>I did not see Dr. Mills reply to this Erroneous Aalysis posted on the
>source site, so I took the liberty of posting a copy there. I
>thought this fairly important as the author is posting references to
>his blog around the web where BLP is referenced as evidence that the
>Rowan results are bogus (or at least could be). In response to my
>repost of Dr. Mills retort, Eli (Rabbit) reponded as follows:
>
>----------------------------------------------------------
>
>BOE means back of the envelope, and the approach of grabbing bond
>energies from diatomics is not as bad as you or RM (Randall Mills)
>thinks. Or perhaps you have a table of more accurate ones? If
>anything the N-H bond was too strong as the reactivity of Raney-
>nickel shows. That hydrogen is mighty available.
>
>If you think any significant hydrogen on R-nickel is molecular, how
>do you explain its activity for hydrogenation reactions?





It is not a question of more accurate heats of formation. They are
accurate to at least three significant figures. It is a question of
using the correct ones. That was not done as evidenced the the
difference between Rabett's erroneous calculated nickel hydride
decomposition energy of a "Net heat of reaction per mole of H2
generated= 2*240 kJ/mol - 436 kJ/mol - 204 kJ/mol = -160 kJ/mol (an
exothermic reaction)" and the experimental result of +8.8 kJ/mole H2
[B. Baranowski, S. M. Filipek, "45 years of nickel hydride‹history
and perspectives", Journal of Alloys and Compounds, 404-406, (2005),
pp. 2-6.]. This post should be redacted at each site that it is
posted. Presuming Rabett is really a professor, I'm sure such an
obvious and fundamental mistake would not be tolerated.




>
>----------------------------------------------------------
>
>Perhaps Dr. Mills or others would like to respoind or I would be
>happy to serve as the middleman.
>
>===============================================================
>--- In SocietyforClassicalPhysics@yahoogroups.com, "Dr. Randell L.
>Mills" <RMills@...> wrote:
>>
>> My response to a personal communication regarding an
>> erroneous analysis posted on a blog site
>> <http://rabett.blogspot.com>http://rabett.blogspot.com follows:
>>
>> The heat of formation of nickel hydride is negative and small
>> (-2.1 kcal mole/H2). It is referenced in my paper R. L. Mills, G.
>> Zhao, K. Akhar, R. Chang, J. He, Y. Lu, W. Good, G. Chu,
>> "Commercializable Power Source from Forming New States of
>Hydrogen",
>> in press (Reference 78 at Eq. (45)).
>>
>> [78. B. Baranowski, S. M. Filipek, "45 years of nickel
>> hydride-history and perspectives", Journal of Alloys and Compounds,
>> 404-406, (2005), pp. 2-6.]
>>
>>
>> http://www.blacklightpower.com/papers/WFC112108WebS.pdf
>>
>>
>> Thus, nickel hydride decomposition is endothermic, not exothermic.
>> Furthermore, Rabett's main mistake is that he has incorrectly
> > calculated the heat of formation of nickel hydride using gaseous
> > diatomic bond energies. Specifically, the cited Ni-H and Ni-Ni
>bond
> > energies regard formation of gaseous covalent diatomic molecules
>from
>> the corresponding gaseous atoms. These energies do not include the
>> energy to vaporize Ni metal to atomic nickel which is +429.7
>kJ/mole
>> Ni (CRC) or +4.45 eV/Ni atom.
>>
>> D. R. Lide, CRC Handbook of Chemistry and Physics, 86th Edition,
>CRC
>> Press, Taylor & Francis, Boca Raton, (2005-6), p. 5-16.
>>
>> (The preamble of the Bond Dissociation Energies section of the CRC
>> that Rabett cites for the gaseous diatomic bond energies used gives
>> the pages for the enthalpy of formation of atoms in the gas phase.)
>>
>> Also, nickel hydride is H dissolved in a Ni metal lattice. It does
>> not comprise covalent Ni-H bonds. Nor, does nickel metal comprise
>> gaseous Ni-Ni covalent bonds.
>>
>> Experimentally, the heat released from commercial R-Ni
>> (Davison) was only detectable by TPD in larger samples as shown by
>I.
>> Nicolau, R. B. Andersen, "Hydrogen in a commercial Raney nickel,"
>J.
>> Catalysis, Vol. 68, (1981), 339-348. The small heat observed by
>> Nicolau with larger samples was attributable to the oxidation
>> reaction of Al by Bayerite that was present at 1.3 wt%
>corresponding
>> to 2.5 X10^-4 moles H2O/g R-Ni. In the Rowan studies, this
>reaction
>> accounted for 1% of the 1 MJ of heat observed based on redundant
>> Bayerite measurements. Similar results were obtained by BLP:
>>
>> http://www.blacklightpower.com/papers/WFC112108WebS.pdf
>>
>> Rabett Erroneous Blog Post:
>> Grabbing one of the discarded Christmas card envelops that the
>gentle
>> readers were so kind as to send and turning it to the back, the
>> chemical reaction would be
>> 2 Ni-H(s) --> Ni-Ni(s) + H2(g)
>> Scaling the 100 to 150 ml/g H2 for Raney nickel up to the 1500 g
>> Rowan/BLP reactor we get (100-150 ml/g)*(1500g) = 150 - 225 liters
>of
>> H2 or .
>> (150-225 liter)/(22.4 l/mole) = 6.7 - 10 moles (a serious amount of
>Hydrogen)
>> To do this right we would have to know the heat of formation of a
>> mole of H atoms on the Raney nickel and a whole lot of details,
>Raney
>> nickel is a very nano material, where structure is everything.
>> However, for the back of our envelope we can use bond strengths
>from
>> the table in the Chem Rubber Bible (aka Chemical Rubber Company
>> Handbook of Chemistry and Physics, 9-64 (2008)).
>> Ni-Ni: 204 kJ/mol
>> Ni-H: 240 kJ/mol
>> H-H: 436 kJ/mol
>> So we break two Ni-H bonds, that costs us 480 kJ/mol and we make
>one
>> Ni-Ni bond getting back 204 kJ/mol and one H-H bond, getting back
>436
>> kJ/mol
>> Net heat of reaction is estimated by adding the energies for the
>> bonds broken and subtracting the energies for the bonds formed. (A
>> negative number means the reaction will be exothermic or give off
>> energy in the form of heat)
>> Net heat of reaction per mole of H2 generated= 2*240 kJ/mol - 436
>> kJ/mol - 204 kJ/mol = -160 kJ/mol (an exothermic reaction)
>> Net heat evolved from 1.5 kg of Raney nickel = (6.7-10.0 mol) x -
>160
>> kJ/mol = - 1072 kJ to -1600 kJ = -1.1 to -1.6 MJ!!
>>
>> --
>>
>
>
>
>------------------------------------
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