Isoperibolic can be made much more independent of cell conditions with multiple isothermal wraps.
If this means multiple layers, some people use that, but it is not needed. One large wrap around the entire cell works. That is what Miles used. A copper jacket. The temperature may vary in the cell, but it is the same anywhere on the jacket, because copper conducts heat well. See p. 55:
Display MoreI am surprised that there is so much angst and uncertainty about this issue. This was highly discussed and heavily worked out in “the early days”. I can't speak for anyone else but I expect it is true for others as well. The phenomenon that Kirk proposes was well anticipated (and better understood) by the design team for our first mass flow calorimeter (up to 1992) and improved in both design and understanding afterwards. Our calorimeters were designed to operate on first principles (first law). Where systematic errors could conceivably occur the calorimeter was designed to be conservative - anticipated errors leading to under-measurement of heat. Some of you will remember me discussing this seemingly endlessly in 1989-1992.
We obviated the precise issue that Kirk speaks about as follows:
1. The electrochemical cell was enclosed (at pressure) in a metal heat integrator (“isothermal wrap” in THH's words).
2. Nothing left the cell except wires and a gas pipe for initial H2or D2gas charging.
3. A complimentary Joule heater was intimately wound into the metal heat integrator axially symmetric to the electrochemical cell.
4. The calorimetry fluid submerged and completely enveloped the integrator bathing externally all surfaces and picking up heat from wherever sourced (BTW there are 7 conspicuous heat sources in FPHE calorimeters, not just 2):
a. The anode (I * V anode)
b. The electrolyte (I2 * R electrolyte)
c. The cathode (I * V cathode)
d. Any excess power
e. The recombiner (I * [V cell-V thermoneutral])
f. The complimentary Joule heater that kept the sum of input power constant (I2 * R heater)
g. The wires (I2 * R wire). Note that since V was measured at the calorimeter boundary only the wires inside the calorimeter contribute to this term, and it is fully measured
5. The thermal efficiency of our early design was ~98%, later improved to 99.3%.
6. Only the missing 0.7 to 2% (that is lost primarily by thermal conduction to the ambient down wires and the pipe) needs to be “calibrated”.
7. Calibration of the first law parameters (I, V, ∂m, ∂t) were performed independently of the calorimeter.
8. At constant input power the presence of excess heat can be inferred qualitatively by a rise in temperature of the outgoing fluid (normally water). Our largest excess power levels were ~300% in input power. Our largest statistical significance (Excess power / measurement uncertainty) is 90 sigma.
9. We tested our assertion that heat was measured equally independent of its source position two ways:
a. Finite element calculation (this is a complex matter not handled by two term algebra) which modeled the entire calorimeter up to its isothermal boundary: submerged in a water bath held at constant temperature ±0.003°C; in a room held constant to ±1°C
b. Experimentally testing the influence of current to the cell and the complimentary Joule heater over a wide range in blank cells (H2O, Pt or poorly loaded Pd cathodes, early before initiation of the FPHE)
10. The calorimeters were proven to be heat-source position-independent already by 1991 when I stopped worrying about this effect for our calorimeters. The fact that long long long hours of calorimetry were performed (>100,000), covering wide variations of cell and heater power, with calorimetric registration of zero excess heat sadly but conveniently reinforces our conviction that the Shanahan hypothesis that heat excess can be incorrectly measured (always positively?) by the displacement of heat sources – plays no significant role in our calorimeters.
11. This last conclusion, equally rigorously supported by their designers and authors, applies to the two other modes of calorimetry with which I am closely familiar: F&P’s partially mirrored dewar design; the heat flow calorimetry of Violante and Energetics (using heat integrating plates).
There are more insidious potential error sources possible particularly in electrochemical calorimetry. Ed discovered one in simple isoperobolic calorimetry for which the thermal barrier was the (pyrex) cell wall (changing wall hydraulics). Others exist and we should always be alert and open to suggestion. On the other side I suggest that the suggestors pay close attention to the literature, make quantitative calculation modeling the physical processes that drive the putative mechanism, and do not make global claims of “it is all wrong because…”.
It is not that I claim that Kirk’s suggested semi-mechanism has never applied to LENR calorimetry. The effect he describes did play a role in the NRL / Coolescence Seebeck calorimeters when the recombiner is more or less well coupled to the predominant heat-flow path. But this was recognized by them. It is not that his “discovery” is never significant, or never could be. It is that the mechanism is well known, was historically anticipated, and is irrelevant to most of the calorimeters with which I am familiar. Even if he could show one case quantitatively, it would not affect the whole of our understanding.
Here endeth the lesson. I will answer only relevant technical questions for clarification (and then probably slowly).
Thanks for this detailed summary.
I was rather expecting that from my memories of what you had done. For such 99%+ efficiency calorimetry I don't see much scope for heat source position errors. And your experiments were (to my knowledge) more carefully conducted than anyone else's.
When going from that to the significance of the results as indicating non-chemical (nuclear) energy transfers the headline figures of 300% don't mean anything by themselves (because of the stored chemical energy issue) : but that is not the argument at hand.
