Karl Waldemar Ziegler (; 26 November 1898 – 12 August 1973) was a
German chemist
A chemist (from Greek ''chēm(ía)'' alchemy; replacing ''chymist'' from Medieval Latin ''alchemist'') is a graduated scientist trained in the study of chemistry, or an officially enrolled student in the field. Chemists study the composition of ...
who won the
Nobel Prize in Chemistry
The Nobel Prize in Chemistry () is awarded annually by the Royal Swedish Academy of Sciences to scientists in the various fields of chemistry. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895, awarded for outst ...
in 1963, with
Giulio Natta, for work on
polymer
A polymer () is a chemical substance, substance or material that consists of very large molecules, or macromolecules, that are constituted by many repeat unit, repeating subunits derived from one or more species of monomers. Due to their br ...
s. The Nobel Committee recognized his "excellent work on organometallic compounds
hich
Ij () is a village in Golabar Rural District of the Central District in Ijrud County, Zanjan province, Iran
Iran, officially the Islamic Republic of Iran (IRI) and also known as Persia, is a country in West Asia. It borders Iraq ...
..led to new polymerization reactions and ... paved the way for new and highly useful industrial processes".
He is also known for his work involving
free-radical
In chemistry, a radical, also known as a free radical, is an atom, molecule, or ion that has at least one unpaired valence electron.
With some exceptions, these unpaired electrons make radicals highly chemically reactive. Many radicals spont ...
s, many-membered rings, and
organometallic compounds, as well as the development of
Ziegler–Natta catalyst
A Ziegler–Natta catalyst, named after Karl Ziegler and Giulio Natta, is a catalyst used in the synthesis of polymers of 1-alkenes ( alpha-olefins). Two broad classes of Ziegler–Natta catalysts are employed, distinguished by their solubility ...
. One of many awards Ziegler received was the
Werner von Siemens Ring in 1960 jointly with
Otto Bayer and
Walter Reppe, for expanding the scientific knowledge of and the technical development of new
synthetic materials.
Biography
Early life and education
Karl Ziegler was born on 26 November 1898 in
Helsa near
Kassel
Kassel (; in Germany, spelled Cassel until 1926) is a city on the Fulda River in North Hesse, northern Hesse, in Central Germany (geography), central Germany. It is the administrative seat of the Regierungsbezirk Kassel (region), Kassel and the d ...
, Germany and was the second son of Karl Ziegler, a Lutheran minister, and Luise Rall Ziegler.
He attended Kassel-Bettenhausen in elementary school. An introductory physics textbook first sparked Ziegler's interest in science. It drove him to perform experiments in his home and to read extensively beyond his high school curriculum. He was also introduced to many notable individuals through his father, including
Emil Adolf von Behring
Emil von Behring (; Emil Adolf von Behring: born Emil Adolf Behring; 15 March 1854 – 31 March 1917), was a German physiologist who received the 1901 Nobel Prize in Physiology or Medicine, the first one awarded in that field, for his discovery ...
, recognized for the diphtheria vaccine.
His extra study and experimentation help explain why he received an award for most outstanding student in his final year at high school in Kassel, Germany.
He studied at the
University of Marburg
The Philipps University of Marburg () is a public research university located in Marburg, Germany. It was founded in 1527 by Philip I, Landgrave of Hesse, which makes it one of Germany's oldest universities and the oldest still operating Prote ...
and was able to omit his first two semesters of study due to his extensive background knowledge. His studies were interrupted however, as during 1918 he was deployed to the front as a soldier to serve in
World War I
World War I or the First World War (28 July 1914 – 11 November 1918), also known as the Great War, was a World war, global conflict between two coalitions: the Allies of World War I, Allies (or Entente) and the Central Powers. Fighting to ...
.
He received his Ph.D. in 1920, studying under
Karl von Auwers.
His dissertation was on "Studies on semibenzole and related compunds" which led to three publications.
