Embed Size (px)
Citation preview
Dale
The Alembic
Newsletter of the Central Wisconsin Section of the American Chemical Society
VOLUME 39, NUMBER 4 May 2012
The Chair’s Corner - Thanks & Congratulations I want to thank all of you who have contributed to our programs this “semester”, as
hosts, as speakers, as meeting attendees or behind-the-scenes workers coordinating
events such as running the Chemistry Olympiad, spearheading the section’s partici-
pation in the Earth Day celebration or organizing the awards banquet. We really are
indebted for your help. Thank you very much for a great job!
This month we will honor three outstanding academics and three men with 50 or 60
years of ACS service. You can learn more about these people in the pages that fol-
low and each deserves your congratulations. I finish out this Alembic with a piece
on commercial fireworks and I hope to see you on May 10th in Eau Claire.
May 2012 CWS ACS Meeting
“ 2 012 Awards Banquet ” Honoring :
● Bryan Weghorn Outstanding High School Chemistry Teacher
● Rahul Pathak Outstanding High School Chemistry Student
● Ashley Van Galen Outstanding College Chemistry Student
Also Honoring :
● 60-year ACS member Donald E. Janssen
● 50-year ACS members
Donald R. Anderson & Raymond A. Sommers
Where: Burgundy’s Restaurant in The Plaza Hotel & Suites
1202 W. Clairemont Avenue
Eau Claire, WI 54701
When: Thursday, May 10, 2012
Gathering & Social Time 5:30 PM
Dinner (banquet menu) 6:00 PM
Award Presentations 7:00 PM
See page 2 for map & pages 3-4 for the 2011 Awardees' pictures & biographies
2012 ACS - CWS
Mini-Directory
Chair
Dale Pillsbury
796N Pripps Road
Park Falls, WI 54552
Phone: (715) 583-4426
E-mail: [email protected]
Chair-Elect Lori Lepak
Department of Chemistry
Univ. Wisc. - Stevens Point
Stevens Point, WI 54481
Phone: (315) 224-1190
E-mail: [email protected]
Immediate Past Chair
Robin Tanke
Department of Chemistry
Univ. Wisc. - Stevens Point
Stevens Point, WI 54481
Phone: (715) 346-4325
E-mail: [email protected]
Secretary - Treasurer Tipton Randall
Phone: (715) 720-1969
E-mail: [email protected]
Councilor C. Marvin Lang
Phone (715) 346-3609
Email: [email protected]
Alternate Councilor James Brummer
Phone: (715) 346-2888
E-mail: [email protected]
Newsletter Editor Dale Pillsbury (see Chair)
Contact Dave Lewis for reservations at (715) 836-4744 or
e-mail: [email protected] by Noon on May 9, 2012
ACS Women Chemists Commit-tee (WCC) invites nominations for the WCC Rising Star Award
This award is intended to: ● Annually recognize ten exceptional early to mid-career female chemists on a national level ● Help promote retention of women in science & technology based careers
For more information Google: www.acs.org/
diversity & rising star award Deadline June 1, 2012
Volume 39, number 4 The Alembic 2012
HIGHLIGHTS FROM CELEBRATING EARTH DAY
Page 2
Directions to
Burgundy ’s Restaurant in the Plaza Hotel & Suites
Burgundy’s Restaurant is located in the Plaza Hotel at 1202 West Clairemont Ave (aka US 12) in Eau Claire. It is on the
frontage road just west of Craig Rd, while Sweetwater’s used to be on the frontage road just east of Craig Rd. The
Mapquest URL for the Plaza Hotel and Suites is: http://classic.mapquest.com/listings/
Plaza_Hotel_and_Suites_Eau_Claire_WI_7039333?placement=results_org_map
The Central Wisconsin Local ACS section joined with WIST (Wisconsin Institute for Sustainable Technology), the UW-
SP Sustainability Coordinator and UW-SP student volunteers to jointly celebrate Earth Day 2012 on April 18. The event
was coordinated with the annual UW-SP Eco Fair and had as a theme “Rethinking Recycling”. In the evening, the sec-
tion hosted Dr. William Carroll, who gave a talk about “Stuff from Garbage” which capped an excellent day of learning.
