AQA A-Level Chemistry alevelchemistry.co.

uk

3.1.1 Atomic structure

SPECIFICATION
‒Structure of an atom
‒Mass number and atomic number
‒Isotopes and calculating Relative Atomic Mass
‒Time of flight (TOF) mass spectrometer
‒Applications of mass spectroscopy
‒Electronic configuration
‒Quantum sub-shells
‒Atomic orbitals
‒Filling of orbitals
‒Electron configurations and periodic table
‒Electron configurations of ions
‒Electronic configurations of period 2 and 3 elements
‒Electronic configuration of d-block elements
‒Periodic trends in ionisation energy
‒Predicting electronic structure using successive ionisation energy

Source: AQA spec

AQA A-Level Chemistry 3.1.1 Atomic structure

Scientists have discovered 118 elements till now. Each element has different properties.
In this article, the structure of an atom and its mass are discussed. Properties of
isotopes are also discussed.
This article also introduces the concepts about how electrons are arranged in an atom.
The atomic orbitals and their shapes are discussed. The number of atomic orbitals a
principal quantum shell carries is also explained in brief. The order in which electrons are
filled in each atomic orbital is an important concept that links with arrangement of
elements in periodic table.

A. Structure of an atom
An atom consists of a nucleus and electrons orbiting around the nucleus. Structure of an
atom is illustrated in figure 1. A nucleus consists of protons and neutrons. Protons are
particles with positive electrical charge and neutrons carry a neutral electrical charge.
Both protons and neutrons have the same mass. An electron carries a negative electrical
charge and almost has no mass.

Figure 1: Structure of an atom

Relative
Particle Location Relative mass
charge
Proton Nucleus 1 +1
Neutron Nucleus 1 0
Electron Shells around   1 -1
1840
the nucleus
AQA A-Level Chemistry 3.1.1 Atomic structure

B. Mass number and atomic number

In a neutral atom, the number of protons and the number of electrons are always equal
because their charge is equal in size but opposite in nature. Each element is
represented in the form of MPX, where X is the symbol of the element, M is the mass
number or nucleon number, and P is the proton or atomic number. Mass number is the
total number of protons and neutrons in the atom. Atomic number is the number of
protons in the atom.
Mass number M
Atomic number P
X
M=n+p

Mass Number of
Atomic Number of
Element Symbol number neutrons
number (p) protons (p)
(p+n) (n)
23
Sodium  
11 𝑁𝑎 23 11 11 12
27
Aluminium  
13 𝐴𝑙 27 13 13 14
40
Calcium  
20 𝐶𝑎 40 20 20 20

C. Isotopes and calculating Relative Atomic Mass

Isotopes are different forms of the same element having different masses. Isotopes have
the same number of protons but different number of neutrons. As the number of protons
is same as the number of electrons in any atom, all isotopes of an element have same
electronic configuration. Therefore, all isotopes of an element react chemically in same
manner. Because, isotopes of an element have different number of neutrons, their mass
numbers varies. Example:

Isotope Isotopes of boron

10 11
Symbol  5 𝐵  5 𝐵
Atomic number (p) 5 5
Mass number (n+p) 11
Number of neutrons (n) 5 6
AQA A-Level Chemistry 3.1.1 Atomic structure

Relative atomic mass is the average mass of one atom of an element compared to one-
twelfth of the mass of one carbon-12 atom. Relative isotopic mass is the mass of one
isotope compared to one-twelfth of the mass of one carbon-12 atom. Relative masses
are ratios of two masses and hence do not have any units.

