.45 nm. Then 120 nm / 1.45 nm is about 83 C-C bonds.