[SPLIT]Older LENR Experiments were bad, good... in general

First I wrote (as quoted by Abd)(note: I actually wrote what is attributed to Abd here...):

Quote from Abd Ul-Rahman Lomax

P.S. I'm not an electrochemist. I do understand electrochemistry however. Again, what I see in this report is more of the "people who are not recognized cold fusion scientists can not contribute" mentality. Of course, that mentality is never correct.

Then Abd replied and messed up the quoting... His reply to me was (note that the back-connectuing of this quote box may be off since I had to patch up what was messed up in the original, just look on page 29 of this thread.):

Quote from Abd Ul-Rahman Lomax

Abd Ul-Rahman Lomax wrote:that's nonsense. This is the fact: if someone actually does the work in this area, they are called a "cold fusion scientist," because nobody else would waste their time with such stupid stuff. That is what pseudoskeptics think, anyway.

I replied (with tongue firmly in cheek):

Quote from kirkshanahan

Abd Ul-Rahman Lomax wrote:
that's nonsense. This is the fact: if someone actually does the work in this area, they are called a "cold fusion scientist," because nobody else would waste their time with such stupid stuff. That is what pseudoskeptics think, anyway.

Who cares what psuedoskeptics think? Their objections are flimsy and easily dismissed. Just ignore them...

The Abd replied:

Quote from Abd Ul-Rahman Lomax

kirkshanahan wrote:
Abd Ul-Rahman Lomax wrote:
P.S. I'm not an electrochemist. I do understand electrochemistry however. Again, what I see in this report is more of the "people who are not recognized cold fusion scientists can not contribute" mentality. Of course, that mentality is never correct.

that's nonsense.

What was shown here as by me, with Kirk calling it nonsense, was actually written by him. He's not careful, I'm afraid. Yes, people make mistakes. But ... this one is amusing.

Which confuses me completely...as usual...

Abd wrote: "You are here making claims. They might be supportable, but you have not supported them. You have not given
specific citations for where you did this. Did you do this in your latest published paper?"

This illustrates what is so frustrating in dealing with Abd, he seems to have no memory, he never carries the context along, each time is new for him...

Abd, I AM TALKING ABOUT THE SAME PAPER I HAVE BEEN TALKING ABOUT THIS WHOLE TIME WE HAVE BEEN HAVING DISCUSSIONS! How many times must I cite it? If we were having this discussion in person, would I need to say every 5 minutes, "The paper we are discussing is the Thermochimca Acta paper from 2002." Do you have that short of a memory?

You even quoted something I wrote that was _referenced_ and you still ask "where's that?" Wow...

Last time...

2002, Thermochimica Acta, original presentation of the systematic error evidence based on reanalysis of data posted by Ed Storms. Noted error was tied to cal constant shifts, suggested mechanism to produce CCS in F&P cells (Thermochimica Acta, 387 (2002) 95)

2005, Thermochimica Acta, a Comment responding to derrogatory comments in a paper by Szpak, Mosier-Boss, Miles, and Fleischmann (SMMF). Key points: noted excess water collection, showed how SMMF data fit the CCS model (Thermochimica Acta, 428 (2005) 207)

2006, Thermochimica Acta, responding to Storms' Comment on original 2002 article. Countered every point raised with literature citations many times. (Thermochimica Acta, 441 (2010) 210)

2010, J. Environmental Monitoring, a Comment on a glowing review of CF (LENR) by Marwan and Krivit. Delineated problems. 'Group of 10' authors replied with a Comment using an invalid strawman argument to address all but one point raised. Denied opportunity to respond. (Note: There was no reason given, so don't put words into the editor's mouth. We have no idea why he truncated the discussion.)
(J. Environmental Monitoring, 12 (2010) 1756 )

2015 - whitepaper - not reviewed - presentation of replies to 'Group of 10', examination of F&P dynamic chemical process modelling as calorimetric method and delineation of problems, examination of F&P HAD claims of 1993, response to Krivit's individual response to 2010 Comment, manuscript of Comment on Kitamura, et al. (SRNL_STI_2012_00678)

{Edit: Oops...made an error...not 2015...2012...]

