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Atoms that have the same number of protons and electrons but different

numbers of neutrons are known asisotopes.


Isotopes have different atomic masses.
The relative abundance of an isotope is the fraction of a single element that
exists on Earth with a specific atomic mass.
Atomic weights are weighted averages calculated by multiplying the relative
abundance of each isotope by its atomic mass, and then summing up all the products.
The relative abundances of each isotope can be determined using mass
spectrometry.
A mass spectrometer ionizes atoms and molecules with a high-energy electron
beam, and then deflects the ions through a magnetic field based on the mass-to-charge
ratio of the ion, \dfrac{m}{z}zmstart fraction, m, divided by, z, end fraction.
The mass spectrum of a sample shows relative abundance of each ion on the yaxis and \dfrac{m}{z}zmstart fraction, m, divided by, z, end fraction along the xaxis.

Introduction: Dissecting an atom


Everything is made out of atoms. Your computer or phone screen, the chair you are
sitting on, you and I are all made out of atoms. If we were to zoom in further using our
very technologically advanced and imaginary chemistry goggles, we'd be able to see
that the atom itself is made out of subatomic particles with specific properties.
An atom is composed of protons, neutrons, and electrons. A proton carries a 111+
+plus charge, an electron carries a 111-minuscharge, and a neutron
carries 000 charge. The nucleus is made up of protons and neutrons, and electrons are
localized outside the nucleus. Since electrons have a negative charge, they are
attracted to the positively charged protons in the nucleus. This gives an atom its
stability, and we can think about this mathematically using Coulomb's law. On a very
simplistic level, we can represent an atom using the following diagram:

A Bohr model of the helium atom.


A neutral helium atom. The protons and neutrons are located in the nucleus, while the
electrons "orbit" outside the nucleus. Image from Wikispaces, CC BY-SA 3.0.
We count 222 protons in the nucleus of this atom, which means that our atom has an
atomic number (\text ZZZ) of 222. Since the identity of an element is determined by
the atomic number, we deduce that our atom must be an atom of helium. In order for
the atom to be neutral, we have 222 electrons to balance out the positive charge from
the protons. But what about the neutrons, which have no charge? This particular atom
of helium happens to have 222neutrons. Does that mean all helium atoms must
have 222 neutrons?
And if so, why?

\text NN\text ZZ
We know that if the nucleus had a different atomic number, then the atom would be a
different element. However, the same is not true of the number of neutrons in the
nucleus. It is possible that atoms of the same element may contain different numbers of
neutrons; such atoms are known as isotopes. This comes from Greek: iso- means
"same," and -tope means "place." Thus, isotopes, because they contain the same
number of protons, occupy thesame place on the periodic table. They differ, however, in
the number of neutrons in their nuclei, which causes them to have different masses.

Particle masses and unified atomic mass units


Atoms are extremely tiny, and the particles within atoms are even tinier. While we can
talk about the masses of atoms and particles in terms of everyday units such as grams
and kilograms, it is much more convenient to use a very tiny unit of mass to discuss
such very tiny things. That unit is known as \text{u}uu, which stands for unified
atomic mass unit. By definition, 1\text{ u}1 u1, space, u is equal to
exactly \dfrac{1}{12}121start fraction, 1, divided by, 12, end fraction of the mass

of a single neutral atom of carbon-121212. The number after the hyphen, 121212, is
the sum of the protons and neutrons for that specific isotope of the element. The reason
carbon-121212 is chosen as the isotope to define the unit \text{u}uu is because it is
the most common isotope of carbon.
My textbook uses "amu" and not "u." What gives?

