Chemical Sciences: A Manual for CSIR-UGC National Eligibility Test for Lectureship and JRF/Mass (mass spectrometry)

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The mass recorded by a mass spectrometer can refer to different physical quantities depending on the characteristics of the instrument and the manner in which the mass spectrum is displayed.

Accurate mass[edit | edit source]

The accurate mass (more appropriately, the measured accurate mass[1]) is an experimentally determined mass that allows the elemental composition to be determined.[2] For molecules with mass below 200 u, a 5 ppm accuracy is sufficient to uniquely determine the elemental composition.[3]

Average mass[edit | edit source]

The average mass of a molecule is obtained by summing the average atomic masses of the constituent elements. For example, the average mass of natural water with formula H2O is 1.00794 + 1.00794 + 15.9994 = 18.01528.

Exact mass[edit | edit source]

The exact mass (more appropriately, the calculated exact mass[1]) is obtained by summing the masses of the individual isotopes of the molecule. For example, the exact mass of water containing two hydrogen-1 (1H) and one oxygen-16 (16O) is 1.0078 + 1.0078 + 15.9994 = 18.0106. The exact mass of heavy water, containing two hydrogen-2 (deuterium or 2H) and one oxygen-16 (16O) is 2.014 + 2.014 + 15.9994 = 20.027.

Isotopomer[edit | edit source]

An isotopomers (isotopic isomers) is an isomers having the same number of each isotopic atom but differing in their positions.[4] For example, CH3CHDCH3 and CH3CH2CH2D are a pair of constitutional isotopomers. An isotopomer should not be confused with an isotopologue, which are chemical species that differ only in the isotopic composition of their molecules or ions. An example is water, where three of its hydrogen-related isotopologues are: HOH, HOD and DOD, where D stands for deuterium (2H).

Mass number[edit | edit source]

The mass number, also called the nucleon number, is the number of protons and neutrons in an atomic nucleus. The mass number is unique for each isotope of an element and is written either after the element name or as a superscript to the left of an element's symbol. For example, carbon-12 (12C) has 6 protons and 6 neutrons.

Molecular mass[edit | edit source]

Theoretical isotope distribution for the molecular ion of caffeine

The molecular mass (abbreviated Mr) of a substance, formerly also called molecular weight and abbreviated as MW, is the mass of one molecule of that substance, relative to the unified atomic mass unit u (equal to 1/12 the mass of one atom of 12C). Due to this relativity, the molecular mass of a substance is commonly referred to as the relative molecular mass, and abbreviated to Mr.

Monoisotopic mass[edit | edit source]

The monoisotopic mass is the sum of the masses of the atoms in a molecule using the unbound, ground-state, rest mass of the principle (most abundant) isotope for each element instead of the isotopic average mass.[5] For typical organic compounds, where the monoisotopic mass is most commonly used, this also results in the lightest isotope being selected. For some heavier atoms such as iron and argon the principle isotope is not the lightest isotope. The term is designed for measurements in mass spectrometry primarily with smaller molecules. It is not typically useful as a concept in physics or general chemistry. Monoisotopic mass is typically expressed in unified atomic mass units (u), also called daltons (Da).s

Most abundant mass[edit | edit source]

Theoretical isotope distribution for the molecular ion of glucagon (C153H224N42O50S)

The mass of the molecule with the most highly represented isotope distribution, based on the natural abundance of the isotopes.[6]

Nominal mass[edit | edit source]

The nominal mass of an ion or molecule is calculated using the integer mass (ignoring the mass defect) of the most abundant isotope of each element.[7] This is the equivalent of suming the mass numbers of all constituent atoms. For example H = 1, C = 12, O = 16, etc. The nominal mass of H2O is 18, for example.

References[edit | edit source]

  1. a b O. David Sparkman, Mass Spec Desk Reference 2nd. ed. p.60 ISBN 0966081390
  2. Grange AH, Winnik W, Ferguson PL, Sovocool GW (2005). "Using a triple-quadrupole mass spectrometer in accurate mass mode and an ion correlation program to identify compounds". Rapid Commun. Mass Spectrom. 19 (18): 2699–715. doi:10.1002/rcm.2112. PMID 16124033. 
  3. Gross, M. L. (1994), "Accurate Masses for Structure Confirmation", J. Am. Soc. Mass Spectrom 5: 57, doi:10.1016/1044-0305(94)85036-4 
  4. International Union of Pure and Applied Chemistry. "isotopomer". Compendium of Chemical Terminology Internet edition.
  5. IUPAC definition of monoisotopic mass spectrum
  6. Goraczko AJ (2005). "Molecular mass and location of the most abundant peak of the molecular ion isotopomeric cluster". Journal of molecular modeling 11 (4-5): 271–7. doi:10.1007/s00894-005-0245-x. PMID 15928922. 
  7. Yergey, James; David Heller, Gordon Hansen, Robert J. Cotter, and Catherlne Fenselau (1983). "Isotopic distributions in mass spectra of large molecules" (PDF). Analytical Chemistry 55: 353–356. doi:10.1021/ac00253a037. Retrieved 2007-09-04.