Career
Karl Ziegler showed an eagerness for science at an early age. He progressed through schooling quickly receiving a doctorate from the
University of Marburg
The Philipps University of Marburg () is a public research university located in Marburg, Germany. It was founded in 1527 by Philip I, Landgrave of Hesse, which makes it one of Germany's oldest universities and the oldest still operating Prote ...
in 1920. Soon after, he briefly lectured at the University of Marburg and the
University of Frankfurt.
In 1926 he became a professor at the
University of Heidelberg
Heidelberg University, officially the Ruprecht Karl University of Heidelberg (; ), is a public university, public research university in Heidelberg, Baden-Württemberg, Germany. Founded in 1386 on instruction of Pope Urban VI, Heidelberg is List ...
where he spent the next ten years researching new advances in organic chemistry.
He investigated the stability of radicals on trivalent carbons leading him to study organometallic compounds and their application in his research. He also worked on the syntheses of multi-membered ring systems.
[ including the Nobel Lecture on 12 December 1963 ''Consequences and Development of an Invention''
] In 1933 Ziegler published his first major work on large ring systems, "Vielgliedrige Ringsysteme" which presented the fundamentals for the Ruggli-Ziegler dilution principle.
In 1936 he became Professor and Director of the Chemical Institute (Chemisches Institut) at the
University of Halle-Saale and was also a visiting lecturer at the
University of Chicago
The University of Chicago (UChicago, Chicago, or UChi) is a Private university, private research university in Chicago, Illinois, United States. Its main campus is in the Hyde Park, Chicago, Hyde Park neighborhood on Chicago's South Side, Chic ...
.
Ziegler, who was a
Patron Member of the
SS received the
War Merit Cross 2nd Class in October 1940.
From 1943 until 1969, Ziegler was the Director of the
Max Planck Institute for Coal Research (Max-Planck-Institut fur Kohlenforschung) formerly known as the Kaiser-Wilhelm Institute for Coal Research (Kaiser-Wilhelm-Institut fur Kohlenforschung) in Mülheim an der Ruhr as a successor to
Franz Fischer.
Karl Ziegler was credited with much of the postwar resurrection of chemical research in Germany and helped found the German Chemical Society (Gesellschaft Deutscher Chemiker) in 1949. He served as president for five years.
He was also the president of the German Society for Petroleum Science and Coal Chemistry (Deutsche Gesellschaft für Mineralölwissenschaft und Kohlechemie), from 1954 to 1957.
In 1971, The Royal Society, London, elected him as a Foreign Member.
[
]
Personal life
In 1922, Ziegler married Maria Kurtz. They had two children, Erhart and Marianna. His daughter, Dr. Marianna Ziegler Witte was a doctor of medicine and married a chief physical of a children's hospital (at that time) in the Ruhr. His son, Dr. Erhart Ziegler, became a physicist and patent attorney. In addition to his children, Karl Ziegler has five grandchildren by his daughter, and five by his son. At least one of his grandchildren, Cordula Witte, attended his Nobel Prize reception as there is a picture of the two of them happily dancing. Ziegler enjoyed traveling around the world with his family, especially on cruises. He even charted special cruises and airplanes for eclipse viewing. It was during a 1972 eclipse-viewing cruise with his grandson that Karl Ziegler became ill. He died a year later.
Ziegler and his wife were great lovers of the arts, particularly paintings. Karl and Maria would present each other with paintings for birthdays, Christmases, and anniversaries. They amassed a large collection of paintings, not necessarily of one particular period, but of paintings they enjoyed. Maria, being an avid gardener, particularly enjoyed flower paintings by Emil Nolde, Erich Heckel
Erich Heckel (31 July 1883 – 27 January 1970) was a German people, German Painting, painter and printmaker, and a founding member of the group ''Die Brücke'' ("The Bridge") which existed 1905–1913. His work was part of the art competition ...
, Oskar Kokoschka
Oskar Kokoschka (1 March 1886 – 22 February 1980) was an Austrian artist, poet, playwright and teacher, best known for his intense expressionistic portraits and landscapes, as well as his theories on vision that influenced the Viennese Expre ...
, and Karl Schmidt-Rottluff. Karl enjoyed pictures of the places that he and his wife called home, including pictures of Halle and the Ruhr valley. Forty-two images from their shared collection were incorporated into a foundation, bequeathed to the Mülheim Ziegler Art Museum.
