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From Wikipedia, the free encyclopedia

Paul John Flory (June 19, 1910 – September 9, 1985) was an American chemist and Nobel laureate who was known for his work in the field of polymers, or macromolecules.[2] He was a leading pioneer in understanding the behavior of polymers in solution, and won the Nobel Prize in Chemistry in 1974 "for his fundamental achievements, both theoretical and experimental, in the physical chemistry of macromolecules".[3]

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  • PC30 Flory Huggins Theorie - Wie gut vertragen sich die Komponenten A und B?

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We now discuss a theory which predicts us how two components on combining behavior. A homogeneous mixture or a heterogeneous mixture? When a batch is created, as the composition of the two phases? etc. This theory is the Flory-Huggins theory. We look at the process of Mischuens from energy and to entropic considerations. Between the particles of the pure component A and component B of the pure exist intra-component interaction. Energies between the particles A; Energies between the particles as In a homogeneous mixture there is additionally Inter-component interactions. Forces and energies between the different components. the Flory-Huggins coefficient describes quantitatively how these forces, this energy relate to each other. when the inter-components interactions, and intra-component interaction are equal, then the Flory-Huggins coefficient equal to zero. Then we speak of a ideal mixture (or ideal solution). If the components are energetically "sympathetic" outweigh the Inter-component interactions. Then is the Flory-Huggins- Coefficient negative. If the predominate in intra-component interactions in the mixture, then the mixture is an endothermic process (components are "unappealing") and the Flory-Huggins coefficient is positive. The Flory-Huggins coefficient allows the calculation of the Mixing enthalpy (heat of mixing) Mix "sympathetic" components exothermically; "unsympatische" components mix endothermic and ideal mixtures formed without heat effect (enthalpy of mixing) Under entropic aspects of the formation of a mixture is favored in any case. Entropy - a measure of the degree of distribution or "Chaos" - increases the mixing in each case; regardless of the energy Conditions. Flory and Huggins enter the following equation for the entropy of mixing; This term is in each case positive. We discuss an ideal mixture (eg, benzene and toluene): The mixing volume is zero. there is no difference between the Final volume and the sum of the output volume. The heat of mixing, ie, the enthalpy of mixing is also zero; the enthalpy of the final state corresponds to the Total Enthalpies of the initial states. The entropy increases when Mixing to in each case. The composition of the mixture, that is, the molar fractions determine the numerical value the entropy of mixing. The free enthalpy - a measure for the instability - therefore takes in each case from the mixing. as you can easily can be calculated by combination of delta H and delta S for Gibbs-Helmholtz. If we take the mixing enthalpy, the mixing entropy and the free enthalpy of mixing on the Apply mixture ratio, we obtain the following three representations. Each graph has x-axis as a measure of tthe composition of the mixture corresponds to the left edge of the pure component A, the right edge of pure component B, therebetween all possible mixtures. For the enthalpy of mixing we get a horizontal line, and each mixture provides the zero enthalpy of mixing For the entropy of mixing, we recognize a maximum at a 50:50 mixture; here takes the entropy most strongly. Accordingly, we have a minimum of the free energy at this point. Here we have a maximum profit of stability. The Flory-Huggins equation describes the free energy - a measure for the instability of the mixture. They includes an enthalpy, and a proportion of total entropy From this function can be used to determine miscibility gaps and phase diagrams In an ideal mixture the function is always convex curve (purple curve) and means The mixture more stable than the pure components the same still applies in greater degree for Mixtures negative Flory-Huggins parameter. (Red curve; convex curved) When the Flory-Huggins parameter is always positive, We come finally to free energy curves with concave curvature. Concave curvature is always equivalent in a miscibility gap. We can to secure such a curve a double tangent from "below" Create (yellow line); Points (between the contact points on the yellow double tangent) correspond to heterogeneous Mixtures that are more stable as homogeneous mixtures (On the green line) In this way we can from the Flory-Huggins curves work out the phase diagram: Unstable is a Mixing between the turning points. ermittlen) Between drawn in red Punten is Unstable mixture and decomposes spontaneously (Spinodal points) Between the points of contact the double tangent and the spinodal points, the mixture metastable. By evaluating the Flory-Huggins curves at different temperatures we can change the width of the miscibility gap in Discuss a function of temperature. In this example, with increasing temperature, the mixture gap narrower - the system has a top critical solution temperature. Above this temperature, the system is always homogeneous; below there is a miscibility gap. (Summary Flory-Huggins theory) Using the Flory-Huggins theory you can mix the two components thermodynamically describe. The entropy of mixing is always positive. The enthalpy of mixing is either negative, Zero, or positive, according to the Flory-Huggins coefficient chi Chi is a measure of whether the two components energetically "Sympathetic, indifferent or unsympathetic" are. The resulting Flory-Huggins equation describes the instability of the mixture. Depending on by Chi this curve only convex or concave portions also. Concave portions indicate miscibility gaps.