Above - Volunteer Dani Widner stands back while another UW-SP student
spins the “wheel of fortune” to try for a prize.
Above - UW-SP chemistry student Tim Rushmere discusses his work on reversible thermoset polymers with UW-SP chemistry professor
Steve Wright and postdoctoral fellow and section chair-elect Lori Lepak.
TIm is working with Dr. John Droske.
Right - Peter Rock (Rock Oil Refining Inc) explains the recycling of used
oil, oil filters & eth-ylene glycol anti-
freeze.
Right - Dr. William Carroll, an engaging speaker, explains a key concept during
his talk entitled “Stuff from Garbage”.
Photos by Ron Tschida, WIST Communications Manager & Robin Tanke
Left - UW-SP Angie Hauer (left-most) and Lizzy Lepinski (center), along with Kayla Skotzke help with
setting up a poster on recycling
Left - UW-SP chemistry professor, Robin Tanke and 2012 ACS Sec-
tion chair, Dale Pillsbury. Robin has served as the coordinator for both
Chemist’s Celebrate Earth Day and National Chemistry Week for sev-
eral years and was the driving force behind the Section’s participation in the UW-SP Earth Day celebration.
Above - Albert Webster, ACS Student President at UW-SP, helps a fellow student with a survey to test recycling savvy. Micelea Downey won the survey prize, a backpack made from recycled materials.
Mr. Rahul Pathak
Outstanding High School Chemistry Student of the Year
Senior, Marshfield High School, Marshfield WI
● Highest score Chemistry Olympiad (a 4 ½ hr, locally administered exam )
● Advanced Chemistry Education: Freshman (Chemistry Honors), Senior (AP Chemistry)
● 2012 Recipient of Vanderbilt Scholarship ($40,000/yr for 4 years)
“Cornelius Vanderbilt Scholars are selected on the basis of academic achievement,
intellectual promise and leadership and contribution outside the classroom.”
● Recipient of National Merit Finalist Scholarship ($2000/yr for 4 years)
● Perfect 36 on ACT
● AP National Scholar (11 AP tests with perfect 5 scores on each)
● Other Scientific Interests:
— National Ocean Sciences Bowl (National Champions 2011 & 2012)
— National Science Bowl (driving force behind 2 of Marshfield High School's two state titles)
— Porcupine Ecology Project
— Health Occupation Students of America - State Champion in HOSA Bowl & Kaiser Permanente Events
— Science Olympiad (First prize at state in Biotechnology)
● Extracurricular Interests
— Member varsity tennis team — Member swim team
— Volunteer at St. Joseph’s Hospital, American Cancer Society Hope Lodge and Marshfield Wildwood Park & Zoo
Page 3
Central Wisconsin Section of the
American Chemical Society
2012 Scholastic Award Recipients
Volume 39, number 4 The Alembic 2012
Mr. Bryan Weghorn
Outstanding High School Chemistry Teacher of the Year
Memorial High School, Eau Claire, WI
THE QUINTESSENTIAL DEDICATED CHEMISTRY TEACHER
“Every day after school, I can guarantee that Bryan will be in Memorial High
School’s Afterschool Study Lab.... with fifteen to thirty students huddled
around him as he explains the current assignments as well as helping others
catch up on assignments that were previously due.”
“[Mr. Weghorn] strives to be the best and get students excited about chemistry, [sic] he is also extremely de-
voted in helping his students understand and learn a subject that may not otherwise be very interesting to most
students.”
