February 13, 2012

VOLUME 39, NUMBER 1
FEBRUARY 2012
The Alembic
February 2012 CWS ACS Meeting
“ Depleted Uranium ”
Speaker: Dr. Jeff Bryan, Professor of Chemistry &
Nuclear Medicine Technology Advisor
University of Wisconsin - LaCrosse, WI
Where:
When:
Alexander House
1131 Wisconsin River Dr.
Port Edwards, WI 54469
7:30 PM Monday, February 13, 2012
Pre-meeting social (5:30 pm) and dinner (6:00 pm) will be held at Café
Mulino in the Hotel Mead, 451 E. Grand Ave, Wisconsin Rapids. Please
contact Dave Thiel at (715) 887-4338 or thiel@wctc.net by Noon on February 13th to make reservations.
See page 2 for directions from the Café Mulino in the Hotel Mead in
Wisconsin Rapids to the Alexander House in Port Edwards
See page 3 for Dr. Bryan’s abstract and biography
The Chair’s Corner – 2012 Looks Pretty Good
Here we are in the second month of 2012 and it is a new year of activities for the
Central Wisconsin section. As shown above, at February‘s meeting we‘ll hear
about depleted uranium. This will be the first of three ACS tour speakers we have
arranged in cooperation with neighboring ACS sections. We‘ll share Dr. Bryan‘s
tour with the North East WI section and the Milwaukee section, while our other
two ACS tour speakers will go up to the Upper Peninsula section in Michigan as
well. In March, we have a guided tour of LignoTech‘s facility in Rothschild, while
on April 18th, OxyChem‘s Dr. William Carroll (2005 ACS President and recently
named chairman of the ACS Board of Directors), will come to Stevens Point to
give his ACS tour presentation about ―Garbage to Stuff.‖ Dovetailing with this
talk, Robin Tanke, professor at UW-SP and immediate past section chair, is partnering with WIST, the UW-Stevens Point Sustainability Coordinator and the Environmental Educators and Naturalists Association (EECA) to come up with a program to promote a better understanding of recycling by students and the public at
large. This event is to be part of the EECA sponsored ECO fair in Stevens Point on
April 18th. The section will finish out the ―spring session‖ in Eau Claire with our
Annual Awards banquet honoring outstanding educators and students. Again, we
Continued on page 2
2012 ACS - CWS
Mini-Directory
Chair
Dale Pillsbury
796N Pripps Road
Park Falls, WI 54552
Phone: (715) 583-4426
E-mail: hollyanddale@aol.com
Chair-Elect
Lori Lepak
Department of Chemistry
Univ. Wisc. - Stevens Point
Stevens Point, WI 54481
Phone: (315) 224-1190
E-mail: Lori.Lepak@uwsp.edu
Immediate Past Chair
Robin Tanke
Department of Chemistry
Univ. Wisc. - Stevens Point
Stevens Point, WI 54481
Phone: (715) 346-4325
E-mail: rtanke@uwsp.edu
Secretary - Treasurer
Tipton Randall
Phone: (715) 720-1969
E-mail: trandall@clearwire.net
Councilor
C. Marvin Lang
Phone (715) 346-3609
Email: cmlang@uwsp.edu
Alternate Councilor
James Brummer
Phone: (715) 346-2888
E-mail: jbrummer@uwsp.edu
Newsletter Editor
Dale Pillsbury
Address & contact: see Chair
Looking for a website to spice up
your lecture .....or entertain your
precocious, science-loving child or
grandchild? Try this British based
“Molecule of the Month” site
http://www.chm.bris.ac.uk/motm/
motm.htm
Pass it on to high school
chemistry teachers too
The Alembic
Volume 39, number 1
February 2012
The Chair ’s Corner ( f rom page 1 )
can thank Amanda Hakemian from UW Woods County/Marshfield for finding the time to take up the coordinator‘s role
for the Chemistry Olympiad, which makes the selection of an outstanding undergraduate student possible.
