Sunday, 2 March 2014

HAVARD UNIVERSITY DORMS PICTURES--- UNITED STATES OF AMERICA.

THE UNIVERSITY OF DODOMA , TANZANIA.

DODOMA UNIVERSITY OF TANZANIA .

Saturday, 1 March 2014

OCH 213. ADVANCED INORGANIC CHEMISTRY----- BY. MWL. JAPHET MASATU.

F. Albert Cotton

Frank Albert Cotton
Born	April 9, 1930 Philadelphia, PA
Died	February 20, 2007 (aged 76) College Station, TX
Institutions	Texas A&M University
Doctoral advisor	Geoffrey Wilkinson
Notable awards	National Medal of Science, Wolf Prize, Priestley Medal, FRS

Frank Albert Cotton (April 9, 1930 – February 20, 2007)^[1] was an American chemist. He was the W.T. Doherty-Welch Foundation Chair and Distinguished Professor of Chemistry at Texas A&M University. He authored over 1700 scientific articles.^[2] Cotton was recognized for his research on the chemistry of the transition metals.

Education

Frank Albert Cotton (known as "Al" Cotton, or "F Albert" on publications) was born on April 9, 1930 in Philadelphia, Pennsylvania. He attended local public schools before Drexel University and then Temple University.^[3] After earning his BA degree from Temple in 1951, Cotton pursued a Ph.D. thesis under the guidance of Sir Geoffrey Wilkinson at Harvard where he worked on metallocenes.^[4] He received his Ph.D in 1955.^[5]

Independent career

Following his graduation from Harvard, Cotton began teaching at MIT. In 1961, at thirty-one years of age, he became the youngest person to have received a full professorship at MIT.^[3] His work emphasized both electronic structure and chemical synthesis. He pioneered the study of multiple bonding between transition metal atoms, starting with research on rhenium halides,^[6] and in 1964 identified the quadruple bond in the Re
2Cl2−
8 ion. His work soon focused on other metal-metal bonded species,^[7] elucidating the structure of chromium(II) acetate.
He was an early proponent of single crystal X-ray diffraction as a tool for elucidating the extensive chemistry of metal complexes. Through his studies on clusters, he demonstrated that many exhibited "fluxionality", whereby ligands interchange coordination sites on spectroscopically observable time-scales. He coined the term "hapticity" and the nomenclature that derives from it.
In 1962 he undertook the crystal structure of the Staphylococcal nuclease enzyme,^[8] solved to 2Å resolution in 1969, published in 1971,^[9] and deposited in the Protein Data Bank (PDB code 1SNS) as one of the first dozen protein crystal structures.^[10]
In 1972 Cotton moved to Texas A&M University as the Robert A. Welch Professor of Chemistry. The following year he was named the Doherty-Welch Distinguished Professor of Chemistry. He also served as the director of the university's Laboratory for Molecular Structure and Bonding.^[3]^[11]

Pedagogical influence

In addition to his research, Cotton taught inorganic chemistry. He authored Chemical Applications of Group Theory.^[12] This text focuses on group theoretical analysis of bonding and spectroscopy.
Among college students, Cotton is perhaps best known as the coauthor of the textbook Advanced Inorganic Chemistry, now in its sixth English edition.^[13]^[14] Coauthored with his thesis advisor, Sir Geoffrey Wilkinson, and now with coauthors Carlos Murillo and Manfred Bochmann, the textbook is colloquially known as "Cotton and Wilkinson." The text surveys coordination chemistry, cluster chemistry, homogeneous catalysis, and organometallic chemistry.^[3]^[15]
Cotton served on various editorial boards of scientific journals, including those of the Journal of the American Chemical Society, Inorganic Chemistry, and Organometallics. He chaired the Division of Inorganic Chemistry of the ACS and was an ACS Councillor for five years. He served on the U.S. National Science Board (1986–1998), which oversees the National Science Foundation, and the Scientific and Technical Advisory Committee of Argonne National Laboratory, and the National Research Laboratory Commission of Texas.
Cotton supervised the thesis research of 116 doctoral students^[11] as well as more than 150 postdoctoral associates.^[5]