Kurt Madsen, Associate Principal, Memorial High School
Abigail Svee, Former student
Volume 39, number 4 The Alembic 2012
The Central Wisconsin Section of theAmerican Chemical Society
60 Years of ACS Membership
Donald E. Janssen
50 Years of ACS Membership
Donald R. Anderson & Raymond A. Sommers
HONOR ROLL
Page 4
● Research Projects
— Structural characterization of methanobactins, which are peptide-derived, copper-binding molecules produced by
methane-oxidizing bacteria (Spring 2011 to date)
* Helped to characterize a new methanobactin with an additional amino acid at its C-terminal (spring 2011)
* NSF-REU Project: Worked in close cooperation with summer development student to chemically modify two
different methanobactins to determine which structural features are required for Cu(II) binding and reduction
(summer 2011)
* Independently proposed using solid state peptide synthesis to chemically synthesize a methanobactin precursor
peptide in vitro (To date an 11-amino acid residue precursor has been synthesized, 2011/2012 school year)
— Presentations of Research
* UW-Eau Claire - 2nd Annual Provost’s Honors Symposium (May 4, 2012)
* National Conference on Undergraduate Research, Weber State University , Ogden, Utah ( March 29-31, 2012)
* UW-Eau Claire - University Research Day (May 2-4, 2011)
● Other interests include
— Center for Awareness of Sexual Assault volunteer
— University Band
— Navigators (Campus interdenominational, evangelical Christian ministry)
— Medical volunteer in Costa Rica and Panama (helped provide medical, dental and veterinary care, Summer 2011)
Ms. Ashley Van Galen
Outstanding College Chemistry Student of the Year
Junior, UW - Eau Claire ( Hometown, River Falls, WI)
● Strongly self-motivated individual
— Near 4.0 GPA, excellent oral & written communication skills and superior group
work skills
— Career goal is to be an MD in an underserved urban population To this end, this sum
mer Ashley will purse a summer internship to deliver AIDS and STD counseling ser-
vices to inner-city youth in Milwaukee Ashley in her Lab
Volume 39, number 4 The Alembic 2012
Page 5
DISPLAY FIREWORKS - ART IN THE NIGHTTIME SKY Because we don’t publish the Alembic during the summer months, I thought the last
issue of the spring semester would be the most appropriate time to examine the chang-
ing chemistry and technology of fireworks. Like most good cooks, people who spe-
cialize in producing fireworks for commercial displays have their own special recipes
and “tricks of the trade”. However, more and more, chemistry, physics and modern
technology are becoming part of the “art” of producing spectacular effects.
Since gunpowder is such an integral part of fireworks history and construction, it is
worth looking at how it was invented. In the first century Taoist alchemists in China
were searching for “the Elixir of Life”, a potion supposedly granting the drinker eter-
nal life and/or youth. They examined sulfur and saltpeter (potassium nitrate)* which had been used as medicinals and it
was quickly learned they would rapidly burn when combined and heated. By the 8th century, charcoal had been added to
the mixture and huŏ yào (fire medicine), or as we know it, gunpowder, was invented. Arab alchemists improved gun-
powder manufacture in the Middle Ages by increasing the purity of the saltpeter and increasing its proportion in the mix-
ture close to the modern standard mix: KNO3: C: S (75:15:10 wt%). Saltpeter is the oxidizer, charcoal is the primary fuel
and sulfur is a secondary and much more easily ignited fuel. Later, Europeans made processing improvements which are
still in place today. Ball milling was used to allow sulfur and saltpeter to thoroughly penetrate the pores in the charcoal, a
step referred to as incorporation. The powder was then mixed with a small amount of water and repeatedly compressed
between heavy rollers (milling). Finally, the milled product was compressed in hydraulic press to produce a cake of slate
-like consistency. The cake was broken up and sieved to give a variety of grain sizes. In America, Irenee du Pont, who
learned gunpowder processing from Lavoisier, tumbled the sieved grains to round the edges, preserving grain shape and
size during transport, thus maintaining uniform combustibility in use. Gunpowder made in this way burns much more
rapidly than the well-mixed, but uncompressed powder. Large grains burned markedly slower than smaller grains and
could be used even in large cannon without bursting the barrel. The material passing the finest sieve was referred to as
meal powder and it burned very rapidly. It was used in fireworks to make black match, which is cotton string which has
been dipped into a slurry of gunpowder mixed with dextrin and some water and then dried. It burns at a rate of about 1
inch/second. However, if the black match is contained in a moderately robust paper tube that is just a bit bigger than the
size than the black match, it will burn at about 60 feet a second. This quick match was and still
is used to communicate fire rapidly between one firework piece to another. It was especially
important for set-piece displays before the advent of electrical firing devices.
The early Chinese alchemists put gunpowder into paper tubes or pieces of bamboo and attached these to arrows to set
fire to an enemies fortifications. Later is was found that if the tube was partially throttled to a smaller diameter than the
bulk of the paper tube or piece of bamboo, the arrow did not require a bow to move and the rocket was invented. Throt-
tling the tube so there was only room for the fuse produced a firecracker. Firecrackers were used by the Chinese to keep
evil demons at bay and they are still are included at the start of Chinese New Year celebrations for the same reason.