After a summer recess, we will start the ―fall session‖ with a gala 40-year anniversary celebration of the chartering of the
Central Wisconsin section. Marv Lang has promised to make it a memorable event. In October, we will host Dr. David
Wiemer, our final 2012 ACS tour speaker from the University of Iowa, who will give a talk on Natural Insecticides. Our
last meeting of 2012 will be in November and the topic is still open, so if anyone has an issue they think will be of particular interest or benefit the section, we will see if we can come up with an appropriate local speaker.
Since I am wearing two hats this year, i.e., Chair and Alembic editor, it seems artificial to have a separate Editor‗s Desk
piece, so let me draw your attention to this month‘s Alembic highlights: ―Meet Lori Lepak‖ is directly below, followed
by a ―Men and Molecules‖ vignette and directions to the February meeting restaurant and talk locations. An abstract and
speaker biography for Dr. Bryan is provided on page 3, while a feature piece honoring African-American chemists who
worked on the Manhattan Project rounds out this issue. I hope you have had a good start to your new year and look forward to meeting more of you at our meetings.
Dale
Meet Lori Lepak — Chair-Elect CWS 2012
Lori Lepak was elected to the Chair-Elect position in November of 2011. Lori was born and raised in
the Finger Lakes town of Auburn, NY southeast of Syracuse. She is a research associate at UW Stevens Point working with Dr. Mike Zach on nano-wire research. Lori graduated from Harvard College
with an AB in Chemistry and received her PhD from Cornell University where she worked on Collagen Thin-Film Devices for Nano Filtration. Since moving to Central Wisconsin she had has some difficulty in finding opportunities to pursue her main hobby, swing dance – postdocing can be like that.
Men and Molecules
Patsy Sherman (1930-2008) was born MinneapoSCOTCHGARD
lis, MN in 1930. She graduated with a bachelors in Block copolymers AAA-BBBB-AAAA-BBBB– etc
chemistry and mathematics in 1952 and joined 3M Graft copolymers AAAAAAAAAAAAAAAA-etc
where she remained throughout her career. In
Bn
Bn
Bn
1953, she was working on an improved synthetic
rubber for jet fuel hoses based on block and graft copolymers involving monomers containing ether
linkages and perfluorooctylsulfonyl groups. A sample of the latex* was dropped, covering a techniPatsy Sherman & Sam Smith cian‘s canvas shoe. The copolymer was not only virtually impossible to remove with conventional
solvents, it also resisted soiling. Patsy was serendipitous enough to realize this extraordinary (and some claimed thermodynamically impossible) material might have commercial applications. Together with her older colleague, Sam Smith,
Patsy pursued development of what became known as Scotchgard, which they initially sought to apply to carpet and upholstery fabrics. In the final development stages, Patsy had to wait outside of the factory mill during the testing of
Scotchgard, as women were not allowed within any production area at that time. Sherman and Smith were granted US
patent 3,574,791 covering the basic formulation of Scotchgard in 1971, 15 years after it had been in commercial production! Scotchgard was an immediate hit with the public and 3M‘s sales of the spectrum of Scotchgard products eventually
increased to $300 million/year. Patsy Sherman rose to become Manager of Technical Development in 1982 and retired
* A latex is a stable aqueous emulsion of a polymer or copolymer.
continued on page 3
Directions for February 13, 2012 Meeting Meal & Talk
Café Mulino is in the Hotel Mead located three blocks east of the Wisconsin River at 451 East Grand Avenue, in Wisconsin Rapids. A social gathering starts at 5:30 PM with supper at 6:00 PM. The Alexander House is reached by going
west on Grand Avenue from the Hotel Mead to the first stop light at 3rd Street. Turn left (south) onto 3rd Street and proceed about 0.7 miles to the Riverview Expressway (Hwy 54/13). Turn right, cross the river, and turn left at the end of the
bridge onto Highway 54/73. Proceed 2.7 miles to the Alexander House on your right (1131 Wisconsin River Drive). The
Alexander House is a combination art gallery and historical museum and will open for us at 7:00 PM. The Mapquest
URL for the trip between Hotel Mead and The Alexander House is given below. Just copy and paste it into your Internet
Browser as given without any spaces: http://mapq.st/zEL9eb
Page 2
The Alembic
Volume 39, number 1
February 2012
“ D epleted Uranium ”
Speaker: Dr. Jeff Bryan, Professor of Chemistry
& Nuclear Medicine Technology Advisor
University of Wisconsin — LaCrosse
Where: Alexander House
1131 Wisconsin River Dr.
Port Edwards, WI 54469
When: 7:30 PM Monday, February 13, 2012
ABSTRACT: Depleted uranium has been implicated as a possible cause to a variety of ailments for veterans of the Gulf
Wars. This presentation will explain what it is and why Gulf War vets were exposed to it. The talk will explore the nuclear and material science of depleted uranium as well as its main military application.
