FURTHER PLANS FOR ITEM 3, AN IN-DEPTH STUDY OF SELECTED CATALYST SYSTEMS

• Document Type: CREST
• Collection: General CIA Records
• Document Number (FOIA) /ESDN (CREST): CIA-RDP79-00798A000300020019-3
• Release Decision: RIFPUB
• Original Classification: K
• Document Page Count: 5
• Document Creation Date: December 9, 2016
• Document Release Date: July 20, 2000
• Sequence Number: 19
• Publication Date: October 4, 1973
• Content Type: LETTER

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THE, UNIVERSITY OF WISCONSIN-MILWAUKEE / MILWAUKEE WISCOfStt -53ZUJ-
DEPARTMENT OF CHEMISTRY
PHONE: [phone]
October 4, 1973
Professor O. V. Krylov
Deputy Director
Institute of Physical Chemistry
'USSR Academy of Science
Moscow, USSR
t/As"t'
,~Px57?-73
-d ,, ,* .73
Re: Further Plans for Item 3, An In-depth Study of Selected
Catalyst Systems
Dear Oleg Valentinovich:
First of all, let me send the sincere thanks of the American
Delegation for the unmatchable hospitality shown us during our recent
trip to Moscow. Moreover, please extend my personal greetings and
thanks to your good wife for the very enjoyable evening which we spent.
in your home. ,It is my hope that when you visit us'here, we may be
able to at least partially repay you for your kindness.
Next, I have some comments concerning our meeting in Moscow and the
document which we signed. The meetings were quite beneficial to me;
I feel that I now have a much better understanding of the research
interests of various individuals. i particularly enjoyed those
opportunities which we had to discuss research on an individual basis
with the people actually doing the work. My chief regret is that the
time required to generate the document prevented me from more such
'discussions. I also deeply regret that circumstances prevented our
visit to Novasibirsk. Perhaps I can fill this gap in my knowledge on
my next visit to the USSR.
I: think that the-agreement which we signed in Moscow is a good one
which looks toward the -future with optimism. Since my return here, I
have been looking into ways and means of adding some ultra-high
vacuum research on single crystals to our program. You will recall-
that in Moscow, Professor Turkevich agreed to use his good offices on
a temporary basis to seek opportunities for junior Russian scientists
to do post-doctoral research in the US. - (Since there were no
provisions made in our budgets for this purpose, the funding of such
activities would necessarily have to come from other sources.)
However, I agreed to try to add such a program to the US effort in the
near future. Since my return here,I have had several conversations"
about this with Professor Baldeschwieler, and, whereas the matter is
not completely settled, I am confident that it will become an
accomplished fact before I receive an answer to this letter. I might
add that we are taking these steps because of the great interest: in
this area in both your laboratory and that of Professor-Boreskov.
I'm sure that you are aware that I regard work' in this area as.a
little remote from the central theme of understanding in some detail
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October 4,-1:973,
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the mechanisms of few simple. catalytic reactions. Nevertheless, I.
agree that this surface chemistry represents a challenging scientific
problem and that it may contribute, in the long run, to the major
themes agreed upon in our exchange of letters of October 31 and.
December 1, 1972.
In Moscow, 'I also promised. that Professor Boudart would-be added to
our program as soon as funds became available. I have every reason
to believe that this will also be accomplished in the. immediate future.
I will write you again about these two additions in the next several
weeks, as I want you to have the information before you come to the US
in November. Incidentally, i would appreciate it if you would write
..me in the immediate future concerning your plans for this-trip. - I
will need some time to make suitable arrangements here and perhaps to
help you visit certain other laboratories.
During 1974, I would like to collaborate directly with Professor V. B.
]Kazansky, and through him with Professor Kh. M. Minachev and Dr. G. M.
Zhidomirov on the general problem of butene isomerization. I believe
that this can be fruitful collaboration, with Kazansky studying the
ground-state from which the carbonium ion is formed; Zhidomirov
contributing quantum calculations to compare with my experimental
data; and Minachev -- his wisdom and advice. I have written Kazansky
separately, concerning this proposal (copy attached). The following
paragraphs contain a description of the work which I propose to carry
out under this program. I am encouraging the other members of the
American team to do likewise, and I hope that you will reciprocate by
having our direct collaborators send us their detailed plans.
It is my view that for strong proton-donating catalysts, such as
zeolites, the reaction schemes for hydrocarbon catalysis can be
adequately described within the framework of carbonium ion chemistry.
For these cases, the frontier. lies in the direction of understanding
some of the finer details of. these processes. These details are no
less important, however, because they include the isolation and
understanding of the factors which control selectivity for the
production of desired products at the expense of others.
The isomerization of the butenes has been used successfully as the
tool in investigations of this kind. A definite and recognizable
pattern of the behavior has been established for carbonium ion
processes, and exceptions to this pattern have been noted for
catalysts which may be characterized as poor proton donors.
Catalysts which may be thought of as bases, e.g., MgO, and those that,
have dual acid-base sites, e.g., alumina, yield quite different
product ratios than those found for carbonium-ion reactions. Some
evidence has been accumulated that in these latter instances, the
reactions involve an intramolecular 1-3 hydrogen shift, whereas in the
carbonium ion process, an intermolecular exchange process (via the
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catalyst protons) occurs. However, insufficient. research-has been
done to date.to make a categorical statement concerning the sequence
of events which occurs in the non-carbonium ion reactions.