Abd wrote:

"You have, in fact, two distinct artifacts asserted, but you call both of them "CCS," which is quite misleading (and which may explain part of the communication problem). Both artifacts involve unexpected recombination. The first proposed artifact is with open cells, where unexpected recombination in the cell is assumed to have not occurred at all. In this case, there is no shift in calibration, at all, at least not from this effect. Rather there is a possible calculation error in terms of how much heat is added back in to represent the stored energy allowed
to leave the cell as unrecombined gases."

Let's break that down a bit: "You have, in fact, two distinct artifacts asserted, but you call both of them "CCS," which is quite misleading (and which may explain part of the communication problem)"

Or...I actually only claim one artifact that expresses slightly differently in open and closed cells...it can depend on how you look at it, but your choosing to discuss the artifact as two instead of as the one I present is your typical muddying of the water. It justs creates confusion because it seems we are talking apples and oranges.

"Both artifacts involve unexpected recombination." - No, the artifact (which technically is the appearance of apparent excess power signals in F&P electrolysis cell calorimetric data analyses) involves unexpected recombination, in particular in unexpected locations.

"The first proposed artifact is with open cells, where unexpected recombination in the cell is assumed to have not occurred at all. In this case, there is no shift in calibration, at all, at least not from this effect."

No, the same problem is postulated, however, the steady-state normally present in the calibration procedures is different from an open cell, which has its ramifications.

"Rather there is a possible calculation error in terms of how much heat is added back in to represent the stored energy allowed to leave the cell as unrecombined gases."

No. There is a possible calculation error in terms of how much heat is added back in to represent the amount of unexpected reconbination occurring in the cell, which is dependent on the location of the heat generation.

So do you see how your attempt to attach your flawed concepts to the skelton of mine ends up giving us a Frankensteinian mishmash? ANd that's exactly what the promary CF researchers do too, most succinctly illustrated by their attempt to label my systematic error a random one.

Then Abd writes:

"The second error is with closed cells, which have catalytic recombiners to capture that heat directly, to return it to the cell environment so a correction is not necessary. In this case, if recombination heat is captured by the calorimeter with a different efficiency than recombination within the electrolyte, there is a possible calorimetric error. In this case, there would be really, not a "shift in calibration," but improper calibration, combined with ignorance about the location of heat generation."

No, same artifact. Same math. Slightly different physical structure which alters the appearance slightly. You are correct with "...there is a possible calorimetric error". But calling it "improper" calibration is not correct. It is using an improper calibration model. If one could treat the results as if coming from a homogenous calorimeter/cell assembly, then they are doing it right. But the math shows there is a systematic error present when one does that whenever the FPHE effect is working, and I believe it arises from the particular facets of the experimental work, and which requires the use of a different calorimeter model to properly account for.

Next quote:
'The story becomes personal,with heavy world-view interpretation, distinguishing "CF'ers" from "good scientists." '

Personal? No. If I could find a scientist in the set of those working in the field who actually handled my criticisms correctly, I would immediately change how I write. But I can't, so the set is all of them. You will note I usually put "good" in quotes, becasue that's a very subjective and loose descriptor. But one characteristic of those who are considered "good" by their peers is that they respond to criticisms calmly and technically astutely, instead of emotionally and with illegitimate logic (Langmuir's "ad hoc explanations"). So if the shoe fits...

"So far, here, the argument is almost entirely "I was right, they were wrong." Fact is neglected. " Fact, I presented a three-tier explanation of anomalous heat. Fact, tier 1 and 2 were never challenged. Fact, tier 1 and 2 were never addressed by CF researchers. Fact, tier 3, a _proposed_ physical/chemical mechanism was attacked in writing and in presentation (see Hagelstein in the YouTube videos of the mini-course he and Swartz put on). Fact, none of the arguments presented in those attacks were conclusive (since I countered them - ex. - SMMF 2004 paper and my 2005 comment; Storms 2006 and my reply) and some were completely incorrect ("CSSH" argument). Seems to me the facts are on the side of my interpretation.