Recognition

Among the awards Cotton received included the U.S. National Medal of Science in 1982,^[16] the Wolf Prize in 2000; and the Priestley Medal, the American Chemical Society's highest recognition, in 1998.^[11]
In 1995, the Department of Chemistry at Texas A&M along with the local section of the American Chemical Society, inaugurated the annual F.A. Cotton Medal for excellence in chemical research. A second award named in his honor, the F. Albert Cotton Award for Synthetic Inorganic Chemistry,^[17] is presented at the National Meeting of the American Chemical Society each year.^[11]
Cotton was a member of the National Academy of Sciences in the United States, and the corresponding academies in Russia, China, the United Kingdom, France, and Denmark, as well as the American Philosophical Society. He received twenty-nine honorary doctorates.^[11]

Run for ACS presidency

Cotton caused a controversy in his run for President of the American Chemical Society for 1984, wherein he mailed a letter to selected members describing his opponent as “a mediocre industrial chemist”.^[18] Cotton ultimately lost the bid to his opponent Dr. Warren D. Niederhauser of Rohm & Haas.^[19]

F.A. Cotton Medal for Excellence in Chemical Research

The F.A. Cotton Medal is awarded annually by the American Chemical Society, and sponsored by the The F. Albert Cotton Endowment Fund. Previous winners have included :
2012 R. Graham Cooks, Purdue University;^[20] 2011 George M. Whitesides, Harvard University; 2010 Peter J. Stang, University of Utah; 2009 Richard N. Zare, Stanford University; 2008 Chi-Huey Wong, The Scripps Research Institute, and National Taiwan University; 2007 Jacqueline K. Barton, California Institute of Technology; 2006 Robin M. Hochstrasser, University of Pennsylvania; 2005 Richard H. Holm, Harvard University; 2004 Albert Eschenmoser, Swiss Federal Institute of Technology, Zurich, and Scripps Research Institute; 2003 Gabor A. Somorjai, University of California, Berkeley; 2002 Ada Yonath, Weizman Institute of Science; 2001 Samuel J. Danishefsky, Department of Chemistry, Columbia University; 2000 Tobin J. Marks, Department of Chemistry, Northwestern University; 1999 Alexander Pines, Department of Chemistry, University of California, Berkeley; 1998 JoAnne Stubbe, Department of Chemistry, Massachusetts Institute of Technology; 1997 Pierre-Gilles de Gennes, École Supérieure de Physique et de Chimie Industrielles de la Ville de Paris, Collège de France; 1996 George A. Olah, Department of Chemistry, University of Southern California; 1995 F. Albert Cotton, Department of Chemistry, Texas A&M University ^[21]

Death

Cotton died on February 20, 2007 in College Station, Texas from complications of a head injury he suffered in a fall in October 2006.^[22] He was survived by his wife, the former Diane Dornacher, whom he married in 1959, and their two daughters, Jennifer and Jane.^[3] The Brazos County Sheriff's Department opened an investigation into his death, describing his death as "suspicious

Geoffrey Wilkinson

Sir Geoffrey Wilkinson

Born	14 July 1921 Springside, England
Died	26 September 1996 (aged 75) London, England
Nationality	United Kingdom
Fields	Inorganic chemistry
Institutions	University of California, Berkeley Harvard University Imperial College
Alma mater	Imperial College
Doctoral advisor	Henry Vincent Aird Briscoe
Known for	Homogeneous transition metal catalysis
Notable awards	Nobel Prize in Chemistry (1973) Fellow of the Royal Society^[1]

Sir Geoffrey Wilkinson FRS^[1] (14 July 1921 – 26 September 1996) was a Nobel laureate English chemist who pioneered inorganic chemistry and homogeneous transition metal catalysis.^[2]

Biography

Wilkinson was born at Springside, Todmorden, in Yorkshire. His father,Henry Wilkinson,^[3] was a master house painter and decorator; his mother,Ruth,^[3] worked in a local cotton mill. One of his uncles, an organist and choirmaster, had married into a family that owned a small chemical company making Epsom and Glauber's salts for the pharmaceutical industry; this is where he first developed an interest in chemistry.
He was educated at the local council primary school and, after winning a County Scholarship in 1932, went to Todmorden Grammar School. His physics teacher there, Luke Sutcliffe, had also taught Sir John Cockcroft, who received a Nobel Prize for "splitting the atom".

