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Chapter

46

Isotopes and Mass


Spectrometry
Introduction
The concept that all substances are composed of elements and atoms goes back at least 2000
years. Originally, only four elements were recognized: air, earth, fire, and water. Each substance
was thought to consist of very small particles, called atoms, that could not be subdivided any
further. This early mental concept of the nature of matter was extremely prescient, considering
there were no experimental results to indicate that matter should be so and none to verify that
it was so. Modern atomic theory is much more rigorously based, and we even have the ability
to see atoms with special tunneling microscopes. All of chemistry is based on how atoms react
with each other.
The idea that air, earth, fire, and water are elements and that there are only these four
elements has long gone, but the basic idea of atoms as the simplest building blocks of matter
is still accepted, although with a proviso. In chemistry, reactions occur between atoms, and, in that
sense, atoms can be regarded as the simplest building blocks. However, the inner structures of
atoms have important consequences, and under special conditions atoms are not regarded as the
simplest building blocks of matter that can exist alone. At this next level, atoms are seen to be
composed of three entities: electrons, protons, and neutrons. In particular, the numbers and masses
of protons and neutrons determine the character of each element. The ratio of protons and neutrons
in an atomic nucleus is important and gives rise to the existence of isotopes. Mass spectrometers
are particularly effective general instruments for exploring the existence and abundance ratios of
isotopes. The next sections explain the structure of atoms and then show how isotopes arise.

Atomic Structure and the Elements


Many elements are familiar to us in everyday life. Iron is an element used for making ships, cars,
spades, etc. There are about 90 such familiar elements, including helium, oxygen, nitrogen, mercury,
platinum, and gold. As an element, iron consists of atoms of iron, the smallest building blocks,
each of which is indivisible by chemical means. A lump of iron comprises millions, trillions, and
zillions of atoms, and the mass of each atom of iron is very small, about 1022 g! In a piece of iron
weighing 50 g, there are about 1023 atoms.

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A lump of iron
(50 g)

There are 26 electrons in the iron atom


but each has little mass. The electrons are
spread out around the nucleus,
occupying most of the space but very
little of the mass.

An atom of iron
-22
(10 g)

An electron, a proton and a neutron

The nucleus of an iron atom contains


26 protons and 30 neutrons, which occupy
very little space but make up most of the
mass of the atom

Figure 46.1
A representation of atomic structure. The various spheres are not drawn to scale. The lump of iron on the left would contain
almost a million million million million (1024) atoms, one of which is represented by the sphere in the top center of the
page. In turn, each atom is composed of a number of electrons, protons, and neutrons. For example, an atom of the element
iron contains 26 electrons, 26 protons, and 30 neutrons. The physical size of the atom is determined mainly by the number
of electrons, but almost all of its mass is determined by the number of protons and neutrons in its dense core or nucleus
(lower part of figure). The electrons are spread out around the nucleus, and their number determines atomic size; but the
protons and neutrons compose a very dense, small core, and their number determines atomic mass.

With only 90 elements, one might assume that there could be only about 90 different substances
possible, but everyday experience shows that there are millions of different substances, such as
water, brick, wood, plastics, etc. Indeed, elements can combine with each other, and the complexity
of these possible combinations gives rise to the myriad substances found naturally or produced
artificially. These combinations of elemental atoms are called compounds. Since atoms of an
element can combine with themselves or with those of other elements to form molecules, there is
a wide diversity of possible combinations to make all of the known substances, naturally or
synthetically. Therefore, atoms are the simplest chemical building blocks. However, to understand
atoms, it is necessary to examine the structure of a typical atom or, in other words, to examine the
building blocks of the atoms themselves. The building blocks of atoms are called electrons, protons,
and neutrons (Figure 46.1).
It might be noted here in passing that, in high-energy physics, even these simplest building
blocks comprise even smaller units such as quarks and gluons. However, these much smaller
building blocks are not concerned in chemical reactions or chemistry and will not be considered
further here. For mass spectrometry, only the structure of the atomic building blocks (electrons,
protons, and neutrons) is of importance.

Electrons
An electron carries one unit of negative electrical charge (Figure 46.2). Its mass is about 1/2000
that of a proton or neutron. Therefore, very little of the mass of an atom is made from the masses
of the electrons it contains, and generally the total mass of the electrons is ignored. For example,
an atom of iron has a mass of 56 atomic units (au; also called Daltons), of which only about 0.02%
is due to the 26 electrons. Thus an iron atom (Fe0) is considered to have the same mass as a doubly
charged cation of iron (Fe2+), even though there is a small mass difference.
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The electron carries one negative electric charge and has a


mass only 1/2000th that of a proton.

The proton carries one positive charge and has a unit atomic
mass. Its actual mass is about 10 -22 to 10 -23g.

