HDTenEightyP/NetNews huggingface dataset:
From: bjgaed@bb1t.monsanto.com
Newsgroups: sci.chem
Subject: Re: Chemists' Responsibilty
Date: 6 Nov 92 12:17:19 CST
Organization: Monsanto Company, St. Louis, MO

In article <david.5.720883349@chem1.chem.dal.ca>, david@chem1.chem.dal.ca 
(Burkholder David) writes:

>>        What do you think a chemist's responsibilty is to the environment 
>>when formulating a new compound? Do we simply make a chemical for its short 
>>term use, or do we consider the possible long term consequences of its 
>>application?
> 
> We certainly need to start thinking about these things, however, the long 
> term consequences usually elude our prescience ... it's more a case 
> of needing to monitor a product as it goes from development to 
> testing to the marketplace and I'm not sure there are mechanisms in 
> place once things are marketable.

Hello?  What planet are you living on?  Ever hear of the Environmental 
Protection Agency (EPA)?  The Food and Drug Administration (FDA)?  The 
Department of Agriculture (USDA)?  The Consumer Protection Agency 
(CPA)?  The Federal Trade Commision (FTC)?  The Department of 
Transportation (DOT)?  The Occupational Safety and Health 
Administration (OSHA)?   The Federal Insecticide, Fungicide, and 
Rodenticide Act (FIFRA)?  The Resource Conservation and Recovery Act 
(RCRA)? The Clean Water Act (CWA)? (To name just a few.)

>> Are some aspects of Chemistry more accountable for environmental 
>> impact than others, and should these disciplines (Inorganic, Organic, 
> 
> Probably not good to make distinctions here if you want to get anywhere with 
> the above necessities.
> 
>>What are the roles of chemists in the future in terms 
> of the >environment? Do we have any?>	
> 
> We have great responsibilities and the potential of, probably, the most 
> useful roles due to our collective past actions and our particular training 
> and orientation.  Chemists are the best trained group to solve the problems 
> they have caused and this needs to be much more emphasized in the 
> educational process.

Either chemists have a role in the future in terms of the environment, 
or they have no role in the future at all.  They will be regulated out 
of existence by others who have no knowledge of science.


--Electric Monk            (Bruce Gaede); 
                            e-mail: bjgaed@ccmail.monsanto.com

"...and then time started seriously to pass."
--Douglas Adams, _Dirk Gently's Holistic Detective Agency_
Newsgroups: sci.chem
Subject: FAQ wanted
From: Ted West <TRW108@psuvm.psu.edu>
Date: Sun, 8 Nov 1992 17:35:32 EST
Organization: Penn State University

Is there a Frequently Asked Questions list for this group?  If anyone has a
copy, I would appreciate one.

Thanks...
_______________________________________________________________________________
TED WEST                                                      What's a 'fubar'?
TRW108 @ PSUVM.BITNET                                              814-862-7589
west @ fubar.bk.psu.edu                                        617 Mifflin Hall
trw108 @ psuvm.psu.edu                                University Park, PA 16802
-------------------------------------------------------------------------------
Newsgroups: sci.chem
From: "david gebhardt" <david.gebhardt@canrem.com>
Subject: picric acid explosion
Reply-To: "david gebhardt" <david.gebhardt@canrem.com>
Organization: Canada Remote Systems
Distribution: sci
Date: 5 Nov 92 00:48:14 EST

On 11-04-92 at 12:01pm, Moroney wrote to All:

>RY>My guess is
>
>RY>2 C6H3O7N3 -----> 3 N2(g) + 3 H2O(g) + 5 CO2(g) + CO(g) + 6 C(s) (soot)

>Is there any reason that CO would be included? Couldn't you have:
>
>4 C6H3O7N3 -----> 6 N2(g) + 6 H2O(g) + 11 CO2(g) + 13 C(s) (soot)

MY>I'd think that at the high temperature of the explosion the formation of CO
MY>would be favored, you'd more likely get something closer to

MY>2 C6H3O7N3 -----> 3 N2(g) + 3 H2O(g) + 11 CO(g) + C(s) (soot)

MY>although in reality there would be some CO2 and more C at the expense of the
MY>CO as the result will be dependant on the C/CO/CO2 equilibrium constant
MY>at the temperature of the explosion.