Biography

Personal life

Flory was born in Sterling, Illinois, on June 19, 1910 to Ezra Flory and Nee Martha Brumbaugh. His father worked as a clergyman-educator, and his mother was a school teacher. His ancestors were German Huguenots, who traced their roots back to Alsace.[4][5] He first gained his interest in science from Carl W Holl, who was a professor in chemistry. Holl was employed in Indiana at Manchester College as a chemistry professor. In 1936, he married Emily Catherine Tabor. He and Emily had three children together: Susan Springer, Melinda Groom and Paul John Flory, Jr. They also had five grandchildren. All of his children pursued careers in the field of science. His first position was at DuPont with Wallace Carothers.[6][7] He was posthumously inducted into the Alpha Chi Sigma Hall of Fame in 2002.[8] Flory died on September 9, 1985, due to a massive heart attack. His wife Emily died in 2006 aged 94.

Schooling

After graduating from Elgin High School in Elgin, Illinois in 1927, Flory received a bachelor's degree from Manchester College (Indiana) (now Manchester University) in 1931 and a Ph.D. from the Ohio State University in 1934. He completed a master's degree in organic chemistry under the supervision of Prof. Cecil E Boord.[9] Flory then pursued his doctorate thesis in physical chemistry studying the photochemistry of nitric oxide, supervised by Prof. Herrick L. Johnston.[10]

Work

In 1934, after receiving his Ph.D., he joined the Central Department of Dupont and Company working with Wallace H. Carothers.[11] After the death of Carothers in 1937, Flory was involved for two years at the Basic Research Laboratory located in the University of Cincinnati. During World War II, there was a need for research to develop synthetic rubber, so Flory joined the Esso Laboratories of the Standard Oil Development Company.[12] During 1943 to 1948 was the Research Laboratory of the Goodyear Tire and Rubber Company. In fact, he was the director of research at the Goodyear Tire and Rubber Company, leading the team for studies on polymers.

After working in the industry, Flory left to work at Cornell University for a lectureship. The lectureship was with the George Fisher Baker Non-Residents. During the lectureship, Flory was able to study and understand a way to treat the effect of the excluded volume. According the nobelprize.org polymers, "would be nonasymptotic with the length of the chain, that is the fear of the contribution by the exclusion of the segment of the chain from the space occupied would increase without a limit as the chain is lengthened. This was the volume on the configuration of polymer chains. In 1957, Flory and his family decided to make the move to Pittsburgh, Pennsylvania. The reason he and his family moved from New York to Pennsylvania was for him to be able to develop a program of basic research in chemistry at the Carnegie Mellon Institute. After his work at the Carnegie Mellon Institute, he accepted a professorship position at Stanford University in the department of chemistry. While he was at Stanford University, he changed his direction of research. The change of view in his studies has to do with the spatial configuration having to do with chain molecules. This have to do with configuration treatments having to do with chain molecules. The treatment is the dependent properties through mathematical methods. Not only is mathematical methods the only treatment but so is the thermodynamics of solutions. After his retirement he Flory remained still very active in the world of chemistry. He was a consultant for Dupont and IBM, not long after he retired. Flory also was involved with the study of the foundations in the Soviet Union started off by the professor MV Volkenstein and his collaborators. He also worked with the late professor of Kazuo Nagai in Japan. He felt the need to fight for scientists who were oppressed in various countries. In addition, he also spoke as the "Voice of America", during a broadcast in Eastern Europe as well as Soviet Union. Flory also worked for the "Committee on Human Rights" which is known as the National Academy of Sciences from 1979 to 1984. During 1980, he worked as a delegate at the scientific forum in Hamburg.