BIOGRAPHY: Jeff C. Bryan was born in Minnesota and raised in California, and believes that
his odd childhood mixture of Jell-O salad and reticence in a free and open society have caused his
various personality quirks. He earned an A.B. in chemistry from the University of California,
Berkeley with emphasis on organic chemistry and Scandinavian studies. He earned his Ph.D.
from the University of Washington studying inorganic chemistry under the supervision of Jim
Mayer. His thesis presented a new chemical reaction, the oxidative addition of multiple bonds to
low-valent tungsten. He then spent a year of postdoctoral work with Warren Roper at Auckland
University investigating iridium-carbon multiple bonds.
He spent five years at Los Alamos National Laboratory, initially as a postdoctoral fellow, then as
a staff member. Under the supervision of Al Sattleberger, he initiated a modestly successful research program synthesizing new compounds of technetium. He then spent eight years at Oak
Ridge National Laboratory as a crystallographer in Bruce Moyer‘s chemical separations group. The major group project
during that time was development of a process to separate 137Cs ions from defense wastes.
He has spent the past eight years as a chemistry faculty member at the University of Wisconsin–La Crosse. There his
scholarship has focused on making nuclear chemistry and radiation physics more accessible to students with limited science and math backgrounds. As part of this effort, he has authored a textbook titled ―Introduction to Nuclear Science‖,
and coauthored a lab manual titled ―Experiments in Nuclear Science‖.
Pre-meeting social hour (5:30 pm) and dinner (6:00 pm) at Café Mulino in the Hotel Mead, 451 E. Grand Ave,
Wisconsin Rapids. Contact Dave Thiel at (715) 887-4338 or thiel@wctc.net by Noon on February 13th
to make reservations.
Scotchgard, continued from page 2
from 3M in 1992 after an illustrious 40-year career.
However, in May 2000, 3M withdrew Scotchgard from the market due to a rising body of evidence that its use resulted in
the bioaccumulation of perfluorooctyl sulfonyl (PFOS) residues, possibly causing birth defects, liver damage and maybe
even cancer. Reformulation of the product was carried out using perfluorobutyl sulfonyl moieties, since these have shorter
half lives within humans. Since the Teflon process uses perfluoro-octanoic acid, and this too bioaccumulates, the biochemistry of both PFOS and perfluoro-alkyl acids (PFAAs) have been a topic of considerable interest. Mammalian research has
been extensive, but complex; female rats retain perfluoro-alkyl residues for hours, while male rats retain residues for days
and humans require nearly 4 years to eliminate PFOS residues. Likewise, it is not completely clear what the PFAA residues
do in the human body or how they are metabolized. Clearly, the story of this highly successful commercial product, discovered by accident, is not complete.
Dale
Page 3
Volume 39, number 1
The Alembic
2012
A Magnificent Seven + One..... and Others
During World War II, Americans began to see, perhaps for the first time, that one segment of the population, i.e., African-Americans, were greatly under-utilized and under-appreciated in America‘s armed conflicts. For example, for the
first time, black Americans were shown to be highly qualified pilots as typified by the Tuskegee Airmen and were potent ground fighters as typified by the 761st Tank Battalion soldiers who helped spearhead relief of the besieged 101st
Airborne troops during the Battle of the Bulge in 1944. But there was another side to the WWII war effort made by
African-Americans, specifically the black American chemists who worked on the Manhattan Project – the massive
effort to create the first atomic bomb. To mark February as Black History Month, let me take you for a trip through
time to the war years of the 1940s to piece together, as best as I can, what these black chemists ―did during the war‖
and what became of them in their later lives. In the process we will also (re?)-acquaint ourselves with the intricate and
arduous nuclear chemistry (and physics) involved in going from uranium oxide as obtained from pitchblende ore to
elemental U-235 and Pu-239. Both of these materials were pursued during the Manhattan project, as it was not at all
clear if either one could be obtained in sufficient amount and purity to build a nuclear bomb which would work. As it
turned out, the Hiroshima bomb, Little Boy, was U-235 based, while the Nagasaki bomb, Fat Man, employed Pu-239.
