Reading again the paper above, I see they referenced a paper by Szpak, et, al from 1998 (Fusion Tech. 33 (1998) 38). AN umarked copy of it is here: lenr-canr.org/acrobat/SzpakSonthebehavc.pdf They show how they measure evolved gases and it *IS* as I thought. They route the gases through a recombiner to make water and then collect the liquid water.
That was a very different experiment, and what techniques were used there may not apply at all. If we needed to know, we'd ask the researchers.
Since this experiment has produced what I consider to be a unique and relevant result, why would you presume that suggesting it may be going on in other experiments of similar physical construction is wrong? They have a typical open cell. They recombined the effluent gases and measured it. They found 6.5% more water than they expected. I at least think this came from a 'normal' physical/chemical process probably active in other similar cells, which leads me to distrust connecting water lost/found measurements with the actual (not theoretical) extent of recombination.
Kirk, you are now mixing papers and experiments, and you are not being careful.
The 7.7 ml was water added to the cell to restore level, the paper is explicit about that; integrated current led to an expectation of 7.2 ml. I think this was a single measurement, at the end. Evaporation could explain the missing water.
I do not "presume" that it is "wrong" to apply what happens in one experiment to others, but on a matter like this, conditions can vary greatly. This. however, is what is odd about the experiment you cited: They needed to add too much water, not too little; your idea would suggest the opposite. You are using this to assert an error level, but it was an experiment with low heavy water usage, due to the nature of the experiment, so error in that measurement is not typical. And this is not the measure you need.
The coverage and analysis here is scattered and unfocused for the most part. For learning, what is being referenced should be clear and verifiable.
I am not seeing a clear logical sequence from a recombination hypothesis, through actual measurements, through an analysis that shows that a recombination artifact could explain excess heat in more than a fraction of the experiments that show XP. Data and evidence from many sources is being cherry-picked to support one particular conclusion. That does not mean that you are wrong, but that you are not confronting the educational problem. To be fair, I have not gone over your latest posts in detail, and you do have more analysis there.
Another possibility. One of the leads to the electrodes breaks internally. No current means immediate unloading to some point. Rest follows above. Again, did broken leads occur before or after...?
This is more or less flopping about. Broken leads would lead to slow unloading, not rapid. Assuming that orphaned oxygen has been vented, the atmosphere in the cell would use up the oxygen left and would move away from explosion, not toward it. There has to be a pressure relief, because of the oxygen, I think, but I'm not sure.
The cell that exploded was being carried when it blew up, by the man who died. Apparently it was jarred, shaking loose water on the recombiner. Definitely, this was a dangerous cell, and procedures at SRI changed ... or they would not have been allowed to continue.
But palladium will spontaneously strip one hydrogen atom from another. That is how it can catalyze recombination, in fact.
That is to say catalysis enables both the forward and the reverse reaction (no problem there, with a such a simple binary reaction). There is a large enthalpy involved, regardless of the catalysis. It takes about 486 kJ/mole to break molecular hydrogen to its atomic constituents. That energy is not an activation energy, it cannot be overcome by catalysis alone. That energy must be supplied as actual work. Either the Pd is not breaking the hydrogen-hydrogen bond, or something already much stranger than LENR / CF is happening.
Nope...H2 dissociation is very definitely exothermic. I gas load a variety of hydride materials and I always monitot the temperature rise that I get when exposing an empty material to H2. Sometimes the rise can be near to 100 degrees C (depends on a variety of parametes of course).
If this is so, then it must be an entropic function, that is the molecular hydrogen is yielding up degrees of freedom and hence the observed exothermy. No chance that atomic hydrogen formation in a gas / gas reaction is exothermic... look up in standard tables.
This model is a simple way of illustrating the idea of different heat detection efficiency in a real cell. The residual disagreement shown above is likely due to some of the assumptions made in the derivation (such as linearity and b=0) plus the fact that real noise isn’t factored in here.
Consider the following diagram, in which there are four electrochemical cells immersed in baths of water and enclosing calorimeters:
Following your convention, let's say zone 1 (Z1) is the electrolyte and zone 2 (Z2) the headspace where recombination occurs. Let's call the cell, i.e., zones 1 and 2, "Z1-2". Each cell is immersed in a bath of water, which we'll call zone 3 (Z3). In this case, the various feedthroughs are either positioned above Z3 or are inserted horizontally into the side.
(1) I understand your suggestion to be that in case 1, where we have no CCS (it's just predictable electrochemistry, without at-the-cathode recombination), to be distinguishable experimentally from case 2, where you have CCS. In the first case you have no apparent excess heat as measured in Z3, and in the second case you have apparent excess heat as measured in Z3. I further understand that when you move the feedthroughs to the side, the situation changes. Now the behavior of both calorimeters is the same, because recombination heat escaping from the top of Z1-2 does not differentially affect the thermocouples in Z3. In neither case will you see apparent excess heat. Is this correct? If so, what do we conclude if we see apparent excess heat in cases 3 and 4? Would you agree that that is evidence against the CCS?
(2) It should be possible to mimic CCS in Z1-2 by fiddling with the position of a resistance heater or heaters, without even doing electrolysis or recombination. If it is true that Z1-2 is not a black box, this should show up as significantly different calibration curves when the fake CCS is applied versus when it is not applied in cases 1 and 2 above. If the calibration curves, treating Z1-2 as the source of heat as measured in Z3, turn out significantly different for cases 1 and 2, when CCS is being artificially mimicked, actual CCS continues to be a worry. If the calibration curves prove to have negligible differences in behavior between cases 1 and 2, then Z1-2 is in fact a black box to Z3, and we have evidence against CCS. We can now derive a calibration equation that incorporates variables pertaining only to Z3 and Z1-2, but not Z1 or Z2. Do you agree?