Abd: "Right off, I notice reading over that paper that what amount to unpublished, unreviewed results were the major focus of much. "

Which paper is that? You don't cite tyour references? How can I understand you if you don't cite a paper? (Sorry, had to do that, just a perverse side of me I guess...) But seriously, are you talking about the 2015 whitepaper? The rest of my pubs _were_ reviewed and published in the scientific literature.

Abd: "...presented as a conference paper." A conference paper has less stature than a stright journal article, but it is still considered part of the scientific literature. I believe Ed would stand by his work. I don't understand your objection given that.

Abd: "Storms has actually done, in this paper, two-zone calibration. However, it is not a two-zone calorimeter. But we can tell the difference between the zones." - First I ever heard of that. I suspect you've redefined "two-zone".

Abd: "...is it available on the internet? "
http://apps.webofknowledge.com/Search.do?product=WOS&SID=4AxEKwfPkX4UzTLoRl4&search_mode=GeneralSearch&prID=aa0511b3-74e7-46a3-9717-eb55c29b7486

If the search terms fail to autofill, use author shanahan, publication name thermochimica acta.

Abd:". Did anyone ever point out to you that you, as reflected in your 2002 paper, may not have understood how Storms calibrated in his 2000 report?"
No, because I understood it.

Abd: "Storms' comment was brief, two pages, and focused. Your reply, published the next year, was five pages and scattered. "

Scattered?? I broke the paper into sections, one for each of Storms' claims. And have you ever noticed it always seem to take more space to counter bad ideas than to state them? There was a quote about that I saw recently that I couldn't find again, but it used a 7X factor I think. I only needed 2.5X.

Abd, quoting my paper: "Storms’ arguments rest on four fundamental points: (1) O2 and H2 bubbles cannot mix on the electrode surface because all bubbles rise rapidly to theelectrolyte surface," - followed by - "Just starting with the first, that is not what Storms stated. It is a straw man argument."

Now, what did Storms' actually say about my proposal... Let's see, he said:

"As anyone who has viewed a Fleischmann–Pons (F–P) electrolytic cell will testify, all D2 is generated at the cathode and all O2 is generated at the anode, with both gases rising rapidly to the surface as bubbles. Bubbles contain mainly only one of these gases. Consequently, significant heat from recombination cannot be produced, as Shanahan proposes, because very few bubbles reach the opposite electrode."

In absolute technical correctness, Storms' allows for a very small percentage of bubbles to get to the other electrode, but the key is he then claims the result is insignificant, which is not significantly different from barring the occurance at all. I paraphrased and simplified (by not masking the negative conclusion in vague "Well...it _might_ be possible..." trickery). The point I claim the CCS might explain all XP signals, whiles Storms says it will always be insignifcant.

...and on and on...

to summarize, Abd takes those parts of what I say that can be manipulated by redefinition, and redefines words and what I've said to mean something else, or to force-fit his ideas into my framework. OTOH, I lay it out plain and straight. To whit: Math says CCS can cause apparent excess heat signals. There is a physical explanation for this. There is an unrecognized chemical process that does that. QED

Quote from Wyttenbach

@Kirk: We have to address two completely different fact:
1) Is PdD reaction of nuclear nature
2) How big is the related excess-heat

Depends on your proposed mechanism (nuclear) as to their separability. The heat is also a product of at least one nuclear reaction, so only if more than one are going on can you separate them.

Quote from Wyttenbach

Regarding 1)

SPAWAR and others have clearly shown, that particle detector surfaces on the (PdD) electrode side look different than on the opposite site.
So I hope You agree that within PdD a nuclear reaction is ongoing.

