FP's experiments discussion

Quote from JedRothwell

If you want to know a lot more about Fleischmann's calorimetry, for example, see:

http://lenr-canr.org/acrobat/MilesMisoperibol.pdf

Miles is better at explaining these things then Fleischmann was. I believe your focus in recent discussions here was on the effects of vaporization. That is an important issue, and as McKubre wrote here, it is measured and included in the calorimetric equations. See especially Appendix I, and look for the term L. See, for example, p. 26:

"The term involving the enthalpy of vaporization (L) contributes -4.9103 mW and -52.9857 mW, respectively, at these two cell temperatures, (Ref. 2)."

[The two temperatures are 40 deg C and 80 deg C. The cell is usually at 40 deg C, and ~5 mW is much smaller than the excess heat in the weeks leading up to the boil-off event. Obviously, vaporization dominates during the boil-off.]

Yes, obviously, vaporization dominates during the boil-off. And boiling was exactly the condition that Fleischmann's "major paper" was aimed to investigate, as stated at the beginning of the abstract (1): "We present here one aspect of our recent research on the calorimetry of the Pd/D2O system which has been concerned with high rates of specific excess enthalpy generation (> 1kWcm^-3) at temperatures close to (or at) the boiling point of the electrolyte solution."

And the specific enthalpy generation greater than 1kWcm^-3 (namely 3700 Wcm^-3) was calculated on page 16 by means of a formula that doesn't appear in either the F&P paper of 1992, or in the Miles paper of 2008. In all the equations presented in their documents, the enthalpy of vaporization L is multiplied by P/(P*-P), whose denominator goes to zero at boiling, so all those sophisticated formulas are unuseful to calculate the enthalpy lost in this condition. In fact on page 16 of (1), they used a much simpler formula, such as:

[1] ΔE_boil = Δm_W,ev L

Where:

ΔE_boil is the enthalpy loss due to boiling

Δm_W,ev is the mass of water effectively evaporated

L is the latent heat of vaporization of water

The big problem is that they implicitly assumed that all the missing water was evaporated. On the contrary, they should have added the following mass balance as well:

[2] Δm_W,ev = Δm_W,cell – Δm_W,drop

Where:

Δm_W,cell is the mass of water lost by the cell not due to electrolysis

Δm_W,drop is the mass of water exiting the cell as water droplets!

If they really believed that the mass of water exiting the cell as droplets was zero, they should have declared it and prove it adequately.

Quote

it could only cause an error in the milliwatt range (or probably micro-watts), whereas the excess was 133 W, so this could not possibly be a significant factor, and it is not relevant.

This only happens when the error calculated at 40°C is arbitrarily compared to the excess heat allegedly generated at 100°C!

(1) http://lenr-canr.org/acrobat/Fleischmancalorimetra.pdf

Quote from Paradigmnoia

In this example there would be two top-up measurement error sources: the syringe 10 ml starting amount measurement, and the remaining amount measurement, (ignoring simple subtraction errors), neither of which would cause the average container level to rise or fall beyond the mean level measurement error (another potential error source) that the container is being topped up to.

Quote from Ascoli65

If they really believed that the mass of water exiting the cell as droplets was zero, they should have declared it and prove it adequately.

Serious researchers (as Fleischmann was) certainly keep the original refill water in a case with measurements stripes. In chemistry you use a pipette that allows you to add water by drops of 0.05ml. Believe if they made once an error > 0.05ml then it must have been due to is illness only...

Ascoli should explain how at 80 degrees C drops can be evaporated...

Quote from mmckubre

I don't trust either.

That's good. But then if you understand and practice the concept, why do you expect me to trust you? You don't tell me the calibration equations you used, even after I asked twice, but expect me to believe your excess energy claims. You don't give any references to where the response to the issues you pointed out, but you expect me to believe they were taken care of, superbly no less. You're not making much sense.