I won't speak for Kirk but what I'm suggesting is that change in cell conditions is difficult to rule out. To take an example, what matters is not just position of heat source, but thermal conductance between sources and sinks. In a system with liquid and bubbles that is difficult to control and so any number of single factor checks may miss something significant that relies on multiple factors (e.g. as just one example change in electrode to liquid thermal conductance and change in power emission at electrode). Also, even for your work, I'm wary of the single factor problem: where effects are ruled out because past rigorous testing has shown them not to be significant but then might re-emerge in combination with other factors. Which is why lots of checking is needed, and for those experiments less well checked than the ones you describe above Kirk's points remain in play.
My position would be that understanding in detail and quantitatively the possible error mechanisms is helpful, and in a skeptical climate best done openly, and the published response to Kirk's commentary has not shown much acknowledgement of that.
I sometimes think that the whole "persistent excess heat mystery in certain electrochemical cells" matter would have been much better and more fairly judged if no-one used the words nuclear or fusion in connection with it. Ever. Until the mystery was better understood than is the case now at which point they might be indicated - or not. That would allow fair consideration, without heated emotions, of the phenomenal aspects.
Cold nuclear synthesis takes place in crust, but as the main element the rotating plasma like a fireball serves! It gives a dynamo effect and processes of cold nuclear synthesis will be on the second plan, plasma and electricity to them created is primary!
Холодный ядерный синтез проходит в земной коре, но главным элементом служит вращающаяся плазма типа шаровой молнии! Это дает динамо-эффект и процессы холодного ядерного синтеза будут на втором плане, первична плазма и электричество им создаваемое!
I won't speak for Kirk but what I'm suggesting is that change in cell conditions is difficult to rule out. To take an example, what matters is not just position of heat source, but thermal conductance between sources and sinks. In a system with liquid and bubbles that is difficult to control and so any number of single factor checks may miss something significant that relies on multiple factors (e.g. as just one example change in electrode to liquid thermal conductance and change in power emission at electrode). Also, even for your work, I'm wary of the single factor problem: where effects are ruled out because past rigorous testing has shown them not to be significant but then might re-emerge in combination with other factors. Which is why lots of checking is needed, and for those experiments less well checked than the ones you describe above Kirk's points remain in play.
That is correct. Kirk’s “semi-mechanism” (I call it semi because it is generic not specific as to physical cause) is conceivable (and therefore must be guarded against) and has applied to some calorimeters (I will give an example below).
What it is not correct is:
a. It was unanticipated by early researchers until Kirk “discovered” it
b. It applies to all forms of calorimetry
c. It can explain all excess heat results (as has been claimed – in person if not in writing).
Ed Storms abandoned the specific form of calorimetry that was used by many early explorers (including all three “famous” negatives). Calorimetry in which heat flow is measured from the difference in temperature across the outer wall of an electrochemical cell with undefined and uncontrolled thermal resistance and no “isothermal wraps”, can be compromised by this form of error – I believe fatally. What Ed discovered was that the controlling thermal barrier is not one but two: the glass (pyrex) wall; the hydrodynamic boundary layer of electrolyte. The first may be considered fixed. The second, in series, is subject to change with changes in electrolysis bubble pattern, natural convection, imposed stirring, temperature, electrolyte viscosity, deposition of crud on the wall, surface tension, etc.
The early “famous” replication by Lewis et al at Caltech was subject to this error form and that may have been the reason why they needed to re-calibrate their calorimeter every day (by pre-supposing that excess power = 0). Here the issue is not so much moving heat source as moving heat leak pathway, which physically makes much more sense. But an analysis of how much their calibration constant needed to be changed each day, in terms of this hypothesis, would be a useful exercise for this community and may be a way for Kirk to redeem and test his hypothesis. My guess is that Lewis would share his data. Harwell and MIT were also subject to this (Storms) error form.
So the effect is not non-existent - it is even relevant - to some. But however this exercise turns out, it will not bear significantly on any of the results that SRI reported, or Fleischmann and Pons (and there are many more results out there to which I would extend this exclusion). We and they were well aware of this issue; appropriate precautions were taken, and elaborated in early talks and papers.
mmckubre,
I found it interesting how Kirk made it a point to mention he was taking a vacation -immediately after his post to you. What timing!
FTR, I like Kirk. Anyways, good to have you engaged here. Hopefully you stay tuned.
Take care
I sometimes think that the whole "persistent excess heat mystery in certain electrochemical cells" matter would have been much better and more fairly judged if no-one used the words nuclear or fusion in connection with it. Ever. Until the mystery was better understood than is the case now at which point they might be indicated - or not. That would allow fair consideration, without heated emotions, of the phenomenal aspects.
Abd and others have said this. I don't buy it. Anyone could see that if it was not an error, it had to be a nuclear effect. Even if F&P had never said that, it would be obvious. Even if the results had leaked out without any comments from them, most scientists would instantly see it is a nuclear effect.
The first result reported was 4 MJ/cm^3 of palladium. That has to be a nuclear reaction. It is far, far beyond the limits of chemistry. Furthermore, there was never any significant amount of chemical fuel in that cell or any other.
Not only that, but soon after the announcement, people at Los Alamos, BARC, TAMU and NCFI confirmed that the effect produces tritium. That, too, is irrefutable proof that the reaction is nuclear.