(3) It should be possible to move the calorimeter boundary out one level by immersing Z3 in yet another water bath, Z4, say. (Things are starting to feel a little forced at this point, I'll just mention.) Now our efficiency is less and our time constant is much longer. But Z1-2 really is a black box to Z4 now, one hopes. Presumably LENR researchers can safely do their excess heat calculations using Z3 as the source of heat as measured in Z4, without worrying about what's going on in Z1 and Z2. Do you agree?
Abd Ul-Rahman Lomax wrote:
That is to say catalysis enables both the forward and the reverse reaction (no problem there, with a such a simple binary reaction). There is a large enthalpy involved, regardless of the catalysis. It takes about 486 kJ/mole to break molecular hydrogen to its atomic constituents. That energy is not an activation energy, it cannot be overcome by catalysis alone. That energy must be supplied as actual work. Either the Pd is not breaking the hydrogen-hydrogen bond, or something already much stranger than LENR / CF is happening.
https://labs.chem.ucsb.edu/zak…onddissociationenergy.pdf , yes, 436.002(4) kJ/mole of H2, dissociation energy.
Finding a value for the heat of absorption of atomic hydrogen, though, is not so easy. Experimentally, what is available is the heat released when hydrogen gas is absorbed into palladium. That is a net energy, after subtracting the dissociation energy. Palladium is famously "hungry for hydrogen," it soaks it up. This is not "catalysis." The palladium is a reactant, it is altered by the reaction, becoming loaded with hydrogen. This reaction, however, can explain the catalysis of recombination.
Palladium does not generate "atomic hydrogen" in its environment, the atomic hydrogen exists in solution in the palladium, it cannot be considered separately, and other reactants generally, cannot reach it. But Stuff Happens at the surface! It is in that, that it serves as a catalyst.
Quotekirkshanahan wrote:
I think this was a misstatement. The temperature rise is from the hydride formation. The dissociation energy reduces that heat, it would otherwise be much larger.
If this is so, then it must be an entropic function, that is the molecular hydrogen is yielding up degrees of freedom and hence the observed exothermy. No chance that atomic hydrogen formation in a gas / gas reaction is exothermic... look up in standard tables.[/quote]This is correct (and obvious). It is endothermic. What is missing is the understanding that the formation of palladium hydride outweighs the dissociation energy.
Here an excerpt from the DTRA Mosier-Boss post:
Citation: 3.2.2 Summary of composite cathode results
In 2010, DoE Electrochemist Shanahan proposed that the source of the pitting observed in
the CR-39 detectors used in Pd/D co-deposition experiments was either due to O2 attack or to
damage due to shockwaves resulting from D2/O2 recombination. Experience has shown that once
the Pd deposit is wet, recombination of the D2 and O2 does not occur. In these experiments, the
Pd deposit was completely immersed in the solution. Consequently, it is unlikely that D2 and O2
recombination is occurring. However, additional experiments were conducted to rule out O2
attack or D2/O2 recombination shockwaves as the source of the pitting observed in the detectors.
.....The results show that no tracks were obtained on the bare half of the cathode, Figure 3.2-3b. .... as expected!
kirkshanahan wrote:
Nope...H2 dissociation is very definitely exothermic. I gas load a variety of hydride materials and I always monitot the temperature rise that I get when exposing an empty material to H2. Sometimes the rise can be near to 100 degrees C (depends on a variety of parametes of course).
I think this was a misstatement. The temperature rise is from the hydride formation. The dissociation energy reduces that heat, it would otherwise be much larger.
Technically you are correct. H2 is a stable molecule, so to dissociate it some energy must be added. The bond energy is as you stated, 436 kj/mole = 104 cal/mole = 4.52 eV. To get fully technical, there is an intermediate stage between molecular hydrogen and Pd hydride, namely surface-bonded H. That also forms on most clean metals, whether they hydride or not. Ni for example normally doesn't hydride in gas loading experiments until the pressure is a few thousand atmospheres. Prior to that is remains on the surfae and a small portion will dissolve in the Ni. The equivalent H/M for Ni at room temp and pressure is ~1x10e-5, whereas Pd under 1 atm of hydrogen at room temp will load up to ~.75-.8. On an energy diagram then starting with H2 + Pd, one has to dissociate H2 on the surface, which would be a combination of the H2 bond energy + 2 x the H-surf energy, then you get more heat back from H-surf + Pd -> PdX at whatever H/M ratio you end up at. The overall process for Pd hydride formation is definitiely exothermic.
Display MoreCitation: 3.2.2 Summary of composite cathode results
In 2010, DoE Electrochemist Shanahan proposed that the source of the pitting observed in
the CR-39 detectors used in Pd/D co-deposition experiments was either due to O2 attack or to
damage due to shockwaves resulting from D2/O2 recombination. Experience has shown that once
the Pd deposit is wet, recombination of the D2 and O2 does not occur. In these experiments, the
Pd deposit was completely immersed in the solution. Consequently, it is unlikely that D2 and O2
recombination is occurring. However, additional experiments were conducted to rule out O2
attack or D2/O2 recombination shockwaves as the source of the pitting observed in the detectors.
.....The results show that no tracks were obtained on the bare half of the cathode, Figure 3.2-3b. .... as expected!
