& y 2.

lsotopes and Mass Spectromet || |

Introduction || |
We owe our knowledge of the existence of isotopes and the isotopic composition of the elements to the |
invention and use of mass spectrometers (Ebbing/Gammon, Section 2.4). In addition, these ingenious ||
devices can be used to determine the masses of isotopes in elements as well as in compounds.

Purpose
Although you will not need a mass spectrometer, you will use the mass spectrum of neon, as well as the |

known abundances of this element’s naturally occurring isotopes, to devise a method for obtaining | 1
isotopic abundances from mass spectra. You will then apply your method to the mass spectra of fi]
mercury, hydrogen chloride, and hydrogen bromide to determine the isotopic composition and atomic ‘i
weights of mercury, chlorine, and bromine. Your instructor may also ask you to explain the mass }
spectrum of elemental bromine.
|

Isotopes
An element is distinguished from any other element by its atomic number. All the atoms of a particular
element have the same atomic number. An atom is also characterized by its mass number. Although the
atoms of a particular element have only one atomic number, they may have two or more different mass
numbers. /sotopes are atoms that have the same atomic number but different mass numbers.

€: bey i\) _ The atoms of most of the elements consist of two or more isotopes. For example, neon consists of three |
; iii: naturally occurring isotopes: *’Ne (10 protons and 10 neutrons), ?'Ne (10 protons and 11 neutrons), and |
°Ne (10 protons and 12 neutrons). The abundances of these isotopes are 90.51%, 0.27%, and 9.22%,
or, in terms of fractional abundance, 0.9051, 0.0027 and 0.0922, respectively. Thus 9051 of every |
10,000 neon atoms are 7°Ne, 27 are 7!Ne, and 922 are 7*Ne.\ |
|
The atomic weight of an element is the weighted average of the exact masses (in atomic mass units) of |1
the naturally occurring mixture of isotopes. Each exact isotopic mass must be multiplied by the
fractional abundance of the isotope, and each result must be added to the others. For an element Y that
consists of isotopes *Y, °Y, and so on, the atomic weight of Y is given by
Atomic weight of Y = (exact mass “Y) x (fractional abundance *Y) + (exact mass PY) x
(fractional abundance °Y) + ...
Using this type of calculation, it can be shown that the atomic weight of neon is 20.18 amu. |)
Mass Spectra of Atoms |
The way a mass spectrometer works is described in your textbook (Ebbing/Gammon, Section 2.4). An |
atom (X) in the gas phase collides with a high-energy electron and loses an electron:

X+e
— X*+2e
The positive ion (X") moves through the mass spectrometer under the combined influences of an |
electric field and a magnetic field until it arrives at a collection point. A special detecting device counts |
| the ions as they arrive at this point.

|
i
|
 42 Experiment 2

The mass of the ion, rather than its chemical nature, determines its exact path. As a result, all of the ions
with the same mass are counted together by the detector. Ions with a different mass arrive at a different b ]

place at the detector and so are counted separately. The total number of counts for each ion is recorded
on a graph called a mass spectrum. Two or more of these graphs are called mass spectra.

Consider the mass spectrum of neon shown in Figure 2.1. It consists of an intense signal at mass
| number 20, a much smaller signal at mass number 21, and a moderately intense signal at mass number
22. You will recall that these are the mass numbers of the three isotopes of neon. The heights of these
signals are proportional to the number of counts at each mass number and, in turn, reflect the fractional
abundances of the isotopes. Make sure you understand this concept by comparing the known fractional
| abundances of neon’s isotopes with the heights of the appropriate signals in the mass spectrum.
Figure 2.1
| The mass spectrum of neon.
Relative Abundance

0 is i9 20 31 2 3 34
Mass (amu)

I| Mass Spectra of Molecules: Fragmentation

When a high-energy electron collides with a molecule, the result is usually a little more complicated
Hi | than when it collides with an atom. Much of the colliding electron’s energy is given to the molecule. If
H | this energy is sufficient, a chemical bond may break and the molecule flies apart. Each fragment can
then acquire a positive charge when it is struck by another electron. Thus the mass spectrum of a
molecule contains signals that are due to fragments of molecules in the mass spectrum, as well as those
that are due to the unfragmented parent molecules.

As an example, consider the mass spectrum of hydrogen iodide (HI) shown in Figure 2.2. The signal at
| mass number 128 is due to HI ions because iodine consists solely of '?’I atoms and the mass number of
Hi hydrogen is 1 (127 + 1 = 128). Note that 'H is the only isotope of hydrogen that affects the mass —
|| spectrum because the isotopic abundance of the other naturally occurring isotope, H (deuterium), is
only 0.015%. Finally, the signal at mass number 127 in Figure 2.2 comes from I jons that result from Ps
fragmentation of the parent molecule. Note that we do not try to explain the relative intensities of signals
due to a parent ion such as HI’ and its fragmentation product, I’. We reserve our interpretation

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 Isotopes and Mass Spectrometry 43

of the relative intensities of two or more signals to those arising from isotopes.