Quote from mmckubre

THH: somewhere up there you mention something like "changes in calibration" of our calorimeters and Kirk also bring up this point. I just want to make sure that you recall that our mass flow method requires very little calorimeter dependent calibration. >99% of the thermal energy leaves with the mass flow.

If you had read and understood the post above where I talk about the Two Zone model, you would realize that the 'goodness' of your calorimeter does not protect you from the CCS problem I pointed out in 2000. In fact, the idea that your calorimeter is so good you don't have to calibrate is just saying that you are assuming a value for k that is equal to the theoretical perfect value. There's an error term that arises from doing that too.

Your whole explanation is equally well applied to Ed Storms' calorimeter. He uses the same equations. You claim 99+%, he claims 98+%, a trivial difference. His baseline noise was claimed at 80 mW as I recall. Also as I recall, your M4 run claimed approximately the same noise level. In his calorimeter, I showed a 2-3% change in calibration constant produced a 780mW 'error'. Your M4 run had a 360mW signal. Are you catching my drift here?

To all:

As usual JR doesn't get my point. The idea that the supposed 7% error in volume measurement might actually be a 35% error just blew past him. But just for you all I will state this clearly.

If recombination is occurring in the cell, the water formed outside the open cell by recombining the offgases will be less than that calculated for 100% Faradaic efficiency. Thus any water volume measurement that shows '100% Faradaic efficiency' can either be correct, or found because entrainment (or something else) replaced the lost water volume (from in-cell recombination). Having more volume than expected definitely says something else is causing water to exit the cell. Two possibilities already brought up are vapor content and entrainment. And BTW, if the 'normal' condition is to have water vapor content in the offgas, then all measures of captured water should exceed the Fartadaic efficiency. Unfortunately, the CF literature has almost no reports of actual amounts of water collected outside the cell. This one in the 2004 SMMF publication is unique AFAIR.

Quote from kirkshanahan

If you had read and understood the post above where I talk about the Two Zone model, you would realize that the 'goodness' of your calorimeter does not protect you from the CCS problem I pointed out in 2000.

Kirk, I seem to recall that someone* once accused you of cherry-picking the points you will argue against, whilst ignoring any posts that you don't like...

Perhaps this is one of those posts here:

Quote from mmckubre

We obviated the precise issue that Kirk speaks about as follows:

1. ... (snip)

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. ...

...Here endeth the lesson. I will answer only relevant technical questions for clarification (and then probably slowly).

Display More

The full version is worth reading.

* indeed...

Quote from Zeus46

Kirk, I seem to recall that someone* once accused you of cherry picking the points you argue against, whilst ignoring any posts you don't like... Perhaps this is one of those posts here:

Not at all. I responded at least twice to that posting in the thread you plucked it from and probably acouple oftimes or more in this thread by stating that none of what Dr. McKubre says is relevant to the CCS/ATER problem. And I'm sure you saw that I pointed out today that Dr. Mckubre's setups are as suceptible to the CCS/ATER problem as anyone else's...

{last response to the troll....}

Quote from Paradigmnoia

Does not one fill a syringe with (for example) 10 ml, then add water electrolyte or whatever as required to a specific level in the container, look at the syringe (which if 7 ml were added would now have 3 left in it), subtract 3 from the original 10 to arrive at the 7 ml added?

I believe that is the usual method. I have also heard of people using medical IV bags and tubes. That excludes air better than a syringe. I do not know how you measure volume with IV bag.

Quote from Paradigmnoia

In this example there would be two top-up measurement error sources: the syringe 10 ml starting amount measurement, and the remaining amount measurement, (ignoring simple subtraction errors), neither of which would cause the average container level to rise or fall beyond the mean level measurement error (another potential error source) that the container is being topped up to. The top-up-to-level error would average out over time, while the syringe measurements could have a cumulative error (that does not lead to an over-full or under-full container).

A cumulative error in one direction would be a bias. It would mean either the syringe is too big or two small (very unlikely!), or you always use it wrong, for example rounding up in every case. (I just found a medical text describing how to use a syringe that warns against this.)

