Topic 2: Atomic Structure and the Periodic table

❖ Isotopes

✓ Atoms of same element with same number of protons but different

number of neutrons

❖ Isotopes have similar chemical properties

✓ They have similar electronic configuration

❖ Relative Isotopic Mass

✓ Mass of an atom of an isotope (of the element) relative to / compared
with 1/12th of the mass of a carbon-12 atom
❖ Relative atomic mass - Ar
✓ Weighted mean mass of an atom of an element relative to / compared
with 1/12th the mass of a carbon – 12 atom.

✓ Average mass of an atom of the element , taking into account the

abundance of each isotope, compared with 1/12th of the mass of a carbon-
12 atom

❖ Mass spectrometry

V Vaporization

High energy
I Ionization
electrons

A Acceleration Electric field

D Deflection Magnetic field

D Detection
❖ Ionisation (High energy electron beam)
✓ Vaporized sample is bombarded / hit with high energy electrons
✓ Knocking out One or more electrons to form +ve charged ions
X(g) + e– → X+(g) + 2e–
❖ Acceleration (Electric field provided by charged plates)
✓ Positive charged ions are accelerated by electric field
✓ Neutral atoms are not accelerated
✓ Positive ions are focussed in to a stream by series of slits
❖ Deflection (Magnetic field)
✓ Positive ions are deflected or separated by a magnetic field
✓ Different ions are deflected by the magnetic field by different extend

The amount of deflection depends on mass to charge ratio m/z ratio

• Ions with larger m/z ratio are deflected less
• Ions with smaller m/z ratio
are deflected more

P : ion with highest

m/z value which is
deflected the least
R : ion with lowest
m/z value which is
deflected the most

• Ion P can be made to reach detector by increasing current

• Ion R can be made to reach detector by decreasing current

❖ Detection
✓ When positive ions hit detector, they absorb electrons and get neutralized
X+ + e– → X
✓ A flow of electrons in the wire is detected.
Sample questions
Q. Describe how positive charged ions are produced in a mass spectrum (2)
✓ Vaporized sample is bombarded with high energy electrons which
knocks out electrons from sample to form positive charged ions
Q. How positive charged ions are separated (2)
✓ Different ions are deflected by the magnetic field by different amounts
according to m/z value
Q. How ions are accelerated (1)
✓ Positive charged ions are accelerated by electric field
Q. Why vacuum is used in mass spectrum (1)
✓ Ions may hit air particle and get deviated
✓ Particles in air also may get ionized and interfere with result by giving
additional peaks
Q. Suggest how, if at all, the electric field in the mass spectrometer would affect
molecules that are not ionized (1)
✓ No effect
Q. Formulae of three ions leaving the electric field in a mass spectrometry are
24
Mg+, 26Mg+ and 26Mg2+. Sketch the path of these ions in the mass
spectrometer as they approach detector region, labelling each path with the
formulae of ions

Calculate m/e value of all the ions

Ion with lowest m/e value deflects
the most
Ion with highest m/e value deflects
the least
For example

m/e of 24Mg+= 24/1 = 24

Mass spectra of monoatomic elements
Mass spectrum of boron is given below

✓ There are two isotopes of boron 10B and 11B

✓ In a sample of boron, 20% of the atoms are 10B and 80% are 11B.
✓ Which species causes a peak at m/z value 11 - 11B+
✓ What m/z value would you expect for a species 10B2+ - 10/2 = 5

Calculate the relative atomic mass of boron

Q. Chlorine has two isotopes Chlorine- 35 and Chlorine 37

A sample of chlorine contains 75.53 % of chlorine-35 atoms.
Calculate the relative atomic mass of this sample of chlorine.
Abundance of 35Cl = 75.53 %
Abundance of 37Cl = 100 – 75.53 = 24.47%

• Divide by 100 if percentage abundance is given.