Well, this would depend on the heat of formation of picric acid. If it
is highly endothermic, then I could go along with this. If you do the
calculations, you get:

Heat of formation of CO2 = -393.51 kJ/mol
Heat of formation of H2O = -241.84 kJ/mol
Heat of formation of CO  = -110.54 kJ/mol

change in enthalpy = enthalpy of products - enthalpy of reactants

for my reaction: change in H = 11(-393.51)+6(-241.84)-4*H(picric)
                             = -5779.65 kJ - 4*H(picric)

for your reaction: change in H = 11(-110.54)+3(-241.84)-2*H(picric)
                               = -1941.46 kJ - 2*H(picric)

If formation of picric is exothermic, then the change in H gets larger
and the reaction becomes more endothermic. This does not seem possible
because of the large value of H(picric) needed to reduce the gap in the
enthalpy change.

If formation of picric is endothermic, the enthalpy change becomes
smaller, and even though the gap grows, your reaction becomes highly
exothermic and it becomes more likely that CO could be produced instead
of CO2 and still cause a large explosion.

David Gebhardt
ComputerPlus
---
  DeLuxe 1.25 #8170  Save a plant...eat a vegetarian.
--
Canada Remote Systems  - Toronto, Ontario
World's Largest PCBOARD System - 416-629-7000/629-7044
Newsgroups: sci.chem
From: johnm@sun1x.actc.res.utc.com (John Montgomery)
Subject: Re: ZPE differences
Organization: United Technologies Research Center
Date: Fri, 13 Nov 1992 19:29:52 GMT

ivar@chem.ut.ee (Ivar Koppel) writes:
: I'm starting a little project for quantum chemical calculations
: of gas-phase acidities and/or keto-enol tautomerism. I have been
: suggested, that in such cases in adition to SCF energy differences
: also differences in zero point vibrational energies (ZPE) play important
: role, but I have no knowledge how to calculate these energies with
: MOPAC 6.0 or Gaussian 88, whitch are the programs available for me now.

With Gaussian 88, you may calculate harmonic vibrational frequencies
(# freq on the route card) and from these estimate vibrational zero
point energies.  Note that the frequency calculation must be done
at a stationary point, that is, one obtained by a gradient optimization.
SCF harmonic frequencies usually overestimate the zero point, and
therefore it is common practice to rescale them.  Pople has suggested
scaling 6-31G* SCF frequencies by 0.8929 when calculating zero
point energies.  Note that semi-empirical theories sometimes are
parameterized to include the zero point, I believe this is the case
for AM1.

In addition to the vibrational zero-point energy, SCF energy differences
also neglect the important effects of electron correlation.  With
Gaussian 88, these effects may be calculated from M\oller-Plesset,
coupled cluster, or configuration interaction methods.  Note that
there is a vast literature on the treatment of electron correlation.

A good starting place to read is Hehre, Radom, Schleyer, and Pople,
"Ab Initio Molecular Orbital Theory" (Wiley-Interscience).  You might
also look at Pople's more recent G1 and G2 methods (published in
J. Chem. Phys.) and Radom's calculations of gas phase acidities using
them (J. Phys. Chem. 95 (1991) 10549).
--
John A. Montgomery      "Evans boldly put 50 atm. of ethylene in a cell
United Technologies      with 25 atm. of oxygen.  The apparatus subsequently
Research Center          blew up, but luckily not before he obtained the
                         spectra shown in Figure 8."
johnm@utrc.utc.com       A.J.Merer and R.S.Mulliken, Chem.Rev. 69, 645 (1969)

Newsgroups: sci.chem
From: rajat@sunny3.che.clarkson.edu (Rajat Kapoor,P303,2124)
Subject: Re: Gold dust a fire hazard?
Organization: Clarkson University
Date: Fri, 13 Nov 1992 19:07:03 GMT