I think that would have to lead to the cell being over-full, or under-full. Here is what cannot happen (despite Shanahan): You have a bias of, say, +0.5 ml per day on average, so you overfill. After 10 days you have added 5 ml too much. Yet at the same time there are exactly 5 ml of water lost to some unknown cause that you failed to notice or take account of in the calorimetric equations. So the water level is just where you predicted, and you fail to detect both your mistake and the unexpected losses. That would be a fantastic coincidence. It is too unlikely.

Here is a guide to reading the dosage of a syringe. There are ways to do it wrong. Fortunately, in these experiments, you have the water level in the cell itself as a backup method.

http://www.registerednursern.com/how-to-read-a-syringe/

JedRothwell ,

I was mostly responding to your comment about the cell level getting higher (or heavier) than it should, when it seemed that the most natural way to replenish the liquid would be to top up to a pre-established level. The cell would rarely be over-filled to any significant amount (maybe at worst a few ml extra once in a while), and that would merely result in requiring less liquid the next top-up, or a longer period before topping up again.

On the other hand, controlling the actual amount added would be where the errors could creep in. Perhaps this potential error is very small, or almost never happens, but in experiments that last for months it might be something quasi significant. If each or some (or blank/standard) cell(s) had a specific reservoir volume from which the top-up syringe was filled that established a firm comparison limit (100 ml maybe) then any slight errors in the fill volume measurements (if any) could be related back to the reservoir volume for consideration of the uncertainty of the top-up volume over some period of time (a week or a month?).

Quote from kirkshanahan

Not at all. I responded at least twice to that posting in the thread you plucked it from and probably acouple oftimes or more in this thread by stating that none of what Dr. McKubre says is relevant to the CCS/ATER problem. And I'm sure you saw that I pointed out today that Dr. Mckubre's setups are as suceptible to the CCS/ATER problem as anyone else's...

So you think that your woolly suppositions about CCS trump McKubre's finite element modelling (with moving heat sources)?

Laughable, at best.

Quote from Paradigmnoia

I was mostly responding to your comment about the cell level getting higher (or heavier) than it should, when it seemed that the most natural way to replenish the liquid would be to top up to a pre-established level.

Exactly! That is how it is done. However, you want a log of how much is added each day. You can estimate that by looking at how far down the water level has fallen, but most cells are fairly large, so that is not precise. So, you use something much more precise such as a syringe. These can measure very small amounts with precision. The 1 ml ones are marked in 0.01 ml increments. I think most cells would need a 10 ml one, which has 0.5 ml marked increments.

You end up with both the amount added with the syringe (very precise) and the amount from the cell water line (less precise). The two should agree.

Fleischmann and Pons had difficulty seeing how far the water level had fallen with their half-silvered cells. You can't see inside them. They had to peek in the top with a dentist's mirror. I saw one of the cells. I think that would be difficult, but doable.

Quote from Paradigmnoia

The cell would rarely be over-filled to any significant amount (maybe at worst a few ml extra once in a while),

I doubt it would be more than 1 ml, but if it was, you just record that in the log.

Quote from Paradigmnoia

On the other hand, controlling the actual amount added would be where the errors could creep in. Perhaps this potential error is very small, or almost never happens, but in experiments that last for months it might be something quasi significant.

Yes, errors will creep in, but as I said above, it is extremely unlikely that these errors will correlate exactly with errors in the calorimetric equations in a way that mutually cancels out. For example, THH speculated that some water might be leaving the cell unaccounted for as vapor during the 2 weeks before the boil off. In other words, the L (enthalpy of evaporation) might be wrong. (That would be the most likely cause. Perhaps THH has something else in mind.)