• Divide by the total abundance if relative abundance is given
Q. Chlorine has two isotopes Chlorine- 35 and Chlorine 37
A sample of chlorine has a relative atomic mass of 35.453.
Calculate the percentage abundance of each of the isotopes of chlorine in this
sample.
Abundance of 35Cl = x %
Abundance of 37Cl = 100 – x %

Abundance of 35Cl = 82.85 %

Abundance of 37Cl = 17.15 %

Mass spectra of diatomic elements

Bromine, Br2 is a diatomic molecule
There are two isotopes of bromine bromine-79 and bromine-81.
Relative abundance of Bromine -79 and bromine 81 are almost equal (50-50%)
Peaks due to Br+
Peak at 79 due to 79Br+ ion
Peak at 81 due to 81Br+ ion
Peaks due to Br2+ (Molecular ion)
79
Br–79Br + at m/z 79+79 = 158
79
Br – 81Br + at m/z 79+81 = 160
81
Br – 79Br + at m/z 81+79 = 160
81
Br–81Br + at m/z 81+81 = 162
Relative peak heights
Relative abundance 79Br : 81
Br is 50 : 50
Probability of forming peaks at 79 and 81 are ½ : ½
Therefore, both peaks must have similar height (1:1)
Probabilities of forming peaks ar 158, 160 and 162
Peak at 158 due to 79Br and 79Br (79Br–79Br +) = ½ x ½ = ¼
Peak at 160 due to 79Br and 81Br or 81
Br and 79Br
(79Br–81Br + or Br – 79Br +) = ½ x½ + ½ x½ = 2/4
81

Peak at 162 due to 81Br and 81Br (81Br–81Br +) = ½ x ½ = ¼

Relative peak heights at 158:160:162 in the ratio 1:2:1
Mass spectrum of chlorine
Chlorine, Cl2 is a diatomic molecule
There are two isotopes of chlorine Cl-35 and Cl-37.
Percentage abundance of Cl-35 is 75 % and Cl-37 is 25%
Peaks due to Cl+
There can be two peaks due to Cl+ Ion
Peak at m/z 35 due to 35Cl+ ion
Peak at m/z 37 due to 37Cl+ ion
Peaks due to Cl2+ (Molecular ion)
35
Cl–35Cl + at m/z 35+35 = 70
35
Cl – 37Cl + at m/z 35+37 = 72
37
Cl – 35Cl + at m/z 37+35 = 72
37
Cl – 37Cl + at m/z 37+37 = 74
Relative peak heights
Relative abundance 35Cl : 37
Cl is 75 : 25 = 3:1
Therefore, peak at 35 and 37 must be in the ratio 3:1 height
Peak at 35 should be 3 times taller than peak at 37

Peak at 70 due to 35Cl and 35Cl (35Cl –35Cl +) = ¾ x ¾ = 9/16

Peak at 72 due to 35Cl and 37Cl or 37
Cl and 35Cl
(35Cl –37Cl + or 37
Cl – 35Cl +) = ¾x ¼ + ¼ x¾ = 6/16
Peak at 74 due to 37Cl and 37Cl (37Cl –37Cl +) = ¼ x¼ = 1/16
Relative peak heights at 158:160:162 in the ration 9:6:1
Molar mass from mass spectra

Molecular ion – entire molecule ionized

CH3CH2CH2CH3 → ( CH3CH2CH2CH3 )+
Molecular ion peak – Peak caused by molecular ion ( Right most significant peak )

1. Deduce the molar mass of the compound referring to mass spectrum

✓ Molar mass of the compound = 58
2. Justify your answer
✓ molar mass of the compound is equal to the m/z value of molecular ion
peak / m/z value of the right most peak
Electronic Configuration

Quantum shells

✓ Principal energy levels or Quantum

shells numbered n = 1,2,3,4..in which 1
is closest to nucleus
✓ Total number of electrons that can fit in
to quantum shells are 2, 8, 18, 32
✓ Each quantum shell contains different
numbers of subshells s, p, d and f

Subshells
Quantum shell Subshells present
1 1s
In 2s, 2p the number 2 represents
2 2s, 2p that these subshells are part of 2nd
quantum shell
3 3s, 3p, 3d
4 4s, 4p, 4d, 4f

Maximum number of electrons that can be present in subshells are

s = 2, p = 6, d = 10, f = 14
Therefore, maximum number of electrons in 3rd quantum shell will be
2 + 6+ 10 = 18 (3s, 3p, 3d)
Orbitals
❖ Orbitals are the region around the nucleus where there is maximum
probability of locating an electron.
❖ Region within an atom that can hold up to two electrons
❖ Each orbital can carry a maximum of 2 electrons
Shape of Orbitals (electron density map of orbitals)

s orbital p orbital
spherical shape dumbbell shape

Subshell Number of orbitals Number of electrons

s 1 1x2=2

p 3 3x2=6

d 5 5 x 2 = 10

f 7 7 x 2 = 14

Electronic configuration
➢ Lowest energy sub-levels are occupied first
➢ Fill each orbital singly before starting to pair up the electrons
➢ Electrons in the same orbital have different spins
For example, carbon has the electronic configuration
1s2 2s2 2p2
Orbitals of the same sub shell occupied singly
by electrons, before pairing of electrons
occurs in order to minimize the repulsion as
electrons repel each other