As a man of many discoveries, Karl Ziegler was also a man of many patents. As a result of his patent agreement with the Max Planck Institute, Ziegler was a wealthy man. With part of this wealth, he set up the Ziegler Fund with some 40 million deutsche marks to support the institute's research. Another namesake is the Karl-Ziegler-Schule, an urban high school that was founded on 4 December 1974, renaming a previously existing school. The school is located in Mülheim, Germany.
Karl Ziegler died in Mülheim
Mülheim, officially Mülheim an der Ruhr (, ; ; ) and also described as ''"City on the River"'', is a city in North Rhine-Westphalia in western Germany. It is located in the Ruhr Area between Duisburg, Essen, Oberhausen and Ratingen. It is ho ...
, Germany on 12 August 1973; his wife died in 1980.
Scientific advancements
Throughout his life, Ziegler was a zealous advocate for the necessary indivisibility of all kinds of research. Because of this, his scientific achievements range from the fundamental to the most practical, and his research spans a wide range of topics within the field of chemistry. As a young professor, Ziegler posed the question: what factors contribute to the dissociation of carbon-carbon bonds in substituted ethane
Ethane ( , ) is a naturally occurring Organic compound, organic chemical compound with chemical formula . At standard temperature and pressure, ethane is a colorless, odorless gas. Like many hydrocarbons, ethane is List of purification methods ...
derivatives? This question was to lead Ziegler on to a study of free radicals
In chemistry, a radical, also known as a free radical, is an atom, molecule, or ion that has at least one unpaired electron, unpaired valence electron.
With some exceptions, these unpaired electrons make radicals highly chemical reaction, chemi ...
, organometallics
''Organometallics'' is a biweekly journal published by the American Chemical Society. Its area of focus is organometallic and organometalloid chemistry. This peer-reviewed journal has an impact factor of 3.837 as reported by the 2021 Journal Citat ...
, ring compounds, and, finally, polymerization processes.
Free radical compounds
While still a doctoral student at University of Marburg
The Philipps University of Marburg () is a public research university located in Marburg, Germany. It was founded in 1527 by Philip I, Landgrave of Hesse, which makes it one of Germany's oldest universities and the oldest still operating Prote ...
, Ziegler published his first major article which showed how halochromic (R3C+Z−) salts could be made from carbinols. Previous work had left the impression that halochromic salts or free radicals (R3C•) required R to be aromatic
In organic chemistry, aromaticity is a chemical property describing the way in which a conjugated system, conjugated ring of unsaturated bonds, lone pairs, or empty orbitals exhibits a stabilization stronger than would be expected from conjugati ...
. He was encouraged to try to synthesize similarly substituted free radicals, and successfully prepared 1,2,4,5-tetraphenylallyl in 1923 and pentaphenylcyclopentadienyl in 1925. These two compounds were much more stable than previous tri-valent carbon free radicals, such as triphenylmethyl. His interest in the stability of tri-valent carbon free-radical compounds brought him to publish the first of many publications in which he sought to identify the steric and electronic factors responsible for the dissociation of hexa-substituted ethane derivatives.
Many-membered ring compounds
Ziegler's work with many-membered ring compounds also utilized the reactive nature of alkali metal compounds. He used strong bases such as the lithium and sodium salts of amines, to accomplish the cyclization of long-chain hydrocarbon
In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and Hydrophobe, hydrophobic; their odor is usually fain ...
s possessing terminal cyano groups. The initially formed ring compound was then converted to the desired macrocyclic ketone product. Ziegler's synthetic method, which included running reactions at high dilution to favor the intramolecular cyclization over competing intermolecular reactions, resulted in yields superior to those of existing procedures (Laylin): he was able to prepare large-ringed alicyclic ketones, C14 to C33, in yields of 60–80%. An outstanding instance of this synthesis was the preparation of muscone, the odiferous principle of animal musk by Leopold Ružička. Ziegler and co-workers published the first of their series of papers on the preparation of large ring systems in 1933. For his work in this area and in free-radical chemistry he was awarded the Liebig Memorial Medal in 1935.
