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2.1 Atoms & Molecules
2.1 Atoms & Molecules
1 𝑎. 𝑚. 𝑢 = 1.660539040 × 10−27 𝑘𝑔
Consider the arrangement of a carbon atom from the periodic table:
From the periodic table, the atom of carbon has symbol C, 6 protons, 6 neutrons and 6
electrons in its natural state.
On the carbon-12 scale:
Proton mass = 1.0074 a.m.u.
Neutron mass = 1.0089 a.m.u.
Electron mass = 0.0005 a.m.u.
Therefore the total mass of carbon-12 atom is:
𝑇𝑜𝑡𝑎𝑙 𝑚𝑎𝑠𝑠 = 𝑡𝑜𝑡𝑎𝑙 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 𝑚𝑎𝑠𝑠 + 𝑡𝑜𝑡𝑎𝑙 𝑝𝑟𝑜𝑡𝑜𝑛 𝑚𝑎𝑠𝑠 + 𝑡𝑜𝑡𝑎𝑙 𝑛𝑒𝑢𝑡𝑟𝑜𝑛 𝑚𝑎𝑠𝑠 = 6 ×
Relative isotopic mass
Def: The relative isotopic mass of an isotope is the ratio of the mass of one atom of that
isotope relative to 1/12th of the mass of one atom of carbon-12.
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑎𝑛 𝑖𝑠𝑜𝑡𝑜𝑝𝑒 𝑜𝑓 𝑎𝑛 𝑒𝑙𝑒𝑚𝑒𝑛𝑡
Relative isotopic mass = 1
× 𝑡ℎ𝑒 𝑚𝑎𝑠𝑠 𝑜𝑓 𝑜𝑛𝑒 𝑎𝑡𝑜𝑚 𝑜𝑓 𝑐𝑎𝑟𝑏𝑜𝑛−12
12
In most cases, however, the charge is +1, so the deflection depends essentially on the
relative mass of the species in the mass spectrometer. If the spectrometer is calibrated, the
masses of all the species can be directly measured.
The greater the number of particles landing at a single point on the detector, the greater
the electric current and the larger the peak. Thus the relative abundance of different
isotopes can be measured.
Since the position at which an ion appears on the detector depends on its mass, different
isotopes appear at different points on the detector. The magnitude of the peak gives the
relative abundance of the isotope.
Thus the relative atomic mass of the element can be calculated from its mass spectrum.
An example of a simple mass spectrum is shown below:
Mass spectrum of Ne
12
×12
= 20.2
Or
Σ (percentage abundance of each isotope x mass of each isotope)
RAM = 100
90 ×20+10×22
= 100
= 20.2
All relative atomic masses have been found using this method.
Deducing relative molecular masses
It is also possible to put molecules into the mass spectrometer. Because the conditions
inside a mass spectrometer are very extreme, the molecules often break up into
smaller pieces. This is known as fragmentation.
The mass spectrum of a molecule can thus look quite complicated, below is a mass
spectrum of pentane:
Relative abundance
72
10 20 30 40 50 60 70
m/z
Many of these peaks result from fragmentation of the molecule, but the peak with the
largest m/e ratio comes from the unbroken molecular ion, in this case C5H12+, and is
called the molecular ion peak. The m/e ratio of this peak (72) will be the relative
molecular mass of the molecule.
The relative molecular mass of a molecule is obtained by looking at the peak in the
spectrum with the largest m/e ratio (i.e. the peak furthest to the right).
Fragmentation
During fragmentation, the free radical molecular ion is broken up. As the molecular
ion contains an odd number of electrons, one of the species into which it fragments
will contain an even number of electrons (this will be a positive ion) and the other will
contain an odd number of electrons (this will be a free radical).
Eg consider the case of ethane:
This is the free radical molecular This species keeps the This species loses
ion unpaired electron and is an the electron and is
uncharged free radical a positively
charged ion
(not detected in mass
spectrometer)
(detected in mass
spectrometer)
R+· X+ + Y·
R+· is the molecular ion and is detected (assuming not all of them fragment)
X+ is the fragment ion and is detected
Y· is the fragment radical and is not detected
Stable ions
Not all possible fragments are detected – some of the fragments form stable ions and these
are more likely to be formed.