& ° ) Figure 2.2

The mass spectrum of hydrogen iodide (H)).

Relative Abundance

Az
S. ae 35 136 127 128 135 130

Concept of the Experiment

(\) You will devise a method for determining the fractional abundances of neon’s isotopes from the mass
spectrum in Figure 2.1. Remember that the height of a signal is proportional to the fractional
abundance. Because you know the correct fractional abundances before you begin, you will be able to
judge the worth of any method you devise.

You will then be able to use your method to obtain the fractional abundances of the isotopes of mercury
from the mass spectrum of this element. Mercury has naturally occurring isotopes with,mass numbers
of 196, 198, 199, 200, 201, 202, and 204.

Next you will obtain the isotopic abundances of the isotopes of chlorine from the mass spectrum of
hydrogen chloride. The isotopes of chlorine have mass numbers of 35 and 37, so a sample of HCl
contains both H*°Cl and H*’Cl molecules. The relative abundances of these molecules will be identical to
the fractional abundances of the *°Cl and *’Cl isotopes. Thus the relative intensities of the signals arising
from H*°Cl‘and H°*’Cl‘ions will reflect the fractional abundances of the two isotopes of chlorine. In
addition, you will see signals from >Cl‘and *’Cl*ions coming from the fragmentation of H*Cl'and
Hol.

In a similar fashion, you will obtain the isotopic abundances of the isotopes of bromine from the mass
spectrum of hydrogen bromide. However, you will be required to deduce the mass numbers of
bromine’s isotopes from the mass spectrum.

You must provide an explanation for the origin of each signal in the spectra before you can calculate
the fractional abundances of chlorine and bromine.

e|> You will be required to calculate the atomic weights of mercury, chlorine, and bromine from your
_Tesults. For purposes of this experiment, you will use mass numbers instead of exact masses.

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 44 Experiment 2

Finally, if your instructor elects, you will be given an opportunity to explain the mass spectrum of
elemental bromine. This substance consists of diatomic (two-atom) molecules, Br>. All of the
halogens &
(fluorine, chlorine, bromine, iodine, and astatine) are diatomic. As you will see if you do this part of the
experiment, interpreting the mass spectrum of a diatomic element with more than one isotope requires
considerably more insight than interpreting that of a monatomic (one-atom) element such as neon.

Procedure

Getting Started
1. Your laboratory instructor may ask you to work with a partner.
2. Obtain the measuring device that you require.

Doing the Experiment

1. Give the origin of each signal in the mass spectra of mercury and hydrogen chloride. These
spectra can be found in Figures 2.3 and 2.4. Make the required measurements (including units)
and record them. Use the same degree of precision with each measurement.

Figure 2.3
The mass spectrum of mercury.
VALLE

Relative Abundance

Lee ff de An

0 196 197 199 200s 201 202 203 204

Mass (amu)

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 Isotopes and Mass Spectrometry 45 |\\
Figure 2.4
The mass spectrum of hydrogen chloride (HCI).

Relative Abundance

o” it
33 34 35 36 37 38 39 ||
Mass (amu) |

2. Consider the mass spectrum of hydrogen bromide (Figure 2.5). What isotopes of bromine would
lead to this spectrum? Record your answers. Make and record the required measurements
(including units).
If required by your laboratory instructor, consider the mass spectrum of elemental bromine (Br).
This spectrum can be found in Figure 2.6. Make and record the required measurements (including
units).
Figure 2.5
The mass spectrum of hydrogen bromide (HBr).
Relative Abundance

Pz) } \|
8

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 Experiment 2

Figure 2.6
The mass spectrum of elemental bromine (Brz). @

Pe
a4

=
om

O99 80 ar “ise 159 160 161 162

Mass (amu)

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posted to a publicly accessible website, in whole or in part.
 Date Student Name
Course/Section Team Members
Instructor

: ) Isotopes and Mass Spectrometry

Prelaboratory Assignment
1. Suppose the mass spectrum of a hypothetical monatomic element X contains a signal at
mass number 13 and another of identical height at mass number 15.
a. Sketch the mass spectrum. Make sure each axis is properly labeled.

b. | How many isotopes are present? Why?

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website, in whole or in part.
LL
ee ee

48
Experiment 2

c. What are the fractional abundances of the isotopes? Why?

