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The mass recorded by a
mass spectrometer
Mass spectrometry (MS) is an analytical technique that is used to measure the mass-to-charge ratio of ions. The results are presented as a ''mass spectrum'', a plot of intensity as a function of the mass-to-charge ratio. Mass spectrometry is used ...
can refer to different physical quantities depending on the characteristics of the instrument and the manner in which the
mass spectrum
A mass spectrum is a histogram plot of intensity vs. ''mass-to-charge ratio'' (''m/z'') in a chemical sample, usually acquired using an instrument called a ''mass spectrometer''. Not all mass spectra of a given substance are the same; for example ...
is displayed.
Units
The
dalton
Dalton may refer to:
Science
* Dalton (crater), a lunar crater
* Dalton (program), chemistry software
* Dalton (unit) (Da), the atomic mass unit
* John Dalton, chemist, physicist and meteorologist
Entertainment
* Dalton (Buffyverse), minor cha ...
(symbol: Da) is the standard
unit
Unit may refer to:
Arts and entertainment
* UNIT, a fictional military organization in the science fiction television series ''Doctor Who''
* Unit of action, a discrete piece of action (or beat) in a theatrical presentation
Music
* ''Unit'' (alb ...
that is used for indicating
mass
Mass is an intrinsic property of a body. It was traditionally believed to be related to the quantity of matter in a physical body, until the discovery of the atom and particle physics. It was found that different atoms and different elementar ...
on an atomic or molecular scale (
atomic mass
The atomic mass (''m''a or ''m'') is the mass of an atom. Although the SI unit of mass is the kilogram (symbol: kg), atomic mass is often expressed in the non-SI unit dalton (symbol: Da) – equivalently, unified atomic mass unit (u). 1&nbs ...
).
[Bureau International des Poids et Mesures (2019): ]
The International System of Units (SI)
', 9th edition, English version, page 134. Available at th
BIPM website
The
unified atomic mass unit
The dalton or unified atomic mass unit (symbols: Da or u) is a non-SI unit of mass widely used in physics and chemistry. It is defined as of the mass of an unbound neutral atom of carbon-12 in its nuclear and electronic ground state and at ...
(symbol: u) is equivalent to the dalton. One dalton is approximately the mass of one a single proton or neutron.
The unified atomic mass unit has a value of .
[Fundamental Physical Constants from NIST](_blank)
/ref> The ''amu'' without the "unified" prefix is an obsolete unit based on oxygen, which was replaced in 1961.
Molecular mass
The molecular mass
The molecular mass (''m'') is the mass of a given molecule: it is measured in daltons (Da or u). Different molecules of the same compound may have different molecular masses because they contain different isotopes of an element. The related quanti ...
(abbreviated Mr) of a substance
Substance may refer to:
* Matter, anything that has mass and takes up space
Chemistry
* Chemical substance, a material with a definite chemical composition
* Drug substance
** Substance abuse, drug-related healthcare and social policy diagnosis ...
, formerly also called molecular weight and abbreviated as MW, is the mass
Mass is an intrinsic property of a body. It was traditionally believed to be related to the quantity of matter in a physical body, until the discovery of the atom and particle physics. It was found that different atoms and different elementar ...
of one molecule
A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bioch ...
of that substance, relative to the unified atomic mass unit
The dalton or unified atomic mass unit (symbols: Da or u) is a non-SI unit of mass widely used in physics and chemistry. It is defined as of the mass of an unbound neutral atom of carbon-12 in its nuclear and electronic ground state and at ...
u (equal to 1/12 the mass of one atom
Every atom is composed of a nucleus and one or more electrons bound to the nucleus. The nucleus is made of one or more protons and a number of neutrons. Only the most common variety of hydrogen has no neutrons.
Every solid, liquid, gas, and ...
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.