From article <1992Nov12.221840.13881@ncsu.edu>, by jrkitchi@eos.ncsu.edu (JOHN ROBERT KITCHIN):
> 
> there are many metallic dusts which are not only flammable when in a
> fine dust, but are pyrophoric (self-igniting).  This is definitely true
> for metals such as aluminum and zinc, which are commonly used for
> explosives and pyrotechnics, so I see no reason why it would be
> different for other metals like gold and platinum

In my opinion, flammibility of fine powders is more of a heat transfer
effect than the conventional "hi surface area = hi energy" theory.

Oxidation of Al, highly exothermic, can lead on to formation of
hot-spots, which by definition is localized phenomena.

For finely divided micro-particles, the temperature rise is global,
owing to its comparatively low heat capacity (mass dependent). This
then further acclerates the oxidation rate, raising the temperature even
more, till ignition point is reached. 

For macro-particles, the adiabatic heat rise on the surface could
be quickly conducted and absorbed by the larger mass, preventing
formation of hot-spots and quenching the reaction, allowing only a 
protective oxide layer to develop.

One may, however, argue that higher surface area of smaller particles
would allow for more efficient heat transfer with surroundings. Well,
at t=0 the temp rise would be non-discriminating, though, later on
one may expect higher loss due to a higher temp differential between
the surface and surroundings, but again, heat generation would outpace
heat loss by convection.

In the present context of Au vs. Al, I would't be surprised if gold
oxide formation were endothermic.

While Al occurs as oxide in nature (bauxite), Au is native.

Rajat


rxn for Gold Oxide formation is  
Newsgroups: sci.chem
From: Gordon_Wong@mindlink.bc.ca (Gordon Wong)
Subject: ORBITAL OVERLAP QUESTION
Organization: MIND LINK! - British Columbia, Canada
Date: Sat, 7 Nov 1992 17:55:45 GMT

I need some confirmation regarding the orbital overlap diagram of the
doubly double-bonded CO2 molecule. The carbon would hybridize to form 2 sp
orbitals and 2 unhybridized p orbitals. Would one sp orbital from the C
atom overlap a p orbital from one O atom to form a sigma bond and the other p
orbital from the C atom form a pi bond with the other p orbital from the O
atom, resulting in the double bond?

I just want to know if this is correct or am I completely off base?
From: ce698@cleveland.Freenet.Edu (A. McPherson)
Newsgroups: sci.chem
Subject: Re: Gold dust a fire hazard?
Date: 13 Nov 1992 18:17:10 GMT
Organization: Case Western Reserve University, Cleveland, Ohio (USA)
NNTP-Posting-Host: hela.ins.cwru.edu


gold might likely be the least reactive of all the metals in terms of
its combustibility, i would agree.  it would be interesting to confirm
the prediction, which is based on fairly well known thermodynamic
principles, with a test, just in case we have missed some other
considerations.  in any event, your logic is well based, and the 
loose comparison i offered with respect to burning aluminum and 
magnesium was not a very good one.
From: ce698@cleveland.Freenet.Edu (A. McPherson)
Newsgroups: sci.chem
Subject: Re: MSDS information required
Date: 12 Nov 1992 16:32:48 GMT
Organization: Case Western Reserve University, Cleveland, Ohio (USA)
NNTP-Posting-Host: hela.ins.cwru.edu


what do you mean by a comparison of MSDS collections, a list, or 
a comparison of the type of information provided?
i have been looking for MSDS collections, or related information tha
is accessible by NET, but no success yet.  there are many printed
collections, such as CCINFO and ICSC, but none on on-line data bases
that i'm aware of.
to answer your last question "what is TOMES".  ToOMES is a commercially availble
data base (might only be CD-ROM though) that contains several data bases,
such as HSDB and Poison Index.  try a medical or toxicology library, they
might subscribe.
-- 
Tobacco, coffee, alcohol, hashish, prussic acid, strychnine are
weak dilutions: the surest poison is time.
               Emerson. Society and Solitude: Old Age
Newsgroups: sci.chem
From: nbx@atom.ansto.gov.au (Ned Blagojevic)
Subject: Re: Heavy water separation
Organization: Australian Nuclear Science and Technology Organisation
Date: Fri, 6 Nov 1992 00:04:33 GMT

