AMERICAN CHEMICAL SOCIETY CALIFORNIA SECTION VOLUME LXXI NUMBER 2 FEBRUARY 2010

Photo taken by Janet Bryant of National WCC

Happy St.Valentine’sPhoto by Day Anastasios John Hart

CHAIR’S MESSAGE PAGE 3 FEBRUARY MEETING PAGE 4 THE NADJIK PHEROME: A BOOK REVIEW (L.RIGALI) PAGE 5 ELK-N-ACS (E. KOTHNY) PAGE 6 FEBRUARY CHEMICAL ANNIVERSARIES (L MAY) PAGE 7 MODERATION & COMMON SENSE (A. PAVLATH) PAGE 8 THE CHEMISTRY OF MINERAL & BOTTLE WATER (W. MOTZER) PAGE 9 BUSINESS DIRECTORY PAGE 11 INDEX OF ADVERTISERS PAGE 11 2 THE VORTEX Published monthly except July & August by the California Section, American Chemical Society. Opinions expressed by the editors or contributors to THE VORTEX do not necessarily THE VORTEX reflect the official position of the Section. The publisher reserves the right to reject copy submitted. Subscription included in $13 annual dues payment. Nonmember subscription $15.

MAGAZINE OF THE CALIFORNIA SECTION, AMERICAN CHEMICAL SOCIETY

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Volume LXXI February 2010 Number 2 Chair’s Message then and California Section dues were Paul Vartanian $1.00/year. For perspective, the yearly dues in 1940 were equal to the cost of the Viva The VORTEX dinner at a Section meeting, $1.00. Now The California Section’s yearly dues are only $15, compared to publication, The VORTEX, the cost of a dinner at a meeting of about celebrated its 70th anniver- $25. sary in January. The VOR- By the early 1970s, the Section had be- TEX began in January come less central to the chemical activi- 1940, at a time when world ties of its members. The topical group conditions were in the be- meetings were a thing of the past, the Santa ginnings of the catastrophe of World War II. Clara Valley Section had been established The United States would not be directly in- in 1954, and the San Joaquin Valley Sub- volved in the war for almost two more years. section was on its way to getting to that Ted Cleveland was the founding editor of The point. Robert Matteson became editor of VORTEX and guided it for almost 30 years The VORTEX in September 1969 and until June 1969. He established its high qual- served until April 1972. Editor William ity in both editorial content and usefulness to Stanley succeeded him in May 1972. Bill the Section members. During that time the guided The VORTEX until March 1976. Section underwent some spectacular changes. Editor Robert Grinstead took over in April Meetings of the Section in 1940 consisted 1976. Bob was the first editor I got to of a main speaker and then four topical group know personally as I usually had to drive gatherings of Analytical, Microchemical, to his home in Walnut Creek at deadline Physical, Inorganic; Biochemical and Organic; time to give him my Chair’s Message dur- Educational; and Industrial Chemistry. As an ing my first term in 1987. The VORTEX example, the March 1940 Industrial group was still publishing upwards of 20 pages heard a talk on the “California Sardine Indus- per edition and carrying on with interest- try” by A. H. Mendonca, after the main talk ing columns and news under Bob’s direc- on “The Aging of Crystalline Precipitates” by tion. I. M. Kolthoff. The VORTEX ran 28 pages (continued on page 7)

FEBRUARY 2010 3 California Section American Chemical Society February Meeting "A Tour of Distillery No. 209" By Arne Hillesland, Ginerator

Date: Saturday, February 27, 2010

Time: 11:00 am (arrive by 10:45 am at site)

Place: Distillery No. 209, Pier 50, San Francisco (south of the Ferry Building, near AT&T Park)

Cost: no cost (Restaurants are in the area for an after tour lunch or snack)