Average mass
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
Water (chemical formula ) is an inorganic, transparent, tasteless, odorless, and nearly colorless chemical substance, which is the main constituent of Earth's hydrosphere and the fluids of all known living organisms (in which it acts as a ...
with formula H2O is 1.00794 + 1.00794 + 15.9994 = 18.01528 Da.
Mass number
The mass number
The mass number (symbol ''A'', from the German word ''Atomgewicht'' tomic weight, also called atomic mass number or nucleon number, is the total number of protons and neutrons (together known as nucleons) in an atomic nucleus. It is approxima ...
, also called the nucleon
In physics and chemistry, a nucleon is either a proton or a neutron, considered in its role as a component of an atomic nucleus. The number of nucleons in a nucleus defines the atom's mass number (nucleon number).
Until the 1960s, nucleons were ...
number, is the number of proton
A proton is a stable subatomic particle, symbol , H+, or 1H+ with a positive electric charge of +1 ''e'' elementary charge. Its mass is slightly less than that of a neutron and 1,836 times the mass of an electron (the proton–electron mass ...
s and neutron
The neutron is a subatomic particle, symbol or , which has a neutral (not positive or negative) charge, and a mass slightly greater than that of a proton. Protons and neutrons constitute the nuclei of atoms. Since protons and neutrons beh ...
s in an atomic nucleus
The atomic nucleus is the small, dense region consisting of protons and neutrons at the center of an atom, discovered in 1911 by Ernest Rutherford based on the 1909 Geiger–Marsden gold foil experiment. After the discovery of the neutron i ...
. The mass number is unique for each isotope
Isotopes are two or more types of atoms that have the same atomic number (number of protons in their nuclei) and position in the periodic table (and hence belong to the same chemical element), and that differ in nucleon numbers (mass numbers) ...
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
Carbon-12 (12C) is the most abundant of the two stable isotopes of carbon (carbon-13 being the other), amounting to 98.93% of element carbon on Earth; its abundance is due to the triple-alpha process by which it is created in stars. Carbon-12 i ...
(12C) has 6 protons and 6 neutrons.
Nominal mass
The nominal mass for an element is the mass number of its most abundant naturally occurring stable isotope, and for an ion or molecule, the nominal mass is the sum of the nominal masses of the constituent atoms. Isotope abundances are tabulated by IUPAC
The International Union of Pure and Applied Chemistry (IUPAC ) is an international federation of National Adhering Organizations working for the advancement of the chemical sciences, especially by developing nomenclature and terminology. It is ...
: for example carbon has two stable isotopes 12C at 98.9% natural abundance and 13C at 1.1% natural abundance, thus the nominal mass of carbon is 12. The nominal mass is not always the lowest mass number, for example iron has isotopes 54Fe, 56Fe, 57Fe, and 58Fe with abundances 6%, 92%, 2%, and 0.3%, respectively, and a nominal mass of 56 Da. For a molecule, the nominal mass is obtained by summing the nominal masses of the constituent elements, for example water has two hydrogen atoms with nominal mass 1 Da and one oxygen atom with nominal mass 16 Da, therefore the nominal mass of H2O is 18 Da.
In mass spectrometry, the difference between the nominal mass and the monoisotopic mass is the mass defect
Nuclear binding energy in experimental physics is the minimum energy that is required to disassemble the nucleus of an atom into its constituent protons and neutrons, known collectively as nucleons. The binding energy for stable nuclei is always ...
. This differs from the definition of mass defect used in physics which is the difference between the mass of a composite particle and the sum of the masses of its constituent parts.
Accurate mass
The accurate mass (more appropriately, the measured accurate mass) is an experimentally determined mass that allows the elemental composition to be determined. For molecules with mass below 200 Da, 5 ppm accuracy is often sufficient to uniquely determine the elemental composition.
