RELATIVE MASS &

MASS SPECTROMETRY
 Atomic number and mass number
• The number of protons in an atom is the atomic number (also
called proton number), Z

• The atomic number for all atoms of the same element is the
same

• The elements are arranged in this order in the Periodic Table

• The mass number (A) is the number of protons and neutrons

in an atom

• Protons and neutrons have the same mass; the mass of an

electron is tiny in comparison

• The mass number for atoms of the same element can vary
 Isotopes

• Isotopes are atoms with the same number of protons but

different numbers of neutrons

• They have the same atomic number but different mass

numbers
 Relative atomic mass
Relative isotopic mass =
mass of a single isotope of an element
1/ mass of one atom of 12C
12

This is the same as the mass number

Relative atomic mass (Ar) =

average mass of atom of element (weighted for isotopes)
1/ mass of one atom of 12C
12

Ar has no units
 Time-of-flight Mass Spectrometry
You should be able to:
• interpret spectra and determine Ar
 Time-of-flight Mass Spectrometer

1. Sample injection
• instrument under high vacuum (prevent collisions with air)
• sample dissolved in a polar, volatile solvent
• injected through capillary tube to create droplets
 Time-of-flight Mass Spectrometer

2. Electrospray ionisation
• inlet connected to + terminal of high voltage supply
• produces positive ions: M  M+ + e-
• solvent evaporates into vacuum
• left with single positively charged particles M+(g)
 Time-of-flight Mass Spectrometer

flight tube

+ -

3. Acceleration
• ions are accelerated towards - terminal
• until they have the same kinetic energy = ½mv2
• heavier ions move more slowly than lighter ones
 Time-of-flight Mass Spectrometer

flight tube

+ -

4. Ion drift
• the ions fly through a tiny hole into the ‘flight tube’
• light ions take a shorter time
• heavy ions take a longer time
 Time-of-flight Mass Spectrometer

flight tube

+ -

5. Ion detection
• positive ions arrive at detector and pick up electrons causing
a small electric current to flow
• the time to reach the detector is recorded
• the intensity of the signal is recorded
 Time-of-flight Mass Spectrometer
20Ne 90.92%
Relative abundance

21Ne 0.26%

22Ne 8.82%

10 20
m/z

6. Data analysis
• mass spectrum produced
• mass/charge ratio on x-axis (m/z)
• relative abundance (proportional to intensity) on y-axis
 Time-of-flight Mass Spectrometer
20Ne 90.92%
Relative abundance

21Ne 0.26%

22Ne 8.82%

10 20
m/z

• as most ions are 1+ charged, m/z gives the mass

• if an ion acquires a 2+ charge its m/z value is halved
 Calculating relative atomic mass
Out of every 100 atoms... 90.92 are 20Ne , 0.260 are 21Ne and 8.82 are 22Ne

Average = (90.92 x 20.0) + (0.260 x 21.0) + (8.82 x 22.0) = 20.179 Ans. = 20.2
100

TIP In calculations of this type... multiply each relative mass by its abundance
add up the total of these values
divide the result by the sum of the abundances

* if the question is based on percentage abundance, divide by 100 but if

it is based on heights of lines in a mass spectrum, add up the heights
of the lines and then divide by that number.

Watch significant figures!!