\text{u}u\text{amu}a, m, u\text{amu}a, m, u\text{u}u


Concept check: How many protons are in the nucleus of an atom of carbon121212?
Show the answer

66121266
As we will now examine in more detail, the bulk of an atom's mass is located in its
nucleus. This is because protons and neutrons are much more massive than electrons.
For example, a proton has a mass of1.673\times10^{-27}\text{ kg}1.67310
27 kg1, point, 673, times, 10, start superscript, minus, 27, end
superscript, space, k, g, or 1.007\text{ u}1.007 u1, point, 007, space, u. A neutron
is slightly heavier, with a mass of 1.675\times10^{-27}\text{ kg}1.67510
27 kg1, point, 675, times, 10, start superscript, minus, 27, end
superscript, space, k, g or 1.009\text{ u}1.009 u1, point, 009, space, u. An
electron, on the other hand, has a mass of only 9.109\times10^{31}\text{ kg}9.1091031 kg9, point, 109, times, 10, start
superscript, minus, 31, end superscript, space, k, g, or 5.486\times10^{4}\text{ u}5.486104 u5, point, 486, times, 10, start superscript, minus, 4, end
superscript, space, u. We can summarize this information in the following table:

Nam
e

Charg
e

Symbol

Mass (\text{kg}
)(kg)left
parenthesis, k, g
, right
parenthesis

Mass (\text{u
})(u)left
parenthesis, u
, right
parenthesis

Locat
ion

111

Inside
nucle
us

_1^1\text{p
}^+11p+start

prot
on

111+
+plus

neut
ron

000

subscript, 1, en
d
subscript, start
superscript, 1,
end
superscript, p,
start
superscript, plu
s, end
superscript

mes, 10, start


superscript, minus,
27, end
superscript

^1\text{n}1
nstart

1.675\times10^
{-27}1.67510

superscript, 1,
end
superscript, n

271, point, 675, ti

1.673\times10^
{-27}1.67310
271, point, 673, ti

mes, 10, start


superscript, minus,

111

Inside
nucle
us

Nam
e

Charg
e

Symbol

Mass (\text{kg}
)(kg)left
parenthesis, k, g
, right
parenthesis

Mass (\text{u
})(u)left
parenthesis, u
, right
parenthesis

Locat
ion

000

Outsi
de
nucle
us

27, end
superscript

\text{e}^-e
elect
ron

111minu
s

e, start

superscript, mi
nus, end
superscript

9.109\times10^
{-31}9.10910
319, point, 109, ti

mes, 10, start


superscript, minus,
31, end
superscript

There are a few things that we should conclude from this table. The first is that protons
and neutrons have masses that are about 2,0002,0002, comma, 000 times greater
than the mass of an electron. As such, electrons are considered to have a negligible
effect upon the overall mass of an atom. (This is a fancy of way of saying that when we
calculate the mass of atoms and molecules, we ignore the mass of electrons). This fact
is illustrated further in the column listing the masses of these particles in \text{u}uu.
The masses have been rounded to the nearest integer; thus, protons and neutrons are
considered to have identical masses of 1\text{ u}1 u1, space, u. While we know that
neutrons are ever-so-slightly heavier than protons, this very small difference in mass is
insignificant for many purposes, and we can simplify things greatly by assuming that
protons and neutrons have equal mass.
We should also note that electrons are considered to have a mass of
~ 0\text{ u}0 u0, space, u. Again, this is not technically true. Keep in mind, however,
that the mass of the electrons is so small in comparison to the masses of the protons
and neutrons in the nucleus that we can simply ignore the electrons' masses altogether.

Mass number and isotope notation


Now that we have an understanding of the different masses and charges of protons,
neutrons, and electrons, we can discuss the concept of mass number. By definition, the
mass number is simply equal to the number of protonsplus the number of neutrons in
the nucleus.