The neutron carries zero electric charge and has a unit atomic
mass. Its actual mass is about 10 -22 to 10 -23g.

An atom of iron has:


(a) 26 electrons and therefore 26 negative charges
(b) 26 protons and therefore 26 positive charges
(c) 30 neutrons with no electric charge

The net atomic charge is zero

An atom of iron has:


(a) 26 electrons having a total mass of 26/2000ths that of a proton
(b) 26 protons with a total mass of 26 atomic units (26 au)
(c) 30 neutrons with a total mass of 30 atomic units (30 au)

The net mass is


56.013 au

An atom of iron has the symbol: Fe


This is the total number of both protons and neutrons
All of the above information is combined: 56 Fe
26

This is the atomic number = the number of protons

Figure 46.2
The top part of the figure gives an indication of the electric charges and relative sizes of the three building blocks of atoms
(electron, protons, and neutrons) that are relevant for the purposes of mass spectrometry. The relative sizes as drawn are
not meant to be to scale. The middle part of the figure shows how the electrons in an atom of iron are mostly responsible
for its size and how the nucleus is responsible for most of the mass. In this simplified discussion, there is no consideration
of packing fractions, which are partly responsible for atomic masses not being whole numbers. The bottom part of the
figure illustrates (by the example of iron) how an atom of any element is designated so as to show the numbers of protons,
neutrons, and electrons it contains.

Although each electron is very small, all of the electrons in an atom move around the nucleus,
sometimes being close to the nucleus and at other times being quite far away. On average, the
distance of the electrons from the nucleus is many times the diameter of the nucleus. Therefore,
although the electrons add very little to the mass of the atom, they do determine the overall size
of the atom (Figure 46.1). Imagine an atom as big as a football, with a small pellet of lead at its
center. The air (electrons) surrounding the lead pellet (nucleus) represents the volume occupied by
the electrons, but the small pellet constitutes most of the mass.
From a chemical and mass spectrometric viewpoint, the other major property of an electron
is its electric charge of one unit. Removal of one electron from an atom or molecule [M] gives
a singly charged cation [M+], and addition of an electron gives a singly charged anion [M]. The
electric charge is necessary for the mass spectrometer to be able to measure a mass-to-charge
(m/z) ratio. Because m/z gives the mass of M+ or M and the difference between these masses
is very small compared with the mass of the neutral species M it can be said that the m/z
value gives the mass M. Although not strictly true, for most purposes it is a close enough
approximation (Figure 46.3).

Protons
Each proton is about 2000 times heavier than an electron, and its mass is one atomic unit.
Importantly, it also carries one unit of positive electric charge (Figure 46.2). The proton is very
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The mass of an atom or ion resides mostly in the nucleus


Atom of iron: Fe0, mass approximately 56.013 from 26 protons,
30 neutrons and 26 electrons
A cation of iron: Fe ++, mass approximately 56.012 from 26 protons,
30 neutrons and 24 electrons
The m/z value for Fe ++, is 56.012/2 = 28.006
Some naturally occurring multi-isotopic elements (approximate % natural abundances
are shown in brackets). Note that only one carbon isotope :is radioactive
14 C (very small)*
6

16 O (99.8)
8

13 C (1.1)
6
17 O(0.04)
8

Sulphur

32 S (95.0)
16

33 S (0.8)
16

34 S (4.2)
16

Bromine

79 Br (50.5)
35
92
42 Mo (15.8)

79 Br (49.5)
35
94
42 Mo (9.0)

95
42 Mo (15.7)

Carbon

12 C (98.9)
6

Oxygen

Molybdenum
Mercury

196 Hg (0.2)
80

18 O (0.2)
8

97
96
42 Mo (16.5) 42 Mo (9.5)

98
100
42 Mo (23.8) 42 Mo (9.6)

198 Hg(10.0) 199 Hg (16.8) 200 Hg (23.1) 201 Hg (13.2) 202 Hg (29.8)
80
80
80
80
80

204 Hg (6.9)
80

Figure 46.3
The upper part of the figure illustrates why the small difference in mass between an ion and its neutral molecule is ignored
for the purposes of mass spectrometry. In mass measurement, 12C has been assigned arbitrarily to have a mass of 12.00000.
All other atomic masses are referred to this standard. In the lower part of the figure, there is a small selection of elements
with their naturally occurring isotopes and their natural abundances. At one extreme, xenon has nine naturally occurring
isotopes, whereas, at the other, some elements such as fluorine have only one.