This report is a classic example of inadequate reading/understanding or deliberate obfustication. such as: "Experience has shown..." 'Experience' didn't anticipate at-the-electrode recombination, which is why it was (and is still) missed. If you simply expose almost any metal surface to gaseous H2 + O2, you will get water. If the surface is covered in water, that water will block the gas from the surface. *However*, if you nucleate and grow a hydrogen bubble on the cathode, the nucleation and growth will push the water away so that the bubble is retained on the bare metal, at least until the point where it can break away. Thus recombination at-the-electrode (ATE) merely requires that a growing H2 bubble combine with an impinging O2 bubble (or vice versa at the anode!), whereupon you have satisfied the 'fire triangle' of fuel + oxidizer + initiator, and you will get burning that may be rapid enough to generate a shock wave. Thus referring to the problem of a wet catalyst and claiming that that 'automatically' negates the ATE recombination mechanism is incorrect.
Re. the 'additional experiments...' I vaguely recall at this point what they refer to. I also recall that at the time I read this it was apparent that their efforts were half-hearted and inadequate. Again illustrating the problem with holding pre-conceived conclusions ("Consequently, it is unlikely that D2 and O2 recombination is occurring. However, additional experiments were..." So, D2 can't react with O2 ATE, but we'll do a couple of little experiemnts to "test" this idea and show it doesn't work..). They have the same problem regarding contamination as a source of anomalous elements.
To be clear there are known multiple causes of pits showing up in etched CR39, some of which have nothing to do with radiation. The fact that plates placed in the electrolyte next to the electrode (or even forming the electrode base) have multiple thousands, if not millions, of pits, while those placed outside the cells have minimal. Furthermore, one of Miley's papers clearly states that 'pit counting' is subjective and thus requires filtering by a human being. Which sounds an awful lot like what Blondlot said about the spots on phosphor screens that 'proved' n-rays existed.
Actual experiments aimed at testing the ATE concept will have to insure that the mixed hydrogen/oxygen bubbles adhere to a clean metal surface to be able to get the 'fire triangle'. I personally think that will be extremely difficult to set up with bubbles introduced externally. It's that clean metal surfce under the growing bubble that's the necessary ingredient.
On the other hand, reproducible, controllable experiments producing signals well above the noise might well substantiate (or disprove) the nuclear hypothesis.
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.
a.) Everyone accepts that H2 present in the cell would combine with O2 in the presence of the now exposed metal electrodes.
Not everyone would put it that way. I would say that as the electrolyte boils away, the cathode is increasingly exposed, and recombination will become routine. The heating would increase, accelerating boil-off, I'd think, it would also accelerate if the input power is constant-current and the electrolyte resistance is increased as electrolyte is lost. (I'm not sure about the effect of increased concentration of the salt added for conductivity). However, there is a lot more deuterium in the cathode than there is available oxygen, once electrolysis stops.
I don't know the experimental details of FP HAD, the boil-off experiments. I don't like it the idea because of how messy it is. Nevertheless this I'd say: any oxygen in the cell will recombine with deuterium, I would expect, once the palladium is exposed. This is not explosive recombination. It would eat up any oxygen very quickly.
Quoteb.) Everything depends on rates. If the D2 evolves slowly, it will not block air ingress because 2H2 + O2 = 2 H2O.
This only happens if there is oxygen! One thing I know about these cells, they had a very narrow gas path. If there is even slow net evolution, the gas flow would be out, not in. Deloading would be net evolution. Of course it all depends on rates; by proposing mechanisms, they can be made to look plausible if rates are ignored. Basically, recombination will occur in most FP-cells ... but the rate is likely to be undetectable or very low.
You then propose some anomaly, but to recombine, the oxygen must reach the cathode or deuterium the anode. And the problem is not really quite as you have stated. If either reaches the recombination electrode, as you describe, recombination becomes possible if there the bubbles merge as you state. however, because oxygen is going to be rare near the cathode, an explosive mixture will not be formed, and the only recombination will be where an oxygen bubble merges with deuterium, which may then recombine -- essentially burn without flame -- at the bubble contact point. Any heating from this would probably lead to immediate bubble release. I would expect as rate that only a small fraction of the oxygen that reaches a cathode bubble would actually recombine. And it is only a small fraction of the oxygen generated that reaches the cathode vicinity.
I became curious about the exact experimental conditions, and looked at http://lenr-canr.org/acrobat/PonsSheatafterd.pdf , which is the Fleischmann Heat After Death paper. Recombination is considered explicitly, but I am not prepared to assess the depth of this.
Fleischmann originally describes being conservative about calorimetry in boil-off (probably for the same reasons that I don't like the idea!), but then found that accuracy was better than expected. Again, it would be substantial work to cover this in detail.
This method of exploring HAD is much sloppier than the Storms technique! However, what is very interesting and relatively easy to understand in the work reported is that hydrogen cells cooled rapidly as soon as current went to zero from being driven to boil-off, but deuterium cells maintained heat They also look at how much heat was generated and found it to be much higher than would be produced by all the deuterium being oxidized. This work, to my knowledge, has never been fully published under peer review.
QuoteThat means the molar content of the gas space decreases which would cause a suction, relieved by air ingress. The O2 in that air will further react with the current D2, further reducing the pressure and causing more reverse flow. OTOH, recombination at the electrode (now over-the-surface) will heat the electrode speeding up D2 release. Wonder who wins the race?...
Most of the D2 is in the cathode and not accessible to the oxygen. it is slowly released. Water does not accumulate in the cell, this would be clearly visible. No, the cell atmosphere would be quickly depleted of oxygen, but deuterium would continue to evolve from the cathode store.
This is mostly moot at this time.
Quotec.) The HAD situation is *radically* different from the normal operating condition. See previous post regarding what this means...