The laboratory work specifically for the Manhattan Project was formally started in August 1942 at Columbia University in New York City, in the name-sake borough of Manhattan. In researching the Internet and derivative sources for
this story, I quickly came across articles which noted the names of several black chemists who were involved in the
Manhattan Project and who either worked at Columbia or at the Metallurgical Lab (later Argonne Lab) run by the University of Chicago. I was able to find some information about 7 of these chemists: Lloyd Albert Quarterman, William
Jacob Knox, George Warren Reid Jr, Edward A. Russell, Ralph Alexander Gardner-Chavis, Moddie Taylor and Harold
Delaney. Later in my searches I found information about Samuel Massie, Jr., who was at Iowa State University. I also
found nominal references to several other black chemists who will be mentioned at the end of this piece.
The Chemistry and Physics of U-235 Enrichment
Natural uranium contains 99.3% U-238 and 0.7% U-235. While both
isotopes can undergo fission by neutron capture (i.e., are fissionable),
only U-235 produces more neutrons than it captures during neutroninduced fission and is thus capable of sustaining a chain reaction ( i.e.,
U-235 is not only fissionable, it is also fissible).
Since U-235 and U-238 are isotopes, they are chemically identical, so
four physical methods had to be employed to separate the isotopes:
thermal diffusion, followed by gaseous effusion, then two stages of
electromagnetic separation. Cascaded high-speed gaseous centrifuges (cf Iran‘s current nuclear program) were not
available during WWII and that approach was quickly abandoned by the Manhattan Project, although it is generally
used for isotope enrichment today.
Before any of these techniques could be employed, however, the uranium (received as purified UO3 or UO2) was converted to UF6: 1. UO3 + H2 → UO2 + H2O 2. UO2 + HF → UF4 + H2O 3. UF4 + F2 → UF6
Uranium hexafluoride is a highly corrosive solid. It readily sublimes at 56.5º C1 atm and has
a 64º C22psia triple point.
Thermal diffusion was the first step of the isotope enrichment procedure. Liquid UF6 was
pumped into a relatively narrow, 48-foot-long pipe which had an internal 400 ºF (204º C)
steam heater. Water circulated in an outer jacket (removed for clarity in diagram to the right)
Convection currents created by the high-temperature inner wall and the relatively-cool
(~130º F, 54º C) exterior wall resulted in the lighter 235UF6 diffusing to the top of the pipe
while the heavier 238UF6 migrated to the bottom of the tube. The S-50 plant at Oak Ridge,
built in an astounding 69 days, had 2,100 such columns, which increased the U-235 content
of the UF6 from ~0.7% to 0.9%.
Gaseous Effusion is a process that occurs whenever a gas is separated from a vacuum by a porous barrier containing
microscopic holes (in this case ~1/4 nm). The gas flows from the high-pressure side to the low-pressure side: it passes
through the holes because there are more "collisions" with holes on the high-pressure side than on the low-pressure
side. Thomas Graham, a Scottish chemist, observed that the rate of effusion of a gas through a porous barrier was in-
Page 4
Volume 39, number 1
The Alembic
2012
versely proportional to the square root of its mass. Thus lighter molecules
235
238
pass through the barrier faster than heavier ones. For UF6 /
UF6
1/2
this becomes [ (235+6*19) /(238+6*19)] or 1.0043. It is little wonder
that the Oak Ridge, TN gaseous effusion plant L-25 required 4,000
235
stages. It was 1/2 mile long and 6 stories high! The U content was
raised to ~7% after the gaseous effusion process.