Electronic configuration of nickel

1s22s22p63s23p64s23d8

Chromium 1s2 2s2 2p6 3s2 3p6 4s1 3d5

Copper 1s2 2s2 2p6 3s2 3p6 4s1 3d10
In each case the 4s orbital contains one electron.
This is because
✓ Completely filled or half filled subshells are more stable
✓ 4s and 3d sub-levels lie very close together in energy, and the 3d being
either half full or completely full is a lower energy arrangement

Electronic configuration of Na+ ion

1s22s22p6
Electronic configuration of Ca2+ ion
1s22s22p63s23p6
Electronic configuration of Cl– ion
1s22s22p63s23p6
Electronic configuration of Ni2+ ion
1s22s22p63s23p64s03d8
Ionization energy
All ionisation energies are endothermic
✓ Energy is required to overcome the electrostatic force of attraction
between the nucleus/protons and the electrons
First ionization energy
✓ Energy required to completely remove an electron from each atom in one
mole of gaseous atom
M(g) → M+(g) + e-
Second ionization energy
✓ Energy required to completely remove an electron from each atom in one
mole of 1+ charged gaseous ion
M+ (g) → M2+(g) + e-
Third ionization energy
✓ Energy required to completely remove an electron from each ion in one
mole of 2+ charged gaseous ion
M2+(g) → M3+(g) + e-
State symbols are must when writing IE equations
IE equations must contain only one mole of electrons
If more than one mole of electrons present, that can be sum of different IEs
For example:
M(g) → M2+(g) + 2e- ( Sum of first and second IE)
M+ (g) → M3+(g) + 2e- ( Sum of second and third IE)
M(g) → M3+(g) + 3e- ( Sum of first second and third IE)

Ionization energies are influenced by

1. the number of protons in the nucleus,
2. the electron shielding (electron – electron repulsion)
3. energy of shell or sub-shell from which the electron is removed
Successive ionisation energy example 1

Each sharp rise / large

jump is caused by
removing electron from a
subshell closer to nucleus /
inner sub-shell

Deduce the electronic configuration and justify

✓ Electronic configuration is 2,8,2
✓ Two large jumps indicate the presence of three quantum shells
✓ Large jump after 2nd IE indicates presence of two electrons in the outer
most shell
Explain what evidence suggest that the element is in second group
✓ Large jump after 2nd IE indicates presence of two electrons in the outer
most shell
Why successive ionization energy increases
✓ Electron is removed from an increasingly positive charge ion
✓ More protons than electrons (Proton : electrons ratio increases)
✓ Ionic radius decreases (electrons are closer to nucleus)
✓ More energy required to overcome greater attraction between nucleus
and electron
Why second ionization energy is larger than first
✓ Electron is removed from a 1+ charged ion
(More protons than electrons)
✓ 1+ charged ion is smaller than atom
✓ More energy required to overcome greater attraction between second
electron and nucleus
Why the difference between 3rd and 2nd IE is larger than the difference between
2nd and 1st IE
✓ Third electron is removed from an inner / lower energy quantum shell
(Closer to nucleus)
✓ First and second electrons are removed from same quantum shell
Example 2

Electronic configuration of the element is 2,8,5

• Two large jumps indicate 3 shells
• Large jump after 5th IE indicates 5 e in the outermost / higher energy shell
• Large jump after 12th IE indicates the presence of 8 electrons in the
second shell and there are 2 electrons which are harder to remove in the
inner most shell
❖ Why logarithm of ionization energies used in the graph
✓ Range is too large to plot
❖ Identify which group in periodic table element A, B and C are present

✓ Element A – group 3 ( large jump after 3rd IE)

✓ Element B – group 2 ( large jump after 2nd IE)
✓ Element C – group 1 ( large jump after 1st IE)
Periodic trends
Why calcium is said to be an s-block element
✓ Highest energy electron / valance electron is in s subshell
Periodicity
✓ When elements are arranged in the increasing order of atomic number,
repeating trend across each period is known as periodicity