The most stable cations are carbocations (eg CH3+, CH3CH2+ and CH3CHCH3+) and acylium
ions (eg HCO+, CH3CO+, CH3CH2CO+). These are thus the fragments most likely to be
detected, and will give the most intense peaks in a mass spectrum.
The main peaks in the mass spectrum of an organic compound will thus be the molecular ion
peak and the peaks corresponding to the most stable ions which can be formed from
fragmentation of the molecular ion.
Eg butanone: CH3CH2COCH3
Expected in the mass spectrum of butanone would be:
m/z ratio Ion responsible Equation to show formation of ion
72 [CH3CH2COCH3]+·
15 [CH3]+ [CH3CH2COCH3]+· [CH3]+ + [CH2COCH3]·
29 [CH3CH2]+ [CH3CH2COCH3]+· [CH3CH2]+ + [COCH3]·
57 [CH3CH2CO]+ [CH3CH2COCH3]+· [CH3CH2CO]+ + [CH3]·
43 [COCH3]+ [CH3CH2COCH3]+· [COCH3]+ + [CH3CH2]·
29
57
Relative abundance
43
15
27 44 72
10 20 30 40 50 60 70
m/z
The most abundant peak is 43, followed by 72 and 29. The peaks at 15 and 57 can also
be accounted for. (It is rarely possible to account for all the peaks in a mass spectrum)
THE MOLE CONCEPT
The Mole
Def: A mole is defined as the amount of any substance that contains the same number of
elementary entities (particles) as there are in 12 grams of the carbon-12 isotope.
The number of moles of any substance can be calculated as shown below:
𝑀𝑎𝑠𝑠 𝑔𝑟𝑎𝑚𝑠)
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑚𝑜𝑙) = 𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑔𝑚𝑜𝑙 −1 )
Where:
Mass represents the weight of the sample.
Molar mass is the relative atomic mass (from periodic table) of the substance in 𝑔/𝑚𝑜𝑙.
Example 2.1.5
1. How many moles are contained i n a sample of 2g of calcium, 𝐶𝑎?
2. Use the periodic table to predict the element that weighs 2.875g and contains
0.125moles?
Solution
𝑀𝑎𝑠𝑠 𝑔𝑟𝑎𝑚𝑠
1. 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑚𝑜𝑙 = 𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑔/𝑚𝑜𝑙
2𝑔
=
40𝑔/𝑚𝑜𝑙
= 0.05 𝑚𝑜𝑙𝑒𝑠 𝐶𝑎
𝑀𝑎𝑠𝑠 𝑔𝑟𝑎𝑚𝑠
2. 𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 𝑚𝑜𝑙 = 𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 𝑔/𝑚𝑜𝑙
2.875𝑔
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 =
0.125𝑚𝑜𝑙
𝑀𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = 23𝑔/𝑚𝑜𝑙
The element is 𝑆𝑜𝑑𝑖𝑢𝑚 because its molar mass = 23𝑔/𝑚𝑜𝑙.
The Avogadro number, 𝑳
Def: Defined as the number of particles in one mole of any substance.
The number is a constant and has the value 6.02 × 1023 𝑚𝑜𝑙 −1 to 3 s.f.
Examples:
1 mole of Ne contains 6.02 × 1023 𝑁𝑒 𝑎𝑡𝑜𝑚𝑠
1 mole of NH3 contains 6.02 × 1023 𝑁𝐻3 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 but 4 × 6.02 × 1023 𝑎𝑡𝑜𝑚𝑠
It is possible to find the number of particles on any given sample according to the
equation:
𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑝𝑎𝑟𝑡𝑖𝑐𝑙𝑒𝑠 = 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 × 𝐴𝑣𝑜𝑔𝑎𝑑𝑟𝑜 𝑛𝑢𝑚𝑏𝑒𝑟
Moles of Gases
All gases occupy equal volume at same conditions of temperature and pressure
(Avogadro’s law).
For example: 22.4 dm3 of ammonia, oxygen, methane and ammonia all contain 1 mol of
gas at 1 atm and 0℃.