HAD as done by Pons and Fleischmann was definitely abnormal. However, as done by Storms, it is as simply as having a thermostatically maintained elevated cell temperature, not far below boiling, as I recall, and turning off the electrolysis. No more oxygen evolution. Any deuterium evolution is from the store in the cathode, and loading does decline. Excess heat was maintained, with basically no change, until the cell temperature was allowed to fall by shutting off the thermostatic heating.
This is unconfirmed, but of high interest.
(someone can track back the original report)
This report is a classic example of inadequate reading/understanding or deliberate obfustication. such as: "Experience has shown..." 'Experience' didn't anticipate at-the-electrode recombination, which is why it was (and is still) missed. If you simply expose almost any metal surface to gaseous H2 + O2, you will get water. If the surface is covered in water, that water will block the gas from the surface.
This is Shanahan, who is denying the experience of many electrochemists. He is claiming an anomaly, something unexpected, but what he alleges doesn't seem to be likely to be a major effect at ll. I don't think anyone is exercised to test the theory more than it has already been tested, and my opinion is that there is plenty of evidence that this idea just plain doesn't work. Still, one point at a time.
Quote*However*, if you nucleate and grow a hydrogen bubble on the cathode, the nucleation and growth will push the water away so that the bubble is retained on the bare metal, at least until the point where it can break away.
Yes. As long as the bubble is attached, there is likely to be access to the unwet surface for the gas in the bubble. As a bubble growing on the cathode, it is a hydrogen bubble, initially.
QuoteThus recombination at-the-electrode (ATE) merely requires that a growing H2 bubble combine with an impinging O2 bubble (or vice versa at the anode!), whereupon you have satisfied the 'fire triangle' of fuel + oxidizer + initiator, and you will get burning that may be rapid enough to generate a shock wave. Thus referring to the problem of a wet catalyst and claiming that that 'automatically' negates the ATE recombination mechanism is incorrect.
Shanahan has avoiding looking at obvious details. First of all, the experience of normal electrolysis is that, at the current densities involved in CF experiments, recombination is very small (perhaps even unmeasurable). Under experimental conditions, very few oxygen bubbles will reach the cathode and they will be, on average, smaller than most bubbles, because larger bubbles would rise rapidly. It seems likely that the average oxygen bubble that makes it to the cathode vicinity is likely to be small, then. So it contacts and perhaps merges with a hydrogen bubble. If the bubble does not immediately rise from the merge process -- likely to disturb its attachment to the cathode -- yes, oxygen would diffuse to the cathode and be recombined immediately. This is not likely, however, to be an explosive mixture. That would require two equal sized bubbles, and it would require that the hydrogen bubble remain attached. Recombination does not originally generate ignition temperatures -- is that correct?
QuoteRe. the 'additional experiments...' I vaguely recall at this point what they refer to. I also recall that at the time I read this it was apparent that their efforts were half-hearted and inadequate. Again illustrating the problem with holding pre-conceived conclusions ("Consequently, it is unlikely that D2 and O2 recombination is occurring. However, additional experiments were..." So, D2 can't react with O2 ATE, but we'll do a couple of little experiemnts to "test" this idea and show it doesn't work..). They have the same problem regarding contamination as a source of anomalous elements.
This is now getting into "this is cold fusion so they must be making mistakes" territory. Basically, they did not exist to satisfy Kirk Shanahan. Kirk has failed to establish his hypothesis in the journals. It is essentially moot, because cold fusion experiments with low heat are not of major import and have not been effective at convincing the mainstream. If there is high heat, and any sort of care about recombination, it's moot, this his theory could not explain it. His theory also cannot explain the heat/helium correlation, which is far more powerful as an indicator of nuclear reaction than any scattered "anomalous elements." It is the correlation with heat that makes the difference, not just the presence of something unexpected.
That evidence is already quite strong. It is likely to be much stronger in short order.
QuoteTo be clear there are known multiple causes of pits showing up in etched CR39, some of which have nothing to do with radiation. The fact that plates placed in the electrolyte next to the electrode (or even forming the electrode base) have multiple thousands, if not millions, of pits, while those placed outside the cells have minimal. Furthermore, one of Miley's papers clearly states that 'pit counting' is subjective and thus requires filtering by a human being. Which sounds an awful lot like what Blondlot said about the spots on phosphor screens that 'proved' n-rays existed.
Pit counting is subject to human subjectivity, yes, which is why this would ordinarily be done blind. This is radically different from "N-rays" and Shanayhan is pulling out all the old tropes.
There is automatic counting, by the way.
I planned to user LR-115 myself, because tracks are far less ambiguous. Pam Boss thought the energy capture range was too narrow for LR-115. Maybe she's right. I'd still like to find out. Tracks in LR-115 are positively beautiful, because the material I have is 6 microns thick, deep red cellulose nitrate, on a 100 micron polyester based. It etches away completely with most tracks, leaving a transparent base. You can see the tracks with the naked eye, at least the area with tracks.
QuoteActual experiments aimed at testing the ATE concept will have to insure that the mixed hydrogen/oxygen bubbles adhere to a clean metal surface to be able to get the 'fire triangle'. I personally think that will be extremely difficult to set up with bubbles introduced externally. It's that clean metal surfce under the growing bubble that's the necessary ingredient.
Clean metal surfaces do not show the FPHE. the experiment is a god-awful mess, I don't wonder that physicists hated it.
QuoteOn the other hand, reproducible, controllable experiments producing signals well above the noise might well substantiate (or disprove) the nuclear hypothesis.