Electromagnetic Separation was developed by E. O. Lawrence at Berkley, and involved the same technology as mass spectrometers, but
was upsized for material preparation. The Oak Ridge, TN plant
238
Limits of Ion Paths
UCl4+
used two sets of the devices, called California University Cyclotrons, or calutrons. The alpha group raised the U-235 content from
Collector
Ionizer
7% to 15%, while the beta group raised it to bomb grade (i.e., 80- Vacuum
Accelerating
90%). The calutrons did not use UF6, as it was too corrosive for
System
the ionizers. This was unfortunate, since for UF6 there would have
UCl4 235UCl4+
235
235
been only two ions to separate, 349 for
UF6 and 352 for UF6
19
Heater
because F is the only natural fluorine isotope. However, natural
35
37
235
238
Cl is ~75% Cl and ~25% Cl, making the UCl4 / UCl4
Magnetic Field Applied Over Ion Path
separations somewhat more difficult. The UF6 was converted to
UCl4 via UO2: UF6 + H2 → UF4 + 2HF, then UF4 + 2H2O(g) → UO2 + 4HF. This was followed by a chlorination
reaction: UO2 + CCl4 → UCl4 + CO2. Other, more complex, wet chemistry paths were also examined to get from UF6
to UO2. After WWII fluidized bed technology combined the hydrogenation and hydrolysis steps shown above.
African-American Chemists Known to Have Worked on U-235 Recovery
Lloyd Quarterman was born in Philadelphia in 1922. In 1943 he earned a BS in Chemistry from St. Augustine‘s College
in Raleigh, North Carolina and joined the Manhattan Project work at Argonne. He designed and operated an electrolysis
tower to generate and purify F2 by electrolysis of molten KHF2. He may have used some of the highly purified graphite
(available from Enrico Fermi‘s uranium reactor work) for his electrodes. Quarterman probably used tubes of anhydrous
NaF to purify his fluorine since this is common practice in the industry today. The purified fluorine was used to prepare
the UF6 employed in the U-235 / U-238 separation.
DuPont was commissioned to build and operate a commercial scale UF 6 plant and agreed to provide the US Government
with 100% of its newly commercialized Teflon polymer which was used in all flexible joints, seals and gaskets in contact
with F2 or UF6. All metals parts in direct contact with F2 or UF6 had to be either made of copper or be nickel plated since
these metals are passivated against further corrosion by the rapid initial formation of surface films of metallic fluoride.
After the war, Quarterman continued to work at Argonne, obtaining a Masters degree from Northwestern University in
1952. He did pioneering work in the area of fluorine chemistry, including the preparation of several inert gas fluorine
compounds, i.e., XeF2, XeF4 and XeF6. He also obtained Raman, ultraviolet and x-ray spectrograms of compounds dissolved in liquid HF, employing a cell he built using special diamond windows. Quarterman died in Chicago in 1982.
William Knox, Jr. was born in New Bedford, MA, in 1904. He earned his undergraduate degree from Harvard,
and a PhD from MIT in 1935. He was a professor at North Carolina AT&T College from 1935-1942. He spent a year as
chair of the Chemistry Department of Talladega College in Alabama, then joined the Manhattan Project at Columbia
University working on the gaseous effusion project. He became the only black supervisor on the project.
After the war, he transferred his experience with highly corrosive materials to work with Eastman Kodak, joining that
firm in 1945. He earned 21 patents with Kodak, retiring in 1960. He then returned to North Carolina AT&T, retiring
from there in 1973. He died in 1995 in Newton, MA at age 91.
George Reed, Jr. was born in Washington, DC in 1920. He obtained a BS (1942) and an MS (1944) in chemistry from
Howard University in that city. He joined Argonne in the U-235 enrichment program, but few details are available, even
at this late date. However, after WWII his work involved studies of the patterns of radiation produced from processing Pu
-239 and U-235 and he may have worked in this area during the war as well. He obtained a PhD at the University of Chicago in 1952 and was promoted to Senior Scientist in 1968. He worked with the Meteoritical Society from 1970—1972.
Reed was part of the team that analyzed moon rocks and was appointed to the lunar sample planning team at NASA from
1972-1980..
