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Chemical Shift
Chemical Shift
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Chemical shift
From Wikipedia, the free encyclopedia
In nuclear magnetic resonance (NMR) spectroscopy, the chemical shift is the resonant frequency of a nucleus relative to a standard. Often the position and number of chemical shifts are diagnostic of the structure of a molecule.[1][2][3] Chemical shifts are also used to describe signals in other forms of spectroscopy such as photoemission spectroscopy. Some atomic nuclei possess a magnetic moment (nuclear spin), which gives rise to different energy levels and resonance frequencies in a magnetic field. The total magnetic field experienced by a nucleus includes local magnetic fields induced by currents of electrons in the molecular orbitals (note that electrons have a magnetic moment themselves). The electron distribution of the same type of nucleus (e.g. 1H, 13C, 15N) usually varies according to the local geometry (binding partners, bond lengths, angles between bonds, ...), and with it the local magnetic field at each nucleus. This is reflected in the spin energy levels (and resonance frequencies). The variations of nuclear magnetic resonance frequencies of the same kind of nucleus, due to variations in the electron distribution, is called the chemical shift. The size of the chemical shift is given with respect to a reference frequency or reference sample (see also chemical shift referencing), usually a molecule with a barely distorted electron distribution.
Contents
1 Operating frequency 2 Chemical shift referencing 3 The induced magnetic field 4 Diamagnetic shielding 5 Factors causing chemical shifts 6 Magnetic properties of most common nuclei 7 Other chemical shifts 8 See also 9 References 10 External links
Operating frequency
The operating (or Larmor) frequency of a magnet is calculated from the Larmor equation[4]
where is the actual strength of the magnet in units like teslas or gauss, and is the gyromagnetic ratio of the nucleus being tested which is in turn calculated from its magnetic moment and spin number with the nuclear magneton and the Planck constant h:
http://en.wikipedia.org/wiki/Chemical_shift
5/8/2012
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Since the numerator is usually in hertz, and the denominator in megahertz, delta is expressed in ppm. The detected frequencies (in Hz) for 1H, 13C, and 29Si nuclei are usually referenced against TMS (tetramethylsilane) or DSS, which is assigned the chemical shift of zero. Other standard materials are used for setting the chemical shift for other nuclei. Thus, an NMR signal that absorbs at 300 Hz higher than does TMS at an applied frequency of 300 MHz has a chemical shift of:
Although the frequency depends on the applied field the chemical shift is independent of it. On the other hand the resolution of NMR will increase with applied magnetic field resulting in ever increasing chemical shift changes.
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5/8/2012
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the signal or shift is downfield or at low field or paramagnetic Conversely a lower chemical shift is called a diamagnetic shift, and is upfield and more shielded.
Diamagnetic shielding
In real molecules protons are surrounded by a cloud of charge due to adjacent bonds and atoms. In an applied magnetic field (B0) electrons circulate and produce an induced field (Bi) which opposes the applied field. The effective field at the nucleus will be B = B0 Bi. The nucleus is said to be experiencing a diamagnetic shielding.
The protons in aromatic compounds are shifted downfield even further with a signal for benzene at 7.73 ppm as a consequence of a diamagnetic ring current. Alkyne protons by contrast resonate at high field in a 23 ppm range. For alkynes the most effective orientation is the external field in parallel with electrons circulation around the triple bond. In this way the acetylenic protons are located in the cone-shaped shielding zone hence the upfield shift.
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Isotope
1 2
H H B B C C N N O O F Si Si P Cl Cl
10 11 12 13 14 15 16 17 19 28 29 31 35 37
H, 13C, 15N, 19F and 31P are the five nuclei that have the greatest importance in NMR experiments: 1H because of high sensitivity and vast occurrence in organic compounds
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C because of being the key component of all organic compounds despite occurring at a low abundance (1.1%) compared to the major isotope of carbon 12C, which has a spin of 0 and therefore is NMR inactive. 15 N because of being a key component of important biomolecules such as proteins and DNA 19F because of high relative sensitivity 31P because of frequent occurrence in organic compounds and moderate relative sensitivity
13
See also
MRI Nuclear Magnetic Resonance Nuclear magnetic resonance spectroscopy of carbohydrates Nuclear magnetic resonance spectroscopy of nucleic acids Nuclear magnetic resonance spectroscopy of proteins Protein NMR Relaxation (NMR) Solid-state NMR Zeeman effect
References
1. 2. 3. 4. 5. 6. 7. ^ Spectrometric Identification of organic Compounds Silverstein, Bassler, Morrill 4th Ed. ISBN 047109700 ^ Organic Spectroscopy William Kemp 3rd Ed. ISBN 0333417674 ^ Basic 1H - 13C-NMR spectroscopy Metin Balei ISBN 0444518118 ^ Chemical Shift | NMRCentral (http://nmrcentral.com/2011/08/chemical-shift/) ^ In units of the nuclear magneton ^ CRC Handbook of Chemistry and Physics 65Th Ed ^ A Short History of Three Chemical Shifts Shin-ichi Nagaoka Vol. 84 No. 5 May 2007 Journal of Chemical Education 801, doi:10.1021/ed084p801 (http://pubs.acs.org/doi/abs/10.1021/ed084p801)
External links
www.chem.wisc.edu (http://www.chem.wisc.edu/areas/reich/handouts/nmr-h/hdata.htm) BioMagResBank (http://www.bmrb.wisc.edu) wwwchem.csustan.edu (http://wwwchem.csustan.edu/Tutorials/NMRTABLE.HTM) Proton chemical shifts (http://www.chem.wisc.edu/areas/reich/handouts/nmr-h/hdata.htm) Carbon chemical shifts (http://www.chem.wisc.edu/areas/reich/handouts/nmr-c13/cdata.htm)
http://en.wikipedia.org/wiki/Chemical_shift
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Online tutorials (these generally involve combined use of IR, 1H NMR, 13C NMR and mass spectrometry) Problem set 1, advanced (http://www.chem.ucla.edu/~webspectra/) (see also this link (http://drx.ch.huji.ac.il/nmr/whatisnmr/whatisnmr.html) for more background information on spin-spin coupling) Problem set 2, moderate (http://orgchem.colorado.edu/hndbksupport/spectprob/problems.html) Problem set 4, moderate, German language (don't let that scare you away!) (http://www.chem.uni-potsdam.de/tools/kombi1.htm) Problem set 5, the best! (http://www.nd.edu/~smithgrp/structure/workbook.html) Combined solutions to problem set 5 (Problems 132) (http://www.nd.edu/~smithgrp/structure/answers1-32.GIF) and (Problems 3364) (http://www.nd.edu/~smithgrp/structure/answers33-64.GIF) Retrieved from "http://en.wikipedia.org/w/index.php?title=Chemical_shift&oldid=490617595" Categories: Nuclear chemistry Spectroscopy Nuclear physics Nuclear magnetic resonance This page was last modified on 5 May 2012 at 03:46. Text is available under the Creative Commons Attribution-ShareAlike License; additional terms may apply. See Terms of use for details. Wikipedia is a registered trademark of the Wikimedia Foundation, Inc., a non-profit organization.
http://en.wikipedia.org/wiki/Chemical_shift
5/8/2012