Wilkinson's catalyst RhCl(PPh₃)₃

In 1939 he obtained a Royal Scholarship for study at Imperial College London, from where he graduated in 1941. In 1942 Professor Friedrich Paneth was recruiting young chemists for the nuclear energy project. Wilkinson joined and was sent out to Canada, where he stayed in Montreal and later Chalk River Laboratories until he could leave in 1946. For the next four years he worked with Professor Glenn T. Seaborg at University of California, Berkeley, mostly on nuclear taxonomy.^[4] He then became a Research Associate at the Massachusetts Institute of Technology and began to return to his first interest as a student - transition metal complexes of ligands such as carbon monoxide and olefins.
He was then at the Harvard University from September 1951 until he returned to England in December 1955, with a sabbatical break of nine months in Copenhagen. At Harvard, he still did some nuclear work on excitation functions for protons in cobalt, but had already begun to work on olefin complexes.
In June 1955 he was appointed to the chair of Inorganic Chemistry at Imperial College London, and from then on worked almost entirely on the complexes of transition metals.
In 1980 he was awarded an honorary doctorate of science from the University of Bath. Imperial College London named a new hall of residence after him, which opened in October 2009.
He was married, with two daughters.

Work

Structure of ferrocene Fe(C₅H₅)₂

He is well known for his development of Wilkinson's catalyst RhCl(PPh₃)₃, and for the discovery of the structure of ferrocene. Wilkinson's catalyst is used industrially in the hydrogenation of alkenes to alkanes.^[5]
He received many awards, including the Nobel Prize for Chemistry in 1973 for his work on “organometallic compounds” (with Ernst Otto Fischer). He is also well known for writing, with his former doctoral student F. Albert Cotton, "Advanced Inorganic Chemistry", often referred to simply as "Cotton and Wilkinson", one of the standard inorganic chemistry textbooks.[

OCH 212. BASIC ORGANIC SPECTROSCOPY ----- BY. MWL. JAPHET MASATU.

BASIC ORGANIC SPECTROSCOPY.

Analysis of white light by dispersing it with a prism is an example of spectroscopy.

Spectroscopy /spɛkˈtrɒskəpi/ is the study of the interaction between matter and radiated energy.^[1]^[2] Historically, spectroscopy originated through the study of visible light dispersed according to its wavelength, by a prism. Later the concept was expanded greatly to comprise any interaction with radiative energy as a function of its wavelength or frequency. Spectroscopic data is often represented by a spectrum, a plot of the response of interest as a function of wavelength or frequency.

Introduction

Spectroscopy and spectrography are terms used to refer to the measurement of radiation intensity as a function of wavelength and are often used to describe experimental spectroscopic methods. Spectral measurement devices are referred to as spectrometers, spectrophotometers, spectrographs or spectral analyzers.
Daily observations of color can be related to spectroscopy. Neon lighting is a direct application of atomic spectroscopy. Neon and other noble gases have characteristic emission frequencies (colors). Neon lamps use collision of electrons with the gas to excite these emissions. Inks, dyes and paints include chemical compounds selected for their spectral characteristics in order to generate specific colors and hues. A commonly encountered molecular spectrum is that of nitrogen dioxide. Gaseous nitrogen dioxide has a characteristic red absorption feature, and this gives air polluted with nitrogen dioxide a reddish brown color. Rayleigh scattering is a spectroscopic scattering phenomenon that accounts for the color of the sky.
Spectroscopic studies were central to the development of quantum mechanics and included Max Planck's explanation of blackbody radiation, Albert Einstein's explanation of the photoelectric effect and Niels Bohr's explanation of atomic structure and spectra. Spectroscopy is used in physical and analytical chemistry because atoms and molecules have unique spectra. As a result, these spectra can be used to detect, identify and quantify information about the atoms and molecules. Spectroscopy is also used in astronomy and remote sensing on earth. Most research telescopes have spectrographs. The measured spectra are used to determine the chemical composition and physical properties of astronomical objects (such as their temperature and velocity).