Page 5
The Alembic
Volume 39, number 1
Production and Isolation of Plutonium –239
2012
238
1
239
U92 + γ
In December of 1942, Enrico Fermi demonstrated U-238 could be converted 239
239
0
U92 (t ½ = 23.5 mins) → Np93 + -1e
to plutonium by neutron capture during the controlled fission of U-235 in
natural uranium containing both U-238 and U-235. (see right). When U-235 239Np93 (t ½ = 56 hrs) → 239Pu94 + -1e0
undergoes fission by neutron capture, it simultaneously produces, on average, 2.5 neutrons, making it possible to sustain a chain reaction. The requisite neutrons to initiate the chain reaction come
from spontaneous natural fission of both uranium isotopes. These are low probability events, but they do occur due to
quantum mechanical tunneling. Fermi employed highly purified graphite to moderate the normally fast neutrons to give
slow, or thermal neutrons, increasing the likelihood they would be captured by both U-235 and U-238 atoms. The chain
reaction was controlled by cadmium-coated control rods placed in the pile between rods made of a mixture of natural
isotopic-ratio uranium metal and uranium oxide lumps. Cadmium is a highly efficient neutron absorber and, as these rods
were removed from the pile, enough neutrons were allowed to be captured by U-235 nuclei to result in a self-sustaining
chain reaction and the gradual formation of Pu-239 from U-238. However, the Pu-239 (like U-235) is fissible, so the
concentration of plutonium went through a maximum. In general, the amount of plutonium present in the ―spent‖ uranium fuel rods from Oak Ridge, TN was <250 ppm,. Recovery of this involved extensive chemical manipulation once
the aluminum casing for the fuel rods had been removed by boiling in aqueous sodium hydroxide in the presence of
NaNO3 to reduce H2 formation. The bismuth phosphate process, which Stan Thompson and Glen Seaborg initially developed, involved first solution of the plutonium, then precipitation of plutonium (IV) as the phosphate. This was occluded
with a co-precipitated bismuth phosphate. Before ion exchange chromatography was available, using such precipitate
―carriers‖ was a mainstay of early transuranium compound isolation, since the amounts of these materials was very tiny.
1. Pu (s) + FP*
HNO3
2. Pu+4(aq) + FP+Y(aq)
Pu+4 (aq) + FP+Y(aq)
Bi(NO3)2
U92 + n0 →
U(s) + 4HNO3 → UO2(NO3)2(aq) + 2H2O + 2NO
Pu3(PO4)4(s) + BiPO4(s) + ~90%FP as phosphates(s) +
~10% FP+Y(aq)
H3PO4
3. Pu3(PO4)4(s) + BiPO4(s) + ~10% FP+Y(aq)
4. Pu+6(aq) + Bi+3(aq) + FP+Y(aq)
H3PO4
HNO3, then
NaBiO3
Pu+6(aq) + Bi+3(aq) + FP+Y(aq)
U+6 soluble
( H2SO4 aids )
Add some Na2Cr2O7 to
keep Pu +6 in step 4
BiPO4(s) + some FP as phosphates + Pu+6(aq) + FP+Y(aq)
+4
+6
5. Pu+6(aq) + FP+Y(aq) + (NH4)2Fe(SO4)2
Pu+4(aq) + FP+Y(aq) Repeat 2-4 & using NaBiO3 for Pu → Pu
6. Pu+6(aq) + KMnO4 + FP+Y(aq) La(III) salts LaF3(s) + FP fluorides(s) + Pu+6(aq) FP solids includes Ce, Sr etc
KMnO4 keeps Pu +6
then HF
oxalic
La(III)
salts
7. Pu+6(aq)
Pu+4(aq) 8. Pu+4 (aq)
LaF3(s) + PuF4(s)
PuF4 occluded in LaF3 ppt
then HF
acid
9. LaF3(s) + PuF4(s) + KOH(aq) → PuO2(s) + La2O3(s)
11. Pu+4 + La+3(aq)
H2O2
13. Pu+4 + trace La+3(aq)
HNO3
La & Pu fluorides are insoluble in HNO3,
but
oxides are soluble. Fluoride removed as
La (aq) + Pu (aq)
KF(aq) in aqueous KOH treatment
+3
+4
Pu2O7(s) + La+3(aq) 12. Pu2O7 + trace La+3+ HNO3
H2O2
Pu2O7(s) + trace La+3(aq)
Pu+4 + trace La+3(aq)
H2O2 ppt‘n repeated to remove as much La+3 as possible
H2O2 doesn‘t precipitate La +3 or other lanthanides, which often have high neutron absorption cross sections and which can
suppress a Pu-239 chain reaction leading to a fizzle, i.e., a low yield plutonium bomb detonation.