Gunpowder was introduced throughout the world during the 13th and 14th centuries, first as an instrument of war and
later for display purposes to accompany religious plays and festivals. By the 16th and 17th
centuries no major court celebration could do with out an elaborate fireworks display.
The famous Royal Fireworks of 1749, commemorated the signing of a peace treaty be-
tween Austria and Prussia in which Britain had supported Austria and France and Spain
were allied with Prussia. The display was set up on the Thames river and nearby shore
with an elaborate set piece called “The Machine” shown in background of the hand-
colored engraving appearing on the next page. George Frideric Handel composed his
“Music for the Royal Fireworks” for this event. Set pieces for such displays were usu-
ally lances (open tubes packed with gunpowder spiked with iron or steel filings or larger
granules of charcoal to produced sparks. To produce more energetic flares, the tubes
Zambelli Inc Chrysanthemum Shells
* Where did the Tang Dynasty alchemist’s KNO3 come from? The ground beneath bat colonies in dry caves was found to contain
calcium nitrates. They were also found in manure pits where highly nitrogenous vegetable matter as well as animal and human waste
(specifically urine) could be converted to calcium nitrate by bacterial fermentation. Leaching the soil from a suitable cave or leaching
the material from bacterial fermentation gave aqueous solutions of crude calcium nitrate. This was filtered through a bed of wood
ashes (containing K2CO3) to give crude KNO3 + CaCO3↓ by metathesis. Concentration, crystalization and recrystallization achieved
purification. The first written record of this metathesis and purification process was given by the Syrian chemist and engineer, Hasan
al-Rammah, in 1270. Since the beginning of the 20th century, KNO3 has been produced from nitric acid made as follows: N2 + 3H2
→ 2NH3 , 4NH3 + 7O2 → 4NO2 + 6H2O (via NO) Finally, 3NO2 + H2O → 2HNO3 + NO (recycled to NH3 oxidation)
Quickmatch
Lances used in set pieces
wood or
clay plug clay plug
with a
hole in it
Volume 39, number 4 The Alembic 2012
could be partially throttled either by using a strong string to constrict a
damped cardboard tube or by using a clay plug with a hole in it. The
more spectacular “fountains of fire” on the barge in the foreground are
called mines or cakes. Both mines and cakes are similar to roman can-
dles in that propelling charges are used to carry bursting charging in the
air and the stars are expelled already burning. Mines are fired from
metal mortars. Cake mines have many mines combined in one piece and
are built with heavier cardboard cases obviating the need for mortars. As
can be seen in the barge in the front of the Royal Fireworks etching,
sometimes small bursting charges were included in 18th century mines
or cakes.
The most obvious change between fireworks from the 18th century and
those from the later half of the 19th century forward is the use of col-
ored fire. The introduction of potassium chlorate as an oxidizer by Ital-
ian fireworks manufactures allowed for the first time the production of
the strong vibrant colors*.
Although mixtures of chlorates with combustibles were quickly found to
be notoriously prone to violently explode when struck or rubbed together, e.g. in sieves, Italian fireworks manufacturers
discovered brilliant colors resulted when the correct combinations were chosen. In all cases they found non-hydroscopic
salts were needed: Red - strontium salts (SrNO3 & SrCO3), Yellow - sodium oxalate, Green - Ba(ClO3)2, and Blue - cop-
per acetoarsenite (aka the highly toxic, Paris Green) or basic copper carbonate [ CuCO3●Cu(OH)2 ]. In general, combina-
tions that generated high temperatures were preferred since MCl+ ions (e.g. SrCl+ & BaCl+) were found to be primarily
responsible for the actual emission lines. However, with CuCl+, the molecular ion was unstable at high temperatures and
lower temperature compositions were used to get the truest blue color, i.e., the blue with the least contamination by
green hues. Another problem with getting good strong blues is the low sensitivity of the human eye to blue. A strong
deep blue hue has been the pyrotechnologists “Holy Grail” for centuries and it continues to be the bane of fireworks
manufacturers. Some older recipes called for adding calomel (Hg2Cl2) to increase the chlorine content of burning com-
positions and deepen hues or intensities. While calomel was once used as a medication, mercury poisonings occurred
amongst fireworks manufacturers and nowadays, solid organic chlorocarbons, e.g., powered PVC or poly-1,1-
dichloroethylene) (Saran) are added to increase chlorine content of flames.