Reservations: RSVP by Wednesday, February 24 to the Section office by e-mail at [email protected] or call (510) 351-9922. Tour limited to 30, no one under 21. Abstract: ist, and he made beer, wine and hard cider in In 1870, William Scheffler bought a patent his spare time as a teenager. for a new design of a pot still in New York. A Bay Area native, a saxophonist, amateur He came west and set up a distillery at Krug chef, gardener and auto mechanic, Arne de- winery in St. Helena, California. In 1880 he clined the offer to attend law school after his purchased his own winery in the Napa Val- graduation from the University of California ley called Edge Hill and the distillery erected at Berkeley with a B.A. in history. It was there was given Federal license No. 209. the early 1980s and with the Silicon Valley After he purchased the Edge Hill prop- as only a short commute, Arne was bound erty, Leslie Rudd, a noted food and wine for a career in high technology management entrepreneur discovered "Registered Distill- as a training, production and quality control ery No. 209" written on a hay barn on the specialist. property. He started his own winery and Twenty-plus years later, after moving from his daughter, Samantha Rudd, now contin- manufacturing and engineering into Artificial ues her father's vision as the owner of Dis- Intelligence software and internet start-ups, tillery No. 209. Arne began volunteering at Distillery 209 in The distillery was set up in San Francisco the summer of 2003. He helped in the initial at Pier 50 to make high quality spirits, gin in commissioning of the copper pot still from particular. The Ginerator starts with a four Forsyths in Scotland, and began working full- times distilled neutral-grain spirit, with which time as Distillery Supervisor in April of 2004. he distills a fifth time to infuse a variety of Working along side Two Scots - the former botanicals. Traditional gin is based on juni- 209 Project Director and a Master Distiller per berry flavor, but Distillery No. 209 uses from Scotland - Arne developed both the 209 citrus, exotic fruits, and spices in its for- Gin recipe and some of the unique distilla- mula. tion techniques that are used in making the gin today. In March of 2005, Arne Hillesland Speaker/Tour Guide: became Head Distiller at Registered Distill- Arne Hillesland is a complete stranger to ery No. 209 and, as a resident of San Fran- distilling spirits, unless you consider that he cisco, is once again rewarded with a short learned the basics of chemistry from his fa- commute. ther who was an aerospace engineer and chem-

4 THE VORTEX The Nadjik Pheromone by bad guys and a few not so usual. There is the obligatory love scene very early in the story Michael K. Hemp: A Book Review and then much later, near the end, there is a L. Rigali story-enhancing brief sexual encounter. The Michael Hemp has a Bay area connection, story line is contemporary with places and graduating as valedictorian from St. Mary’s people we read about in the news every day. College High School in Berkeley and com- Through the years as a Pulitzer Prize win- pleting undergraduate work at UC Berkeley. ning reporter, Wolf has gained inside infor- The guideline used for publishing articles in mation on some covert and secret projects, the Vortex is that the content be chemistry or enough so that he is on the radar of many science related. This article is a brief review bad guys. And these bad guys have their of a thrilling, can-not-put-the-book-down spy way with him, almost. We soon discover novel with a little chemistry and science. In that there may be one or more bad guys who the Nadjik Pheromone, Michael Wolfson, want the development work on the Nadjik (Wolf), the hero of the story, inspires the Pheromone project terminated along with development of a special Gas Chromatograph Wolf and any history of this potentially /Mass Spectrometer (GC/MS) to detect bio- powerful lie detecting system. The various logical molecules that are released when a scenes and dialogs with native warlords and person lies. Some of the ideas for the plot secret agents from Afghanistan, Pakistan, may have been generated during the time that Hawaii, Silicon Valley and Carmel all feel Michael Hemp worked at Shell or later served and sound authentic. as a Special Intelligence Officer to three Com- The story is told in slightly more than 300 manders-In-Chief of the Strategic Air Com- pages and may demand completing in a single mand, Offutt AFB, Omaha, Nebraska. sitting. The story has all of the usual suspects as