Mass number=(# protons)+(# neutrons)


Just as atomic number defines an element, we can think of the mass number as defining
the specific isotope of a particular element. In fact, a common way of specifying an
isotope is to use the notation "element name-mass number" such as in carbon-121212,
which is a carbon atom with a mass number of 121212. Using that information, we can
calculate the number of neutrons in an atom of carbon-121212 as follows.
We can rearrange the equation for mass number to solve for the number of neutrons:

# neutrons=mass number(# protons)=126=6neutrons in carbon-12

Therefore, we see that an atom of carbon-121212 has 666 neutrons in the nucleus.
Let's try another example.
Concept check: Chromium-525252 is the most stable isotope of chromium.
How many neutrons are contained in a single atom of chromium- 525252?
Show the answer

525252522424242424245252
# neutrons=mass number(# protons)=5224=28neutrons
52522828
We have now seen that isotopes are defined by their mass number, which is equal to
the sum of the number of protons and neutrons. To show this most simply, chemists
commonly use the following notation to indicate atomic number, mass number, and
charge, all in one symbol:

Isotope notation for helium-4 and magnesium-24.


Isotopic notation for neutral hydrogen-333 (left) and the magnesium-242424 cation
with a 2+2+2, plus charge (right).
Above we have the isotopic notation for neutral hydrogen-333 and the magnesium242424 cation. In the center of each is the chemical symbol for each element. On the
lower left is the atomic number, which corresponds to the number of protons in the
atom's nucleus. Above the atomic number is the mass number, which is equal to the
sum of the number of protons and the number of neutrons in the atom. To the upper
right of the chemical symbol is the net charge on the species, if any. Keep in mind that
for neutral atoms, the net charge is 000, and nothing will be written in this space.

Atomic mass vs. mass number


Atomic mass is a concept that is very closely related to mass number. The atomic mass
is the mass of a specific isotope of an element expressed in units
of \,\text{u}uspace, u or \text{amu}amua, m, u. Since the mass of a neutron and
the mass of a proton are both very, very close
to 1\,\text{amu}1amu1, space, a, m, u, the atomic mass of an isotope is often very
close to the mass number. However, they are different! The mass number is an integer,
since we always count whole numbers of protons and neutrons (that is, you can't
have 1.051.051, point, 05 protons, or 0.270.270, point, 27 neutrons). The mass
number is also (usually) written as being unitless. In comparison, the atomic mass is
only a whole number if you round to the nearest integer, and atomic mass has units of
mass (\text{u}uu).
Another term that students often might find confusingly similar to atomic mass and
mass number is atomic weight, which is also a related but different term. Don't worry,
though, we will discuss atomic weight in the following section!

Relative abundance and atomic weight


There are 222 stable isotopes of chlorine: chlorine-353535, and and chlorine-373737.
What about chlorine-36?

3636353537373636301,000\,\text{years}301, comma, 000, space, y, e, a, r, s

And yet, if you look on the periodic table, you'll find that the mass of an atom of chlorine
is given as 35.45\text{ u}35.45 u35, point, 45, space, u. Where do the numbers
after the decimal come from? If you guessed that this number might be the mass of
anaverage atom of chlorine, you would be correct. In fact, all of the masses that you see
on the periodic table are averages that are based on the masses and abundances of all
the stable isotopes of each element. These average masses are referred to as atomic
weights. In comparison, atomic mass refers to the mass of a specific isotope. We use
atomic masses to calculate the atomic weight of a given element.
Let's now further consider the atomic weight of chlorine. As we said before, chlorine
has 222 stable isotopes: chlorine-353535 and chlorine-373737. The atomic weight of
chlorine given on the periodic table is 35.45\text{ u}35.45 u35, point, 45, space, u.
This begs the question, why isn't the atomic weight of chlorine simply the average
of 353535 and 373737, which would be 36\,\text u36u36, space, u?
The answer has to do with the fact that different isotopes have different relative
abundances, meaning that some isotopes are more naturally abundant on Earth than
others. In the case of chlorine, chlorine-353535 has a relative abundance
of 75.76\%75.76%75, point, 76, percent, whereas chlorine-373737 has a relative
abundance of 24.24\%24.24%24, point, 24, percent. Note that relative abundances
are percentages, and thus the relative abundances of all the different stable isotopes of
an element will add up to100\%100%100, percent. The atomic weight that you find on
the periodic table is actually a weighted average calculated from these values. To better
illustrate this, let's calculate the atomic weight of chlorine.
When calculating molecular weight, do we use atomic weight or atomic mass?