Exact mass
The exact mass of an isotopic species (more appropriately, the calculated exact mass) 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 + 15.9949 = 18.0105 Da. The exact mass of heavy water, containing two hydrogen-2 (deuterium
Deuterium (or hydrogen-2, symbol or deuterium, also known as heavy hydrogen) is one of two Stable isotope ratio, stable isotopes of hydrogen (the other being Hydrogen atom, protium, or hydrogen-1). The atomic nucleus, nucleus of a deuterium ato ...
or 2H) and one oxygen-16 (16O) is 2.0141 + 2.0141 + 15.9949 = 20.0229 Da.
When an exact mass value is given without specifying an isotopic species, it normally refers to the most abundant isotopic species.
Monoisotopic mass
The monoisotopic mass is the sum of the mass
Mass is an intrinsic property of a body. It was traditionally believed to be related to the quantity of matter in a physical body, until the discovery of the atom and particle physics. It was found that different atoms and different elementar ...
es of the atom
Every atom is composed of a nucleus and one or more electrons bound to the nucleus. The nucleus is made of one or more protons and a number of neutrons. Only the most common variety of hydrogen has no neutrons.
Every solid, liquid, gas, and ...
s in a molecule
A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bioch ...
using the unbound, ground-state, rest mass of the principal (most abundant) isotope for each element. The monoisotopic mass of a molecule or ion is the exact mass obtained using the principal isotopes. Monoisotopic mass is typically expressed in daltons.
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
Iron () is a chemical element with symbol Fe (from la, ferrum) and atomic number 26. It is a metal that belongs to the first transition series and group 8 of the periodic table. It is, by mass, the most common element on Earth, right in f ...
and argon
Argon is a chemical element with the symbol Ar and atomic number 18. It is in group 18 of the periodic table and is a noble gas. Argon is the third-most abundant gas in Earth's atmosphere, at 0.934% (9340 ppmv). It is more than twice as abu ...
the principal isotope is not the lightest isotope. The mass spectrum peak corresponding to the monoisotopic mass is often not observed for large molecules, but can be determined from the isotopic distribution.
Most abundant mass
This refers to the mass of the molecule with the most highly represented isotope distribution, based on the natural abundance
In physics, natural abundance (NA) refers to the abundance of isotopes of a chemical element as naturally found on a planet. The relative atomic mass (a weighted average, weighted by mole-fraction abundance figures) of these isotopes is the atomic ...
of the isotopes.
Isotopomer and isotopologue
Isotopomer
Isotopomers or isotopic isomers are isomers with isotopic atoms, having the same number of each isotope of each element but differing in their positions. The result is that the molecules are either constitutional isomers or stereoisomers solely ...
s (isotopic isomers) are isomer
In chemistry, isomers are molecules or polyatomic ions with identical molecular formulae – that is, same number of atoms of each element – but distinct arrangements of atoms in space. Isomerism is existence or possibility of isomers.
Iso ...
s having the same number of each isotopic atom, but differing in the positions of the isotopic atoms. For example, CH3CHDCH3 and CH3CH2CH2D are a pair of structural
A structure is an arrangement and organization of interrelated elements in a material object or system, or the object or system so organized. Material structures include man-made objects such as buildings and machines and natural objects such a ...
isotopomers.
Isotopomers should not be confused with isotopologue
In chemistry, isotopologues are molecules that differ only in their isotopic composition. They have the same chemical formula and bonding arrangement of atoms, but at least one atom has a different number of neutrons than the parent.
An exampl ...
s, which are chemical species that differ in the isotopic composition of their molecule
A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and bioch ...
s or ion
An ion () is an atom or molecule with a net electrical charge.
The charge of an electron is considered to be negative by convention and this charge is equal and opposite to the charge of a proton, which is considered to be positive by conven ...
s. For example, three isotopologues of the water molecule
Water () is a polar inorganic compound that is at room temperature a tasteless and odorless liquid, which is nearly colorless apart from an inherent hint of blue. It is by far the most studied chemical compound and is described as the "uni ...
with different isotopic composition of hydrogen are: HOH, HOD and DOD, where D stands for deuterium (2H).