I am no physicist but the first time I saw the details of the experiments and how much heat they produce, I knew at once it had to be nuclear (or a mistake). Fleischmann pointed out that we know this for the same reason the Curies knew the heat from radium could not be chemical. Because radium produces thousands of times more heat than any chemical reaction per gram of fuel, and because there are no chemical transformations in the radium. Fleischmann showed that calorimetry was one of the most sensitive and important tools in elucidating nuclear reactions at first. M. Curie wrote:
"Radium possesses the remarkable property of liberating heat spontaneously and continuously. A solid salt of radium develops a quantity of heat such that for each gram of radium contained in the salt there is an emission of one hundred calories per hour. Expressed differently, radium can melt in an hour its weight in ice. When we reflect that radium acts in this manner continuously, we are amazed at the amount of heat produced, for it can be explained by no known chemical reaction.The radium remains apparently unchanged. If, then, we assume that it undergoes a transformation, we must therefore conclude that the change is extremely slow; in an hour it is impossible to detect a change by any known methods.
As a result of its emission of heat, radium always possesses a higher temperature than its surroundings. This fact may be established by means of a thermometer, if care is taken to prevent the radium from losing heat."
https://history.aip.org/exhibits/curie/article_text.htm
I also knew cold fusion could not be a miniature version of plasma fusion. I figured that out 5 seconds into reading the Wall Street Journal article. F&P were still alive, so that was ruled out. I did not know much about plasma fusion -- honestly, I still don't -- but I used to hang around in the Cornell plasma fusion lab, so I knew that much! I was amazed that any scientist said: "This can't be fusion because plasma fusion would produce a deadly flux of neutrons, so it must be a mistake." How illogical! Yes, of course it can't be that kind of fusion. So if it isn't a mistake, it has to be something else.
I also knew cold fusion could not be a miniature version of plasma fusion. I figured that out 5 seconds into reading the Wall Street Journal article. F&P were still alive, so that was ruled out. I did not know much about plasma fusion -- honestly, I still don't -- but I used to hang around in the Cornell plasma fusion lab, so I knew that much! I was amazed that any scientist said: "This can't be fusion because plasma fusion would produce a deadly flux of neutrons, so it must be a mistake." How illogical! Yes, of course it can't be that kind of fusion. So if it isn't a mistake, it has to be something else.
JedRothwell : After the master/phd study the mind of most scientists is formed. Most of them anyway never had the ability to question the models they learnt. The remaining ones, that have to teach the new generation cannot be blamed for not committing they might teach the wrong story.
Up to now nuclear & particle physics was based on kinetic experiments. Unluckily people only use the nice Pauli/Dirac formalism (that by the way can be expressed with one quaternion equation) to understand the results, where charges are points or densities and the result are waves or densities.
Even worse: Most physicists still believe that there is a "coulomb style" strong force potential, what is blatantly wrong. We only have magnetic flux/mass that is rotating.
Nevertheless, in the limit, the behavior of a particle collision must be conform (momentum) to Newtons laws.
Now we go back to LENR. In LENR the reacting particles/isotopes have no (or a very small) linear(kinetic) momentum. Even more severe, the reacting partners retain their symmetry = no stimulus for asymmetric decay.
Radiation needs either an excess momentum or a nuclear gamma level that is triggered by the reaction. Only the second may be the case. But most elements have gamma levels that are out of reach for the gained energy. Especially 4-He has no way to either radiate or decay under LENR conditions.
Unluckily the early PD experiments were the 4-He production experiments, that need a new physical model of dense matter for a complete understanding. But which physicist is able to accept, that he learned, taught etc. outlandish rubbish? And that this state of failure happens since about 100 years!
LENR is the tomb stone of the standard model!
Returning after a nice holiday break, with a response to Mizuno's bucket of water
Quotes of Dr. McKubre’s comments are enclosed in “” below.
“I am surprised that there is so much angst and uncertainty about this issue.”
That’s probably due to the fact that you don’t seem to understand the issues. This is most clearly illustrated by your co-authorship of the 2010 J. Envir. Mon. article that replied to my comment on the prior Marwan and Krivit paper. Trying to a) pass off the CCS as a ‘hypothesis’ is incorrect, and likewise b) trying to assign my description of an issue as ‘random’ when I clearly and multiple times have called it ‘systematic’ is also incorrect. Now, the way I heard the paper was constructed was that the various authors contributed parts to Marwan and he combined them, so perhaps you missed the fact that my whole thesis and results were incorrectly presented. Do you stand by your supposed use of the term “random Shanahan CCSH” from that paper?
“This was highly discussed and heavily worked out in “the early days”. I can't speak for anyone else but I expect it is true for others as well.”
Really, so why did you apply an incorrect approach to you data analysis then?
“The phenomenon that Kirk proposes was well anticipated (and better understood) by the design team for our first mass flow calorimeter (up to 1992) and improved in both design and understanding afterwards. Our calorimeters were designed to operate on first principles (first law).”