Of course that is possible, but if L is wrong, it is very unlikely that it happens to be wrong in just the right amount to hide a persistent bias measuring the make-up water added to the cell. As I said, a bias is unlikely; what you would expect is a daily variation of about ~0.5 ml. Since your measurement error would be positive one day and negative the next, it would not cover up your mistake in calculating L (evaporation). I assume a problem with L would always be in one direction: positive, always removing more water than you expect, or negative, leaving more than you expect.

Incidentally, Fleischmann calculated L taking into account barometric pressure, which the lab recorded. So he got a very precise value.

The half-silvered cells held 2.5 moles of water (45 ml). See:

http://lenr-canr.org/acrobat/Fleischmancalorimetra.pdf

Figure 2 shows the effect of adding make up water (abrupt drop in temperature) and following that the calibration pulses. A clever person can estimate how much water was added by measuring the temperature drop, which would be a third method of confirming the amount added.

The L calculation is described in Appendix I:

http://lenr-canr.org/acrobat/MilesMisoperibol.pdf

The point of all this is: the physics equations should model the cell behavior. One important way they model it is to predict how much water leaves the cell from the combined effects of electrolysis and evaporation. If the measured amount of water that leaves the cell is significantly different from what the model predicts, the model is wrong. If they agree closely, the model is right, and THH and Shanahan are wrong. It cannot be coincidence that such a detailed model based on purely conventional physics just happens to agree with the measured amounts.

Note that this aspect of the model has nothing to do with excess heat or the claims of cold fusion. When there is excess heat, the temperature is higher than predicted, but L (evaporation) depends on whatever the temperature may be, regardless of the source of heat. The amount lost to electrolysis is also unrelated to the cold fusion effect.

Quote from Wyttenbach

Ascoli should explain how at 80 degrees C drops can be evaporated...

I didn't say that drops were evaporated, whatever the temperature. My position is much simpler: at any temperature there is some liquid entrained by the gas stream and his quantity can easily explain any apparent excess heat resulting at that temperature.

At low and intermediate temperatures, the D2+O2 gas bubbles generated by electrolyses carry some mist (thin droplets) within them, as well as the vaporized D2O, whose quantity increases with input power and temperature. As power increases and temperature approaches the boiling point, the bubbles become larger and also include larger droplets. In the final stage of the boil-off, the "grand finale", a sort of foam (mostly liquid) exits the cell.

You can get an idea of the capacity of these bubbles to carry mist and/or droplets looking at the following video (1), at t=2m17s:

https://www.youtube.com/watch?v=PXaijlN1AKo#t=2m17s

The 4 cells in the short video are the same of the tests described in the F&P paper presented at ICCF3 (2). The starting time (22:13:58) is when half of the water of the first cells has already boiled away. The video allows to appreciate the intensity of the rising bubbles also in the other 3 cells whose temperatures were much lower, about 60°C, as shown in the following jpeg.

(1) https://www.youtube.com/watch?v=PXaijlN1AKo

(2) http://lenr-canr.org/acrobat/Fleischmancalorimetra.pdf

Quote from Ascoli65

I didn't say that drops were evaporated, whatever the temperature. My position is much simpler: at any temperature there is some liquid entrained by the gas stream and his quantity can easily explain any apparent excess heat resulting at that temperature.

If that were the case, the model would not predict the correct amount of water leaving the cell. The amount of make-up water measured over the course of the experiment would be quite different from what the model predicts. It would have to be quite different for this effect to be large enough to produce the apparent excess heat.

The model is entirely conventional 19th century physics. The model predicts the amount of water lost to within the limits of the measurements. Have you found an error this model? If you have not, and if there is no measurable deviation from the predicted behavior, why do you say there might be a deviation? What is your speculation based on? You seem to be asserting that an invisible, impossible-to-measure or detect process is underway that by a fantastic coincidence produces exactly the same behavior as ordinary 19th century physics predict. How can we tell the difference between what you say, and what all of the textbooks have said for the last 150 years? How can anyone test or falsify your claim?