Always check out for the following terms:
Standard temperature and pressure (s.t.p) which is 0℃ (273K) and 101.325kPa (1atm) respectively.
Room temperature and pressure (r.t.p) which is 25℃ (298K) and 101.325kPa (1atm) respectively.
At s.t.p, 1 mole of any gas occupies 22.4dm3 (22400cm3) or 22.4 litres.
At r.t.p, 1 mole of any gas occupies 24 dm3 (24000cm3) or 24 litres.
At standard temperature and pressure, gases occupy less volume compared to room
temperature and pressure.
This is because as temperature is increased the intermolecular forces holding the gases
together become less significant until the gas reach ideality.
When the gas reaches ideal state, the intermolecular forces become negligible.
Example 2.1.8
Use the data booklet to calculate the volume of 1.505 × 1023 molecules of hydrogen at:
Standard temperature and pressure.
Room temperature and pressure.
Solution
Recall:
1 𝑚𝑜𝑙𝑒 = 6.02 × 1023 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠
Let the number of moles of hydrogen be x
𝑥 = 1.505 × 1023
1.505 × 1023
𝑥=
6.02 × 1023
𝑥 = 0.25 𝑚𝑜𝑙𝑒𝑠
22.4𝑑𝑚3
At s.t.p, 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑔𝑎𝑠 = 𝑛𝑜. 𝑜𝑓𝑚𝑜𝑙𝑒𝑠 × 𝑚𝑜𝑙𝑎𝑟𝑔𝑎𝑠 𝑣𝑜𝑙𝑢𝑚𝑒 = 0.25𝑚𝑜𝑙𝑒𝑠 × 𝑚𝑜𝑙
= 5.6 𝑑𝑚3
24𝑑𝑚3
At r.t.p, 𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑔𝑎𝑠 = 𝑛𝑜. 𝑜𝑓𝑚𝑜𝑙𝑒𝑠 × 𝑚𝑜𝑙𝑎𝑟𝑔𝑎𝑠 𝑣𝑜𝑙𝑢𝑚𝑒 = 0.25 × 𝑚𝑜𝑙
= 6𝑑𝑚3
DETERMINATION OF EMPIRICAL AND MOLECULAR FORMULA
Note that at room temperature all the other reactants or products are in gaseous
state except the water produced hence the volume of water is negligible i.e. 0𝑐𝑚3 .
Example 2.2.7
A chemist measured 20𝑐𝑚3 of a hydrocarbon that required 100𝑐𝑚3 oxygen gas for
complete combustion. Upon complete combustion, 60𝑐𝑚3 of carbon dioxide was
produced. Calculate the molecular formula of the hydrocarbon.
Solution
Recall:
𝑦 𝑦
𝐶𝑥 𝐻𝑦 𝑔 + 𝑥 + 𝑂2 𝑔 → 𝑥𝐶𝑂2 𝑔) + 𝐻2 𝑂 𝑙)
4 2
3 3 3
20𝑐𝑚 100𝑐𝑚 60𝑐𝑚 0𝑐𝑚3
If 1𝑐𝑚3 of 𝐶𝑥 𝐻𝑦 𝑔 is burnt in oxygen, 3𝑐𝑚3 of carbon dioxide would be produced i.e. 𝑥 =
3
Substituting for x,
𝑦
3+ =5
4
𝑦=8
The molecular formula of the compound is 𝐶3 𝐻8
Assessment exercise 2.1: Atoms and molecules
1. Define the following terms:
a. Isotope
b. Relative atomic mass
c. Avogadro’s number [3]
2. Bromine has two isotopes, with mass numbers 79 and 81. Its relative atomic mass is often given as
80. What does that tell you about the relative abundance of the two isotopes? [2]
3. Deduce the relative atomic mass of Silicon, given the following isotopic information (28Si 92.21%,
29Si 4.70%, 30Si 3.09%). [2]
4. Deduce, giving reasons, the relative molecular mass of compound A, which has the following
mass spectrum: 29 [1]
Relative abundance 57
43
15
72
10 20 30 40 50 60 70
m/z
5. A compound contains C 62.08%, H 10.34% and O 27.58% by mass. Find its empirical formula and its
molecular formula given that its relative molecular mass is 58. [2]