JR: Yes.
If these claims were true, and they became generally known, Shanahan would win
a Nobel prize. I am not exaggerating.

KS: Yes you are. One doesn’t
win Nobel prizes by pointing out others’ mistakes. This is pure Jedism.

JR: I
cannot imagine a professional scientist who sincerely believed he had made such
an important discovery doing nothing to bring it to the attention of the wider
scientific community for decades.

KS: Jed demonstrating his lack of understanding
again. Finding the systematic effect in
Ed’s data was an interesting scientific discovery, but in the end will be of
interest to about 3 people across the planet IMO. The rest is more Jedism.

JR: I also cannot imagine that such fundamental
laws and techniques, that have been so widely used, are wrong.

KS: More Jed misunderstanding. The specific details of this situation
(F&P-type cell electrolysis/calorimetry) are what causes the problem, not
the basic method itself. Although it is
true that one of the earliest criticisms (not mine!) of F&P’s work was the
use of single-point temp measurement.
That can be afflicted with hot or cold spot problems. That in turn is fixed by using more
thermocouples (or whatever), up to the level of a fully-integrating calorimeter
like the good Seebeck and mass flow ones used by Storms and McK for
example. However, that just reduces the
magnitude of the problem, it doesn’t fully remove it. And thus the need to quantitatively evaluate
things. In Ed’s 98.4% calorimeter, the
error is on the order of a watt. Ed
thought it was on the order of 80 mW.

JR: When someone claims he has found a problem with
"practically __every
known analytical chemistry method,__" that sounds to me like an
out-of-control ego, or an Einstein wannabe.

KS: That would sound that way because you refuse
to understand what I am saying. 99.998+%
of analytical methods (all types) use calibration. That means an equation to convert the
measured quantity for the inherent inaccuracy of the technique, whatever that
may be. Get the coefficients of the
equation wrong, your computed answer is wrong.
It’s as simple and as understandable, by those who want to, as that.

JR: One of these people who
thinks Relativity is wrong and he alone knows the answer.

KS: Jedism. Or maybe he thinks he’s psychic.

JR: I think the chances that
there is a measurable, significant problem with "every known analytical
chemistry method" is astronomically small.

KS: This is an example of Jed’s use of
misdirection. Taken by itself, his
statement is correct. However, his use
of it is to imply in the case of F&P calorimetry, there *also* is no problem. But the fact is that for *any* method, one has to prove that by quantitatively evaluating error.

JR: Of course there are problems.
As you go to finer and finer measurements, and more decimal places, you will
find more complex laws of physics apply, until you get to something like
quantum theory (I suppose).

KS: Amusing.
Jed almost has it right, but not really.
All ‘laws of physics’ apply all the time. The problem is in what proportion. One determines that by quantitative error
evaluation. And yes, the Heisenberg
Uncertainty Principle limits how small you can go. But the experiment that is limited by that is
rare, almost to the point of non-existence.
Most are well above that limit, where deterministic thinking is still
useful. (deterministic thinking == quantitative
error evaluation)

JR: The general laws in a
chemistry textbook are nearly all approximations that do not take into account
every known aspect of physics.

KS: Exactly, which is why you
have to evaluate your error to see if you need to add in more terms or tweak them up, as in the
case of F&P calorimetry where there are no terms in the energy balance
equation for entrainment and evaporation.
Which is why Szpak, et al, in their 2004 paper that I commented on in
2005, find an excess of water exiting the cell.