I refer to the model here, in Appendix I. Let us know if you spot an error in it:

http://lenr-canr.org/acrobat/MilesMisoperibol.pdf

You seem to be saying there is liquid entrained water, and it is not included in the model, but for some reason no one can measure it, and it does not change the amount of make up water or the water level. What is that supposed to mean, anyway? If it is large enough to make the excess heat go away, why is it also so small it cannot be measured?

Ascoli refers to the boil off segment of the experiment, where boiling dominates. The calorimetric model still applies. He once again speculates that there may be droplets removed, even though such droplets have not been detected by any conventional methods. Not by measuring the salts left in the cell. Not by doing calibrations. Not by any method. He cannot suggest a method that would reveal these invisible, undetectable drops. Once again, his hypothesis cannot be tested or falsified. There is no way to distinguish between his imaginary physics and conventional, textbook, 19th century physics.

Quote from Ascoli65

The video allows to appreciate the intensity of the rising bubbles also in the other 3 cells whose temperatures were much lower, about 60°C, as shown in the following jpeg.

Those are from electrolysis. That's D2 and O2, not boiling.

Quote from JedRothwell

Ascoli refers to the boil off segment of the experiment, where boiling dominates. The calorimetric model still applies. He once again speculates that there may be droplets removed, even though such droplets have not been detected by any conventional methods.

Ascoli does not even watch the videos he posts. There Fleischmann says that he uses a closed cell... Please end of the troll discussion!

Quote from Wyttenbach

Ascoli does not even watch the videos he posts. There Fleischmann says that he uses a closed cell... Please end of the troll discussion!

Well, the boil-off cells in that video were open. They are described here:

http://lenr-canr.org/acrobat/Fleischmancalorimetra.pdf

The cells that Fleischmann describes in this video came after that. As you say, they were closed, reflux boiling cells. They are described here:

http://lenr-canr.org/acrobat/RouletteTresultsofi.pdf

The method of calorimetry is quite different. Your point is correct, needless to say. If, as Ascoli, THH and others claims, these open boil off cells are not actually producing excess heat during the boil off phase, then why did the closed reflux boiling cells produce heat? For that matter, why did the open boiling cells produce heat before the boil-off, and after the boil-off, but not during it? Again, the method of calorimetry was different in all three phases, and it was different again with the reflux cells. Four methods, four excess heat results, but only one is wrong? Or are all four wrong, for different reasons? And why is it that Ascoli and the other cannot give us a hypethesis that might be tested, confirmed or falsified? Why can't they propose a test that would reveal whether they are right or wrong? Oh wait, every test of that nature, such as inventorying the salts or doing a calibration already shows they are wrong, and they can't think of any other test.

Why can they only propose hypotheses that would produce exactly the same results as conventional physics? Conventional physics prove beyond doubt the heat is real, so they need to come up with imaginary physics instead, such as drops of water leaving the cell that are so small no one can measure them, and they have no effect on the salts, yet at the same time they are so large they produce a false reading of 145 W of excess heat.

Quote from Wyttenbach

Ascoli does not even watch the videos he posts. There Fleischmann says that he uses a closed cell...

In the meanwhile JR told you that the cells I'm talking about were open.

An advise. In addition to watching them, videos must also be listened to, and possibly understood!

Quote

Please end of the troll discussion!

Who is the troll? And why are you asking to end this discussion? Have you finished all your arguments?

Quote from JedRothwell

[The video allows to appreciate the intensity of the rising bubbles also in the other 3 cells whose temperatures were much lower, about 60°C, as shown in the following jpeg.]

Those are from electrolysis. That's D2 and O2, not boiling.

You can tell those bubbles are from electrolysis because:

1. They are fine bubbles. Bubbles from boiling are larger.

2. They come from both the anode and cathode, whereas boiling with cold fusion only occurs on the cathode. Only the cathode gets hot enough to boil the water. That, by the way, is additional proof that the effect is anomalous. When you boil off the water with electrolysis power in a calibration, both the anode and cathode get hot, and both produce boiling, because they have about the same volume (in this particular cell).