SPAWAR have not eliminated my proposed method to induce pitting in etched CR-39 plates (on both sides). Given that carrying a CR-39 chip in your pocket for awhile induces pitting, I think that will be hard to do. It doesn't take an enormous (i.e. 'nuclear') energy to get pits. No Pd-D nuclear reaction from my POV.

Quote from Wyttenbach

Regarding 2)

kirkshanahan wrote:
Abd, you refuse to truly explore the mundane chemistry option. You always assume everything a CFer claims is correct, and never see the obvious problems a real skeptic would.

The impact of recombination is temperature and pressure dependent and must be accounted for. Recombination is just a waste of input energy and lowers then output of D(H). Typical losses in wrong setups are 1.5% of the output D2. Or the other way round You over estimate the out put energy (worst case) by 1.5%. In a calorimeter where You measure the total energy (out-in) that is absolutely no problem. But in a differential setup the error can multiply.

Display More

T and P dependent - yes and no - the heat will be directly dependant on the amount of material reacting. T and P changes can change some things related to its detection. Might be interesting to try an F&P cell at 1/2 atm to see what that does. Should change the bubble size I think. Changing cell T from room temp up to 100 C or so doesn't seem to do all that much. People have claimed it does but the reproducibility of the effect isn't good enough to be sure.

Your 1.5% number smacks of the _electrochemical_ recombination. That's not what I am talking about. Yes, the CF community is fixated on that number, but they refuse to acknowledge that my CCS mechanism makes that number irrelevant.

But I also see you have failed to understand the CCS mechanism. Weren't you paying attention when I claimed it could explain a 780 mW XP peak, and probably much larger signals? That's well beyond 1.5%.

Quote from Wyttenbach

Thus Kirks critic (see below) is only relevant for a subset of the used calorimetry.

Ummm...yes, the CCS mechanism I proposed is specific to F&P cells, but the idea that, if your apparatus, whatever that is, has a CCS, then its results will be in error applies everywhere. That's just simple math.

Quote from Wyttenbach

kirkshanahan wrote:
No to all of that hogwash. I have established my case in the journals to the satisfaction of any neutral observer. I demonstrated how a slight change (+/- 2.5% max) in cal constants 'flatlined' an excess heat signal, and I showed a systematic trend in the data. I pointed to the need to use a two-zone calorimeter model at a minimum to get correct conclusions from the calorimetric data. I showed how studies by SMMF fit my proposals, including the speculative mechanism. I was denied the chance to point out extreme errors on the part of CFers in two separate cases. Errors that invalidated objections to my proposals. I did point out that the use of strawman arguments and other dubious techniques illustrated the inability of the CFers to come up with any truly relevant or significant objection, which would stimulate 'good' scientists to pause and consider.

But this is wishful thinking:

No. It isn't proven beyond the shadow of a doubt, but so far I've heard nothing that dissuades me from believing it is reasonable.

Quote from Wyttenbach

kirkshanahan wrote:
No He measurements have been shown to be above room air He concentrations, so leaks are feasible. Further, two time based processes, whether they are related or not, will show correlation to some random extent.

With this You completely stay out of the game. Stringham measured over 500ppm He4 and a good agreement between heat/He.

I haven't studied all of Stringham's work, especially since Little a) had problems with his calorimetry and b) came out with the conclusion that measuring ultrasonic power in was very tricky. Which paper do you refer to?

Quote from kirkshanahan

I haven't studied all of Stringham's work, especially since Little a) had problems with his calorimetry and b) came out with the conclusion that measuring ultrasonic power in was very tricky. Which paper do you refer to?

JCMNS Vol 14!

Quote from kirkshanahan

The overall process for Pd hydride formation is definitiely exothermic.