Theory

One of the central concepts in spectroscopy is a resonance and its corresponding resonant frequency. Resonances were first characterized in mechanical systems such as pendulums. Mechanical systems that vibrate or oscillate will experience large amplitude oscillations when they are driven at their resonant frequency. A plot of amplitude vs. excitation frequency will have a peak centered at the resonance frequency. This plot is one type of spectrum, with the peak often referred to as a spectral line, and most spectral lines have a similar appearance.
In quantum mechanical systems, the analogous resonance is a coupling of two quantum mechanical stationary states of one system, such as an atom, via an oscillatory source of energy such as a photon. The coupling of the two states is strongest when the energy of the source matches the energy difference between the two states. The energy $(E)$ of a photon is related to its frequency $(\nu)$ by $E = h\nu$ where $h$ is Planck's constant, and so a spectrum of the system response vs. photon frequency will peak at the resonant frequency or energy. Particles such as electrons and neutrons have a comparable relationship, the de Broglie relations, between their kinetic energy and their wavelength and frequency and therefore can also excite resonant interactions.
Spectra of atoms and molecules often consist of a series of spectral lines, each one representing a resonance between two different quantum states. The explanation of these series, and the spectral patterns associated with them, were one of the experimental enigmas that drove the development and acceptance of quantum mechanics. The hydrogen spectral series in particular was first successfully explained by the Rutherford-Bohr quantum model of the hydrogen atom. In some cases spectral lines are well separated and distinguishable, but spectral lines can also overlap and appear to be a single transition if the density of energy states is high enough.

Classification of methods

Spectroscopy is a sufficiently broad field that many sub-disciplines exist, each with numerous implementations of specific spectroscopic techniques. The various implementations and techniques can be classified in several ways.

Type of radiative energy

Types of spectroscopy are distinguished by the type of radiative energy involved in the interaction. In many applications, the spectrum is determined by measuring changes in the intensity or frequency of this energy. The types of radiative energy studied include:

Electromagnetic radiation was the first source of energy used for spectroscopic studies. Techniques that employ electromagnetic radiation are typically classified by the wavelength region of the spectrum and include microwave, terahertz, infrared, near infrared, visible and ultraviolet, x-ray and gamma spectroscopy.
Particles, due to their de Broglie wavelength, can also be a source of radiative energy and both electrons and neutrons are commonly used. For a particle, its kinetic energy determines its wavelength.
Acoustic spectroscopy involves radiated pressure waves.
Mechanical methods can be employed to impart radiating energy, similar to acoustic waves, to solid materials.

Nature of the interaction

Types of spectroscopy can also be distinguished by the nature of the interaction between the energy and the material. These interactions include:^[1]

Absorption occurs when energy from the radiative source is absorbed by the material. Absorption is often determined by measuring the fraction of energy transmitted through the material; absorption will decrease the transmitted portion.
Emission indicates that radiative energy is released by the material. A material's blackbody spectrum is a spontaneous emission spectrum determined by its temperature. Emission can also be induced by other sources of energy such as flames or sparks or electromagnetic radiation in the case of fluorescence.
Elastic scattering and reflection spectroscopy determine how incident radiation is reflected or scattered by a material. Crystallography employs the scattering of high energy radiation, such as x-rays and electrons, to examine the arrangement of atoms in proteins and solid crystals.
Impedance spectroscopy studies the ability of a medium to impede or slow the transmittance of energy. For optical applications, this is characterized by the index of refraction.
Inelastic scattering phenomena involve an exchange of energy between the radiation and the matter that shifts the wavelength of the scattered radiation. These include Raman and Compton scattering.
Coherent or resonance spectroscopy are techniques where the radiative energy couples two quantum states of the material in a coherent interaction that is sustained by the radiating field. The coherence can be disrupted by other interactions, such as particle collisions and energy transfer, and so often require high intensity radiation to be sustained. Nuclear magnetic resonance (NMR) spectroscopy is a widely used resonance method and ultrafast laser methods are also now possible in the infrared and visible spectral regions.

Type of material

Spectroscopic studies are designed so that the radiant energy interacts with specific types of matter.

