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الموضوع: The Nature of Mass Spectra

  1. #1
    عضو ذهبي الصورة الرمزية اسراء
    تاريخ التسجيل
    Aug 2011
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    1,442

    افتراضي The Nature of Mass Spectra

    A mass spectrum will usually be presented as a vertical bar graph, in which each bar represents an ion having a specific mass-to-charge ratio (m/z) and the length of the bar indicates the relative abundance of the ion. The most intense ion is assigned an abundance of 100, and it is referred to as the base peak. Most of the ions formed in a mass spectrometer have a single charge, so the m/z value is equivalent to mass itself. Modern mass spectrometers easily distinguish (resolve) ions differing by only a single atomic mass unit, and thus provide completely accurate values for the molecular mass of a compound. The highest-mass ion in a spectrum is normally considered to be the molecular ion, and lower-mass ions are fragments from the molecular ion, assuming the sample is a single pure compound.
    Atomic mass is given in terms of the unified atomic mass unit (symbol: μ) or dalton (symbol: Da). In recent years there has been a gradual change towards using the dalton in preference to the unified atomic mass unit. The dalton is classified as a "non-SI unit whose values in SI units must be obtained experimentally". It is defined as one twelfth of the rest mass of an unbound atom of carbon-12 in its nuclear and electronic ground state, and has a value of 1.660538782(83)x10-27 kg.
    The following diagram displays the mass spectra of three simple gaseous compounds, carbon dioxide, propane and cyclopropane. The molecules of these compounds are similar in size, CO2 and C3H8 both have a nominal mass of 44 Da, and C3H6 has a mass of 42 Da. The molecular ion is the strongest ion in the spectra of CO2 and C3H6, and it is moderately strong in propane. The unit mass resolution is readily apparent in these spectra (note the separation of ions having m/z=39, 40, 41 and 42 in the cyclopropane spectrum). Even though these compounds are very similar in size, it is a simple matter to identify them from their individual mass spectra. By clicking on each spectrum in turn, a partial fragmentation analysis and peak assignment will be displayed. Even with simple compounds like these, it should be noted that it is rarely possible to explain the origin of all the fragment ions in a spectrum. Also, the structure of most fragment ions is seldom known with certainty.
    Since a molecule of carbon dioxide is composed of only three atoms, its mass spectrum is very simple. The molecular ion is also the base peak, and the only fragment ions are CO (m/z=28) and O (m/z=16). The molecular ion of propane also has m/z=44, but it is not the most abundant ion in the spectrum. Cleavage of a carbon-carbon bond gives methyl and ethyl fragments, one of which is a carbocation and the other a radical. Both distributions are observed, but the larger ethyl cation (m/z=29) is the most abundant, possibly because its size affords greater charge dispersal. A similar bond cleavage in cyclopropane does not give two fragments, so the molecular ion is stronger than in propane, and is in fact responsible for the the base peak. Loss of a hydrogen atom, either before or after ring opening, produces the stable allyl cation (m/z=41). The third strongest ion in the spectrum has m/z=39 (C3H3). Its structure is uncertain, but two possibilities are shown in the diagram. The small m/z=39 ion in propane and the absence of a m/z=29 ion in cyclopropane are particularly significant in distinguishing these hydrocarbons.
    Most stable organic compounds have an even number of total electrons, reflecting the fact that electrons occupy atomic and molecular orbitals in pairs. When a single electron is removed from a molecule to give an ion, the total electron count becomes an odd number, and we refer to such ions as radical cations. The molecular ion in a mass spectrum is always a radical cation, but the fragment ions may either be even-electron cations or odd-electron radical cations, depending on the neutral fragment lost. The simplest and most common fragmentations are bond cleavages producing a neutral radical (odd number of electrons) and a cation having an even number of electrons. A less common fragmentation, in which an even-electron neutral fragment is lost, produces an odd-electron radical cation fragment ion. Fragment ions themselves may fragment further. As a rule, odd-electron ions may fragment either to odd or even-electron ions, but even-electron ions fragment only to other even-electron ions. The masses of molecular and fragment ions also reflect the electron count, depending on the number of nitrogen atoms in the species.
    Ions with no nitrogen
    or an even # N atoms
    odd-electron ions
    even-number mass
    even-electron ions
    odd-number mass
    Ions having an
    odd # N atoms
    odd-electron ions
    odd-number mass
    even-electron ions
    even-number mass
    This distinction is illustrated nicely by the follwing two examples. The unsaturated ketone, 4-methyl-3-pentene-2-one, on the left has no nitrogen so the mass of the molecular ion (m/z = 98) is an even number. Most of the fragment ions have odd-numbered masses, and therefore are even-electron cations. Diethylmethylamine, on the other hand, has one nitrogen and its molecular mass (m/z = 87) is an odd number. A majority of the fragment ions have even-numbered masses (ions at m/z = 30, 42, 56 & 58 are not labeled), and are even-electron nitrogen cations. The weak even -electron ions at m/z=15 and 29 are due to methyl and ethyl cations (no nitrogen atoms). The fragmentations leading to the chief fragment ions will be displayed by clicking on the appropriate spectrum. Repeated clicks will cycle the display.
    4-methyl-3-pentene-2-one N,N-diethylmethylamine
    When non-bonded electron pairs are present in a molecule (e.g. on N or O), fragmentation pathways may sometimes be explained by assuming the missing electron is partially localized on that atom. A few such mechanisms are shown above. Bond cleavage generates a radical and a cation, and both fragments often share these roles, albeit unequally.

    عضو في نادي ماركا الأكاديمي


  2. #2
    مشرفة الاقسام الاكاديمية الصورة الرمزية تمارا احمد
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    Jul 2011
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    افتراضي رد: The Nature of Mass Spectra

    Thanks a lot

    عضو في نادي ماركا الأكاديمي


  3. #3
    مراقب عام الصورة الرمزية Eiman
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    Jul 2011
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    افتراضي رد: The Nature of Mass Spectra

    شكرا اسراء
    من جد وجد ....... ومن سار على الدرب وصل

  4. #4
    عضو ذهبي الصورة الرمزية نداء محمد
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    Aug 2011
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    افتراضي رد: The Nature of Mass Spectra

    Thank you

    عضو في نادي ماركا الأكاديمي


  5. #5
    عضو مميز الصورة الرمزية قمر بلحاج
    تاريخ التسجيل
    Jul 2012
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    افتراضي رد: The Nature of Mass Spectra

    جزاكم الله خيرا

    عضو في نادي ماركا الأكاديمي


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