Example: Calculating the atomic weight of chlorine


When we want to calculate a weighted average, we multiply the value of every item in
our set (in this case, the atomic mass of each isotope of chlorine) by its relative
abundance expressed as a fraction, and then sum up all of our products. This can be
written as follows:

atomic weight=i=1n(relative abundanceatomic mass)i


If we apply this formula for chlorine, we get the following.

atomic weight of chlorine=(0.757634.969 u)


+(0.242436.966 u)=26.49u+8.960u=35.45 u
Thus, we can see that because chlorine-353535 is about 333 times more abundant
than chlorine-373737, the weighted average is closer to 353535 than to 373737.
Concept check: Bromine has two stable isotopes - bromine- 797979 and
bromine-818181. The relative abundance of each isotope
is 50.70\%50.70%50, point, 70, percent and 49.30\%49.30%49, point, 30, p
ercent, respectively. Is the atomic weight of bromine closest
to 797979, 808080, or 81\text{ u}81 u81, space, u?
Show the answer

50/5050, slash, 501:11, colon, 1808079.90\text{ u}79, point, 90, space, u

Mass spectrometry

We now know how to find atomic weights by calculating weighted averages using
relative abundances. But where do these relative abundances come from? For example,
how do we know that 75.76\%75.76%75, point, 76, percent of all chlorine on Earth is
chlorine-353535?
The answer is that these relative abundances can be determined experimentally using a
technique called a mass spectrometry.

A schematic of a mass spectrometer.


A diagram of a mass spectrometer. A sample is injected into the machine, vaporized by
a heater, and then ionized by a stream of high-energy electrons. The resulting Ions are
accelerated through parallel electric plates, and then deflected in a magnetic field
before they reach a detector. Image from Openstax, CC BY 4.0.
In a mass spectrometer, a sample containing the atoms or molecules of interest is
injected into the instrument. The sample (typically in an aqueous or organic solution) is
immediately vaporized by a heater, and the vaporized sample is then bombarded by
high-energy electrons. These electrons are powerful enough to knock electrons off
atoms in the sample, which creates cationic versions of the sample. These cations are
then accelerated through electric plates and subsequently deflected by a magnetic
field.
Once the ions reach the magnetic field, they are deflected a different amount
depending on their speed and charge. Ions that are moving more slowly (the heavier
ions) are deflected less, and ions that are moving more quickly (the lighter ions) are
deflected more. (Think of the force you need to apply to accelerate a bowling ball,
versus the force necessary to accelerate a tennis ball. It's much easier to accelerate the
tennis ball!) Also, the higher the charge on the ion, the more it will be deflected.
The amount that the ions are deflected is inversely proportional to their mass-to-charge
ratio, \dfrac{m}{z}zmstart fraction, m, divided by, z, end fraction, where mmm is
equal to the mass of the ion, and zzz is equal to the charge. The detector records
the \dfrac{m}{z}zmstart fraction, m, divided by, z, end fraction values for each ion,
as well how many of each ion it sees. The relative abundance for a specific ion within
the sample can be calculated by dividing by the number of ions of that type by the total
number of ions detected. The instrument then generates amass spectrum for the
sample, which plots relative abundance against the mass-to-charge ratio, \dfrac{m}
{z}zmstart fraction, m, divided by, z, end fraction.
Concept check: A sample of copper is injected into a mass spectrometer. After
the sample is vaporized and ionized, the ions ^{63}\text{Cu}^{2+}63Cu2+
start superscript, 63, end superscript, C, u, start superscript, 2, plus, end
superscript and ^{65}\text{Cu}^{2+}65Cu2+start superscript, 65, end
superscript, C, u, start superscript, 2, plus, end superscript are detected.
Which ion is deflected more inside the spectrometer?
Show the answer