Atoms

Atomic spectroscopy was the first application of spectroscopy developed. Atomic absorption spectroscopy (AAS) and atomic emission spectroscopy (AES) involve visible and ultraviolet light. These absorptions and emissions, often referred to as atomic spectral lines, are due to electronic transitions of outer shell electrons as they rise and fall from one electron orbit to another. Atoms also have distinct x-ray spectra that are attributable to the excitation of inner shell electrons to excited states.
Atoms of different elements have distinct spectra and therefore atomic spectroscopy allows for the identification and quantitation of a sample's elemental composition. Robert Bunsen and Gustav Kirchhoff discovered new elements by observing their emission spectra. Atomic absorption lines are observed in the solar spectrum and referred to as Fraunhofer lines after their discoverer. A comprehensive explanation of the hydrogen spectrum was an early success of quantum mechanics and explained the Lamb shift observed in the hydrogen spectrum led to the development of quantum electrodynamics.
Modern implementations of atomic spectroscopy for studying visible and ultraviolet transitions include flame emission spectroscopy, inductively coupled plasma atomic emission spectroscopy, glow discharge spectroscopy, microwave induced plasma spectroscopy, and spark or arc emission spectroscopy. Techniques for studying x-ray spectra include X-ray spectroscopy and X-ray fluorescence (XRF).

Molecules

The combination of atoms into molecules leads to the creation of unique types of energetic states and therefore unique spectra of the transitions between these states. Molecular spectra can be obtained due to electron spin states (electron paramagnetic resonance), molecular rotations, molecular vibration and electronic states. Rotations are collective motions of the atomic nuclei and typically lead to spectra in the microwave and millimeter-wave spectral regions; rotational spectroscopy and microwave spectroscopy are synonymous. Vibrations are relative motions of the atomic nuclei and are studied by both infrared and Raman spectroscopy. Electronic excitations are studied using visible and ultraviolet spectroscopy as well as fluorescence spectroscopy.
Studies in molecular spectroscopy led to the development of the first maser and contributed to the subsequent development of the laser.

Crystals and extended materials

The combination of atoms or molecules into crystals or other extended forms leads to the creation of additional energetic states. These states are numerous and therefore have a high density of states. This high density often makes the spectra weaker and less distinct, i.e., broader. For instance, blackbody radiation is due to the thermal motions of atoms and molecules within a material. Acoustic and mechanical responses are due to collective motions as well.
Pure crystals, though, can have distinct spectral transitions and the crystal arrangement also has an effect on the observed molecular spectra. The regular lattice structure of crystals also scatters x-rays, electrons or neutrons allowing for crystallographic studies.

Nuclei

Nuclei also have distinct energy states that are widely separated and lead to gamma ray spectra. Distinct nuclear spin states can have their energy separated by a magnetic field, and this allows for NMR spectroscopy.

Organic Chemistry/Spectroscopy

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There are several spectroscopic techniques which can be used to identify organic molecules: infrared (IR), mass spectroscopy (MS) UV/visible spectroscopy (UV/Vis) and nuclear magnetic resonance (NMR).
IR, NMR and UV/vis spectroscopy are based on observing the frequencies of electromagnetic radiation absorbed and emitted by molecules. MS is based on measuring the mass of the molecule and any fragments of the molecule which may be produced in the MS instrument.

UV/Visible Spectroscopy

UV/Vis Spectroscopy uses ultraviolet and/or visible light to examine the electronic properties of molecules. Irradiating a molecule with UV or Visible light of a specific wavelength can cause the electrons in a molecule to transition to an excited state. This technique is most useful for analyzing molecules with conjugated systems or carbonyl bonds.

NMR Spectroscopy

Nuclear Magnetic Resonance (NMR) Spectroscopy is one of the most useful analytical techniques for determining the structure of an organic compound. There are two main types of NMR, ¹H-NMR (Proton NMR) and ¹³C-NMR (Carbon NMR). NMR is based on the fact that the nuclei of atoms have a quantized property called spin. When a magnetic field is applied to a ¹H or ¹³C nucleus, the nucleus can align either with (spin +1/2) or against (spin -1/2) the applied magnetic field.
These two states have different potential energies and the energy difference depends on the strength of the magnetic field. The strength of the magnetic field about a nucleus, however, depends on the chemical environment around the nucleus. For example, the negatively charged electrons around and near the nucleus can shield the nucleus from the magnetic field, lowering the strength of the effective magnetic field felt by the nucleus. This, in turn, will lower the energy needed to transition between the +1/2 and -1/2 states. Therefore, the transition energy will be lower for nuclei attached to electron donating groups (such as alkyl groups) and higher for nuclei attached to electron withdrawing groups (such as a hydroxyl group).
In an NMR machine, the compound being analyzed is placed in a strong magnetic field and irradiated with radio waves to cause all the ¹H and ¹³C nuclei to occupy the higher energy -1/2 state. As the nuclei relax back to the +1/2 state, they release radio waves corresponding to the energy of the difference between the two spin states. The radio waves are recorded and analyzed by computer to give an intensity versus frequency plot of the sample. This information can then be used to determine the structure of the compound.