This I do not have evidence to dispute, although it seems contradictory to some known reduction reactions in the chemistry of several transition metals-- if that is applicable to such hydride "oxidations" (i.e. electron loss) . But, irrespective of that, there is the interesting and still not clearly answered a related issue that can be rephrased:

If hydrogen in highly loaded Pd (reputedly vital to the FPHE) is actually in the form of atomic or perhaps ionic H, then the resulting spontaneous deloading of such 0.9 to 1.0 PdD electrodes in say an Heat After Death or HAD scenario, would give direct recombination to molecular hydrogen at or near the surface. That nearly spontaneous process must return a strongly exothermic enthalpy of nearly −436 kJ/mol.... which considerably exceeds the energy of hydrogen oxidation itself at −286 kJ/mol ... but which requires no oxygen.

I would much appreciate learned discussion / disposition of the above.

Quote from Abd Ul-Rahman Lomax

Kirk was correct, it's well-known. This implies the reverse, that deloading is endothermic, and it is. However, both loading and deloading can be complicated by other reactions taking place.

Correct, and this is central to my quest here. Proper accounting of the enthalpies may have been done in the near or distant past, but as a relatively new "outsider", I think those need to be readily demonstrated to satisfy and educate those of us seeking to understand. The energy balances may follow tortuous paths as you appear to suggest, but to my understanding, such intermediates are largely "activation intermediates" or "transition states" which do not affect the overall enthalpy. Going through various circuitous paths does not affect the overall enthalpy, if the beginning reactants and final products are the same.

Quote from Abd Ul-Rahman Lomax

Abd quoting Longview: ..." then the resulting spontaneous deloading of such 0.9 to 1.0 PdD electrodes in say an Heat After Death or HAD scenario, would give direct recombination to molecular hydrogen at or near the surface. That nearly spontaneous process must return a strongly exothermic enthalpy of nearly −436 kJ/mol.... which considerably exceeds the energy of hydrogen oxidation itself at −286 kJ/mol ... but which requires no oxygen."

Quote from Abd Ul-Rahman Lomax

Completely missed here is the heat of formation of PdD, which is returned upon what I call the "evaporation" of hydrogen from the surface. The heat expected is not seen, and for obvious reasons. I'm not looking up the heat of formation of PdD, but it obviously exceeds the heat of formation of H2 from H. Palladium spontaneously soaks up hydrogen, it loves it. that could not happen unless absorption were exothermic, as it is.

In my view you, Abd, are unnecessarily and uncharacteristically but "obviously" uninformed here. You definitely need to have the numbers for PdD formation. There is every likelihood that it is far less than the 436 kJ/mol for molecular hydrogen formation from atomic hydrogen (actually one the most energetic chemical reactions known, by the way). Spontaneity, as you surely do, or at least should, know reflects much more than negative enthalpy.... such enthalpy yield being necessary but not sufficient to drive a reaction-- depending on "activation energies". I leave open the likelihood that PdD formation may not form atomic deuterium.... if it did, it would have to be an endothermic reaction. Much earlier I suggested that the exothermicity of the PdD "reaction" resulted from the loss of degrees of freedom of hydrogen on moving into the palladium context (a delta S, that is entropically driven factor in the overall Gibbs free energy relation). This surely can release heat, and probably at the level observed. But, I predict here, that in spite of the "hunger" of hydrogen and Pd for one another, those molar enthalpies are likely to be puny compared to atomic hydrogen pairing with itself. That Pd - D "hunger" most likely reflects the low energy of activation for that "alloy" formation rather than some large enthalpy.

Abd's assertion (below) that the hydrogen species within Pd (implying it is not ionic, atomic or molecular) is the most cogent (relevant and significant) of his comments here:

Quote from Abd Ul-Rahman Lomax

This is not a good description of hydrogen within the lattice. This is a metal and "conduction band" electrons are shared.

I find the idea that PdD is still effectively a metal and that the hydrogen itself participates in conduction band electronics plausible. The specific heat, thermal and electrical conductivity of PdD may well confirm this.

A final note: the electronic qualities and chemical behaviors of "natural" 0.7 PdD versus a supernaturally loaded 0.9 to 1.0 molar ratio PdD, are surely quite distinct. I suspect as distinct as Pd is from PdD.