Well technically I haven’t been able to check your work because you wouldn’t supply me with calibration equations from your massive 1998 EPRI report, and the prior one only presented Figures, not ‘raw’ data as you did in the attached CD on the 1998 report. However, in your M series runs, you observed two runs without any apparent excess heat and two with. I took the two without and used them as ‘calibration runs’ for a more standard type of calibration equation approach (using y=mx+b) than your transfer function approach, and I found a) the excess heat peak height was predictably variable (i.e. consistent with my claims and concerns) when the calibration constants were varied by a few percent, and b) that there were significant baseline shifts present that somehow disappeared when you used your transfer function calibration method. I would still love to see how you do that. I might find it useful myself some day. Care to share at this point?
But I’ve seen no evidence you ever considered the ‘lumped parameter’ approach problem that allows the CCS problem to appear when the heat distribution in the cell changes from the calibration state. I suppose it’s possible you handled this, but you’ve never explained how that I can find. Please give me a reference to where I can obtain this information for study. Thanks.
“Where systematic errors could conceivably occur the calorimeter was designed to be conservative - anticipated errors leading to under-measurement of heat.”
I see no evidence your design fixes the lumped parameter approach. You should note that this problem is not a calorimeter design problem, it is a data analysis method problem. However, an altered calorimeter/cell design might potentially minimize the issue.
“Some of you will remember me discussing this seemingly endlessly in 1989-1992."
I didn’t get involved until 1995, so no, I don’t ‘remember’. This is why all of what you are talking about should be written down somewhere. Reference?
“We obviated the precise issue that Kirk speaks about as follows:
1. The electrochemical cell was enclosed (at pressure) in a metal heat integrator (“isothermal wrap” in THH's words).”
And Ed Storm’s calorimeter also did the same thing with the heat-collecting fluid, but that still left ‘the problem. Likewise, you wrap does not prevent the problem.
“2. Nothing left the cell except wires and a gas pipe for initial H2or D2gas charging.”
Yes, yes, closed cell. So was Ed’s calorimeter.
“3. A complimentary Joule heater was intimately wound into the metal heat integrator axially symmetric to the electrochemical cell.”
Did it or was it used to probe changes in the heat distribution in relation to proposed high and less high heat capture efficiency zones? No. Didn’t think so…
“4. The calorimetry fluid submerged and completely enveloped the integrator bathing externally all surfaces and picking up heat from wherever sourced (BTW there are 7 conspicuous heat sources in FPHE calorimeters, not just 2):”
Just like Ed’s (effectively, Ed used a different design of course, but tried to do the same thing in his design. He achieved ~98.4% (as I recall) total efficiency, yet saw a fictitious 780 mW excess heat signal).
Recall my little box diagram in the prior post. Call the high efficiency zone ‘Zone 1’, and presume it was where the electrolyte was. The gas space is ‘Zone 2’ and normally contains all penetrations through the cell wall, which remain together when exiting the calorimeter (i.e. these are the primary unaccounted for heat loss pathways)..
“a. The anode (I * V anode)
b. The electrolyte (I2 * R electrolyte)
c. The cathode (I * V cathode)
d. Any excess power”
All Zone 1.
“e. The recombiner (I * [V cell-V thermoneutral])”
Zone 2.
“f. The complimentary Joule heater that kept the sum of input power constant (I2 * R heater)”
Power compensation calorimetry, fine. Henry Randolf (sp?) of SRNL used the same thing for his study as presented at ICCF1.
This is technically a new wrinkle for me as I haven’t explicitly discussed power comp calorimetry before, but it’s not a significant one. The heat flowing out of the cell plus the heater power is held constant. When ‘excess heat’ appears, to keep the temperature the same, the heater power is decreased and the drop measured and reported as positive excess heat.
But, heat lost up the tubes and wires never figures into this balance except via the correction that calibration gives, so if the heat loss changes, specifically by dropping when heat moves from the recombiner to the electrode for example, you get your CCS.
“g. The wires (I2 * R wire). Note that since V was measured at the calorimeter boundary only the wires inside the calorimeter contribute to this term, and it is fully measured”
I’m not concerned with power losses in wires and leads. I know some have claimed that as a problem in some cases, but I’m talking specifically about a CCS. If you lose power in the leads and don’t correct for that, shame on you, but I’d guess you did. What I am concerned with is how much heat from wherever is lost and not accounted for up the wires, and if that changes during an experiment. Apples and oranges here.
“5. The thermal efficiency of our early design was ~98%, later improved to 99.3%.”
A.) Ed’s as also 98% or so. B.) I’d like to look over you calcs. Reference?
“6. Only the missing 0.7 to 2% (that is lost primarily by thermal conduction to the ambient down wires and the pipe) needs to be “calibrated”.”
Correct. And changes in that during an experiment are one way a CCS could be induced.
“7. Calibration of the first law parameters (I, V, ∂m, ∂t) were performed independently of the calorimeter.”
Fine. You still calibrated. That means you are dependent on a maintained steady state condition to maintain calibration equation veracity. I propose you did not maintain a constant steady state due to some interesting physics and chemistry.
“8. At constant input power the presence of excess heat can be inferred qualitatively by a rise in temperature of the outgoing fluid (normally water). “
Not if there is a change in the steady state heat distribution as I postulate.
“Our largest excess power levels were ~300% in input power. Our largest statistical significance (Excess power / measurement uncertainty) is 90 sigma.”
Your 90 sigma is a bogus number. Your 1 sigma value is only one component of the total variation and a minor one at that. Looking at the baseline noise in inadequate. Ed’s experiments that I reanalyzed had a claimed 1 sigma of ~80mW and a peak signal of ~780mW for an ~10sigma signal. But in fact a 2-3% change in the calibration constant wiped out that 780mW signal, showing that 1 sigma was at least 780/3=260mW, not 80. You aren’t calculating the error in your results properly.
“9. We tested our assertion that heat was measured equally independent of its source position two ways:
a. Finite element calculation (this is a complex matter not handled by two term algebra) which modeled the entire calorimeter up to its isothermal boundary: submerged in a water bath held at constant temperature ±0.003°C; in a room held constant to ±1°C”
As a chemical process modeling expert, I know the ‘Golden Rule’ of modeling: A model is only as good as the assumptions (equations and parametric ranges and values) you put into it. Did you try to simulate the effect of a heat distribution change such as I propose?
“b. Experimentally testing the influence of current to the cell and the complimentary Joule heater over a wide range in blank cells (H2O, Pt or poorly loaded Pd cathodes, early before initiation of the FPHE)”
Again, you need to try to account for my scenario. Did you do so? Also, the numerical results from this are of interest. What averages and standard deviations did you obtain from the different calibrations you did on a particular configuration?
“10. The calorimeters were proven to be heat-source position-independent already by 1991 when I stopped worrying about this effect for our calorimeters. “
Where can I examine this data? (recall that unpublished data/results doesn’t count)
“The fact that long long long hours of calorimetry were performed (>100,000), covering wide variations of cell and heater power, with calorimetric registration of zero excess heat sadly but conveniently reinforces our conviction that the Shanahan hypothesis that heat excess can be incorrectly measured (always positively?) by the displacement of heat sources – plays no significant role in our calorimeters.”
Really? I thought we all understood that ‘excess heat’ was a rare event. That’s all you established with the above studies.
Also, regarding “(always positively?)”: This is just another example that proves you have not even considered my explanations. Your comment indicates you are still stuck on ‘random’. But your calibration methods as described above are clearly not random, and thus the change that we know as the FPHE is thus not random either. (The reason the excess is always positive is that you always calibrate with an ‘inactive’ electrode (or heater).)
“11. This last conclusion, equally rigorously supported by their designers and authors, applies to the two other modes of calorimetry with which I am closely familiar: F&P’s partially mirrored dewar design; the heat flow calorimetry of Violante and Energetics (using heat integrating plates).”
It is really immaterial to my theses what type of calorimeter is used. All of them have heat losses. All of them are calibrated (or assumed to be perfect, which is just assuming a particular set of calibration constants). All of them are studying the same system (I only refer to electrolysis cells) . Thus all of them are susceptible.
“There are more insidious potential error sources possible particularly in electrochemical calorimetry.”
I never said there weren’t. My CCS thing is just one potential error. It does not address others. But it seems to be quite large in relation to reported signals.
“Ed discovered one in simple isoperobolic calorimetry for which the thermal barrier was the (pyrex) cell wall (changing wall hydraulics). Others exist and we should always be alert and open to suggestion.”
Exactly. Like the whole CCS/ATER thing…
“On the other side I suggest that the suggestors pay close attention to the literature, make quantitative calculation modeling the physical processes that drive the putative mechanism, and do not make global claims of “it is all wrong because…”."
ROFL. A.) I’ve real ‘all’ the literature (an assertion, maybe I only hit 94%, but the point is I’ve read enough). B) My whole CCS thing derives from quantitative re-calculation based on real data. C) You cut off the important part with your ellipsis. It should have read: it is all wrong because a common mistake is being made in the data analysis. In other words, there is a systematic error in the calorimetric data analysis of F&P-type experiments that produces
spurious excess heat signals.
“It is not that I claim that Kirk’s suggested semi-mechanism has never applied to LENR calorimetry. The effect he describes did play a role in the NRL / Coolescence Seebeck calorimeters when the recombiner is more or less well coupled to the predominant heat-flow path. But this was recognized by them.”
Thanks for writing that. I have pointed out many times before that Seebeck calorimeters can show the problem, but every time I do JR screams at me that I am wrong. Perhaps now he will learn something. However, what you write about the mechanism isn’t quite what I say.
“It is not that his “discovery” is never significant, or never could be. It is that the mechanism is well known, was historically anticipated, and is irrelevant to most of the calorimeters with which I am familiar. “
No. The problem is quantitatively documented in one highly efficient mass-flow calorimeter, and easily extended to all other calibrated methods, and is never tested for in any CF excess heat reports. So it appears to be unanticipated and highly relevant.
“Even if he could show one case quantitatively, it would not affect the whole of our understanding.”
Really? If I show a systematic error in your methods it is of no value to your whole understanding? Really?
“Here endeth the lesson.”
Hardly-eth. It seemeth to barelyeth have beguneth…
“I will answer only relevant technical questions for clarification (and then probably slowly).”
Ditto. One can check many of my posts on this forum however for more details.
Putting it simply, I don't see this as a physically feasible shift in mass flow calorimeters. Specifically, an efficiency of more than 100% is not possible, and temperature change in the measured cell cannot increase efficiency above 100%. Finally, the detected heat must be proportional to cell efficiency. There may be second order effects but this would seem to make positive calibration constant shift bounded +1.6%, and realistically quite a bit lower than this.
So, where is the error in my math then? I calculated the local calibration constants that would zero out excess heat, examined the results, and found that the required changes were trivial. I offered explanations for that that were, to me at least, very physically feasible. Please elaborate on where you see an error in my analysis.
In fact it is not possible to have a 100% efficient real calorimeter, because a real calorimeterr needs sensing elements to detect changes, and those elements provide heat loss pathways. One can get very good though, up to 98-99%.
I assume you mean systematic errors by "second order effects".
The same argument does not apply to calorimeters where close-to-cell temperatures are used as proxies for heat flow since these can have changes unrelated to calorimeter efficiency due to lack of isothermality.
I believe I disagree with this statement if I understand it correctly. If I place a temperature sensing device 'close to the cell' why would changes in cell temperature arising from a more efficient detection of internal heat not register in the device? I think it would. You just add another layer of complexity to the thermal transfer conditions without changing the base problem. However, that added layer can have additional problems above and beyond the CCS thing. Is that what you mean?
For such 99%+ efficiency calorimetry I don't see much scope for heat source position errors.
Well, Ed's calorimeter was 98.4% efficient and showed a 780mW excess heat signal. If Mike's 99.3% calorimeter was the M series calorimeter, he only saw a 360mW signal. Cut the lost heat in half, cut the excess heat signal in half, seem straightforward to me...:) I know. The point is that without calculating the actual errors from calibration constant variation, you can't conclude there is no room for the detection of apparent excess heat due to a CCS.
What it is not correct is:
a. It was unanticipated by early researchers until Kirk “discovered” it
b. It applies to all forms of calorimetry
c. It can explain all excess heat results (as has been claimed – in person if not in writing).
What I have actually said:
a. There is no evidence anyone considered a CCS error in any study to date. (Please cite contradicting examples.)
b. The possibility it applies does apply to all calorimetric methods in theory, if they use a calibration equation, either explicitly or implicitly.
c. It might explain all excess heat results, but that needs to be quantitatively checked. There are limits to what might be explained and exceeding those would possibly indicate actual excess heat.
Some corrections to Alhfors list of my publications:
Ahlfors lists a pub as: Storms, E., Shanahan, K. L. in Thermo. Acta. 441 (2006) 207-209 - that is not my paper and I should not be listed as author. I published the following paper which started on page 210.
Not included in the list were:
Discrete event simulation of an analytical laboratory
K. L. Shanahan ,R. E. Beck, C. E. Taylor, and R. B. Spencer
Analytica Chimica Acta, 282(1993), 679
and Presentations/Proceedings papers:
A Dynamic Simulation Model of the Savannah River Site High Level Waste Complex
M. V. Gregory, J. E. Aull, R. A. Dimenna, G. K. Georgeton, T. Hang, T. E. Pate, P. K. Paul, K. L. Shanahan, F. G. Smith, G. A. Taylor, and S. T. Wach
Presented at WM '95, Tucson, AZ by co-author, Feb. 1995 (Proceedings published)
http://www.iaea.org/inis/colle…ublic/26/045/26045355.pdf
Dynamic Simulation of the In-Tank Precipitation Process
T. Hang, M. V. Gregory, K. L. Shanahan, and D. D. Walker
presentation at 1994 Simulation Multiconference by coauthor, April 1994 (Proceedings published)
https://www.osti.gov/scitech/servlets/purl/10121261
A Dynamic Simulation Model of the Savannah River High Level Waste Tank Farm
M. V. Gregory, K. L. Shanahan, and T. Hang
presentation at 1994 Simulation Multiconference by coauthor, April 1994 (Proceedings published)
https://www.osti.gov/scitech/servlets/purl/10107914
KL Shannahan, JE Aull, RA Dimenna - 1994 - osti.gov
https://www.osti.gov/scitech/servlets/purl/10188180
A recent presentation by a co-author which may not have been published:
Electron Microscopy of Helium Bubbles in a Palladium Alloy
Proceedings of the Tritium2016 Conference, April 17-22, 2016, Charleston, SC
David B. Robinson, Mark R. Homer, Joshua D. Sugar, E. Lynn Bouknight, Kirk L. Shanahan
Fusion Science and Technology, 71, (2017), not published (?)
From my 'pre-doc':
J . Q . Searcy and K . L . Shanahan, Thermal Decomposition of the New
Explosive 2-(5-Cyanotetrazolato)pentaamminecobalt(III) Perchlorate,
SAND78-0466, Sandia National Laboratories, August 1978 .
Well, it’s been a month and no response. Maybe McKubre forgot. Here’s a reminder. (I answered this once, but I did this independently so as to hopefully add more detail.)
Note I use the old Internet '>' symbol to indicate what Dr. McKubre wrote in the following. My responses follow as usual.
>We obviated the precise issue that Kirk speaks about as follows:
Hmmm…not likely….
>1. The electrochemical cell was enclosed (at pressure) in a metal heat integrator (“isothermal wrap” >in THH's words).
And then placed inside the calorimeter? Or is the metal wrap the cell boundary?