Aromatics in H-NMR Electron Donating Groups vs. Electron Withdrawing Groups
On monosubstituted rings, electron donating groups resonate at high chemical shifts. Electron donating groups increase the electron density by releasing electrons into a reaction center, thus stabilizing the carbocation. An example of an electron donating group is methyl (-CH3).
Accordingly, electron withdrawing groups are represented at low chemical shifts. Electron withdrawing groups pull electrons away from a reacting center. This can stabilize an electron rich carbanion. Some examples of electron withdrawing groups are halogens (-Cl, -F) and carboxylic acid (-COOH).
Looking at the H NMR spectrum of ethyl benzene, we see that the methyl group is the most electron withdrawing, so it appears at the lowest chemical shift. The aromatic phenyl group is the most electron donating, so it has the highest chemical shift.

Disubstituted Rings
The sum of integrated intensity values for the entire aromatic region shows how many substituents are attached to the ring, so a total value of 4 indicates that the ring has 2 substituents. When a benzene ring has two substituent groups, each exerts an influence on following substitution reactions. The site at which a new substituent is introduced depends on the orientation of the existing groups and their individual directing effects. For a disubstituted benzene ring, there are three possible NMR patterns.

Note that para-substituted rings usually show two symmetric sets of peaks that look like doublets.
The order of these peaks is dependent on the nature of the two substituents. For example, the three NMR spectra of chloronitrobenzene isomers are below:

Mass Spectroscopy

A mass spectroscope measures the exact mass of ions, relative to the charge. Many times, some form of seperation is done beforehand, enabling a spectrum to be collected on a relatively pure sample. An organic sample can be introduced into a mass spectroscope and ionised. This also breaks some molecules into smaller fragments.
The resulting mass spectrum shows:
1) The heaviest ion is simply the ionised molecule itself. We can simply record its mass.
2) Other ions are fragments of the molecule and give information about its structure. Common fragments are:

species	formula	mass
methyl	CH₃⁺	15
ethyl	C₂H₅⁺	29
phenyl	C₆H₅⁺	77

Infrared spectroscopy.

Absorbing infrared radiation makes covalent bonds vibrate. Different types of bond absorb different wavelengths of infrared:
Instead of wavelength, infrared spectroscopists record the wavenumber; the number of waves that fit into 1 cm. (This is easily converted to the energy of the wave.)
For some reason the spectra are recorded backwards (from 4000 to 500 cm^-1 is typical), often with a different scale below 1000 cm^-1 (to see the fingerprint region more clearly) and upside-down (% radiation transmitted is recorded instead of the absorbance of radiation).
The wavenumbers of the absorbed IR radiation are characteristic of many bonds, so IR spectroscopy can determine which functional groups are contained in the sample. For example, the carbonyl (C=O) bond will absorb at 1650-1760cm^-1.

Summary of absorptions of bonds in organic molecules

w:Infrared Spectroscopy Correlation Table

Bond	Minimum wavenumber (cm^-1)	Maximum wavenumber (cm^-1)	Functional group (and other notes)
C-O	1000	1300	Alcohols and esters
N-H	1580	1650	Amine or amide
C=C	1610	1680	Alkenes
C=O	1650	1760	Aldehydes, ketones, acids, esters, amides
O-H	2500	3300	Carboxylic acids (very broad band)
C-H	2850	3000	Alkane
C-H	3050	3150	Alkene (Compare intensity to alkane for rough idea of relative number of H atoms involved.)
O-H	3230	3550	H-bonded in alcohols
N-H	3300	3500	Amine or amide
O-H	3580	3670	Free –OH in alcohols (only in samples diluted with non-polar solvent)

Absorptions listed in cm^-1.

Typical method

^[1]

Typical apparatus

A beam of infra-red light is produced and split into two separate beams. One is passed through the sample, the other passed through a reference which is often the substance the sample is dissolved in. The beams are both reflected back towards a detector, however first they pass through a splitter which quickly alternates which of the two beams enters the detector. The two signals are then compared and a printout is obtained.
A reference is used for two reasons: