Summary of Chemistry Textbook Section 1.

2: The Mass Spectrometer

Separating atoms by mass
- Mass spectrometer complex instrument can be considered as a number of separate
components (each with a specific function)
- Underlying principle is that the movement of charged particles will be affected as they pass
through a magnetic field
- Degree to which these particles deflect from their original path will depend on their mass
and their charge i.e. mass/charge (m/z) ratio
(DIAGRAM)
- Operation of mass spectrometer is a series of stages as the particles move through the
instrument
1. Vaporization: Analysis sample heated and vaporized and passed into an evacuated tube
particles are separate from one another
2. Ionization: Atoms or molecules bombarded by a stream pf high energy electrons and
one or more electrons are knocked off each atom or molecule result: most commonly
1+ charge but sometimes 2+ charge
3. Acceleration: Positively charged ions are accelerated along the tube due to attraction to
negatively charged plates ions move through slits that control the direction and
velocity of their motion
4. Deflection: Stream of ions passed into a very strong magnetic field which deflects the
ions trough a curved path. If the size of the magnetic field is fixed, a light ion with be
deflected more than a heavy ion and a 2+ ion will be deflected more than a 1+ ion of the
same mass.
The deflection of the ions depends on the mass/charge (m/z) ratio.
Modern mass spectrometers strength of field is variable. If ions are deflected to the
same point, a stronger magnetic field is required to deflect a heavy ion than a light ion.
Stronger magnetic field require to deflect an ion with a 1+ charge than a 2+ charge.
5. Detection: Detected electronically device measures location and the number of
particles that collide with it
6. Recording: Percentage abundance (

) of the
different isotopes is recorded as a graph called a mass spectrum.
Peak produced = mass spectrum for each isotope
Position of peaks = ratio of



- In simple elemental mass spectra (ions generated carry only single charges):
- Number of peaks = number of isotopes of the element present + their isotopic masses
- Higher the peak = the more that isotope is present in the sample
- Peak heights converted abundance fraction or percentage abundance to allow for
calculation of relative atomic mass
EXAMPLE:
Copper has two isotopes and the peak heights of the two copper isotopes are 11.1 and 4.9
units. The abundance fractions can be determined:

To convert these abundance fractions to percentage abundances we simply multiply by 100:

- Generate the relative scale of atomic masses chemists chose the most abundant isotope of
the element carbon, carbon-12, and assigned it a relative mass of exactly 12 units.
- Carbon-12 chosen because:
Very cheap and is widely available
It is relatively easy to isolate and purify
Not toxic in anyway
- Decided to assign carbon a mass of 12 units rather than 1 because the number mirrored the
mass number of the isotope
- Protons and neutrons are the basic building blocks of atom, the relative atomic mass will
closely parallel the number of these fundamental particles in the nucleus of the element
- Mass spectrometer showed that the lightest of all the elements was found to bedeflected 12
times further than the standard carbon-12 isotope and the most common isotope of
magnesium was deflected half as far as carbon-12.
- THEREFORE, hydrogen lightest relative mass close to 1, magnesium relative mass
close to 24
- Mass spectrometers now used for analysis of substances in conjunction with NMR (nuclear
magnetic resonance) or IR (infrared) spectrometers
Calculating relative atomic mass
- Relative atomic mass (RAM) RAM of an element is defined as the weighted mean of the
masses of its naturally occurring isotopes on a scale in which the mass of an atom of the
carbon-12 isotope is 12 units exactly A
r

- Determine the RAM of any element X we multiply the relative isotopic mass (RIM, symbol I
r
)
of each naturally occurring isotope by its abundance fraction and add these values.

() (

)
- If the abundance fraction is expressed as a percentage, the formula becomes:

()
(

Worked example 1:
Use the data provided to determine the relative atomic mass of magnesium.

Solution

()
(

)

()

()
Isotope Relative isotopic mass Percentage abundance
24
Mg 23.99 78.70
25
Mg 24.99 10.13
26
Mg 25.98 11.17
Sample gas
(Vaporization) - Gas
heated, vaporised and
passed into an
evacuated tube
causing particles to
separate.
Electron beam
(Ionization) - Atoms or
molecules bombarded
by a stream of high
energy electrons
causing one or more
electrons to be
knockedoff each atom
leaving a 1+ or rare 2+
charge.
Accelerating plates
(Acceleration) -
Positively charged ions
are accelerated along
the tube by attraction
to negatively charged
plates passing through
slits which control the
direction and velocity.
Magnet (Deflection) -
Stream of ions passed
into a very strong
magnetic field which
deflects the ions
through a curved path.
Detecting screen
(Detection) - Ions are
detected electronically
by a device that
messages both the
location and th
enumber of particles
that collide with it.

()
Relative atomic mass of magnesium is 24.31
Worked example 2
Gallium has two naturally occurring isotopes:
60
Ga with a relative isotopic mass of 68.93 and
71
Ga with a relative isotopic mass of 70.92. Given that the relative atomic mass of gallium is
69.72, determine the percentage abundance of each isotope.
Solution
Let the percentage abundance of the lighter isotope be x%. The abundance of the other
isotope must be (100 x) %, so:

()
(

)

( )

( )




The percentage abundance of
69
Ga is 60.30% and of
71
Ga 39.70%.
Section 1.2 Exercises
1. Draw a flowchart to summarize the major parts of a mass spectrometer. Annotate the
flowchart to explain the function of each part of the mass spectrometer.
2. Draw a mass spectrum for chlorine, which has 75% of the chlorine-35 isotope and 25%
of the chlorine-37 isotope.


3. Define the term relative atomic mass. The weighted means of the relative isotopic
masses of the isotopes of an element.
4. An isotope of an element is deflected twice as much as an atom of carbon-12. What
can be deduced about the weight of that isotope? It can be deduced that the weight of
that isotope will be half the weight of carbon-12 as the lighter the ion the more it will be
deflected.
5. Carbon has two stable natural isotopes, carbon-12 and carbon-13. Calculate the
relative atomic mass of carbon, given that the relative isotopic masses and percentage
abundances are 12.00 (98.89%) and 13.00 (1.11%) respectively.

()
(

()

()

()
The relative atomic mass of carbon-12 is 12.0111.

6. The element thallium has two isotopes, thallium-203 and thallium-205. The relative
isotopic masses and relative abundances are 202.97 (11.4) and 204.97 (26.6)
respectively. Determine the abundance fraction of each isotope and the relative
atomic mass of thallium.

()

()

()

7. Calculate the relative atomic mass of silicon from the following data.
Isotope Abundance % Isotopic mass
28
Si 92.2 28.0
29
Si 4.7 29.0
30
Si 3.1 30.0

()

()

()

8. Boron has a relative atomic mass of 10.81. It has two isotopes, boron-10 of RIM 10.01
and boron-11 of RIM 11.01. Determine the percentage abundances of each isotope.

( )

( )




The percentage abundance of boron-10 is 20% and the percentage abundance of boron-
11 is 80%.

9. The mass spectrum of copper is shown in figure 1.2.2. Use the information given in
that graph to calculate the relative atomic mass of copper.

()

()

()
10. It is very difficult to separate
72
32
Ge and
74
32
Ge but relatively easy to separate
74
32
Ge
and
74
32
Se, although the first two have different mass numbers and the second two
have the same mass numbers. Explain why this difference occurs.
74
32
Ge and
74
32
Se are
different elements and therefore behave differently both physically and chemically
making it easier to separate them.
11. A pure sample of calcium-40 is passed through a mass spectrometer. Explain why the
mass spectrum is found to have a small peak at m/z = 20 and a much larger peak at
m/z = 40. Before going through the process of the mass spectrometer the mass of
calcium is 40 and the sample has no charge however, during the process of the mass
spectrometer the sample of calcium undergoes ionization where the sample is
bombarded by a stream of high energy electrons and one or more electrons are knocked
off from the sample, most commonly resulting in a 1+ charge but sometimes a 2+
charge. The position of the peaks across the horizontal axis indicates the ratio of


and as the most common charge of an ion is 1 and not 2 there is a larger
peak at m/z = 40 due to a higher concentration of that type.
12. For each of the following pairs select the ion that will require the greater magnetic
field to deflect it by a fixed amount.
A)
39
K
+
and
28
Si
+

B)
10
B
+
and
10
B
2+

C)
35
Cl
2+
and
37
Cl
+