small and is confined to the nucleus of the atom (along with any neutrons), and the mass of the
atom resides almost entirely in this very dense nucleus. The nucleus is not the most important
factor in determining atomic size (the electrons do that), but it does determine where most of
the mass of the atom resides.
The unit positive charge on the proton balances the unit negative charge on the electron. In
neutral atoms, the number of electrons is exactly equal to the number of protons. In an iron atom
(Fe0), there are 26 electrons and just 26 protons. A cation is formed by removing electrons not by
adding protons. An ion M+ has one electron less than the neutral atom M0. Similarly, an anion M
is formed by adding an electron and not by subtracting a proton from M0.
The number of protons in an atom determines which atomic species is present. The simplest
element hydrogen has two atoms, each of which has just one proton. No element other than
hydrogen has only one proton. The next element (helium) has two protons in each atom, and so
on through all of the known elements. Iron, as has been shown, has 26 protons, and that number
of protons is the reason it is iron and not, say, lead. In fact, each element is characterized by its
atomic number, which is the number of protons in an atom of the element (Figure 46.2). Hence,
an atom of iron is represented by the symbol for iron (Fe) with a number written as a subscript
in front of it; 26Fe signifies iron of atomic number 26. The designation 17Cl signifies chlorine of
atomic number 17 (17 protons in the nucleus).

Neutrons
A neutron is characterized by having no electrical charge but has one unit of atomic mass, the
same as that of a proton (Figure 46.2). Neutrons, like protons, reside in the atomic nucleus
and contribute to the mass of the atom. The chemistry of an atom, like its size, is determined
by the electrons in the atom. The mass of the atom is characterized mainly by the total number
of neutrons and protons in the nucleus (atomic binding energies are ignored in this discussion).
For mass spectrometric purposes of measurement, it is the mass that is important in establishing
m/z values.
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Atomic Nucleus and Isotopes


1

Consider a nucleus of the simplest element, hydrogen, of atomic number 1; it is designated 1H .


There is one proton (and of course one electron), and the atomic mass is 1 Da (mostly from the
one proton). The total number of protons plus neutrons is then indicated by a another (super1
scripted) prefix. In this present case it is 1H (Figure 46.2). The chemistry of hydrogen is mostly
determined by that one electron, but its mass is determined mostly by the one proton. There is
another type of hydrogen atom called deuterium, which includes a neutron in its nucleus and has
2
its own symbol, D. However, it is less confusing to write it as 1H . This type of hydrogen atom
1
also has one electron and one proton, and its chemistry is the same as that of 1H . Because the
2
nucleus of 1H contains one neutron and one proton, its atomic mass is 2. There are two types of
hydrogen atom, one about twice as heavy as the other, but the general chemistry of the two is
identical for most purposes. These two kinds of hydrogen atom are called isotopes. The predom1
2
inantly abundant isotope is 1H , and the isotope in much lesser abundance is 1H . These isotopes
3
are not radioactive. However, there is even a third isotope of hydrogen called tritium ( 1H ), which
has two neutrons and one proton in its nucleus and is three times heavier than the first hydrogen
1
3
isotope, 1H . All of these hydrogen isotopes react chemically in the same way, and only the 1H
isotope is radioactive.
Some elements in their natural state have only one isotope, as with fluorine, phosphorus, and
rhodium but others have several isotopes, as with carbon (three), oxygen (three), and molybdenum
(seven). A few examples are given in Figure 46.3. A small proportion of naturally occurring isotopes
is radioactive, but most isotopes are not. The radioactivity results from the nucleus being unstable,
which happens if the numbers of protons and neutrons in a nucleus become seriously unbalanced.
12
13
Nuclei of carbon having six protons and six neutrons ( 6C ) or six protons and seven neutrons ( 6C )
14
are stable and not radioactive, but the carbon isotope with six protons and eight neutrons ( 6C ) is
unstable and is radioactive (Figure 46.3).
Recently, it has become possible to create isotopes that do not exist naturally. These are the
artificial isotopes, and all are radioactive. For example, 13 artificially created isotopes of iodine
are known, as well as its naturally occurring monoisotopic form of mass 127. Mass spectrometry
is able to measure m/z values for both natural and artificial isotopes.

Isotope Ratios
Approximate Abundance Ratios
Naturally occurring isotopes of any element are present in unequal amounts. For example, chlorine
exists in two isotopic forms, one with 17 protons and 18 neutrons (35Cl) and the other with 17
protons and 20 neutrons (37Cl). The isotopes are not radioactive, and they occur, respectively, in a
ratio of nearly 3:1. In a mass spectrum, any compound containing one chlorine atom will have two
different molecular masses (m/z values). For example, methyl chloride (CH3Cl) has masses of 15
(for the CH3) plus 35 (total = 50) for one isotope of chlorine and 15 plus 37 (total = 52) for the
other isotope. Since the isotopes occur in the ratio of 3:1, molecular ions of methyl chloride will
show two molecular-mass peaks at m/z values of 50 and 52, with the heights of the peaks in the
ratio of 3:1 (Figure 46.4).
This example can be used in reverse to show the usefulness of looking for such isotopes.
Suppose there were an unknown sample that had two molecular ion peaks in the ratio of 3:1 that
were two mass units apart; then it could reasonably be deduced that it was highly likely the unknown
contained chlorine. In this case, the isotope ratio has been used to identify a chlorine-containing
compound. This use of mass spectrometry is widespread in general analysis of materials, and it
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The two isotopes of chlorine are