We have that. Heat/helium is reproducible, and already multiply confirmed. It's a different concept of reproducibility, but just as valid, if not more so. The dead cells -- that don't generate XE for unknown reasons -- become strong controls, as alike the experimental cells as possible. If they show helium, there is almost certainly leakage. They don't show helium, so far.
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.[/quote]
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.
kirkshanahan wrote:a.) Everyone accepts that H2 present in the cell would combine with O2 in the presence of the now exposed metal electrodes.
Not everyone would put it that way. I would say that as the electrolyte boils away, the cathode is increasingly exposed, and recombination will become routine.
In other words, you accept that H2 present in the cell would combine with O2 in the presence of the now exposed metal electrodes.
The heating would increase, accelerating boil-off, I'd think, it would also accelerate if the input power is constant-current and the electrolyte resistance is increased as electrolyte is lost.
The time plots of cell voltage using a constant current input show dramatically increasing voltage during the boiloff period. Power = current times voltage, so the input power is no longer constant if the current truly is fixed. Sometimes constnat current power supplies can be driven out of the controllable region, which may well happen here. F&P don't show current time profiles in the paper I was referring to via my overlaid V and T plots. Also Power = current squared times resistance (using Ohm's Law). That means that cell resistance is increasing too.
(I'm not sure about the effect of increased concentration of the salt added for conductivity).
Minor variation, but yes it will be different from using pure water or other electrolyte mixes.
However, there is a lot more deuterium in the cathode than there is available oxygen, once electrolysis stops.
Really? You're sure of that. Now recall all we are talking about is enough recombination to maintain an illusionary temperature at the thermistor. You realize that given the cell construction, the thermistor is one of the earliest components exposed when the electrolyte level drops. That means it converts from measureing temp in the liquid to temp in the gas. The gas phase has much lower thermal conductivity than the liquid, and there is no particular mechanism for mixing it (unlike the bubbles in the liquid in noremal operation). That screams 'hot spot problems' to me. It definitely means a different calibration curve, changing the whole time the boil-off is happening. But I wouldn't expect to see any discontinuity in the temp vs. time plots to blatantly give this away. The transition will be smooth and natural.
When the electrolyte is boiled off, it looks to me like ther may be 5-10 cc left below the Pd electrode. But at that point the circuit is broken and no electrolysis is occurring. However, it was up until this point, which means that the cell has water vapor, hydrogen, and oxygen in it. How much is unclear. The boiling liquid should have given a water vapor pressure equal to the atmospheric pressureat that point since it is an open cell. Yet the electrolysis gases were still there to. In actuality, the final gas composition is unknown becasue we don't know the details of mixing and flow out. So we have to guess to address your problem.
I estimate the cell volume at the electrolysis stop point is ~50cc. O2 will be 1/3rd of the electroysis gases, but you also have lots of water vapor, and extra hydrogen from the Pd unloading that occurs once the external voltage is no longer applied (circuit is broken). But 'good' Pd is supposed to unload slowly, so what shall we guess? O2 is maybe 10% of the volume? Might be. That means there is ~0.16 mmoles O2 present. You'd have the 0.32 mmoles H2 from electrolysis + the unloading gas... The Pd electrode is supposed to be a 12.5 mm long 2mm dia. rod. I calc that holds total about 2.25 mmoles H2. What fraction has come out? Who knows? Guess 10% again, i.e. .225 mmoles, so you have in the gas approximately 0.16 mmoles O2 and 0.545 mmoles H2. The needed ratio is 2 H2 per 1 O2, so 0.32 mmoles of that hydrogen can react or ~59% of what's available. That's not 'a lot more deuterium', that's under 2X what is needed.
Of course, this is all guesswork right? The point is to decide is the idea is even reasonable, and I think the above shows it is.
Then you have to remember you have a different thermal situation from when the unit wasoriginally calibrated. The high heat capture efficiency zone I talk about has been reduced to insignificance, leaving only the low efficiency zone to do calorimetry with. Of course, we have no way to know what that effciency really is either... Maybe the Pd rod is glowing white hot, but heat flow pathways only let a little get to the thermistor. (Yes, I exaggerate for effect here, it's very unlikely the Pd is white hot, but 10-20 degrees elevated? maybe)
Bottom line, we don't really know what is going on in the cell becasue we have no idea how a practically empty cell responds to a localized heat source. (Simplistic thinkers will claim here that's nothing has changed, the cal equation is still good. Not likely.)
This is not explosive recombination.
You know the composition and have checked the explosive mix ranges to see if the cell is within the danger zone? Wow, I'm impressed! How did you determine the gas phase composition?
This only happens if there is oxygen!
Which there is...
One thing I know about these cells, they had a very narrow gas path. If there is even slow net evolution, the gas flow would be out, not in.
A guesstimate on your part. The actual fact is that none of us knows what is going on in the cell at this point.
Basically, recombination will occur in most FP-cells ... but the rate is likely to be undetectable or very low.
I disagree, I think it will certainly be detectable and might be very high...so now what do we do....choose a favorite based on what? Number of words we write?
You then propose some anomaly, but to recombine, the oxygen must reach the cathode or deuterium the anode.
In fact if you are talking about heat generation during the 'heat after death' period, you are right, but chemistry tells us the gases will mix. How fast and how completely is debateable of course, in the absence of any actual data.
I could go on (and on and on...) but the real point is that the system has radically changed in HAD events, and that changes everything. However, the CFers always assume it really doesn't. Not a safe bet in my book...
But one more point...
This method of exploring HAD is much sloppier than the Storms technique! However, what is very interesting and relatively easy to understand in the work reported is that hydrogen cells cooled rapidly as soon as current went to zero from being driven to boil-off, but deuterium cells maintained heat They also look at how much heat was generated and found it to be much higher than would be produced by all the deuterium being oxidized. This work, to my knowledge, has never been fully published under peer review.