>2. Nothing left the cell except wires and a gas pipe for initial H2 or D2 gas charging.
The primary unmeasured heat loss pathways.
>3. A complimentary Joule heater was intimately wound into the metal heat integrator axially >symmetric to the electrochemical cell.
OK. Did you ever compare the results using this heater for calibration vs. electrolytic calibration? Ed Storms found they differed slightly, and his Joule heater was immersed in the electrolyte.
>4. The calorimetry fluid submerged and completely enveloped the integrator bathing externally all >surfaces and picking up heat from wherever sourced
So, question from 1.) answered. Cell with wrap inside calorimeter.
>(BTW there are 7 conspicuous heat sources in FPHE calorimeters, not just 2):
Of course, but considering two is a minimal picture to understand how the CCS happens. With 7 you have lots more possibilities I suppose.
>a. The anode (I * V anode)
>b. The electrolyte (I2 * R electrolyte)
>c. The cathode (I * V cathode)
I.e., the standard non-electrolysis power. Once Vth is exceeded one gets electrolysis, which gives H2 + O2 with their energy content given by I * Vth
>d. Any excess power
If any….
>e. The recombiner (I * [V cell-V thermoneutral])
As above (a,b,c)…
>f. The complimentary Joule heater that kept the sum of input power constant (I2 * R heater)
Yup…
>g. The wires (I2 * R wire). Note that since V was measured at the calorimeter boundary only the >wires inside the calorimeter contribute to this term, and it is fully measured
Yup, and not considered an issue.
>5. The thermal efficiency of our early design was ~98%, later improved to 99.3%.
Good for you.
>6. Only the missing 0.7 to 2% (that is lost primarily by thermal conduction to the ambient down wires and the pipe) needs to be “calibrated”.
As I noted above…
>7. Calibration of the first law parameters (I, V, ∂m, ∂t) were performed independently of the calorimeter.
Hmmm…this will be an ideal situation in most cases, meaning that you will include the terms you think of and won’t include terms you don’t think of. Especially since you are deriving these things 'independent' of the calorimeter. They would necessarily be based in some theory, not actual measurements. But I believe this to be an irrelevant point to the CCS issue. Your model is still a lumped parameter one, meaning you have no capability in it to detect when a CCS has occurred and thus you are incapable of compensating for it.
>8. At constant input power the presence of excess heat can be inferred qualitatively by a rise in >temperature of the outgoing fluid (normally water). Our largest excess power levels were ~300% in >input power. Our largest statistical significance (Excess power / measurement uncertainty) is 90 >sigma.
As yes, the old 90 sigma ploy… My work with Ed’s data showed that a 1-3% change in calibration constants produces up to 780 mW apparent excess heat signal. Ed liked to say his calorimeter had a 70-80mW error band, but that is just the instrument noise. It doesn’t include the impact of CCS/ATER. CCS/ATER upped his error band by 10x. What this shows is one needs to compute error bars correctly. I have been bashing the Beiting report on the same basis in another thread here on L-F. How did you compute yours?
>9. We tested our assertion that heat was measured equally independent of its source position two ways:
>a. Finite element calculation (this is a complex matter not handled by two term algebra) which modeled the entire calorimeter up to its isothermal boundary: submerged in a water bath held at constant temperature ±0.003°C; in a room held constant to ±1°C
I have previously said finite element simulation is the ultimate form of my simplified 2-zone model. Instead of 2 zones, you’d have thousands. So, good for you that you used FE. But as a modeler, I know the secret. The model can only model what you put into it. So, what %recombination at the electrode values did you use in your FE sim runs? (Note I suggest here several values are needed, ranging from 0 to 100%)
>b. Experimentally testing the influence of current to the cell and the complimentary Joule heater
>over a wide range in blank cells (H2O, Pt or poorly loaded Pd cathodes, early before initiation of the FPHE)
This would not simulate a change in heat distribution from the base case of 0% ATER. What you are simulating is 0% ATER + heater changes + electric current/voltage changes. It might answer my prior question about how close the Joule heater and electrolytic calibration came out.
>10. The calorimeters were proven to be heat-source position-independent already by 1991 when I stopped worrying about this effect for our calorimeters. >The fact that long long long hours of calorimetry were performed (>100,000), covering wide variations of cell and heater power, with calorimetric registration of >zero excess heat sadly but conveniently reinforces our conviction that the Shanahan hypothesis that heat excess can be incorrectly measured (always >positively?) by the displacement of heat sources – plays no significant role in our calorimeters.
None of that suggests you tried altering the heat distribution inside the cell, which is what ATER does, and thereby induces a CCS. You have simply verified that you did a lot of work while not understanding this problem.
(BTW- What's the deal with the "always positive" comment? Do you calibrate with active electrodes? No? So why are you confused by the fact that the FPHE produces a one-sided signal when you always calibrate at 0%ATER?)
>11. This last conclusion, equally rigorously supported by their designers and authors, applies to the >two other modes of calorimetry with which I am closely >familiar: F&P’s partially mirrored dewar design; the heat flow calorimetry of Violante and Energetics (using heat integrating plates).
Since the last conclusion was irrelevant, so are these other examples.
>There are more insidious potential error sources possible particularly in electrochemical >calorimetry.