Organometallic compounds
Ziegler's work with free radicals led him to the organo compounds of the alkali metal
The alkali metals consist of the chemical elements lithium (Li), sodium (Na), potassium (K),The symbols Na and K for sodium and potassium are derived from their Latin names, ''natrium'' and ''kalium''; these are still the origins of the names ...
s. He discovered that ether scission opened a new method of preparing sodium and potassium alkyls, and found that these compounds could easily be converted to the hexa-substituted ethane derivatives. The nature of the substituent could be easily and systematically altered using this synthetic route by simply changing the identity of the ether starting material.
Lithium alkyls
Later, in 1930, he directly synthesized lithium alkyls and aryls from metallic lithium and halogenated hydrocarbons via metal–halogen exchange. This convenient synthesis spurred numerous studies of RLi reagents by others, and now organolithium reagent
In organometallic chemistry, organolithium reagents are chemical compounds that contain carbon–lithium (C–Li) bonds. These reagents are important in organic synthesis, and are frequently used to transfer the organic group or the lithium atom ...
s are one of the most versatile and valuable tools of the synthetic organic chemist. Ziegler's own research on lithium alkyls and olefins was to lead directly to his discovery of a new polymerization technique some 20 years later.
Living polymerization
In 1927, he found that when the olefin
In organic chemistry, an alkene, or olefin, is a hydrocarbon containing a carbon–carbon double bond. The double bond may be internal or at the terminal position. Terminal alkenes are also known as α-olefins.
The International Union of Pu ...
stilbene Stilbene may refer to one of the two stereoisomers of 1,2-diphenylethene:
* (''E'')-Stilbene (''trans'' isomer)
* (''Z'')-Stilbene (''cis'' isomer)
See also
* Stilbenoid
Stilbenoids are hydroxylated derivatives of stilbene. They have a C6–C ...
was added to an ethyl ether solution of phenylisopropyl potassium, an abrupt color change from red to yellow took place. He had just observed the first addition of an organoalkali metal compound across a carbon-carbon double bond. Further work showed that he could successively add more and more of the olefinic hydrocarbon butadiene
1,3-Butadiene () is the organic compound with the formula CH2=CH-CH=CH2. It is a colorless gas that is easily condensed to a liquid. It is important industrially as a precursor to synthetic rubber. The molecule can be viewed as the union of two ...
to a solution of phenylisopropyl potassium and obtain a long-chain hydrocarbon with the reactive organopotassium end still intact. Oligomer
In chemistry and biochemistry, an oligomer () is a molecule that consists of a few repeating units which could be derived, actually or conceptually, from smaller molecules, monomers.Quote: ''Oligomer molecule: A molecule of intermediate relativ ...
s such as these were the forerunners of the so-called " living polymers".
Polyethylene
Since Ziegler was working at the Max Planck Institute for Coal Research, ethylene
Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon–carbon bond, carbon–carbon doub ...
was readily available as a byproduct from coal gas. Because of this cheap feedstock of ethylene and the relevance to the coal industry, Ziegler began experimenting with ethylene, and made it a goal to synthesize polyethylene of high molecular weight. His attempts were thwarted because a competing elimination reaction kept occurring causing an anomalous result: instead of ethylene being converted into a mixture of higher aluminum alkyls, its dimer, 1-butene
1-Butene (IUPAC name: But-1-ene, also known as 1-butylene) is the organic compound with the formula CH3CH2CH=CH2. It is a colorless gas, but easily condensed to give a colorless liquid. It is classified as a linear alpha-olefin (terminal alkene). ...
, was almost the only product. It was reasoned that a contaminant must have been present to cause this unexpected elimination reaction, and the cause was eventually determined to be traces of nickel salts. Ziegler realized the significance of this finding; if a nickel salt could have such a dramatic influence on the course of an ethylene-aluminum alkyl reaction, then perhaps another metal might delay the elimination reaction
An elimination reaction is a type of organic reaction in which two substituents are removed from a molecule in either a one- or two-step mechanism. The one-step mechanism is known as the E2 reaction, and the two-step mechanism is known as the E1 r ...