Never published probably means I've never seen it. But a couple of things stand out already...
a) protium (H2, i.e. regular hydrogen) is NOT A CONTROL for deuterium. They have different loading rates and extents at the same voltage. They will likewise unload differently. The fact that the H2 cell was different from the D2 cell is EXPECTED. And remember too that the H2 cell wasn't giving 'excess heat', meaning its special active state (SAS) is not present. The D2 cell on the other hand might possibly still have its SAS, and be giving more rapid recombination, which would give higher heat signals and cause more reverse flow, adding more O2 to the cell, which gives more heat...etc.
b) "...much higher than would be produced..." That would be based upon a flawed calibration equation that gave apparent excess heat in the normal operating situation being applied to the abnormal one of the HAD. right?
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.
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.
I guess that makes him a pseudo-skeptic. Oh dear! Life gets more and more complicated, Matron will have to sort it out.
This is Shanahan, who is denying the experience of many electrochemists.
Shanahan has avoiding looking at obvious details.
Again, Abd has perfect knowledge of my thoughts, actions, and motivations. He's really a very scary guy! Think about it...what if he was focusing on you??
Shanahan has avoiding looking at obvious details. First of all, the experience of normal electrolysis is that, at the current densities involved in CF experiments, recombination is very small (perhaps even unmeasurable).
You're ridiculous here Abd. THE WHOLE POINT OF MY SINGLE CONTRIBUTION TO THIS FIELD IS THAT THERE IS AN UNRECOGNIZED SYSTEMATIC ERROR PRESENT IN THESE EXPERIMENTS THAT HAS A HIGH PROBABILITY OF BEING AT THE ELECTRODE RECOMBINATION. You either are attempting to reviatalize the electrochemical recombination red herring or grossly limiting any possible ATE recombination without showing why it must be limited.
That would require two equal sized bubbles,
**2** H2 + **1** O2 = 2 H2O - O2 bubbles should be 1/2 the size of H2 bubbles for optimum stoichiometry. (So you actually supported my mechanism without realizing it...)
This is now getting into "this is cold fusion so they must be making mistakes" territory. Basically, they did not exist to satisfy Kirk Shanahan. Kirk has failed to establish his hypothesis in the journals.
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.
It is essentially moot, because cold fusion experiments with low heat are not of major import and have not been effective at convincing the mainstream. If there is high heat, and any sort of care about recombination, it's moot, this his theory could not explain it.
Most of the 'high-heat' cases I have tried to investigate has less information presented than the cases we have been discussing. Sort of like trying to discern what Rossi actually does. If you have a specific case to look at, point it out. Otherwise you're just blowing smoke.
His theory also cannot explain the heat/helium correlation, which is far more powerful as an indicator of nuclear reaction than any scattered "anomalous elements."
Of course it can and I and others did in this forum. Have you been asleep? You're heat/helium correlation is a bogus number for several reasons. First, the appearance of excess heat signals indicates the presence of the FPHE (that's the Fleischmann-Pons-Hawkins Effect) which appears to be casued by mini-explosions at the cathode. These mini-explosions emit shockwaves, which are known as vibrations in other cases, and have been detected by piezoelectric transducers. In gas handling systems, vibrations are a bane, becasue they cause leaks. 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. Also specfically, the He data from Miles is always cited but I have pointed out a fallacy inherent in the data based on the time variable used to compute the He atoms/watt/sec values. Further, any process measurement (i.e. amount of He) is typically autocorrelated because the chemistry limits the possible next number of the sequence to a limited set. And finally, the 'excess heat' values are likely ficticious and the product of a CCS.
It is the correlation with heat that makes the difference, not just the presence of something unexpected.
What correlation...see comment directly above...
That evidence is already quite strong.
...in support of some unusual but non-nuclear process(es) causing some excitement due to misinterpretation.
It is likely to be much stronger in short order.
Stronger confused interpretations?? Just what we need...
Pit counting is subject to human subjectivity, yes, which is why this would ordinarily be done blind. This is radically different from "N-rays" and Shanayhan is pulling out all the old tropes.
There is automatic counting, by the way.
Not if you believe George Miley. He recommends against blind counting (and automated counters fall in that baliwick) because of all the spurious pits one typically finds in CR-39 plates. (This excludes the one placed in the electrolyte at the electrode. They are a separate subset with OOM more pits than usual.)
Clean metal surfaces do not show the FPHE. the experiment is a god-awful mess, I don't wonder that physicists hated it.
Wow...I write and I write and I write, but Abd never gets it... CLEAN METAL SURFACES (with SAS present) ARE PROBABLY THE CAUSE OF THE FPHE.
We have that. Heat/helium is reproducible, and already multiply confirmed.
Nope.
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...
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.[/quote]
BTW, I was told by Ed Storms, and I believe it was an actual reviewer comment (might have been Ed again), that I shouldn't expect to be able to contribute to the field until I'd 'worked' in it for at least two years. This is an oft-heard comment in many fields, and is typically true. The problem with it here is that Ed thinks I need to build cells and calorimeters and run experiments. There are definitiely tricks of the trade that require some time to learn if that were the basis of my objections, but it isn't. My objections and comments focus primarily on what is called 'data analysis'. I just analyzed their results differently and came to a different conclusion, which may or may not be correct. The 'good' scientist however, will incorporate the fact that I have done so, and his/her next set of experiments will be modified to try to eliminate one or the other conclusion (without pre-bias). That's where the cold fusion scientists fall flat on their face. Instead they try every tactic they can, including illegitimate ones, to avoid having to do that.