FEBRUARY 2010 5 ELK-N-ACS indigo and zaffre) are smalt and Berlin blue. Smalt, also known as King’s blue, which con- Dyes and colors tains more Co or Azure blue, which is the in art (part III). darkest product was discovered in 1584. It Evaldo Kothny consisted of a finely ground up silicate glass In previous parts I formulated with cobalt and potassium and II, the most im- (K2CoSi4O10), then leached with cold water portant earth colors as it may hydrolyze under other conditions, of antiquity were then dried. Impurities are alumina or zinc presented, which can oxide. be summarized as rust, charcoal and a few The slaughtering operation furnishes large odd artificial reds. In most cases, the tones quantities of blood. Nowadays one known of these pigments are not pure and new sub- use is as a fertilizer, however, in antiquity it stances were found with better characteris- was beaten to remove the fibrinogen and then tics. it was applied as a paint for preserving wood. Blue pigments were scarce and very expen- But soon it was discovered that it could be sive. As example, the material denominated transformed: dried blood incorporated into Lazurite, consisted of natural ground-up and molten potassium carbonate and extracted refined lapis lazuli (a sulfosilicate), which into water produced a new material, the light originally was worth its weight in gold. How- yellow potassium hexacyanoferrate. The re- ever, this substance was synthesized in 1928 action of this salt with ferric sulfate pro- and called ultramarine blue. This substance duced a stable blue pigment that was discov- is a calcium aluminum silicate where the silica ered in Berlin in 1704. Thus it was named in the formula is partly replaced by sulfur of Berlin blue, although it was also known as valence 4; and the oxygen is partly replaced Paris blue or Prussian blue. The ion by sulfur of valence 2. It is made by firing a hexacyanoferrate or the free ferrocyanide was mixture of clay, soda, sulfur, silica and rosin also called prussic acid. Chinese blue has the between 750 to 1380oC in a closed furnace. same configuration as Berlin blue, but the The heating and cooling ramp and the pro- molecular water normally retained is removed portion of the ingredients are factors that by heating to 250oC. determine the color and quality of the mate- Ferric ferrocyanide was the ingredient of rial. The product can be produced with a the most brilliant greens when mixed together violet or a greenish hue. After its synthesis, with lead chromate. Industrially, the mixing it became popular as inexpensive house paint occurred inside a vat by precipitating first admixed with slaked lime or as bluing for the ferrocyanide, then adding a soluble lead white fabric. compound and finally a solution of chro- Egyptian blue, also called Ancient blue or mate under controlled pH conditions. copper blue, is an artificial bright calcium- Thenard’s blue (CoOAl2O3) of 1911 is ob- copper silicate (CaCuSi4O10) known earlier tained by impregnating alum and ZnO with a than 2000 years BC. It is made by mixing soluble Co salt, drying and calcinating this stoichiometric amounts of lime, copper ox- mix at 1300 to 1700 oC. ide and silica with 10% soda, then heating Sometimes one may find natural blue min- for 6 to 16 hours at 700-900oC and leaching erals which had not had the fortune of being with dilute acid. used as a pigment. Such are the cases of cer- Zaffre, mentioned in some old writings, is a tain iron silicates (Ferrous hydrous alumino- rare dark blue natural oxide containing cobalt silicates, e.g., glaucophane, dumortierite). and nickel. These are typically found in areas of strong The two first blue pigments discovered in tectonic pressures. Joining those silicates is AD that joined with all the blues and blue- vivianite, a dark blue ferrous phosphate greens known since ancient times (azurite, . Fe3(PO4)2 8H2O). All these minerals have lazurite, Egyptian blue, malachite, turquois, (Continued on page 7)

6 THE VORTEX (Continued from page 6) insufficient tinting power and would barely qualify as pigment. Among the copper pigments, probably the oldest is malachite green which is an impure basic copper carbonate. It was first synthe- sized around 1800 and marketed as Bremen green. From it could be obtained a blue pig- ment by heating that was similar to the natu- ral substance called Azurite. About at that same time, “Verdigris”, was made. Verdigris of 1800 originally made by corroding copper sheets to moist air and acetic acid, can also be obtained by low temperature melting of Cu sulfate with lead acetate. The cooled melt is ground up and leached for removal of soluble lead compounds. A variety of names for this pigment exist depending on the ratio of acetate:hydroxide:water, which is 2:1:5 for the common verdigris.

February Chemical Anniversaries Leopold May February 6, 1860 One hundred and fifty years ago, Nikolai D. Zelinsky, was born on (Continued from page 3) this date. He was a researcher on the cataly- Now, The VORTEX has entered a new phase sis of disproportionation reactions of hydro- as an electronic publication guided by its fifth carbons and the bromination of fatty acids editor, Lou Rigali, who took over the helm in (Heil-Volhard-Zelinsky reaction). April 1994. Lou has done a great job in February 12, 1785Two hundred and carrying on the traditions of The VORTEX as twenty-five years ago, Pierre L. DuLong was costs rose and the Section members became born on this date. He discovered nitrogen more acquainted with modern ways of get- trichloride in 1813; and was a researcher on ting chemical information like using the refractive indices and specific heats of gases. Section’s web site. With the conversion to In 1819, he and AlexisTherese Petit discov- electronic editions, we hope to add editorial ered the Law of constancy of atomic heat and content to The VORTEX and use the reduced suggested that acids were compounds of hy- printing and mailing expenses for other Sec- drogen in 1815. He devised formula for heat tion activities. Lou also has done well in value of fuels (DuLong Formula). leading the quick conversion of The VOR- February 14, 1917Twenty-five years ago in TEX to the electronic format, while still pro- 1985, Herbert A. Hauptman and Jerome Karle viding paper copies for those members re- shared the Nobel Prize in Chemistry for their quiring them. For 70 years The VORTEX outstanding achievements in the development has been an integral part of the California of direct methods for the determination of Section and we hope it continues to meet the crystal structures. Herbert A. Hauptman was members expectations as a source of infor- born on this date. mation on Section activities.