. Ziegler and his student H. Breil found that salts of chromium
Chromium is a chemical element; it has Symbol (chemistry), symbol Cr and atomic number 24. It is the first element in Group 6 element, group 6. It is a steely-grey, Luster (mineralogy), lustrous, hard, and brittle transition metal.
Chromium ...
, zirconium
Zirconium is a chemical element; it has Symbol (chemistry), symbol Zr and atomic number 40. First identified in 1789, isolated in impure form in 1824, and manufactured at scale by 1925, pure zirconium is a lustrous transition metal with a greyis ...
, and especially titanium
Titanium is a chemical element; it has symbol Ti and atomic number 22. Found in nature only as an oxide, it can be reduced to produce a lustrous transition metal with a silver color, low density, and high strength, resistant to corrosion in ...
did not promote the R2AlH-elimination but, instead, enormously accelerated the "growth" reaction. Simply passing ethylene, at atmospheric pressure, into a catalytic amount of TiCl3 and Et2AlCl dissolved in a higher alkane led to the prompt deposition of polyethylene. Ziegler was able to obtain high molecular weight polyethylene (MW > 30,000) and, most importantly, to do so at low ethylene pressures. The Ziegler group suddenly had a polymerization procedure for ethylene superior to all existing processes.
Ziegler–Natta catalyst
In 1952, Ziegler disclosed his catalyst
Catalysis () is the increase in rate of a chemical reaction due to an added substance known as a catalyst (). Catalysts are not consumed by the reaction and remain unchanged after it. If the reaction is rapid and the catalyst recycles quick ...
to the Montecatini Company in Italy, for which Giulio Natta was acting as a consultant. Natta denoted this class of catalysts as "Ziegler catalysts" and became extremely interested in their ability and potential to stereoregularly polymerize α-olefins such as propene. Ziegler, meanwhile concentrated mainly on the large-scale production of polyethylene
Polyethylene or polythene (abbreviated PE; IUPAC name polyethene or poly(methylene)) is the most commonly produced plastic. It is a polymer, primarily used for packaging (plastic bags, plastic films, geomembranes and containers including bott ...
and copolymers of ethylene
Ethylene (IUPAC name: ethene) is a hydrocarbon which has the formula or . It is a colourless, flammable gas with a faint "sweet and musky" odour when pure. It is the simplest alkene (a hydrocarbon with carbon–carbon bond, carbon–carbon doub ...
and propylene
Propylene, also known as propene, is an unsaturated organic compound with the chemical formula . It has one double bond, and is the second simplest member of the alkene class of hydrocarbons. It is a colorless gas with a faint petroleum-like o ...
. Soon the scientific community was informed of his discovery. Highly crystal
A crystal or crystalline solid is a solid material whose constituents (such as atoms, molecules, or ions) are arranged in a highly ordered microscopic structure, forming a crystal lattice that extends in all directions. In addition, macros ...
line and stereoregular polymers that previously could not be prepared became synthetically feasible. For their work on the controlled polymerization of hydrocarbons through the use of these novel organometallic catalysts, Karl Ziegler and Giulio Natta shared the 1963 Nobel Prize in Chemistry.
Awards and honours
Karl Ziegler received many awards and honors. The following highlights some of the most significant awards:
* Liebig-Denkmünze medal (1935); This medal was awarded by the present day German Chemical Society and is given to a German chemist for their outstanding accomplishments and creativity. Ziegler received the award because of his work in the synthesis of multi-membered ring systems and stable tri-valent carbon radicals.
* War Merit Cross, 2nd class (19 October 1940)
*Carl Duisberg Plakette (1953); This award is given for outstanding service to the promotion of chemistry from the German Chemical Society.
* Lavoisier Medal (1955); This award is given by the French Chemical Society to scientists in various disciplines of chemistry.
*Carl Engler Medal (1958); This award is given by the German Society of Petroleum Science and Coal Chemicals, of which he was the president in earlier years.
