Atomic Structure and The Periodic Table
Atomic Structure and The Periodic Table
is made up of empty space around a very small, dense nucleus that contains
protons and neutrons
≈0
= 16.0044
= 16.00
Intro:
• Mass Spectrometry is a powerful analytical technique
• It is the most useful instrument for accurate determination of the
abundance and mass of each of its isotopes.
• It is also used to find the relative molecular mass of molecules (later in
Unit 2)
• In the analysis process the sample element will undergo several
changes in number of stages. Following are the main stages involved.
Stage 1: Vaporisation
Initially the element sample will be heated to convert its state to the gaseous
X (s) ---------- > X (g)
Stage 2: Ionisation
The vaporised sample subsequently bombarded with high energy electrons
(the electrons are ‘fired’ from an electron gun)
As the sample is bombarded by these electrons, an electron is knocked off
each particle, forming a 1+ ion
X(g) ---------- > X+(g) + e
Stage 3: Acceleration
The 1+ ions formed are accelerated using an electric field
They are all accelerated to have the same kinetic energy
Since all 1+ ions will have the same kinetic energy, their velocity will only
depend on their mass.
Fact: Lighter ions will move faster, and heavier ions will move slower
Stage 4: Deflection
The 1+ ions will pass through a tube surrounded by a strong electro-magnet
The time of flight of each 1+ ion in this tube depends on their velocity –
which depends on the mass and charge of ions
FYI: there is possibility that during ionisation, even 2+ or 3+ ions also could
generate. If so, there deflection would be affected – greater the charge
higher the deflection and vice versa.
Therefore, the deflection is based on the consideration of both parameters,
mass, and charge. It is as a ratio – m/z or m/e --- > mass/ charge ratio
Stage 5: Detection
As the ions hit on the detector plate and generate a small current which is
amplified to make a signal on a screen.
The final result which appears on the recorder/ screen is called a “mass
spectrum”.
The mass spectrum should be further analysed and interpret to discover
more information about the sample element that analysed.
Interpreting a Mass spectrum
Consider the mass spectrum of boron given below that obtained from the
mass spectrometry.
Shells, n
Subshells
Each of the principal quantum shell/energy level is split into subshells which
are given the letters s, p and d
Elements with more than 57 electrons also have an f shell
The energy of the electrons in the subshells increases in the order s < p < d
The order of subshells appears to overlap for the higher principal quantum
shells as seen in the diagram below:
Shells Sub-shells
Orbitals
Subshells contain one or more atomic orbitals
Orbital – is specific space/ volume within an atom where an electron is likely
to be found
Orbitals exist at specific sub-shells and electrons can only be found at these
sub-shells, not in between them
Each atomic orbital can be occupied by a maximum of two(2) electrons
This means that the number of orbitals in each subshell is as follows:
s sub-shell : one(1) orbital (1 x 2 = total of 2 electrons)
p sub-shell : three (3) orbitals ( 3 x 2 = total of 6 electrons)
d sub-shell : five (5) orbitals (5 x 2 = total of 10 electrons)
f sub-shell : seven (7) orbitals (7 x 2 = total of 14 electrons)
Sub-shells
Orbital
More about orbitals……
s orbital
The s orbitals are spherical in shape
The size of the s orbitals increases with increasing shell number
Ex: the s orbital of the third quantum shell (n = 3) is bigger than the s
orbital of the first quantum shell (n = 1)
Normally drawn as
p orbital
The p orbitals have a dumbbell or “Figure 8” shape
Every shell has three p orbitals except for the first one (n = 1)
The p orbitals occupy the x, y and z axes and point at right angles to each
other, so are oriented perpendicular to one another in three planes
The lobes of the p orbitals become larger and longer with increasing shell
number
Normally drawn as
10Ne
Electrons with similar spin repel each other which is also called spin-
pair repulsion
Fact: Ions- Atoms either lose(to form cations, +) or gain electrons( to form
anions, -) from/to the furthest sub-shell of the valence shell.
Task: use the s, p, d notation to write the full electronic configuration of the
following ions in the table.
11 Na+
13 Al3+
16 S2-
20 Ca2+
21 Sc3+
23 V2+
24 Cr2+
26 Fe2+
27 Co3+
29 Cu2+
35 Br–
Ionisation energy, IE
The literal meaning of Ionisation energy implies that it is the energy involves
in making ions from atoms.
However, it is not the case.
Definition: The energy required to remove one mole of electrons from one
mole of gaseous atoms of an element to form one mole of
unipositive (1+) gaseous ions.
Na
Ca
Cl
H
Second Ionisation Energy, IE2
Mg
Al
Cl
Ar
Explanation: The larger the radius, the greater the distance between the
nucleus and the outer shell electron(s)
Increasing distance weakens the strength of the attractive
forces
Less energy is required to remove the outer shell electron(s)
2. Nuclear charge
Explanation: The greater the shielding effect is, the weaker the attractive
forces between the positive nucleus and the negatively charged
electrons
Less energy is required to overcome the weakened attractive
forces
Explanation:
• the nuclear charge increases (FYI-proton number increases)
• atomic radii increase (FYI- adding of more shells of electrons)
• shielding increases (FYI-as there are more shells of electrons)
• These factors outweigh the increased nuclear charge.
• Less energy is required to ionise
Trend 2: Ionisation energy across a period (limited to Period 2 & 3)
Description: “General” increase
Period 2 Period 3
Explanation:
• the nuclear charge increases
• the atomic radii of the atoms decrease (FYI: as the outer shell is pulled
closer to the nucleus due to increasing nuclear charge, so the distance
between the nucleus and the outer electrons decreases_
• The shielding by inner shell electrons remains reasonably constant (FYI:
as electrons are being added to the same shell)
• It becomes harder to remove an electron as you move across a period;
more energy is needed to overcome nuclear attraction on the last
electron
Summary:
Ionisation Energy Trends across a Period & going down a Group Table
Successive ionisation energies of an element
This is all about the energy involved as the electrons of an atom are
kept removing one after the other(successively)
Fact: The successive ionisation energies of an element increase as the
nuclear attractive forces increase due to decreasing shielding and an
increase in the proton to electron ratio
• The first electron,4s2 removed has the lowest IE1 as it is easily removed
from the atom due to the spin-pair repulsion of the electrons in the 4s
orbital
• The second electron,4s1 is more difficult to remove than the first
electron as there is no spin-pair repulsion and greater p : e ratio
• The third electron, 3p6 is much more difficult to remove than the
second one corresponding to the fact that the third electron is in an
inner shell (n=3) which is closer to the nucleus (3p). So, there is big
“jump” between the 2nd and 3rd ionisations. – indicates the change of a
shell from valence to inner shell
• Removal of the fourth electron is more difficult as the orbital is no
longer full, and there is less spin-pair repulsion
• The big jumps on the graph show the change of shell and the small
jumps are the change of subshell
Electronic configuration and the blocks of element in the Periodic table:
Elements in the periodic table are divided into 4 blocks, s, p, d and f based
on to which sub-shell the last electron is filling in.
Group 1 & 2 – s block
Group III to VIII – p block
Transition metals – d block
(Refer the picture below)