Blitzlicht, based on a mix of Mg powder and KClO3 was invented in 1887 for use in flash photography. Fireworks made
since about 1890 incorporated not only color-producing compositions, but compositions incorporating magnesium or
Page 6
A modern 4 inch
mine w/o cover
200 shot cake Zambelli Inc Mines
Stars dusted
with priming
Match
Medium grain
gunpowder
(propellant)
light weight
casing
Mine Design
* Jan Baptist van Helmont discovered chlorine gas in 1630 when he reacted NH4Cl + HNO3. Comte Claude-Louis Berthellot found
chlorine reacts with potassium hydroxide to give KOCl while he was working to make chlorine a suitable bleach for textiles. By 1786-
7 he also found excess chorine reacted with potassium hydroxide to give KClO3 and this salt, like KNO3, was a good oxidizer. How-
ever, it formed highly shock sensitive explosive mixtures with sulfur and his efforts to substitute it for KNO3 destroyed a powder mill
in 1788, killing 6 people. In 1828 Justus Liebig increased the yields of KClO3 from Berthellot’s process by using Ca(OH)2
1. 2 Ca(OH)2 + 2C12 → Ca(OC1)2 + CaCl2 + 2H2O 2. 4H2O + 4Cl2 → 4HOC1 + 4HC1
3. Ca(C1O)2 + 4HOC1 → Ca(C1O3)2 + 4HC1 4. 4 Ca(OH)2 + 8HC1 → 4CaCl2 + 8 H2O
Summarizing equations 1-4 one gets 5. 6Ca(OH)2 + 6Cl2 → Ca(C1O3)2 + 5CaCl2 + 6H2O Finally metathesis is employed:
6. Ca(C1O3)2 + 2KC1 → CaCl2 + 2KC1O3 The KClO3, being much less soluble in water than the Ca(Cl)2, crystalizes out. The yields
were an acceptable 70% and the process was employed on a commercial scale.
W. von Hisinger and J. Berzelius produced sodium chlorate in 1802 by the electrolysis of an aqueous NaCl solution, but it wasn’t until
1886 that a commercial electrolysis unit was set up in Villers-St. Sepulchre in Switzerland. Electrolysis simply supplied the requisite
NaOH and Cl2 in situ. The electrochemical production of KClO3 was found to be impractical since, being less soluble, it coated the
electrodes. Metathesis is employed instead: NaClO3 + KCl → KClO3 + NaCl The electrochemical method via NaClO3 followed by
KCl metathesis is still used today to produce KClO3.
Page 7
Volume 39, number 4 The Alembic 2012
later aluminum (and more recently, magnesium-aluminum alloy) or titanium as powders or chips to produce intensely
white flash or glitter effects. Magnesium-based flash compositions were the least stable both during manufacture and
storage, hence the move to aluminum, Al-Mg alloys or titanium based mixes.
In talking about mines, we alluded to stars and some are easy to see in the picture of the 4” mine shown on page 6. They
can be round as shown there, cylindrical, or square depending on how they are made and what they are to look like as
they burn. They usually contain one or more color compositions and perhaps a final flash composition. Since aluminum
and titanium based compositions are somewhat difficult to ignite, often an inner flash composition needs to be “dusted”
with a composition which is easy to ignite. If multiple colors
are to be seen, then a composition of low intensity burning
color is used as a “changing relay” so the colors do not blend
in to one another. In the example shown to the right, a square
flash composition star is covered with the same composition,
but containing a glue (dextrin, glutinous rice starch etc) to
give a ball shape, then a layer of easy-to-ignite composition
is applied, followed by blue burning composition, charging
relay composition, red burning composition and finally a
dusting of easy-to-ignite priming composition e.g., meal powder, to ensure the star ignites as it is thrown from the mine
or shell. The stars have to be thoroughly dried between each layer application making for labor-intensive manufacture.