* FP = miscellaneous byproducts from the fission of 235U and 239Pu
FP+Y= ionic species formed from the FPs
Due to poor long-term stability, plutonium peroxide (Pu2O7) had to be calcined (500º C) to give PuO2 or re-dissolved in
HNO3 to give Pu(NO3)4. Typically Pu(NO3)4 was shipped as a damp paste by the Hanford, WA plutonium nuclear reactor
and plutonium recovery plant to the Los Alamos facility for final processing to plutonium metal and bomb construction.
At Los Alamos, the nitrate paste was reduced with hydroxylamine nitrate and a bit of sulfamic acid to Pu(III) and was
precipitated as Pu(III) oxalate with oxalic acid, since Pu(IV) oxalate gave poorer precipitates. The Pu(III) oxalate was
calcined to PuO2 and treated with HF to give PuF4. This was reduced by the Ames Process at high temperature to plutonium metal with calcium usually in the presence of iodine.
Page 6
Volume 39, number 1
The Alembic
February 2012
African-American Chemists Who Probably Worked on Pu-239 Recovery
Based on oblique references and the type of work these chemists pursued after WWII ended, it is believed they worked
on the plutonium recovery part of the Mannhattan project. This may well have included scale-up work since Thompson
and Seaborg‘s initial work was done using very small samples of plutonium.
Edwin Russell was born in Columbia, SC in 1913. He obtained an MS in chemistry from Howard University in Washington, DC) in 1937 and was an assistant and Instructor at Howard from 1936 to 1942. While he went to the University
of Chicago for a PhD in surface chemistry in 1942, he became involved in the Argonne lab until 1947, never completing
his doctorate. At Argonne he worked on the separation of the plutonium produced in Fermi‘s nuclear reactor and rose to
a position of section leader. In 1947 he moved to Allen University in Columbia, SC first as a chemistry professor and
then rose to chairman of the Division of Science. In 1953 he took a position at DuPont‘s Savannah River Laboratory in
Aiken, SC which involved bio-assay, radioactive tracer work, ion exchange chromatography and radioactive waste treatment which may give an idea of some of his work at Argonne. He died in 1996 with 11 patents to his name.
Ralph Gardner-Chavis was born in Cleveland, OH in 1922. Gardner-Chavis graduated with a BS in Chemistry from the
University of Illinois, Champaign-Urbana in 1943 and then joined the Manhattan Project at Argonne. He worked under
Enrico Fermi and Nathan Sugarman, whose duties included measuring the efficiency of the first atom bomb at Alamogordo, NM. After WWII, Gardner-Chavis worked at Argonne until 1947 in the Health Physics group, where people
working with radioisotopes were monitored. Gardner-Chavis joined Sohio, in Cleveland in 1949 and did pioneering work
using the newly available infrared spectroscopy to study catalysis, simultaneously earning a PhD from Case. He became
a Group Leader, but was assigned only one woman chemist. When Sohio refused to pay his way to a Catalysis Conference in Moscow in 1968 to present an invited paper on his work, and then paid for a less-qualified white employee to be
sent to the conference, Gardner-Chavis left Sohio and joined Cleveland State University as an associate professor. He
continued his catalysis research in that position, while enjoying teaching, until he retired in 1985 with emeritus status.
Moddie Taylor was born in Nymph, AL in 1912. He earned a BS and an MS from Lincoln University in Jefferson City,
MO in 1935 and 1938, respectively. He graduated from the University of Chicago with a PhD in 1943, then joined the
Argonne group. His area of interest was rare earth chemistry, which fit in well with the plutonium recovery project. In
1948 he joined Howard University in Washington, DC as an associate professor, becoming a full professor in 1959 and
head of the chemistry department from 1969 to 1976. He continued to pursue lanthanide chemistry research and had
many publications. In 1960, Taylor was selected as one of the six top chemistry teachers in the US by the Manufacturing
Chemists Association (later CMA). He retired as a professor emeritus in 1976 and died later that year.