Quote from Longview

although it seems contradictory

No disrespect intended but if it seems contradictory to you, your thinking is off. It is absolutely not contradictory, it is as it is and it follows the standard definition of exo- and endothermic. H2 absorption is exothermic.

Quote from Longview

If hydrogen in highly loaded Pd (reputedly vital to the FPHE) is actually in the form of atomic or perhaps ionic H, then the resulting spontaneous deloading of such 0.9 to 1.0 PdD electrodes in say an Heat After Death or HAD scenario, would give direct recombination to molecular hydrogen at or near the surface.

Yes, except ionic H is unlikely. The H atom electron gets donated to the metal bands and then the H+ in the lattice is screened ('balanced') by the band electrons indiscriminately, as opposed to the atomic case where 1 electron charge negates the one proton charge, but the end result is the same, the charge is balanced. Only the potential localization of partial charges would change from metal to metal, but it is never 100% localized in a metal.

"Spontaneous' deloading occurs because something has upset the equilibrium. You recall equilibrium is a dynamic situation right? Not static. There are two reactions ongoing: H going into the metal and H coming out of the metal. This goes on all the time. At equilibrium the rates in and out are balanced. The rates depend on pressures and concentrations. When you drop the pressure in a 'gas-loading' (or 'unloading') experiment as I do, you have upset the equilibrium and the system then attempts to reestablish it by moving gas out of the metal and into the gas phase. But it takes energy to take H from inside the metal and form H2. SO the metal cools and then (usually) gets returned to the original state by drawing heat from the environment, which in turn is replenished from a heater. In the electrochemical cell, the voltage serves the same purpose as pressure, so when you change the voltage the equilibrium is upset, and the system again seeks to reestablish it.

Quote from Longview

That nearly spontaneous process must return a strongly exothermic enthalpy of nearly −436 kJ/mol.... which considerably exceeds the energy of hydrogen oxidation itself at −286 kJ/mol ... but which requires no oxygen.

This is where you are backwards. The energy was released when the H went into the metal. Going the opposite direction requires adding that energy back to form the H2 molecule. In an unheated system, that causes the metal to cool. In a real process then, to get the H out, you have to heat the metal.

And Abd is correct in noting that you always have to consider anything else that might be going on that would contribute its characteristics to the overall observations. Any oxygen would 'exothermically' react to form H2O.

P. S. I don't believe there are any valid HAD events.

Quote from Abd Ul-Rahman Lomax

In his view, and with some evidence, he claims that the high loading causes particular kinds of surface cracking and that this creates the necessary nuclear-active-environment (NAE).

Funny how he finally begins to come around to what was obvious from his Y2K experiments that I reanalyzed... He use a Pt anode AND a Pt cathode and got a respectable 780 mW 'excess heat' signal. Pt does not hydride. People have tried valiantly to get it to with no success. That means it's a surface reaction. Thus the bulk H concentration (or D) in PdH(D) is only of secondary importance. What is much more important is the surface characteristics. Cracks are surfaces, so that agrees. But is that the crucial factor? Only if it can be shown to be one by experimentally controlling it and getting reproducible results from controlling it.

Quote from Abd Ul-Rahman Lomax

He showed a "heat after death" experiment where he turned off the electrolytic current during an excess heat episode, while maintaining electrolyte temperature thermostatically with a separate heater (which would adjust supplemental heat to maintain constant temperature, this is also a calorimetric method). Even though the cathode loading would decline, and he was measuring that, the heat continued without decline, until, after many hours, he allowed the cell to cool and the reaction turned off.

Good calorimeters are well insulated, meaning that their heat loss rates are low. 'Several hours' is probably just the expected time, especially if one considers the effect that cessation of electrolysis has on mixing. Again, the problem lies in assuming that what goes on in the cell has no impact on the thermal characteristics of the calorimeter.