I don’t disagree, but I’m not talking about them. I am specifically talking about recombination heat appearing at the electrode.
>Ed discovered one in simple isoperobolic calorimetry for which the thermal barrier was the (pyrex) cell wall (changing wall hydraulics). Others exist and we >should always be alert and open to suggestion. On the other side I suggest that the suggestors pay close attention to the literature, make quantitative >calculation modeling the physical processes that drive the putative mechanism, and do not make global claims of “it is all wrong because…”.
Which is exactly what I did, and I have not found anyone who correctly models the cell-calorimeter setup to allow for the impact of ATER to be seen.
>It is not that I claim that Kirk’s suggested semi-mechanism has never applied to LENR calorimetry. The effect he describes did play a role in the NRL / >Coolescence Seebeck calorimeters when the >recombiner is more or less well coupled to the predominant heat-flow path.
In your cell and Ed’s and others I have looked at, the root cause of the CCS is not the predominant heat flow path, but the heat flow path of the unmeasured heat lost, which is what gives you less than 100.000000000…% heat capture efficiency.
>But this was recognized by them. It is not that his “discovery” is never significant, or never could be.
Ahhh..blade to my heart there Mike…
>It is that the mechanism is well known, was historically anticipated, and is irrelevant to most of the calorimeters with which I am familiar.
Ummm...since you haven’t demonstrated any comprehension of what I assert the problem is, this statement is inaccurate. You simply can’t evaluate that until you a) understand what I am saying, and b) check it.
>Even if he could show one case quantitatively, it would not affect the whole of our understanding.
I did show one case quantitatively (actually two but from the same calorimeter, just had some feedback noise in it so Ed reran it and I used the second run for my paper. The first run did the same thing though after you subtracted the feedback problem out. More complex to explain though, so I just left it out. Actually, maybe it was 20 cases (10 voltage sweeps in each run). Tricky how to count that right?). And it clearly should affect the whole of your understanding but clearly hasn’t.
>Here endeth the lesson. I will answer only relevant technical questions for clarification (and then probably slowly).
But you haven’t 'moved' at all, and it’s been almost a month since the ICCF ended, and you’ve posted twice elsewhere on L-F since then. Just planning on continuing to ignore me?
Oh, P.S. – Why is it you guys keep trying to redefine my acronyms. When I wrote the original paper I scoured the literature to see what acros had been used so that I wouldn’t create confusion over acronyms. You yourself wrote of the Fleischmann-Pons Heat Effect but you used ‘FPE’ as the acronym. I therefore chose ‘FPHE’ to represent the Fleischmann-Pons-Hawkins Effect to underscore that I was talking about a non-nuclear effect. Now you’re trying to steal my acronym and redefine CCS. Not polite at all…
Oh, P.P.S. Still waiting for your special qualifications…
Beating a dead horse one more time, just because it's so much fun, no one has proven anything I have suggested in print is wrong (except Abd and my discussing the wrong figure in the 2010 JEM paper, kudos to Abd, even though he gets everything else wrong too, just like Jed).
Beating a dead horse one more time, just because it's so much fun, no one has proven anything I have suggested in print is wrong
It would be more accurate to say that Marwan et al. think they proved that you are wrong, but you disagree with them. Let the reader decide:
Yeah, it's a shame they are so deluded. I mean, the title of my first paper in 2002 was "A Systematic Error...", and they talk about the "random Shanahan CCSH". Can't get much worse than that. I mean, I learned about systematic vs. random errors in freshman chemistry class (if not before in high school, I don't actually recall), and these are PhDs for heaven's sake.
Oh, BTW, it is fair and balanced to report the response to your Marwan reference whenever you cite it. That can be found at:
http://coldfusioncommunity.net…4/SRNL-STI-2012-00678.pdf
I mean, how is the 'reader to decide' if they don't get all relevant points of view, right?
I mean, how is the 'reader to decide' if they don't get all relevant points of view, right?
If that is how you feel, I suggest you send me a copy of this paper with permission to upload it to LENR-CANR.org.
Yeah, it's a shame they are so deluded. I mean, the title of my first paper in 2002 was "A Systematic Error...", and they talk about the "random Shanahan CCSH".
This is not a delusion. It is a disagreement. You think the error is systematic. They think it is random. I think it is imaginary.
If that is how you feel, I suggest you send me a copy of this paper with permission to upload it to LENR-CANR.org.
Ummm...I gave you a link...
This is not a delusion. It is a disagreement. You think the error is systematic. They think it is random. I think it is imaginary.
C'mon Jed, if the situation was reversed and I was saying that their claim to see a random error meant there was a systematic error present, what would you say to me?
When author 'A' writes 'X', it is incorrect to say 'A' wrote 'Z'. Period.
Ummm...I gave you a link...
I do not keep track of links, except the ones in LENR-CANR.org, which I have at my fingertips. But in any case, if you want people to read your paper, I suggest you send it to me with permission to upload it to LENR-CANR.org.
When author 'A' writes 'X', it is incorrect to say 'A' wrote 'Z'. Period.
I disagree. As long as you reference the author's paper, and you make it clear the author says X where you say Z, I see no problem with this. If you claimed the author says Z, that would be deceptive.