Trends in atomic radius

Down the group Across the period

✓ Atomic radius decreases across the

✓ Atomic radius increases down the period
group ✓ Number of protons increases
✓ Number of protons increases ✓ electrons are in the same
✓ electrons are in higher energy (quantum) shell
(quantum) shell ✓ Experience similar shielding
✓ More shielding ✓ electron – electron repulsion
✓ electron – electron repulsion increases as the number of
generally decreases. electrons in outermost shell
✓ so there is a decrease in attractive increases
force between the nucleus and ✓ so there is an increase in attractive
(outer) electrons. force between the nucleus and
(outer) electrons.
Trends in Ionization energy

Down the group Across the period

✓ Number of protons increases

✓ Number of proton increases
(nuclear charge increases)
(nuclear charge increases)
✓ Shielding increases
✓ Shielding remains the same / more
✓ Electron is removed from a higher
electron – electron repulsion
energy / further away quantum
✓ Electron is removed from a same
shell
(energy) quantum shell
✓ Atomic radius increases
✓ Atomic radius decreases
✓ Increase in shielding and energy of
✓ Increase in number of protons is
quantum shell is more significant
more significant
than increase in nuclear charge
✓ Stronger attraction between
✓ Weaker attraction between
nucleus and outermost electron
nucleus and outermost electron
✓ More energy is required to remove
✓ Less energy is required to remove
electron
electron

Across the period While labelling or plotting graph

Highest first IE in each period will be
noble gases
Lowest first IE in each period will be
group 1 elements
B – Lower than Be but higher than Li
O – Lower than N but higher than C
Al – Lower than Mg but higher than Na
S – Lower than P but higher than Si
❖ Which element in the Periodic Table has the highest first ionization energy?
Justify your answer.
✓ Helium
✓ More protons / higher nuclear charge than hydrogen
✓ Electron removed is close to nucleus
✓ Less shielding
✓ Strong attraction between outer electron and nucleus

❖ Ionization energy of beryllium is larger than that of lithium

✓ Beryllium has more proton than Li
✓ Shielding remains the same / more electron – electron repulsion in Be
✓ Electron is removed from a same (energy) quantum shell
✓ More energy is required to remove electron in Be

❖ Why ionisation energy of boron is lower than Be

Be - 1s2 2s2 B - 1s2 2s2 2p1
✓ Outermost electron of boron is in higher energy subshell (2p) / Further
away from nucleus / more shielded by 2s electrons
✓ More electron – electron repulsion
✓ Less energy is required to remove electron

❖ Why ionisation energy of Al is lower than Mg

Mg - 1s2 2s2 2p6 3s2 Al - 1s2 2s2 2p6 3s2 3p1
✓ Outermost electron of aluminium is in higher energy subshell (3p) /
Further away from nucleus / more shielded by 3s electrons
✓ More electron – electron repulsion
✓ Less energy is required to remove electron
❖ Why ionisation energy oxygen is lower than that of nitrogen
N 1s2 2s2 2p3 O - 1s2 2s2 2p4
✓ Oxygen loses a paired electron
✓ Greater repulsion btw paired electrons
✓ less energy is required to remove a paired electron

❖ Why first IE of fluorine is higher than oxygen

✓ Outermost electron in the same quantum shell / subshell
✓ Fluorine has more protons than oxygen
✓ Strong attraction between outer electron and nucleus
✓ Repulsion between paired electron in oxygen reduces IE

❖ Why ionisation energy S is lower than that of P

P - 1s2 2s2 2p63s2 3p3 S - 1s2 2s2 2p63s2 3p4
✓ Sulfur loses a paired electron
✓ Greater repulsion btw paired electrons
✓ less energy is required to remove a paired electron
Trend in Melting temperature

Na, Mg and Al

✓ Giant metallic structure

✓ Na+ while Mg2+ and Al3+ ( ionic charge increases)
✓ Number of delocalized electrons per ion increases
✓ Ionic radius decreases
✓ Metallic bond strength increases
✓ More energy is required to separate

Silicon

✓ Giant covalent structure

✓ Large amount of energy required to break many strong covalent bonds

S, P, Cl and Ar

✓ Melting/ boiling temperature depends on strength of London forces

✓ S exist as S8 , phosphorus as P4, chlorine as Cl2 and argon a monoatomic
element
✓ Strong London force in sulphur as it contains a greater number of
electrons