Quote from Abd Ul-Rahman Lomax

researchers who did not obtain high loading (specifically all of the famous early negative replicators) did not see the effect

No, some did. This was another sign that McKubre's demand for high loading was not a true requirement.

Quote from Abd Ul-Rahman Lomax

In the Arata experiment where Arata loads palladium black with deuterium, he sees an initial heat release that is the chemical release. His nuclear claims are in a lower and much longer-sustained additional heat that comes after this. Anyone working with cold fusion must understand that initial release of heat.

And just to add...the initial phase also produces an excess of free oxygen, which can react with any free hydrogen and produce extra heat from that known reaction. That's why unless you take all this into account directly (which can be complicated by how fast oxygen might be purged from an open system before reacting for example) you have to wait a considerable time before you start trying to measure whther there is an excess or not.

Quote from Longview

Abd Ul-Rahman Lomax wrote:
Completely missed here is the heat of formation of PdD, which is returned upon what I call the "evaporation" of hydrogen from the surface. The heat expected is not seen, and for obvious reasons. I'm not looking up the heat of formation of PdD, but it obviously exceeds the heat of formation of H2 from H. Palladium spontaneously soaks up hydrogen, it loves it. that could not happen unless absorption were exothermic, as it is.

In my view you, Abd, are unnecessarily and uncharacteristically but "obviously" uninformed here. You definitely need to have the numbers for PdD formation. There is every likelihood that it is far less than the 436 kJ/mol for molecular hydrogen formation from atomic hydrogen (actually one the most energetic chemical reactions known, by the way).

FYI, the heat of formation of "PdD" is not a simple number. For PdH, Flanagan et al have reported:

"Differential heats of absorption of hydrogen by palladium have been measured with an adiabatic calorimeter. For the first time calorimetric heats have been determined for bulk palladium in the single phase, α and β, regions. The heat of absorption in the α-phase (25°C) was found to be 23.32 ± 4.45 kJ (mol H2)–1 and in the β-phase the isosteric heats decrease with hydrogen content from 46.5 (H-to-Pd = 0.61) to 27.3(H-to-Pd = 0.69). (The measured differential (adiabatic) heats have been corrected for compression work to give isosteric heats.) Heats of sorption determined in the α-phase of palladium black reflect contributions due to both absorption and chemisorption of hydrogen. Some preliminary heats of sorption are also reported at – 78°C and at –195°C with palladium black." J Chem. Soc. Farad. Trans. 1, 1974,70, 814-
http://pubs.rsc.org/en/content…14/unauth#!divAbstract824

Some people have reported that H absorption near H/Pd=1 is actually endothermic.

It's never as simple as you'd like...

(Preview: The data cited by kirkshanahan, shows that the entry of hydrogen / deuterium into the electrode may be entirely molecular, that is it remains effectively or actually H2. The figures Kirk presents here are expected and are but a small fraction of the H2 dissociation energies. If the energies of splitting H2 and subsequent re-association aren't seen there, then the reaction... that is dissociation to the atomic form.... simply does not occur. )

Longview wrote:
"That nearly spontaneous process must return a strongly exothermic enthalpy of nearly −436 kJ/mol.... which considerably exceeds the energy of hydrogen oxidation itself at −286 kJ/mol ... but which requires no oxygen."

Quote from kirkshanahan

This is where you are backwards. The energy was released when the H went into the metal. Going the opposite direction requires adding that energy back to form the H2 molecule. In an unheated system, that causes the metal to cool. In a real process then, to get the H out, you have to heat the metal.

Backwards? This energetics point has been obvious from the beginning. And that is why I see nothing to support the idea that atomic hydrogen is present. Either there are reactions yielding some measurable evidence of exothermic minus 400+ kJ/mol or there are not. The absence of the energetics of molecular hydrogen dissociation, and particularly the sign (exothermic energy yield) of reciprocal hydride re-association energy says plainly and clearly that it is not there at any level that can substantially counter the endothermic desorption of H2. The behaviors (taking Kirk at his word) seen are consistent only with simple molecular hydrogen/deuterium, that is the species involved is H2/D2 and nothing more or less.