Research

After receiving his doctorate in 1934, he dealt with a variety of issues with physical chemistry. This having to do with the kinetics and mechanisms of polymeric substances. Having to do with the distribution of molar mass, solution of thermodynamics and hydrodynamics. In addition, during 1934, he also was able to discover that when polymeric chains will keep growing if they are mixed with other molecules when present. Flory also discovered the understanding of the term 'theta.' In other words, is the constant of hydrodynamic. With the theta point that is the neutral volumes interactions. In conclusion to the development of the theta point it has been confirmed and studied in a variety of laboratories by many scientists. Both natural and synthetic polymers have been studied throughout the theta point. Throughout this a better understanding of macromolecules was provided. It helped with the creation of basis under rational interpretations of physical measurements. The measurements have relations to both the solutions of polymers and quantitative characteristics. Some work completed by Paul Flory during his time includes the development in the quantitative correlations between the chain molecules and chemical structure of properties. This has to do with the way polymers are composed and what are composed of polymers. One piece of material formed through polymers is plastic. In the mid-1930s, Flory discovered how polymers are dissolved in a solvent. Leading to becoming outstretches which is caused by the forces of both polymers and solvent parts. He even had part finding a solution to polymers.

Career and polymer science

Flory's earliest work in polymer science was in the area of polymerization kinetics at the DuPont Experimental Station. In condensation polymerization, he challenged the assumption that the reactivity of the end group decreased as the macromolecule grew, and by arguing that the reactivity was independent of the size, he was able to derive the result that the number of chains present decreased with size exponentially. In addition polymerization, he introduced the important concept of chain transfer to improve the kinetic equations and remove difficulties in understanding the polymer size distribution.

In 1938, after Carothers' death, Flory moved to the Basic Science Research Laboratory at the University of Cincinnati. There he developed a mathematical theory for the polymerization of compounds with more than two functional groups and the theory of polymer networks or gels. This led to the Flory-Stockmayer theory of gelation, which equivalent to percolation on the Bethe lattice and in fact represents the first paper in the percolation field.

In 1940 he joined the Linden, NJ laboratory of the Standard Oil Development Company where he developed a statistical mechanical theory for polymer mixtures. In 1943 he left to join the research laboratories of Goodyear as head of a group on polymer fundamentals. In the Spring of 1948 Peter Debye, then chairman of the chemistry department at Cornell University, invited Flory to give the annual Baker Lectures. He then was offered a position with the faculty in the Fall of the same year. He was initiated into the Tau chapter of Alpha Chi Sigma at Cornell in 1949.[8] At Cornell he elaborated and refined his Baker Lectures into his magnum opus, Principles of Polymer Chemistry which was published in 1953 by Cornell University Press. This quickly became a standard text for all workers in the field of polymers, and is still widely used to this day.

Flory introduced the concept of excluded volume, coined by Werner Kuhn in 1934, to polymers. Excluded volume refers to the idea that one part of a long chain molecule can not occupy space that is already occupied by another part of the same molecule. Excluded volume causes the ends of a polymer chain in a solution to be further apart (on average) than they would be were there no excluded volume. The recognition that excluded volume was an important factor in analyzing long-chain molecules in solutions provided an important conceptual breakthrough, and led to the explanation of several puzzling experimental results of the day. It also led to the concept of the theta point, the set of conditions at which an experiment can be conducted that causes the excluded volume effect to be neutralized. At the theta point, the chain reverts to ideal chain characteristics – the long-range interactions arising from excluded volume are eliminated, allowing the experimenter to more easily measure short-range features such as structural geometry, bond rotation potentials, and steric interactions between near-neighboring groups. Flory correctly identified that the chain dimension in polymer melts would have the size computed for a chain in ideal solution if excluded volume interactions were neutralized by experimenting at the theta point.

Among his accomplishments are an original method for computing the probable size of a polymer in good solution, the Flory-Huggins Solution Theory, the extension of polymer physics concepts to the field of liquid crystals, and the derivation of the Flory exponent, which helps characterize the movement of polymers in solution.

The Flory convention

see Flory convention for details.

In modeling the position vectors of atoms in macromolecules it is often necessary to convert from Cartesian coordinates (x,y,z) to generalized coordinates. The Flory convention for defining the variables involved is usually employed. For an example, a peptide bond can be described by the x,y,z positions of every atom in this bond or the Flory convention can be used. Here one must know the bond lengths , bond angles , and the dihedral angles . Applying a vector conversion from the Cartesian coordinates to the generalized coordinates will describe the same three-dimensional structure using the Flory convention.