^{63}\text{Cu}^{2+}start superscript, 63, end superscript, C, u, start


superscript, 2, plus, end superscriptmmzz^{65}\text{Cu}^{2+}start
superscript, 65, end superscript, C, u, start superscript, 2, plus, end
superscript^{63}\text{Cu}^{2+}start superscript, 63, end superscript, C, u, start
superscript, 2, plus, end superscript\dfrac{m}{z}start fraction, m, divided by, z, end
fraction\dfrac{m}{z}start fraction, m, divided by, z, end fraction
^{63}\text{Cu}^{2+}start superscript, 63, end superscript, C, u, start
superscript, 2, plus, end superscript

Analyzing the mass spectrum of zirconium

Let's suppose we analyzed a sample of elemental zirconium (atomic number 404040)


using mass spectrometry. After putting the sample through the instrument, we would
get a mass spectrum that looks approximately as follows, where the height of a peak is
roughly proportional to the relative abundance for a given value of \dfrac{m}{z}zm
start fraction, m, divided by, z, end fraction:

The simulated mass spectrum for zirconium.


The simulated mass spectrum for a sample of elemental zirconium. Image from
Openstax, CC BY 4.0.

Concept check: Based on this spectrum, what is the most common isotope of
zirconium in our sample?
Show the answer

\text{Zr}-90Z, r, minus, 90
Based on the relative height or intensity of the peaks at a given mass-to-charge ratio,
we can find the relative abundances of the isotopes. Using this information, we can
calculate the atomic weight of zirconium by finding a weighted average of the atomic
masses for each isotope. To try this calculation yourself, see the practice problem
below!
Nowadays, we already know the atomic weights for all the most common elements, and
so it is not often necessary to analyze individual elements using mass spectrometry
(except to teach students!). Most of the time, working chemists use mass spectrometry
in the lab in order to help them determine the structure or identity of unknown
molecules and compounds. In today's world, mass spectrometry is an invaluable
analytical tool, not only in chemistry, but also in medicine, forensics, environmental
science, and other important fields.

Summary

Atoms that have the same number of protons and electrons but different
numbers of neutrons are known asisotopes.
Isotopes of a given element have different atomic masses.
The relative abundance of an isotope is the fraction of a single element that
exists on Earth with a specific atomic mass.
Atomic weights are weighted averages calculated by multiplying the relative
abundance of each isotope by its atomic mass, and then summing up all the products.
The relative abundances of each isotope can be determined using mass
spectrometry.
A mass spectrometer ionizes atoms and molecules with a high-energy electron
beam, and then deflects the ions through a magnetic field based on the mass-to-charge
ratio of the ion, \dfrac{m}{z}zmstart fraction, m, divided by, z, end fraction.
The mass spectrum of a sample shows relative abundance of each ion on the yaxis and \dfrac{m}{z}zmstart fraction, m, divided by, z, end fraction along the xaxis.
Attributions and references

1.
2.

Try it!
Based on the simulated mass spectrum of zirconium above, we get the following atomic
masses and relative abundances for the isotopes of zirconium:

Isotope
Atomic
mass (\te
xt uuu)
Relative
abundan
ce (\%
%percent)

\
text{Zr-}
90Zr-90Z,

\
text{Zr-}
91Zr-91Z,

\
text{Zr-}
92Zr-92Z,

\
text{Zr-}
94Zr-94Z,

\
text{Zr-}
96Zr-96Z,

r, negative
, 90

r, negative
, 91

r, negative
, 92

r, negative
, 94

r, negative
, 96

89.90589.
90589, poi

90.90690.
90690, poi

91.90591.
90591, poi

93.90693.
90693, poi

95.90895.
90895, poi

nt, 905

nt, 906

nt, 905

nt, 906

nt, 908

51.4551.4
551, point,

11.2211.2
211, point,

17.1517.1
517, point,

17.3817.3
817, point,

2.802.802

45

22

15

38

, point, 80

What is the atomic weight of zirconium based on our mass spectrometry


sample?
Express your answer as a decimal rounded to the nearest hundreth.

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