2 Nanas Devise a general method for determining the fractional abundances

of two or more isotopes
from a mass spectrum. Your method must include some means of measuri
ng the signals.
You must state the type of measuring device that you will need to
apply your method. You
must also indicate how you will use the measurements to obtain the
fractional abundances.

b. Test your method by determining the fractional abundances of neon’s

isotopes from
the mass spectrum in Figure 2.1. When you compare your results
to known €
abundances (shown on page 43), remember to take the precision
of the measurements
into account.

Mass Number Measurement with Units

Calculation:

@
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 Isotopes and Mass Spectrometry 49

€ ) Student name: Course/Section: Date:

Comments: |

| 3. a. What does “fragmentation” in a mass spectrometer mean?

b. How will fragmentation affect the mass spectrum of hydrogen chloride? Explain in one or
two sentences..

4
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to a publicly accessible website, in whole or in part.
 Date Student Name
Course/Section Team Members
Instructor

e ) Isotopes and Mass Spectrometry

Results

1. Mercury peaks

Mass Number Measurements with Units

2. Hydrogen chloride, HCl, peaks

Mass Number Formula Measurements with Units

9
51
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52 Experiment 2

3. Hydrogen bromide, HBr, peaks €

Mass Number Formula Measurements with Units

How many isotopes of bromine are indicated by the number of peaks in the mass spectrum?
Explain how you came to this conclusion.

4. Bromine, Br2, peaks (optional)

Mass Number Formula Measurements with Units €

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 Isotopes and Mass Spectrometry 53

Student name: Course/Section: Date:

Questions
1. Calculate the fractional abundances of the isotopes of mercury, chlorine, and bromine.

)
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54
Experiment 2

2. Using the method outlined on page 43, calculate the atomic weights of mercury, chlorine, and
bromine from your data. Use mass numbers rather than exact masses. Compare your results to the
€
actual atomic weights of these elements, and comment on any discrepancies.

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duplicated, or posted to a publicly accessible website, in whole or in part.
 Isotopes and Mass Spectrometry 55

) Student name: Course/Section: Date:

3. (Optional) Why does the mass spectrum of Br contain three signals whose heights are almost in
the ratio of 1:2:1? What combinations of isotopes are responsible for these signals? It may help
to suppose that the fractional abundances of the isotopes are exactly equal. Then think about the
probability of combining the various isotopes of bromine atoms into diatomic molecules. Finally,
why does the spectrum contain two other signals of roughly equal height? What are the origins of
these signals?

e:
a)

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é ) 3A. The Empirical Formula of an Oxide

Introduction
Every chemical compound has a chemical formula that can be determined by a combination of
experiments and calculations. For most ionic compounds, such as magnesium oxide, the empirical
formula (the simplest formula) is the formula that is used for the compound. An empirical formula is
the formula with the smallest integer (whole-number) subscripts (Ebbing/Gammon, Section 3.5).

Purpose
You will be able to determine the empirical formula for magnesium oxide from the results that you will
obtain by burning magnesium in air.

What Happens When an Element Is Burned in Air?

Molecular oxygen, alone or in air, is a very reactive substance when it is heated. Many elements will
react with it. When an element reacts and combines chemically with molecular oxygen, an oxide (a
compound of the element with oxygen) is usually formed.

Molecular nitrogen, the chief component of air, is a rather unreactive substance, even at a high
temperature. Only the more active metals will react and combine chemically with molecular nitrogen
during heating. When nitrogen does react with an active metal, a nitride (a compound of the element
with nitrogen) is formed.

Although the amount of molecular nitrogen in the air is approximately four times the amount of
molecular oxygen, more oxide than nitride is formed when an active metal is burned in air. The reason
is the superior reactivity of molecular oxygen.

Concept of the Experiment

In this experiment, you will burn a known amount of magnesium in air producing magnesium oxide and
smaller amounts of magnesium nitride (Mg3N>). Water will convert the nitride to magnesium hydroxide
[Mg(OH)>] with the liberation of ammonia (NH3). Heat will cause conversion of the hydroxide to the
oxide with the loss of gaseous water.
Because the product will consist solely of the oxide after this treatment, you can determine the mass of
oxygen that is present in the oxide from its mass and the original mass of the magnesium. The laws of
conservation of mass, as well as the concept of a mole, will lead you to the method by which you can
determine the empirical formula of this oxide (Ebbing/Gammon, Sections 1.3 and 3.2).

Procedure

Getting Started
1. Your laboratory instructor may wish to provide special safety precautions concerning the bulk
supply of magnesium ribbon.
2. Ask your laboratory instructor about discarding the magnesium oxide that you will prepare in this

) 3.
experiment.
Obtain a crucible and lid. Wash, rinse, and dry them.

57
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