Again, that is something the "droplet" hypothesis cannot explain. Why would it cause apparent heat on one electrode only?

Quote from Ascoli65

In the meanwhile JR told you that the cells I'm talking about were open.

An advise. In addition to watching them, videos must also be listened to, and possibly understood!

You apparently did not listen, or you would know that Fleischmann described closed cells that boiled for months. You should have known that already. Obviously, that means the open boil off cells were really boiling. The "droplet" hypothesis cannot explain boiling in a closed reflux cell. It can't explain the other things I mentioned, and neither you, nor THH, Shanahan or any other pathological skeptic has even tried to explain these things. You wave your hands and weasel out whenever anyone asks you for evidence. Shall we make a list?

1. A heat balance of zero in several different calibrations.
2. All of the salts left in the cell.
3. Boiling with no input power, much longer and hotter than in the calibrations.
4. Boiling with Pd-D2O only, and not with Pt, H2O or a resistance heater. How can the choice of metal or water affect cause the "droplet" theory to work? How can the source of heat do this?
5. Melted plastic when the calibration leaves the plastic underwater.
6. Excess heat a week before the boiling, and for up to a day after it. Why did it stop for 10 minutes only?
7. Boiling on the cathode only.
8. Droplets so small they cannot be detected, yet so large they produce a gigantic error, making 30 W look like 150 W.
9. Impossible physical theories that violate 18th and 19th century laws of physics, yet -- by some miracle -- produce exactly the same results as conventional theories, so that there is no test that can distinguish which is right, and no way to falsify the new theories. The conventional theories prove there is excess heat; the impossible theories rely on things like droplets too small to measure that leave no physical, measurable trace, yet magically remove most of the water. This is pathological science.

Quote from JedRothwell

Ascoli refers to the boil off segment of the experiment, where boiling dominates. The calorimetric model still applies.

Actually, I'm referring to the claims contained in the "major paper" of Fleischmann (1), the co-founder of CF. This document is the cornerstone of the whole CF/LENR building, and it is wrong. Badly wrong.

This document deals with boiling, as stated in the abstract: "We present here one aspect of our recent research on the calorimetry of the Pd/D2O system which has been concerned with high rates of specific excess enthalpy generation (> 1kWcm^-3) at temperatures close to (or at) the boiling point of the electrolyte solution."

An example of calculation of these alleged "high rates of specific excess enthalpy generation" is contained on page 16. The procedure includes the computation of the "Enthalpy Output in Vapour" that is derived by a (incorrect) formula which is not even included in the calorimetric model described from page 3 onwards. How can a model be applied to the boil off segment of an experiment if it does not include the formula used to compute the balances of mass and enthalpy?

All the formulas of the calorimetric model are numbered, can you please tell me the number which corresponds to the formula used at page 16 to calculate the "Enthalpy Output in Vapour"?

Let's first clarify this major point, then we can talk about the other flaws of the models.

(1) http://lenr-canr.org/acrobat/Fleischmancalorimetra.pdf

PS

Quote from JedRothwell

You apparently did not listen, or you would know that Fleischmann described closed cells that boiled for months.

For what I can understand, Fleischmann says (from 2:30): "So now we have to devise cells which can be maintained on the boiling conditions for 3 months."

So the cells he was talking about were still to be designed. They couldn't have "boiled for month" at that time. I don't even found any paper that describe such a test.

Quote from Ascoli65

For what I can understand, Fleischmann says (from 2:30): "So now we have to devise cells which can be maintained on the boiling conditions for 3 months."

So the cells he was talking about were still to be designed. They couldn't have "boiled for month" at that time. I don't even found any paper that describe such a test.

They were devised. I just pointed you to the paper that describes the 3 month test. You won't read it, and even you do read it, you will not understand it any more than you understand thermodynamics, boiling, and other middle-school level science, but here it is again:

http://lenr-canr.org/acrobat/RouletteTresultsofi.pdf