35
37
Cl and
Cl, which occur naturally in the abundance ratio of 3:1.
17
17

The "35" isotope


plus 15

The "35" isotope

The "37" isotope


plus 15

The "37" isotope


Add 15 mass units for CH 3

1
50

Two mass units separation

52

Still two mass units separation

Figure 46.4
A diagrammatic illustration of the effect of an isotope pattern on a mass spectrum. The two naturally occurring isotopes
of chlorine combine with a methyl group to give methyl chloride. Statistically, because their abundance ratio is 3:1, three
35Cl isotope atoms combine for each 37Cl atom. Thus, the ratio of the molecular ion peaks at m/z 50, 52 found for methyl
chloride in its mass spectrum will also be in the ratio of 3:1. If nothing had been known about the structure of this compound,
the appearance in its mass spectrum of two peaks at m/z 50, 52 (two mass units apart) in a ratio of 3:1 would immediately
identify the compound as containing chlorine.

makes use of only approximate ratios of isotopes because that is all that is necessary for identification. It is not usually necessary to know if the ratio is 3.001:1.00 or 3.002:1.00; all that is needed
is a ratio near 3:1. Where there are several isotopes of an element, the actual pattern of masses and
abundances is enough for identification. It would be very difficult to miss the evidence for mercury
or molybdenum in a mass spectrum, since there are seven isotopes with distinctive patterns of
abundances and mass differences (Figure 46.3). These uses of isotopes are discussed in Chapter
47. However, there are other uses of isotopes that require very accurate determinations of their
ratios of abundances.

Accurate Abundance Ratios


The use of accurate isotope ratio measurement is exemplified here by a method used to determine
the temperature of the Mediterranean Sea 10,000 years ago. It is known that the relative solubility
of the two isotopic forms of carbon dioxide (12CO2, 13CO2) in sea water depends on temperature
(Figure 46.5).
Ratio
r

T
o

Sea temperature in C

Ratio =

Abundance of
Abundance of

12

CO2

13

CO 2

Height of peak at m/z 44


Height of peak at m/z 45

Figure 46.5
By experimentally determining the ratio of abundances of 12C and 14C isotope peaks for CO2 dissolved in sea water at
various temperatures, a graph can be drawn relating the solubility of 12CO2 compared with that of 13CO2 (the ratio described
above). On extracting the CO2 from sediment containing the shells (calcium carbonate) of dead sea creatures by addition
of acid, a ratio (R) of abundances of 12CO2 to 13CO2 can be measured. If this value is read from the graph, a temperature
T is extrapolated, indicating the temperature of the sea at the time the sediment was laid down. Such experiments have
shown that 10,000 years ago the temperature of the Mediterranean was much as it is now.
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One method for measuring the temperature of the sea is to measure this ratio. Of course, if
you were to do it now, you would take a thermometer and not a mass spectrometer. But how do
you determine the temperature of the sea as it was 10,000 years ago? The answer lies with tiny
sea creatures called diatoms. These have shells made from calcium carbonate, itself derived from
carbon dioxide in sea water. As the diatoms die, they fall to the sea floor and build a sediment of
calcium carbonate. If a sample is taken from a layer of sediment 10,000 years old, the carbon
dioxide can be released by addition of acid. If this carbon dioxide is put into a suitable mass
spectrometer, the ratio of carbon isotopes can be measured accurately. From this value and the
graph of solubilities of isotopic forms of carbon dioxide with temperature (Figure 46.5), a temperature can be extrapolated. This is the temperature of the sea during the time the diatoms were alive.
To conduct such experiments in a significant manner, it is essential that the isotope abundance
ratios be measured very accurately.
This accurate measurement of the ratio of abundances of isotopes is used for geological dating,
estimation of the ages of antiquities, testing athletes for the use of banned steroids, examining fine
details of chemical reaction pathways, and so on. These uses are discussed in this book under
various headings concerned with isotope ratio mass spectrometry (see Chapters 7, 14, 15, 16, 17,
47, and 48).

Conclusion
Isotopes of an element are formed by the protons in its nucleus combining with various numbers
of neutrons. Most natural isotopes are not radioactive, and the approximate pattern of peaks they
give in a mass spectrum can be used to identify the presence of many elements. The ratio of
abundances of isotopes for any one element, when measured accurately, can be used for a variety
of analytical purposes, such as dating geological samples or gaining insights into chemical
reaction mechanisms.

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