Organization: Australian Nuclear Science and Technology Organisation
Keywords: D2O toxicity 

In article <dexter.720820821@aries> dexter@aries.scs.uiuc.edu (Annette Dexter) writes:
>tomas_e@LINK.Physchem.KTH.SE (Tomas Eriksson) writes:
>
>>And - I'd advice against drinking water that's enriched in deuterium. 
>>The rates of many reactions in the body is tunnel-effect dependent, 
>>which means that if you get a D atom instead of an H atom at the wrong 
>>place, the rate of the reaction can decrease rather much. And to 
>>deliberately include deuterium in quite a lot of molecules of your body 
>>could do strange things to your physiology. (Not that I really expect 
>>you to die of a single sip of water with a few percent deuterium in it.)
>
>	Perhaps this is an urban legend, but I've been told that drinking
>about 500 mL of D2O will kill you.  If that is true, it would be a pretty
>hard poison to detect, too, unless some coroner came up with the bright
>idea of running a mass spec on corpse tissue extracts.  And even then...
>
>	Annette

Not correct! Heavy water is used for body composition studies regularly in 
quantities up to 100ml as a tracer for water. I have injected approximately
100 ml of pure (no tritium) D2O on a number of occasions with no ill effects.
The comment about the physiology is correct but it must be stated that this is 
totaly reversible. Animals and I believe humans can tolerate (short term)
D2O levels of up to 20% or more with no ill efffects (just on 10 kg D2O for 
a "standard "  75kg man). This has been documented.

Easyer method of detecting D2O (>0.05%) is FTIR, CaF2 cell 0.1mm path length.


Ned 

nbx@atom.ansto.gov.au
ANSTO, Sydney Australia

*** After years of WordPerfect vi is just a distant memeory****
From: b_duke@darwin.ntu.edu.au (Brian Duke)
Newsgroups: sci.chem
Subject: Re: ORBITAL OVERLAP QUESTION
Date: 13 Nov 92 07:22:08 +0900

In article <1992Nov08.194440.38866@ux1.cts.eiu.edu>, cfthb@ux1.cts.eiu.edu (Howard Black) writes:
> In article <17235@mindlink.bc.ca> Gordon_Wong@mindlink.bc.ca (Gordon Wong) writes:
>>I need some confirmation regarding the orbital overlap diagram of the
>>doubly double-bonded CO2 molecule. The carbon would hybridize to form 2 sp
>>orbitals and 2 unhybridized p orbitals. Would one sp orbital from the C
>>atom overlap a p orbital from one O atom to form a sigma bond and the other p
>>orbital from the C atom form a pi bond with the other p orbital from the O
>>atom, resulting in the double bond?
>>
>>I just want to know if this is correct or am I completely off base?
> 
>     The latter.  The oxygens are sp2, thus, the sigma bond results from
> overlap of C(sp)-O(sp2), and the pi bond from C(p)-O(p).  The other two
> O(sp2) hybrids contain the unshared electron pairs.
> -- 
Gordon is not completely off-base, if I follow him correctly. Since
there are no other atoms attached to the O, we can not argue for 
hybridisation from the steric arrangement around the O. From this point
of view sigma C(sp)-O(pz) [let z be axis of molecule.] is just as reasonable
as sigma C(sp)-O(sp2). The pi bonds of course are C(px)-O(px) on one side,
and C(py)-O(py) on the other side. The question can be partly answered
by looking at high level quantum chemical calculations. The anwer is that
the s orbitals on O are involved in the sigma bond, but not to the full
extent of sp2, but more of course than the zero involvement of just p.

The answer lies between Gordon and Howard, but in my view closer to 
Gordon since there is no reason to invoke hybridisation on the O.