FEBRUARY 2010 7 Moderation and sure. Each of them has various efficiencies from both energy and economy points of Common Sense, view. The bottom line is that the energy con- XX tent of the hydrogen obtained is always less A. Pavlath than the amount of energy invested in ob- During the past two taining it. Depending on the reports, the en- years I discussed in ergy efficiency is 50-80% of the electric en- The VORTEX the pros ergy used. To this we have to add the effi- and cons of increasing ciency of obtaining electricity and the effi- our energy supply us- ciency of using hydrogen in whatever pro- ing various alternate pulsion system used in transportation to get resources in addition the true picture of using hydrogen. The cost to fossil fuels. It is evident that most of them of hydrogen on site is $0.32/lb, but off-site, can provide additional energy in form of elec- requiring transportation in liquid form, is tricity. The question discussed in the previ- $1.00-1.40/lb. On the plus side, the efficiency ous segment was the utilization of such elec- of a hydrogen fueled engine is 8% higher tricity in everyday use. Through high volt- than its gasoline counterpart. Using fuel cells age transmission lines the lighting, heating can provide 2-3 times more efficiency, but and cooling of the house can be helped. But much more development is required to be- at the same time, totally electric cars, not come an everyday economical transporta- hybrids, still have technological and economi- tion possibility. cal problems. Can we use electricity practi- Is hydrogen the answer to the solution of cally in transportation? the environmental problems attributed to the In the beginning, I mentioned that hydro- use of fossil resources? Obviously the use of gen is not an alternate energy source, but a hydrogen instead of fossil fuels would help carrier. By using hydrogen for transporta- cut down carbon dioxide generation. There is tion we do not gain additional amount of no question that using hydrogen, wherever it energy, we just use existing one in a different is possible, could abate the environmental way. The argument in favor for hydrogen is problems related to carbon dioxide. How- that it is environmentally clean and it does ever, frequently, enthusiasm creates blind not create carbon dioxide. However, we do spots and we only see the advantages. not have natural hydrogen resources, there- Hydrogen represents safety problems. The fore, we have to manufacture it. The ques- explosion of the Hindenburg air craft sev- tion is, what processes are available for ob- enty years ago created an everlasting warn- taining it? ing. Its household use could create more dif- Since hydrogen is essential for manufactur- ficulties than natural gas. In addition there is ing artificial fertilizers through the Haber- an unknown environmental factor. Can we Bosch synthesis, its production process is use hydrogen in every day life without any well established, but it uses almost exclu- leakage to the atmosphere? Since it is the sively fossil fuel as a starting material. Pres- lightest gas, it tends to rise. Will it be com- ently, about 50% of the hydrogen is pro- pletely destroyed before reaching the ozone duced from natural gas, about 30% from oil, layer? In case of the fluorocarbons, we were and 15% by coal gasification. The rest is able to replace them easily with other aero- obtained by dissociating water through ei- sols. What happens if we find out a possible ther high temperature (~1000o(C) or elec- harmful effect of hydrogen spillage on the trolysis. The high temperature process in environment when our life will be already some nuclear power plants would help their based on hydrogen? I might sound as a bro- efficiency by utilizing some of the heat which ken record but moderation and common is not converted into useable energy. sense must be common. There are various types of water electroly- sis: low and high temperature and high pres-

8 THE VORTEX 2- MCL for 500 mg/L for SO4 . The MCL for The Chemistry of - - NO3 , NO2 are 10 and 1.0 mg/L, respectively Mineral and Bot- Other Minor or Trace Constituents tled Water (Part 3) Important trace elements may include alu- Bill Motzer minum (Al2+) iron (Fe2+ and Fe3+), manga- Both bottled and tap nese (Mn2+ and Mn4+), arsenic [As(III) and water may be derived As(V)] and lead (Pb2+). (I have written the from surface sources (riv- arsenic as an oxidation state because it tends ers and reservoirs) or to form mostly anionic complexes.) The cur- groundwater. Most of it (about 99.9%) con- rent arsenic primary MCL is 0.010 mg/L. Other trace elements of particular concern sists of H2O composed of the stable iso- topes of oxygen: 16O (99.757%), 17O are chromium (Cr) which can occur as Cr(III) (0.038%), and 18O (0.205%), hydrogen in- or Cr(VI) largely in the form of chromate 1 2- 2- cluding hydronium or H (99.985%), deute- [CrO2 ] or dichromate (Cr2O4 ) ions. Cr(VI) rium or 2H (0.015%), and very small amounts is a known human carcinogen (see Valencing of radiogenic tritium (3H), which is largely Oxidation States in the October 2007 Vor- the residual effect of post WWII atmospheric tex). nuclear weapons testing and emissions from Other Parameters nuclear power plants. The remainder, if it is Hardness is a condition by which the cal- “fresh” water, generally has a total dissolved cium and magnesium ions form insoluble resi- solids (TDS) content of less than 1,000 mg/ dues with soap. Hardness is determined by