Harold Delaney was born in Philadelphia in 1919. He earned a BS (1941) and an MA (1943) from Howard University in
Washington, DC. He joined Argonne in 1943, but no reference can be found to his area of work. After leaving Argonne
he worked as an assistant professor at North Carolina AT&T in Greensboro, NC from 1945-1948. He was a faculty
member at Morgan State University in Baltimore from 1948-1969 and earned a PhD from Howard in 1958. He also
worked for DuPont from 1966-1969. In 1974 he became the first male president of Manhattanville College, then solely a
woman‘s college, located in Purchase NY. He retired as vice president of the American Association of State Colleges
and Universities in Washington, DC in 1987. An outstanding administrator, Delaney died in Pilot Mountain, NC in 1994.
Samuel Massie, Jr. was born in North Little Rock, AR in 1919. He received a BS in chemistry from Arkansas Agricultural, Mechanical and Normal College (now U of Arkansas, Pine Bluff) in 1937 and an MS from Fisk College in Nashville, TN in 1940. He then enrolled in Iowa State University in the PhD program under Henry Gilman, but then became
part of the Manhattan Project under Dr. Frank Spedding. The Ames Process was heat and beat chemistry at its finest:
UF4 was sealed in a heavy metal ―bomb‖ with magnesium or calcium metal. It was heated to temperatures in the 1500º C
range to produce a metallic uranium slug and alkali metal fluoride slag. Similar processing was employed for reducing
PuF4 to plutonium metal, iodine often being added. By October 1942, 100 lbs/week was being produced. After the war,
Massie earned his PhD at Iowa State in 1946. He taught at what had become Fisk University (1947-1948), moved on to
Langston University in Tulsa, OK (1948-1953) before returning to Fisk (1953-1960). In 1969 the NSF named him associate director of special projects in science education. He then moved to Howard University as a professor of pharmaceutical chemistry. In 1966 he was the first African-American to be appointed to the faculty at the Naval Academy in Annapolis. He was named chair of the chemistry department and held that position until his retirement in 1993. In 1998 he
was selected by C&E News as one of the greatest chemists of all time. He died in Laurel, Maryland in 2005 .
Other African-Americans who were known to have worked as chemists on the Manhattan Project include: Clyde Dillard
(later professor and Dean of students at Brooklyn College, CUNY), Benjamin Scott, George Turner, Cecil White, Sydney Thompson and possibly Sherman Carter and Harold Evans (chemists/physicists/mathematicians?). Unfortunately, I
could find no details of these men‘s war-time contributions.
Dale
Page 7
The Alembic (February 2012)
Newsletter of the Central Wisconsin Section, ACS
c/o Chemistry Department (#605516)
University of Wisconsin – Stevens Point
Stevens Point, WI 54481
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Member Address Label
Central Wisconsin Section, ACS Meetings and Programs - 2012
Date (Day)
Location
Speaker/Event
Host
Feb 13, 2012
Wisconsin Rapids
Dr. Jeff Bryan
Dave Thiel
March 13, 2012
LignoTech, Rothschild
LignoTech Tour
Tony Young / Jerry Gargulak
April 18, 2012
Stevens Point
Willam Carroll OxyChem ( A CS )
Robin Tanke
May 2012
Eau Claire
Awards Banquet
Dave Lewis
Sept 2012
Stevens Point
40th Anniversary of Section
Marv Lang
Oct 2012
TBA
Dr. David Wiemer
TBA
Mark the above dates and locations on your calendar; plan now to attend and participate in
the Section’s various meetings and activities. Future issues of the Alembic will give exact locations and arrangements for these meetings. Of further interest are the following national
and regional events:
Spring National Meeting, San Diego, CA - March 25-29, 2012
Chemists Celebrate Earth Day ( CCED ) - April 22, 2012
ACS 43rd Central Regional Meeting, Dearborn, MI—June 5-8, 2012
Page 8