Display MoreAbd Ul-Rahman Lomax wrote:
kirkshanahan wrote:a.) Everyone accepts that H2 present in the cell would combine with O2 in the presence of the now exposed metal electrodes.
Not everyone would put it that way. I would say that as the electrolyte boils away, the cathode is increasingly exposed, and recombination will become routine.
In other words, you accept that H2 present in the cell would combine with O2 in the presence of the now exposed metal electrodes.
Except that I would state it reversed. Under the conditions described, there will be more hydrogen than oxygen, and so the O2 will combine with the H2 at the exposed electrodes, as long as they are dry and there is still oxygen. I don't think this is controversial at all. Shanahan seems to think that it might be. Is that true, Kirk?
When recombination occurs, water is generated. If this wets the electrodes, they will not catalyze recombination until they dry. There will be no bubbles in this case.
The atmosphere of the cell is, originally, O2 rich, because much hydrogen is loaded into the cathode. However, at that point, there is no exposed cathode. In FP HAD experiments, loading has completed and evolved H2 and O2 will be equal, from electrolysis. Even a relatively short period of this would equalize the H2 and O2 in the atmosphere. As the electrodes are exposed, then, two things will happen: recombniation will start, reducing O2 and H2, but some of the H2 will come from cathode release. At this point the concentration of oxygen in the atmosphere will decline.
The process has complexities. Kirk raises some of them. However, there are ways to test this, and a powerful one would be control experiments with hydrogen. And that was done. The phenomenon asserted by Shanahan does not appear to actually occur.
A bubbler and check valves could be used to prevent oxygen from being sucked back into the cell if the pressure lowers enough.
@Kirk: We have to address two completely different fact:
1) Is PdD reaction of nuclear nature
2) How big is the related excess-heat
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.
Regarding 2)
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.
Thus Kirks critic (see below) is only relevant for a subset of the used calorimetry.
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 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.
Abd Ul-Rahman Lomax wrote:
Shanahan has avoiding looking at obvious details. First of all, the experience of normal electrolysis is that, at the current densities involved in CF experiments, recombination is very small (perhaps even unmeasurable).
You're ridiculous here Abd. THE WHOLE POINT OF MY SINGLE CONTRIBUTION TO THIS FIELD IS THAT THERE IS AN UNRECOGNIZED SYSTEMATIC ERROR PRESENT IN THESE EXPERIMENTS THAT HAS A HIGH PROBABILITY OF BEING AT THE ELECTRODE RECOMBINATION. You either are attempting to reviatalize the electrochemical recombination red herring or grossly limiting any possible ATE recombination without showing why it must be limited.
Shouting doesn't help, Kirk. I'm aware of your claim, but I because there are many other readers, I may continue to repeat the obvious. If you going to take an isolated position, one fo the first steps to take is to respect the mainstream position, not to attack it. A sane response here would start with "Yes, that is the normal expectation." Not "ridiculous."
I don't have to justify the common expectation. However, Kirk, you have proposed two mechanisms to explain cold fusion calorimetry. One applies to open cells, and is unexpected recombination which creates an appearance of excess heat if the gases are assumed to have escaped, taking the heat of combination away with them, which is then added back into the heat calculations, but if they did not actually escape, then this is an error..
Now, you seem to acknowledge that such recombniation is not "normal." It is an anomaly, a "systematic unrecognized error," but, in fact, cold fusion researchers do recognize the possibility of recombination error and address it. Some take steps to rule it out. I would suggest for you that you start by explaining why such recombination is not normal. What factors suppress it?
What steps do CF researchers take to rule it out?
You are facing social rejection. Call it an information cascade. How can errors in an information cascade be corrected?
This is the problem that cold fusion faces, actually. What are functional ways to address it?
I can tell you want doesn't work. Calling people WRONG doesn't work! This is basic to communication skills. Sometimes it is missing from the training of scientists.
The other mechanism asserted applies to closed cells with recombiners. In that case, error is asserted to arise from heat being generated in the electrolyte (at the electrodes) instead of in the recombiner. If the heat capture ratio differs for the two locations, and if the electrolytic has higher capture ratio, over the recombiner, then calibrations based on heat applied in the electrolyte will differ from those based on heat generated in the head space, where the recombiner generally is.
You, rather unfortunately, called this a "calibration constant shift," which then collided with how researchers think of calibration constants. There is no change in calibration constant, for a given heat condition. By claiming CCS, researchers will notice how stable their calibration constants are!
However, you seem to have missed something. In the Storms experiment that you were reviewing, Storms had two calibrations. One was "Joule heating." this was a resistor in the head space, apparently. And one was "electrolytic," where electrolytic power was applied, but presumably without excess heat. There was a difference. It confirms your shift idea. But only slightly!
This could have been improved by having a calibration resistor in both locations. That could not be done with the head space resistor Storms used, unless it was sheathed.
However, you are facing a fundamental and probably unresolvable problem at this time. Nobody with any inclination to spend money on research or to do it, is exercised to check your theory, because you have failed to engage them. I'm telling you a bit of why. You don't like it, perhaps. That dislike is part of what would keep you disempowered.
It is highly likely that the issue of systematic recombination artifact (of the two kinds) is about to be definitively ruled out. I have asked for suggestions for that research, because I might be able to communicate them to the researchers. Unfortunately, perhaps, I don't yet know exact protocols. Still there are three extant protocols that the work is likely to resemble in some way or other: Miles' work on heat/helium, SRI M4, and ENEA/Apicella/Violante Laser 2 to Laser 4.