L (0.1%). TDS are defined as the total quan- the range of calcium carbonate (CaCO3) con- tity of inorganic salts and small amounts of centration in water in mg/L, which is known organic matter in mg/L remaining when a water as calcium hardness or the range of magne- sample is evaporated. By comparison, sea sium expressed as CaCO3 (magnesium hard- water has a TDS of about 34,650 mg/L ness). Total hardness (HT) can be calculated (~3.47%). using the formula:

Major Constituents HT = 2.5 Ca + 4.1 Mg Metal (cation) and nonmetal (anion) analy- where Ca and Mg are concentrations mea- sis of water can involve a substantial number sured in mg/L. Published hardness ranges of constituents or it may involve only those vary: considered to be the most important. Gener- Description of Water Hardness Ranges Hard- ally, the major cations and anions examined ness Range in mg/L of CaCO3 in a water analysis are sodium (Na+), potas- sium (K+), calcium (Ca2+), magnesium Hem (1988)* Todd (1980)** 2- 0 - 60 0 - 75 Soft (Mg2+), chloride (Cl-), sulfate (SO4 ), bi- - 2- 61 - 120 75 - 150 Mod. Hard carbonate (HCO3 ) and carbonate (CO3 ). - 121 - 180 150 - 300 Hard Minor anions include nitrate (NO3 ), nitrite - >180 > 300 Very Hard (NO2 ), phosphate (PO42-), dissolved am- * Study and Interpretation of the Chemical monia (NH3) and nitrogen gas (N2). The major solutes in groundwater generally Characteristics of Natural Water: U.S. Geol. have the following relative abundances (from Survey Water Supply Paper 2254, 263 p. greatest to least): ** Groundwater Hydrology, John Wiley & - 2- 2+ 2- - 2+ Sons, New York, NY., 535 p. HCO3 (± CO3 )> Ca > SO4 >Cl >Mg + + - - Most bottled and tap water derived from >Na >K > N (as N2, NH3, NO2 , NO3 ) > 2- surface water sources generally are soft but PO4 Of the above listed constituents only Cl-, groundwater sources can be moderately hard 2- - - to hard. SO4 , NO3 , and NO2 , have regulatory re- quirements; these are secondary maximum Naturally Occurring Organic Constituents concentration/contaminant levels (MCLs) of Natural organic compounds may be found in - 2- (Continued on page 10) 250 mg/L for Cl , and SO4 and a primary

FEBRUARY 2010 9 (continued from page 9) compounds. These may occur in very trace amounts (measured in nanograms per liter or surface water and to a minor extent in shal- ng/L) and are either absent or virtually non- low groundwater but are most likely absent existent in treated water. Some of the “newer” in deep groundwater. Runoff from organic contaminants of concern (COC) include phar- soil may contain several thousand mg/L of maceutical and personal care products various organic compounds that may include (PPCPs) and n-nitroso-dimethylamine alkaloids, n-alkanes, organic cyanides, ph- (NDMA). Many PPCPs rapidly degrade thalates, porphyrins, and terpenes and hu- when released into the environment; others mic and fulvic acids. Microorganisms (prin- are persistent. cipally bacteria) degrade or decompose these Micro-organisms soil hydrocarbons. Natural organic com- Bacteria and viruses are largely eliminated pounds generally are not toxic but do influ- in drinking water by chlorination or the addi- ence geochemical and biochemical processes tion of chloramaine. More modern methods in water bodies. Disinfection of water with include ultrafiltration, UV oxidation and/or chlorine and its subsequent reaction with ozonization. organic substances may form trihalomethane Just 200 years ago, most Americans es- (THM) compounds such as chloroform, chewed drinking any water, relying instead which may pose problems because it is con- on consuming hard apple cider, beer, and wine sidered as a human carcinogen. For that rea- because the alcohol generated by fermenta- son, many water treatment works have tion eliminated most harmful bacteria. The changed to chloramine (NH Cl). Humic sub- 2 next time you turn on the tap or open a bottle stances can also influence heavy metal spe- of water, remember that for the most part, in ciation through compound complexion. the U.S., we have a reliable and safe drinking Synthetic organic compounds can include water supply. many thousands of commercially produced

10 THE VORTEX BUSINESS DIRECTORY

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