As pointed out earlier, the Chinese invented the first rockets which were basically throttled tubes containing a
rapidly burning composition. Rockets popular in the 19th and early 20th century were made with a conical-
shaped hole in the propellant, so more burning surface area was available and more lifting power was created.
The bottom was throttled to about a 1/3 of the propellant tube’s width. Another clay plug was put above the pro-
pellant, with a hole containing a fuse to lead fire to an upper bursting charge with stars. A stick was affixed to
the side which balanced the rocket at a point just below the bottom clay throttling plug. Depending on manufac-
tures, the upper bursting charge could have a cone top or a simple, empty paper conical cap could be added.
While such rockets were attractive, especially if largish pieces of charcoal were including in the propellant so
one saw a fiery tail as the rocket streaked up, in general the star bursts were disappointing. The problem with
fireworks rockets are the same as those with rockets used for space flight, i.e., when the rocket takes off, it has
to carry not only the bursting charge weight, but also all the fuel to get the bursting charge up in the air. The
payload weight to total weight is a relatively small ratio for skyrockets.
Cylindrical shells were the Italian pyrotechnologists answer to the problem. A
mortar was used and the bursting charge was thrown into the air by a lifting
charge. A typical cylindrical shell is shown to to the right. These type of shells
can contain multiple bursts of stars as well as a salute (flash + bang). In Japan,
round shells were developed which give beautifully symmetrical bursts like the
Zambelli family’s chrysanthemum burst at the beginning of this article. These can
be made with plastic hemispheres, but the traditional Japanese method of making
glued newspaper hemispheres produces the most attractive displays. Mathematical
calculations for the design of these spherical shells have been made by Dr. Takeo
Shimizu (Director of the Koa Fireworks Co., Tokyo) and are quite complex and
rather impressive.
In the last 20-30 years potassium and ammonium perchlorate have largely re-
placed potassium chlorate as an oxidizer because their compositions are much less
shock sensitive. Perchlorates are made via the electrolysis of chlorates between
platinum electrodes. NaClO4 can be metathesized to KClO4, NH4ClO4 etc
Electrical firing is usually used nowadays to increase safety, albeit premature fir-
ing of displays by induced currents in the wires used in such displays can be a dangerous problem. With the relatively
recent trend towards choreographing music and fireworks displays, some American fireworks families like the Gruccis
are starting to incorporate microchip timers in shell design for more precise timing of bursts. The Gruccis even dream of
using microchips to create animated displays... perhaps even fire writing in the nighttime sky.
Finally, whether you chose to see a fireworks display or not, I want to wish each of you a safe and enjoyable summer,
and hope to see you in the September for the 40th anniversary celebration of the founding of our section.
Dale
Quickmatch
Quickmatch cutaway leader
Safety cap Shell Casing(kraft paper)
Glue
Cylindrical Shell
Cross Match
Time fuse
Black match
Inner shell casing
Burst charge
Stars
Black powder lift charge
Gray -Interior square flash charge with flash charge
pasted to it to make it round
Yellow - Igniter composi-tion to ensure flash charge takes fire
Red - Red burning composition
Black - Low intensity changing relay composition
Blue - Blue burning composition
Green - Easily ignitable priming composition
The Alembic (May 2012)
Newsletter of the Central Wisconsin Section, ACS
c/o Chemistry Department (#605516)
University of Wisconsin – Stevens Point
Stevens Point, WI 54481
Member Address Label
Central Wisconsin Section, ACS Meetings and Programs - 2012
Date (Day) Location Speaker/Event Host
May 10, 2012 Eau Claire Awards Banquet Dave Lewis
Sept 14, 2012 Stevens Point 40th Anniversary of Section Marv Lang
Oct 17, 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 lo-cations and arrangements for these meetings. Of further interest are the following national and regional events:
ACS 43rd Central Regional Meeting, Dearborn, MI - June 5-8, 2012
16th Annual Green Chemistry & Engineering Conference, Washington DC, June 18-20, 2012
244th ACS National Meeting & Exposition, Philadelphia, Pennsylvania, August 19-23, 2012
Mark your calendar … plan to come:
Central WI Section Awards Banquet
Burgundy’s Restaurant in the Plaza
Hotel & Suites, Eau Claire, WI
Thursday, May 10th at 6:00 PM