Bottom Line #One: There is evidence that molecular hydrogen/deuterium prevails in loaded Pd, and evidence of no hydride per se.

Quote from kirkshanahan

No disrespect intended but if it seems contradictory to you, your thinking is off. It is absolutely not contradictory, it is as it is and it follows the standard definition of exo- and endothermic. H2 absorption is exothermic.

My advice, don't fret over others' "thinking" and whether it agrees with your preconceptions. It appears you may need to consider how the logic of science proceeds. That is a "contradiction" indicates that one or more operating assumption may be incorrect.

Returning to the actual issue at hand: The modest energy and sign of numbers you give from Flanagan etal, recited below, are completely consistent with entropic changes-- as I mentioned earlier: the loss of degrees of freedom for molecular hydrogen (deuterium) as it enters the metal. It would only be in true hydrogen dissociation that large energies would be seen, and these would be of the opposite sign. I have been maintaining correctly that H2 dissociation is highly ENDOthermic. Any proper accounting of H2 absorption needs at least an awareness of the possibility that atomic H may be formed, may be present, and therefore may energetically recombine. The Flanagan data you cite below suggests clearly that no such dissociation occurs:

Quote from kirkshanahan

FYI, the heat of formation of "PdD" is not a simple number. For PdH, Flanagan et al have reported:

"Differential heats of absorption of hydrogen by palladium have been measured with an adiabatic calorimeter. For the first time calorimetric heats have been determined for bulk palladium in the single phase, α and β, regions. The heat of absorption in the α-phase (25°C) was found to be 23.32 ± 4.45 kJ (mol H2)–1 and in the β-phase the isosteric heats decrease with hydrogen content from 46.5 (H-to-Pd = 0.61) to 27.3(H-to-Pd = 0.69). (The measured differential (adiabatic) heats have been corrected for compression work to give isosteric heats.) Heats of sorption determined in the α-phase of palladium black reflect contributions due to both absorption and chemisorption of hydrogen. Some preliminary heats of sorption are also reported at – 78°C and at –195°C with palladium black." J Chem. Soc. Farad. Trans. 1, 1974,70, 814-
pubs.rsc.org/en/content/articl…14/unauth#!divAbstract824

Bottom Line #Two: Investigations in CF/LENR need to separately account for modest entropic energetics, and need to avoid drawing enthalpic conclusions from such data.

(And thanks for the citation and those data, Kirk).

No, hydrogen in a metal hydride like Pd is not molecular. The only way to see molecular hydrogen inside a metal hydride is to have it desorb from an internal surface like in a bubble and enter a void as a gas (assuming you have a technique that can do so). Then it is molecular. This is essentially what Arata did with his 'double structure' cathodes that he hollowed out and filled with Pd black. The void space left betweeen the Pd black particles was filled with gaseous hydrogen.

I haven't worked through your thermo, but if it drives you to conclude molecular hydrogen in PdD, then your thermo is wrong. I don't have the time to find your error.

Quote from Longview

Bottom Line #One: There is evidence that molecular hydrogen/deuterium prevails in loaded Pd, and evidence of no hydride per se.

Where did You read this? Crystallography tells an other story!

Longview wrote:

"Bottom Line #One: There is evidence that molecular hydrogen/deuterium prevails in loaded Pd, and evidence of no hydride per se. "

Quote from Wyttenbach

Where did You read this? Crystallography tells an other story!

It is my preliminary deduction from simple, but generally inescapable thermodynamics. It may be in contradiction to crystallographic evidence. Let's compare the evidences!

Longview, please read http://lenr-canr.org/acrobat/OrianiRAthephysica.pdf

Quote from Longview

It may be in contradiction to crystallographic evidence. Let's compare the evidences!

A good starter as usual is Wiki: https://en.wikipedia.org/wiki/Palladium_hydride.