I hope this helps to clarify this problem.
-- 
                  Brian Salter-Duke (Brian Duke)
School of Chemistry and Earth Sciences, Northern Territory University
        GPO Box 40146, Casuarina, NT 0811, Australia.
Phone 089-466702   FAX 089-410460    E-mail B_DUKE@DARWIN.NTU.EDU.AU
Newsgroups: sci.chem
From: "david gebhardt" <david.gebhardt@canrem.com>
Subject: picric acid explosion
Reply-To: "david gebhardt" <david.gebhardt@canrem.com>
Organization: Canada Remote Systems
Distribution: sci
Date: 6 Nov 92 09:52:11 EST

On 11-05-92 at 9:00pm, William Johnson wrote to All:

WJ> 2) Since real detonations aren't "ideal," all sorts of other stuff
WJ>gets produced in quantities ranging from traces to possibly significant
WJ>amounts.

I agree with you. It started out as a question about what was actually
produced and seemed to become more and more ideal as we went along
(i.e. assume absence of oxygen, etc.). A non-ideal case would be far
too complex for any type of prediction.

WJ>BTW, is it asking too much to expect people to try the technical literature
WJ>first before answering -- or asking -- questions like this?

Unfortunately, I don't have access to any of the technical references
anymore. Up until I graduated in '91, I could look information up in
the school library. Now I run my own company and only really have access
to the local library for information. In a town of 30,000, they don't
get a lot of technical journals or books. <g> I did my best later to
do some enthalpy calcs and stuff, but I only had three textbooks to work
with.

Thanks for the info!

David Gebhardt
ComputerPlus
---
  DeLuxe 1.25 #8170  Electricity was invented by rubbing cats backwards
--
Canada Remote Systems  - Toronto, Ontario
World's Largest PCBOARD System - 416-629-7000/629-7044
From: dietz@cs.rochester.edu (Paul Dietz)
Newsgroups: sci.chem
Subject: Re: Heavy water separation
Date: 7 Nov 92 13:33:08 GMT
Article-I.D.: cs.1992Nov7.133308.22904
Organization: Computer Science Department University of Rochester

A little more on heavy water separation...

The technique the Germans (actually, the Norwegians, under occupation)
in WW2 were using was electrolysis.  There is a substantial difference
in the rate at which hydrogen isotopes are evolved at the cathode in
an electrolytic cell -- something like a factor of 4, if I recall
correctly.

Because almost all the cost of making heavy water is in the steps
involving low concentrations, if you can go from natural concentration
--> 4x natural, you've saved most of the cost.  Advocates of the
so-called "solar-hydrogen economy," where PV or wind generators are
used to make hydrogen by electrolysis, would do well to consider what
this would imply: it would become easier for any country with hydrogen
production to also make heavy water, and therefore also make plutonium
(in heavy water/natural uranium reactors; both Israel and India went
this route).  Note that natural (as opposed to enriched) uranium
is sufficiently abundant that it cannot be easily controlled.

I've heard that one of the effects of large intake of heavy water
on rats is "caudal necrosis":  their tails fall off.

	Paul F. Dietz
	dietz@cs.rochester.edu
Newsgroups: sci.chem
From: jeroen@dxcern.cern.ch (Jeroen Belleman)
Subject: Re: Gold dust a fire hazard?
Organization: CERN European Laboratory for Particle Physics
Date: Fri, 13 Nov 1992 10:08:36 GMT

In article <1992Nov13.033411.22073@dsuvax.dsu.edu>
rolfe@dsuvax.dsu.edu (Tim Rolfe) writes:
>I thought gold was so UNreactive that even concentrated nitric acid
>by itself doesn't bother it --- you need aqua regia. Given this, I
>do find it surprising to hear that gold can be oxidized, even finely
>divided.

Exactly my idea. Many people seem to think that any fine powder,
especially metal powder, is a fire hazard. But there has to be
something in the air it wants to react with. As far as I know,
the O2 in the air is not a sufficiently strong oxidizer for Au.
Even for a half noble metal as Hg, the reaction would rather go
the other way, (I.e. 2HgO -> 2Hg + O2) although admittedly at
room temperature, nothing much happens.