Japanese workers have recently established a direct correlation
between the activity of SnO2-MoO3 catalyst for the production of
acetone, by oxidation of propylene, and their activity. Similarly,
Soviet scientists have found evidence of the intervention of acid
properties in catalytic oxidation. These findings suggest a new area
for investigation, viz., the effect of the acidity of the catalysts
on their activity and selectivity in oxidation reactions. Therefore,
the catalysts which we are preparing for part of the joint
collaboration dealing with catalytic oxidation reactions will be
evaluated as acid (or base) catalysts. Soviet contributions to the
catalysts banks will be examined in a similar fashion.
'Three problem areas have been mentioned above: (1) the understanding
of the finer details of carbonium ion reactions and the origin of
;selectivity in these reactions; (2) systematizing and classifying the
-characteristics of the non-conforming reactions with a view to
establishing their mechanisms; and (3) characterizing the surfaces of
the catalyst made for oxidation research in terms of their acidic or
basic character. This is about all that can be accomplished during
the first year and perhaps that is optimistic. There are, however,
two other large and important problems which should be undertaken in
the near future. These are: (1) the determination of the surface
density and distribution of-catalytically active centers and (2) the
characterization of these sites (kind and strength), perhaps by
spectroscopic means. I would envision that these would be done in
? collaboration with Professor K. V. Topchieva and Professor G. K.
']Boreskov.
Catalysts prepared for this work will be entered into the catalysts
banks. Attempts-will be made to devise model catalyst systems such
,as alumina or germania built onto the surface of silica at below
monolayer coverage. Some pure oxides will also be examined and ah
attempt will be made to prepare these in such a way that they will
have a respectable surface areas. These will include MgO, CaO, SrO,
TiO2, ZnO, A1203.' I would also like to include some selected zeolites.
Perhaps Professor Minachev can furnish some of these.
The next stage in our collaboration must involve an exchange of
personnel. Time is-becoming critical in this connection. It is my
.understanding that; because of the vacation schedule in the Soviet
Union, it is desirable that our people arrive there not later than
February I.' Ordinarily this is not a problem in the US, 'but during
the summer of 1974, Professor Keulks and I will be moving our
laboratories to a new building. This will undoubtedly disrupt work
for a week or two, so that we also would like to have the Soviet
junior scientists at an early date. My personal situation is still
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more complicated in that I moved here only a month ago and it will
take several-more months to get the necessary equipment set up for my
project. On the other hand, we have problems which you don't. As I
understand it from the USSR the junior scientists will be coming from
your several Institutes. Presumably, these people have fairly stable,
permanent employment. In the US, both post-doctoral students and
-graduate students have termination dates which occur at times known
some months in advance. Our problem then is to arrange for them to
visit the Soviet Union at times which coincide with their termination
dates. If this cannot be done, the individual moves on to another
.position and usually becomes lost from the program forever. Another
problem is that mast of our candidates have several alternatives-
including industrial employment, which at-times can be tempting
because of the high salaries which are paid. In a word, for each
particular junior scientist, we have only a narrow window in time in
which we can get him to commit himself to accept an appointment. in
the Soviet Union before he accepts another option. I tell you these
things so that you can better appreciate our situation. Presently
our.hands remain tied until we learn what the salary will be for our
junior scientists in the Soviet Union. You will recall that we
discussed this matter in your office and that Professor Boreskov
said that'the approval of a committee will be necessary on our
proposal to pay them the equivalent of $750 per month in Rubles. As
soon as this information is available, please let us know so that we
can make definite offers to our people. Otherwise, some of our best
prospects may escape us.
As I see it,- there is one other major problem. This is the appropriate
matching of junior scientists with positions. The development of the
program in the US was based on premise that the USSR would send a
-junior scientist to work with each of the principal investigators and
that we would reciprocate by sending an equal number to the
corresponding principal investigators in your country, i.e., an
exchange of people to fill positions. In point of fact, I see
pressures developing on both sides to create positions that fit the
needs of the people who are available. This creates a dilema which
must be resolved in the near future. I mention it at this time so
that you can give it some consideration before you visit the US later
this fall and so that we can' discuss it at that time.
Finally, I have from Professor Weinberg, a copy of a letter from
Professor Yu. Yermakov in which he states."money will be paid by
Professor Turkevich'from the fund of the USA government in accord with
the program of scientific collaboration between our countries" ;(for
the support of a junior Soviet scientist in the laboratory of
Professor Weinberg). This is a misunderstanding. Professor Turkevich
could not and did not commit funds earmarked for research in his
laboratory for this purpose. He promised only to look for a suitable
position in a laboratory where ultra-high vacuum research is being
carried out; the financial support could necessarily. come from either
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Professor .Oz V. Krylov
October 4, 1973
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the USSR or other sources in this country. In addition-,'however, I--
stated that I would take stops to add another principal investigator
to our side of the program at the earliest possible moment. And, as
I ,noted above, this is being done.
With, kindest personal regards, I am
Sincerely yours,
W. Keith Hall --
Distinguished Professor of Chemistry
WKH:nd
Enclosures
cc:. Prof. Boreskov
Prof. Minachev
Prof. Kazansky
Prof. Keulks
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