Kendrick mass
The Kendrick mass The Kendrick mass is defined by setting the mass of a chosen molecular fragment, typically CH2, to an integer value in amu ( atomic mass units). It is different from the IUPAC definition, which is based on setting the mass of 12C isotope to exactly ...
is a mass obtained by multiplying the measured mass by a numeric factor. The Kendrick mass is used to aid in the identification of molecules of similar chemical structure from peaks in mass spectra
A mass spectrum is a histogram plot of intensity vs. ''mass-to-charge ratio'' (''m/z'') in a chemical sample, usually acquired using an instrument called a ''mass spectrometer''. Not all mass spectra of a given substance are the same; for example ...
. The method of stating mass was suggested in 1963 by the chemist
A chemist (from Greek ''chēm(ía)'' alchemy; replacing ''chymist'' from Medieval Latin ''alchemist'') is a scientist trained in the study of chemistry. Chemists study the composition of matter and its properties. Chemists carefully describe th ...
Edward Kendrick.
According to the procedure outlined by Kendrick, the mass of CH2 is defined as 14.000 Da, instead of 14.01565 Da.
The Kendrick mass for a family of compounds is given by
:
For hydrocarbon analysis, = CH2.
Mass defect (mass spectrometry)
The mass defect
Nuclear binding energy in experimental physics is the minimum energy that is required to disassemble the nucleus of an atom into its constituent protons and neutrons, known collectively as nucleons. The binding energy for stable nuclei is always ...
used in nuclear physics is different from its use in mass spectrometry. In nuclear physics, the mass defect is the difference in the mass of a composite particle and the sum of the masses of its component parts. In mass spectrometry the mass defect is defined as the difference between the exact mass and the nearest integer mass.
The Kendrick mass defect is the exact Kendrick mass subtracted from the nearest integer Kendrick mass.
Mass defect filtering can be used to selectively detect compounds with a mass spectrometer based on their chemical composition.
Packing fraction (mass spectrometry)
The term packing fraction was defined by Aston as the difference of the measured mass ''M'' and the nearest integer mass ''I'' (based on the oxygen-16
Oxygen-16 (16O) is a stable isotope of oxygen, having 8 neutrons and 8 protons in its nucleus. It has a mass of . Oxygen-16 is the most abundant isotope of oxygen and accounts for 99.762% of oxygen's natural abundance. The relative and absolute ...
mass scale) divided by the quantity comprising the mass number multiplied by ten thousand:
:.
Aston's early model of nuclear structure
Understanding the structure of the atomic nucleus is one of the central challenges in nuclear physics.
Models The liquid drop model
The liquid drop model is one of the first models of nuclear structure, proposed by Carl Friedrich von Weizsäcke ...
(prior to the discovery of the neutron
The discovery of the neutron and its properties was central to the extraordinary developments in atomic physics in the first half of the 20th century. Early in the century, Ernest Rutherford developed a crude model of the atom, based on the go ...
) postulated that the electromagnetic fields of closely packed protons and electrons in the nucleus would interfere and a fraction of the mass would be destroyed. A low packing fraction is indicative of a stable nucleus.
Nitrogen rule
The nitrogen rule The nitrogen rule states that organic compounds containing exclusively hydrogen, carbon, nitrogen, oxygen, silicon, phosphorus, sulfur, and the halogens either have (1) an ''odd nominal mass'' that indicates an ''odd number'' of nitrogen atoms are p ...
states that organic compound
In chemistry, organic compounds are generally any chemical compounds that contain carbon-hydrogen or carbon-carbon bonds. Due to carbon's ability to catenate (form chains with other carbon atoms), millions of organic compounds are known. The ...
s containing exclusively hydrogen
Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
, carbon
Carbon () is a chemical element with the symbol C and atomic number 6. It is nonmetallic and tetravalent
In chemistry, the valence (US spelling) or valency (British spelling) of an element is the measure of its combining capacity with o ...