* Werner von Siemens Ring (1960); This ring is awarded by the Werner von Siemens Foundation and is considered the highest German award for individuals who by their performance and skills opened up new technological paths.
*Nobel Prize in Chemistry
The Nobel Prize in Chemistry () is awarded annually by the Royal Swedish Academy of Sciences to scientists in the various fields of chemistry. It is one of the five Nobel Prizes established by the will of Alfred Nobel in 1895, awarded for outst ...
(1963); " isexcellent work on organometallic compounds has unexpectedly led to new polymerization reactions and thus paved the way for new and highly useful industrial processes."
* Swinburne Medal of the Plastics Institute, London (1964); This award recognizes an individual who has made a significant advancement to the science, engineering or technology of plastics.
* Grand Merit Cross with Star and Sash (''Großes Verdienstkreuz mit Stern und Schulterband'') of the Federal Republic of Germany (1964)
*International Synthetic Rubber Medal of Rubber and Plastics Age (1967)
*Grand Federal Cross of Merit
The Order of Merit of the Federal Republic of Germany (, or , BVO) is the highest state decoration, federal decoration of the Federal Republic of Germany. It may be awarded for any field of endeavor. It was created by the first List of president ...
(Order of Merit of the Federal Republic of Germany)(1969); Ziegler was given this award for his work in the area of Science and Technology.
* Pour le Mérite for Arts and Sciences (formerly Peace Class) (1969)
*Foreign Member of the Royal Society
The Royal Society, formally The Royal Society of London for Improving Natural Knowledge, is a learned society and the United Kingdom's national academy of sciences. The society fulfils a number of roles: promoting science and its benefits, re ...
(1971)
*Wilhelm Exner Medal
The Wilhelm Exner Medal has been awarded by the Austrian Industry Association, (ÖGV), for excellence in research and science since 1921.
The medal is dedicated to Wilhelm Exner (1840–1931), former president of the Association, who initialize ...
(1971).[Editor, ÖGV. (2015). Wilhelm Exner Medal. Austrian Trade Association. ÖGV. Austria.]
*Memorial tablet of the German Chemical Society
The German Chemical Society () is a learned society and professional association founded in 1949 to represent the interests of German chemists in local, national and international contexts. GDCh "brings together people working in chemistry and th ...
under the Historic Landmarks of Chemistry program (''Historische Stätten der Chemie'') at the Max Planck Institute for Coal Research in Mülheim an der Ruhr
Mülheim, officially Mülheim an der Ruhr (, ; ; ) and also described as ''"City on the River"'', is a city in North Rhine-Westphalia in western Germany. It is located in the Ruhr Area between Duisburg, Essen, Oberhausen and Ratingen. It is home ...
(2008)
*Honorary doctorates from the Technical University of Hannover, Giessen University, University of Heidelberg
Heidelberg University, officially the Ruprecht Karl University of Heidelberg (; ), is a public university, public research university in Heidelberg, Baden-Württemberg, Germany. Founded in 1386 on instruction of Pope Urban VI, Heidelberg is List ...
and Darmstadt Technical University
*The ''Karl-Ziegler-Schule'' in Mülheim was named after Ziegler
*The Karl Ziegler Foundation is located at the German Chemical Society and gives the Science Award, the (worth 50,000 euros)
See also
* Dienone–phenol rearrangement
* List of Nobel laureates in Chemistry
References
External links
* including the Nobel Lecture, 12 December 1963 ''Consequences and Development of an Invention''
{{DEFAULTSORT:Ziegler, Karl
1898 births
1973 deaths
People from Hesse-Nassau
Förderndes Mitglied der SS
20th-century German chemists
University of Marburg alumni
German polymer scientists and engineers
German Nobel laureates
Nobel laureates in Chemistry
Werner von Siemens Ring laureates
Grand Crosses with Star and Sash of the Order of Merit of the Federal Republic of Germany
Foreign members of the Royal Society
Recipients of the Pour le Mérite (civil class)
Max Planck Society people
Academic staff of Goethe University Frankfurt
Presidents of the German Chemical Society
Max Planck Institute directors