What specific measures could be used there to rule out a recombination, CCS problem? If they are cheap and easy, they might happen.
However a clear showing of XE and helium production correlated tightly at something close to the theoretical deuterium conversion value would conclusively rule out that alleged "systematic error," and I don't think that you have ever accepted that.
I have asked you, given your body of theory, what you would expect as results from that work. You have, so far, ignored that question.
Abd Ul-Rahman Lomax wrote:
That would require two equal sized bubbles,
**2** H2 + **1** O2 = 2 H2O - O2 bubbles should be 1/2 the size of H2 bubbles for optimum stoichiometry. (So you actually supported my mechanism without realizing it...)
Sorry, brain fault. Let me remember: it is H *2* O.
My concern is study and exploration, not proving this or that. Yes, this pushes the situation toward Shanahan's ideas, a little. However, there is a mountain to overcome. The fundamental question is what actually happens in electrolysis, and what this "unexpected behavior" is, exactly.
Abd Ul-Rahman Lomax wrote:
This is now getting into "this is cold fusion so they must be making mistakes" territory. Basically, they did not exist to satisfy Kirk Shanahan. Kirk has failed to establish his hypothesis in the journals.
No to all of that hogwash. I have established my case in the journals to the satisfaction of any neutral observer.
Great, where are they? Are there any journal editors who are "neutral observers"? Hogwash? What here is "hogwash"? This is talking about researchers and what moves them, and it is not Kirk Shanahan.
When there is a back and forth in the journals, how do we know if one side "established their case" more than the other?
There is a standard answer to this: secondary source mention of the discussion, and especially such in peer-reviewed journals. Kirk is here, isolated, where nobody is actually accepting his ideas, though some are willing to look at them (as am I). What he is reduced to is sputtering "hogwash," like a ...
Like a cranky old man who is losing touch with society and reality.
Kirk wants others to spend time and money to confirm or disconfirm his ideas. Outside of some narrow possibilities, which I've been describing to no effect, this is just not going to happen. There is extensive discussion of possible artifact in the cold fusion community. This one seems dead in the water. In order to confirm this, one has to have a CF experiment going with apparent XE, and then test for certain things. That is not easy; the hard part is the first part, not the second. So to get his hypothesis tested, he has to engage the actual reasearchers, if not journal editors. His approach fails to do that, isn't that obvious? Tell people who have been doing certain work for decades that they are stupid and wrong and blind, what results do you expect?
Once in a while, if you happen to have truly found something they actually overlooked, you might find some researchers who will overlook your terminal rudeness. It is not smart, however, to assume that this will happen, because most people will simply not continue to read.
Kirk, it doesn't matter what I write. What matters, in terms of what you want to accomplish -- what is that? -- is what is actually happening, and you can tell, if you look and give up your entrenched, established story of how wrong it all is. Reality is never wrong.
QuoteI 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
.
Are you attempting to convince someone with this recital? Who? 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 is it: http://newenergytimes.com/v2/l…anReplyToKrivitMarwan.pdf . There you have:
QuoteIn 2002, this author published a reanalysis[2] of laboratory data claimed to have shown unequivocal excess heat3 (or more correctly, power), wherein a previously unrecognized systematic error was demonstrated to have the capacity to explain the observations without invoking a nuclear reaction. This error was termed the ‘calibration constant shift’ (CCS). This explanation was challenged twice,[4,5] and responses published,[6,7] although the first challenge was non specific. The second challenge focused on the proposed speculative mechanism for how the CCS might have occurred in F&P type cells rather than on the CCS explanation itself. The responses clarified the issues and left the CCS unchallenged as a potential explanation of apparent excess heat signals.
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.
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.
QuoteI 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.
The story becomes personal, with heavy world-view interpretation, distinguishing "CF'ers" from "good scientists." From this, rejection by people doing cold fusion research becomes quite predictable. So far, here, the argument is almost entirely "I was right, they were wrong." Fact is neglected. Right off, I notice reading over that paper that what amount to unpublished, unreviewed results were the major focus of much. The 2000 work criticized was http://lenr-canr.org/acrobat/StormsEexcesspowe.pdf, which is unconfirmed work (AFAIK) by Ed Storms, presented as a conference paper.
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.
Shanahan's response was published in a journal: http://lenr-canr.org/acrobat/ShanahanKapossiblec.pdf (draft, not the final version. Kirk, if you wrote the final version, you could ask Jed to update the copy. Only if it is the as-published version, with the journal formatting, would that be improper. You could still edit your draft to make it match as-published without formatting. Nobody is going to say boo!)
Storms responded with http://lenr-canr.org/acrobat/StormsEcommentonp.pdf
You replied to Storms. I have a copy of that paper, but for others, is it available on the internet?
There is a lot I could write now. However, I will start with one question. 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?
Storms' comment was brief, two pages, and focused. Your reply, published the next year, was five pages and scattered. Besides a juvenile tit-for-tat in the abstract (compare with the Storms abstract) -- and the abstract can be seen at http://www.sciencedirect.com/s…cle/pii/S0040603105005721 -- You have this:
QuoteIn summary, Storms’ arguments rest on four fundamental
points: (1) O2 and H2 bubbles cannot mix on the electrode surface because all bubbles rise rapidly to the electrolyte surface, (2) recombination heat arising from any such possible recombination cannot account for the observed magnitudes of apparent excess heats (3) calibration studies of cold fusion calorimetric apparati do not support any unexpected or unexplained phenomena such as the CCS, and (4) Shanahan misinterprets and/or fails to acknowledge said results. These points will now be addressed.
Just starting with the first, that is not what Storms stated. It is a straw man argument.
