@Kingofthekush420 & @cyclopath & @Myrrdin… all excellent points that tie together into a cohesive theory from a hypothesis I’ve kicked around for a while to answer my obsequious question, “Wtf do they mean by pseudo-first order rxn?” Hypothesis: The effects of product concentration and pressure (which steer 2nd order rxn mechanisms) on the rxn rate are present, but fairly limited.
Here is how your results coalesce the theory of “pseudo-1st-order” for me, along with my and many others’ observations that almost ALL decarboxylation seems to actually occur at the interfaces of the fluid… most especially right where the liquid resin contacts the heated solid surface.
In the herb, this is practically impossible to observe, but each resin gland also has a lot of interface with air, which IS the heated surface in a baked sample. This would explain why we see that herb generally decarboxylates faster than larger volume aliquots of resin (as @Myrrdin observes here), and why even old school heads know that spreading the honey out thin in a pan works to decarb much faster than deep resin in a pot or jar.
Also, nanoscale materials science and common sense tells us that interfaces have greater energy than the bulk beneath them. Nucleation of bubbles in boiling and crystals in precipitation are both phenomena of the interface. A pointed needle penetrates a given surface (interface) with less force than a flat-end rod of equal mass… in many ways this surface area phenomenon is about the difference in energy of the interfaces.
Pressure does affect the rate of the decarb rxn, and it’s backward from what one might expect from CO2 being a gas and the product. This speaks to @Kingofthekush420’s point regarding energy removal by the escaping gas… similar to that seen in simple evaporative cooling. Instead of pressure slowing down the rxn (as might be the case in any 2nd order rxn involving 1 solid reactant breaking into 2 products), pressure speeds it up a little (as would be the case in a 2nd order rxn involving 2 gaseous reactants condensing to 1 solid product). Why? Well, if we treat the heat energy AS a reactant, this backward and limited effect of pressure may become clearer…
A. Pressure traps the heat by keeping the gas from expanding and leaving with its heat, AND
B. It keeps the bubbles smaller and therefore more numerous as they are unable to expand and coalesce, which increases the heated surface area in the immediate vicinity, allowing more molecules to react, BUT
This is naturally limited by the fact that
C. The majority of the molecules in that area have already reacted to create the gas bubbles in the first place, AND
D. Heat energy also dissipates by convection through a medium, (which is minimized as pressure increases, keeping new molecules from entering the more stationary hot zone) and by radiation through space, spreading over a larger area, which attenuates the exposure strength by the inverse square law… so at even one nanometer distance, the energy available to any molecule in the field along the expanded radiant area has been cut significantly.
Incidentally, such power attenuation at distance is probably why ONLY molecules right at the heated interface (where direct heat conduction occurs) will react in the first place… there’s just not enough energy left as the heat spreads outward with distance from its point (molecule) of origin! Although there might be faster convection with lower pressure as @cyclopath may have been guessing, IF it weren’t that the product is a gas able to expand and cool!
So the decarboxylation rxn really is just a 1st order (thermodynamically mediated) reaction, but because of the nature of its products (in this case, the molten dilatant fluid of generally amorphous solid: cannabinoids, and a highly linear non-polar molecular gas: CO2), it also has limited capacity to be driven apparently backwardly, but not reversed (which would be 2nd order) by pressure!
No wonder chemists just summarize that obvious but overtly complicated explanation as “pseudo”!