, nitrogen
Nitrogen is the chemical element with the symbol N and atomic number 7. Nitrogen is a nonmetal and the lightest member of group 15 of the periodic table, often called the pnictogens. It is a common element in the universe, estimated at se ...
, oxygen
Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements as wel ...
, silicon
Silicon is a chemical element with the symbol Si and atomic number 14. It is a hard, brittle crystalline solid with a blue-grey metallic luster, and is a tetravalent metalloid and semiconductor. It is a member of group 14 in the periodic tab ...
, phosphorus
Phosphorus is a chemical element with the symbol P and atomic number 15. Elemental phosphorus exists in two major forms, white phosphorus and red phosphorus, but because it is highly reactive, phosphorus is never found as a free element on Ear ...
, sulfur
Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formula ...
, and the halogen
The halogens () are a group in the periodic table consisting of five or six chemically related elements: fluorine (F), chlorine (Cl), bromine (Br), iodine (I), astatine (At), and tennessine (Ts). In the modern IUPAC nomenclature, this group is ...
s either have an odd nominal mass
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.
Units
The dalton (symbol: Da) is the standard unit tha ...
that indicates an odd number
In mathematics, parity is the property of an integer of whether it is even or odd. An integer is even if it is a multiple of two, and odd if it is not.. For example, −4, 0, 82 are even because
\begin
-2 \cdot 2 &= -4 \\
0 \cdot 2 &= 0 \\
41 ...
of nitrogen atoms are present or an even nominal mass that indicates an even number
In mathematics, parity is the property of an integer of whether it is even or odd. An integer is even if it is a multiple of two, and odd if it is not.. For example, −4, 0, 82 are even because
\begin
-2 \cdot 2 &= -4 \\
0 \cdot 2 &= 0 \\
41 ...
of nitrogen atoms are present in the molecular ion
Mass spectral interpretation is the method employed to identify the chemical formula, characteristic fragment patterns and possible fragment ions from the mass spectra. Mass spectra is a plot of relative abundance against mass-to-charge ratio. It i ...
.
Prout's hypothesis and the whole number rule
The whole number rule
In chemistry, the whole number rule states that the masses of the isotopes are whole number multiples of the mass of the hydrogen atom. The rule is a modified version of Prout's hypothesis proposed in 1815, to the effect that atomic weights are mu ...
states that the masses of the isotopes are integer
An integer is the number zero (), a positive natural number (, , , etc.) or a negative integer with a minus sign (−1, −2, −3, etc.). The negative numbers are the additive inverses of the corresponding positive numbers. In the language ...
multiples of the mass of the hydrogen
Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula . It is colorless, odorless, tasteless, non-toxic, an ...
atom. The rule is a modified version of Prout's hypothesis
Prout's hypothesis was an early 19th-century attempt to explain the existence of the various chemical elements through a hypothesis regarding the internal structure of the atom. In 1815 and 1816, the English chemist William Prout published two p ...
proposed in 1815, to the effect that atomic weight
Relative atomic mass (symbol: ''A''; sometimes abbreviated RAM or r.a.m.), also known by the deprecated synonym atomic weight, is a dimensionless physical quantity defined as the ratio of the average mass of atoms of a chemical element in a giv ...
s are multiples of the weight of the hydrogen atom.
See also
*List of elements by atomic mass
This is a list of the 118 chemical elements which have been identified as of 2022. A chemical element, often simply called an element, is a type of atom which has the same number of protons in its atomic nucleus (i.e., the same atomic number, or ...
*Dalton (unit)
The dalton or unified atomic mass unit (symbols: Da or u) is a non-SI unit of mass widely used in physics and chemistry. It is defined as of the mass of an unbound neutral atom of carbon-12 in its nuclear and electronic ground state and at ...
References
External links
web tools to compute molecule masses & isotopic distribution
{{Mass spectrometry
Mass
Mass spectrometry