Awards and honors

Flory was elected to the United States National Academy of Sciences in 1953 and the American Academy of Arts and Sciences in 1957.[13][14] In 1968, he received the Charles Goodyear Medal. He also received the Priestley Medal and the Golden Plate Award of the American Academy of Achievement[15] in 1974. He received the Carl-Dietrich-Harries-Medal for commendable scientific achievements in 1977.[16] Flory received the Nobel Prize in Chemistry in 1974 "for his fundamental achievements both theoretical and experimental, in the physical chemistry of the macromolecules."[17] Additionally in 1974 Flory was awarded the National Medal of Science in Physical Sciences. The medal was presented to him by President Gerald Ford. This award was given to him because of his research on the "formation and structure of polymeric substances".[18]

Published books

With over 300 writings, both published and unpublished, throughout his lectureship at the university with the research and teaching led to his first published book. The book published by Cornell University was called the "Principles of Polymer Chemistry." The book was then the basis use of information for undergrad students. It was the standard principle for many decades, used by many professors. Another book which was published by Flory was "Statistical Mechanics of Chain Molecules." The book was published in 1969, worked to summarize different parts both molecules theories and applications. In 1985, the book written by Paul Flory called, "Selected Works of Paul Flory." This summarized much of his work and studies.

Bibliography

  • Flory, Paul. (1953) Principles of Polymer Chemistry. Cornell University Press. ISBN 0-8014-0134-8.
  • Flory, Paul. (1969) Statistical Mechanics of Chain Molecules. Interscience. ISBN 0-470-26495-0. Reissued 1989. ISBN 1-56990-019-1.
  • Flory, Paul. (1985) Selected Works of Paul J. Flory. Stanford Univ Press. ISBN 0-8047-1277-8.

References

  1. ^ "SCI Perkin Medal". Science History Institute. May 31, 2016. Retrieved March 24, 2018.
  2. ^ Pecora, Robert (November 1986). "Obituary: Paul John Flory". Physics Today. 39 (11): 116–117. Bibcode:1986PhT....39k.116P. doi:10.1063/1.2815221.
  3. ^ "The Nobel Prize in Chemistry 1974". NobelPrize.org. Retrieved July 11, 2023.
  4. ^ "Paul J. Flory – Biographical". nobelprize.org. 1974. Retrieved January 28, 2024. I was born on 19 June, 1910, in Sterling, Illinois, of Huguenot-German parentage, mine being the sixth generation native to America.
  5. ^ Johnson, William S.; Stockmayer, Walter H.; Taube, Henry (2002). "Paul John Flory 1910–1985" (PDF). Biographical Memoirs of the National Academy of Sciences: 4. Retrieved January 28, 2024. The Flory family traces its roots back to Alsace, then England, later to Pennsylvania, and then to Ohio.
  6. ^ Mangravite, Andrew (2001). "Finding Aid to the Paul J. Flory papers, 1931–1985 bulk 1950–1978". Science History Institute. Retrieved March 27, 2018. Click on 'Paul J. Flory papers finding aid' for full finding aid.
  7. ^ Morris, Peter J. T. (1986) Polymer Pioneers: A Popular History of the Science and Technology of Large Molecules Center for History of Chemistry, Philadelphia. pp. 70–73. ISBN 0941901033
  8. ^ a b Fraternity – Awards – Hall of Fame. Alpha Chi Sigma (May 23, 2018). Retrieved on 2018-07-17.
  9. ^ "Paul John Flory: A Biographical Memoir" (PDF).
  10. ^ "Paul J. Flory | Nobel Prize-Winning American Chemist | Britannica". www.britannica.com. June 15, 2023. Retrieved July 11, 2023.
  11. ^ "Paul J. Flory | Nobel Prize-Winning American Chemist | Britannica". www.britannica.com. June 15, 2023. Retrieved July 11, 2023.
  12. ^ "Paul John Flory: A Biographical Memoir" (PDF).
  13. ^ "Paul J. Flory". www.nasonline.org. Retrieved August 15, 2022.
  14. ^ "Paul John Flory". American Academy of Arts & Sciences. Retrieved August 15, 2022.
  15. ^ "Golden Plate Awardees of the American Academy of Achievement". www.achievement.org. American Academy of Achievement.
  16. ^ "Carl-Dietrich-Harries-Medal for commendable scientific achievements". dkg-rubber.de. DKG. Retrieved July 2, 2022.
  17. ^ "The Nobel Prize in Chemistry 1974". The Nobel Prize. Nobel media. Retrieved July 24, 2019.
  18. ^ "The President's National Medal of Science: Recipient Details". National Medal of Science. National Science Foundation. Retrieved July 24, 2019.

External links

This page was last edited on 29 April 2024, at 21:19
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