I rather suspect this was brought to us in the same spirit that
makes people write 'Can be harmful if swallowed' on a box of
sand for parakeets.

Best regards,
Jeroen Belleman
jeroen@dcxcern.cern.ch
From: kgrossha@radford.vak12ed.edu (Kurt Grosshans)
Newsgroups: sci.chem
Subject: Re: abbrev electron config
Date: 8 Nov 92 18:32:04 GMT
Organization: Virginia's Public Education Network (Radford)

rickert@cco.caltech.edu  writes:
> The 3d and 4s orbitals are of very similar energy, and which
> one is higher depends upon the exact nuclear charge and 
> electronic configuration involved. In the case of iron, it
> is easier to ionize 4s electrons than 3d electrons, so the configuration
> is written [3dn][4s2] or whatever. But for calcium, the 4 s orbitals
> are of lower energy, which is why they fill first.

Well....a low ionization energy is indicative of low energy
electrons. I am joining this thread late in the game so I do
not know the origin...but a text book put out by Prentice Hall
shows all electron configurations in chronological order. This
may be in error, or they are reminding the student that the 4s
is still farther away from the nucleus than the 3d, just lower
in energy. A 4s electron has a higher probability of penetrating
the charge clouds of the inner electrons than the 3d and thus
tends to pick up lower energy electrons.
-- 
=-=-=-=-=-=-=-=-=-==-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-=-==-=-=-=-=
Kurt Grosshans
kgrossha@radford.vak12ed.edu
Newsgroups: sci.chem
From: dexter@aries.scs.uiuc.edu (Annette Dexter)
Subject: Re: Heavy water separation
Organization: University of Illinois at Urbana
Date: Fri, 6 Nov 1992 00:07:59 GMT

neufeld@helios.physics.utoronto.ca (Christopher Neufeld) writes:

>>	Perhaps this is an urban legend, but I've been told that drinking
>>about 500 mL of D2O will kill you.
>>
>   I was talking with a local isotope expert here a year or so ago about
>this very subject. He said that a 10% substitution of D for H in the body
>is about enough to foul up gene expression by altering the base-pair
>binding strengths (remember those rungs are secured by hydrogen bonds).
>This is fatal. I don't imagine it has been seen in humans, though.

	There are many, many sites in the body which could be affected by
the presence of D2O.  Personally (but I will admit this as bias) I think
enzymes are a more likely target.  The (maximum) predicted primary isotope
effect resulting from D substitution for H is 7, ie. a reaction being slowed
by a factor of seven if D/H transfer is involved in the rate-determining
step for a reaction.  One could certainly imagine enough D2O slowing down
glycolysis to the point where not enough energy was available to maintain
cellular integrity.  Or the target might include an enzyme such as acetyl-
cholinesterase, necessary for cholinergic nerve maintenance.   

>   You don't get severe trouble right away from drinking deuterated
>water. I don't think the body does much switching of hydrogen atoms
>between water and nucleic acid bases. 

	You are coming dangerously close to vitalism by saying "the body"
switches hydrogens around.  Hydrogen-bonded H/D exchanges only slowly with
external medium, so I would expect that *inactive* genes would not undergo
H exchange before D2O was "chased" from the body by normal water intake.
But the process of exchange is an entirely chemical phenomenon.

	I think D2O is best viewed as a nonspecific and slow-acting toxin.
Effects of *any* toxin affecting gene expression are likely to be slow, 
but the slowness of an effect does not then demonstrate the toxin is acting 
on genes.  I put a vote in for slowing of general metabolism.

	Any other opinions?

	Annette 

******************************************************************************
Annette Dexter				    *	"Republicans understand the
dexter@aries.scs.uiuc.edu		    *    importance of bondage between
Department of Biochemistry		    *    parent and child."
University of Illinois, Urbana-Champaign    *		-- Dan Quayle
******************************************************************************




Newsgroups: sci.chem