The relative composition of isotopes of Boron found mass by spectroscopy and is given
in the table below:

  Boron-10 Boron-11
Relative
10 11
isotopic mass
Relative
23 100
abundance

Based on this data, the relative atomic mass of Boron is calculated:

D. Time of flight (TOF) mass spectrometer

A mass spectrometer separates the atoms of a particular sample according to their
masses. When a sample is placed in the mass spectrometer, the sample is converted to
positively charged ions, highly accelerated and reach the detector. When a sample of an
element with isotopes is placed, a mass spectrum with peaks showing their relative
abundances is obtained.
AQA A-Level Chemistry 3.1.1 Atomic structure

This process takes place in vacuum so that air molecules do not disturb the process.
The samples can be ionised using electron impact or electrospray ionisation.
• In electrospray ionisation, the sample is dissolved in volatile polar solvent and is
injected through a needle. The needle is connected to positive terminal of high
voltage supply. In this method, tiny droplets of sample are produced that are
positively charged (after gaining an electron from the solvent). The solvent
evaporates in the vacuum and the positively charged (MH+) ions are then attracted
towards the negative plate.
M (molecule) + H+ (proton from solvent) → MH+
• In electron impact, sample is vaporised, and an electron gun fires high energy
electrons at the sample and the outer electron is removed forming positive ions. This
method is used to ionise elements and substances with low formula mass.
X(g) +e- → X+(g) +2e-
Electrospray injection is used for ionising larger organic molecules as the electron
impact process may result in its fragmentation.
The positively charged ions are accelerated towards the negatively charged plate. The
velocity at which the particles travel depends on its mass. Lighter particles travel faster.
The constant kinetic energy (KE) is related to the velocity of the particles (v) and time as
given by the equations ,
  2 𝐾𝐸   𝑑 𝑚
𝑣=
√ 𝑚
𝑡= =
𝑣 √
2 𝐾𝐸
where m is the mass of the particle.
The ions are recognised by the difference in the time taken to travel through the length
of the tube. The heavier particles have a longer drift time (t). The ions reach a detector
and produce a small current due to transfer of electrons. The amount of current
produced is proportional to the abundance of a particular isotope in the sample. The
result is a graph between m/z (mass/ charge ratio) and relative abundance. A time of
flight mass spectrometer is shown in the figure below.

Figure 2: Time of flight

mass spectrometer
AQA A-Level Chemistry 3.1.1 Atomic structure

E. Applications of mass spectroscopy

The composition of each isotope can be found out through results of mass spectrometer.
This data is used to calculate the relative atomic mass of the element. The mass
spectroscopy result for Boron is given in the figure below.

Figure 3: Mass spectroscopy result for Boron

It can be noted that there are two isotopes of Boron: 10 and 11. The relative abundance
for B-10 is 23 and for B-11 is 100 in the sample. Using this data, the relative atomic
mass of boron is calculated.
In organic chemistry, mass spectrum of an unknown compound is used to identify it. The
unknown compound’s mass spectrum is compared with mass spectrums of known
compounds from database to find a match. This method is called as fingerprinting.
Consider ethanol with molecular formula C2H5OH. The relative molecular mass of
ethanol can be found to be 46 using its mass spectrum as shown in the figure below.

Figure 4: Mass spectrum of ethanol

AQA A-Level Chemistry 3.1.1 Atomic structure

F. Electronic configuration
The electrons around the nucleus are arranged in principal quantum shells (symbol
n). The number maximum number of electrons a sub-shell can hold is based on the
formula, 2n2 where n is the number of main level. The arrangement of electrons in an
atom is called its electronic configuration. Each principal quantum shell can hold a
maximum number of electrons as per the table given below.

Maximum number of electrons

Quantum shell
(2n2)
n=1 2
n=2 8
n=3 18
n=4 32

The quantum shell n=1 is the closest to the nucleus, n=2 is the next shell and so on.
Examples:

Number of electrons
Number of
Element
electrons n=1 n=2 n=3
Helium 2 2    
Carbon 6 2 4  
Magnesium 12 2 8 2

He C

Mg

Figure 5: Arrangement of electrons

AQA A-Level Chemistry 3.1.1 Atomic structure

G. Quantum sub-shells
The principal quantum shells (except for n=1) are split into sub-shells. The sub-
shells are sub-divided as s, p, d an f.

• n=1 principal quantum shell consists of

one s sub-shell and carries maximum principal
quantum maximum
quantum
of 2 electrons. sub- number of
shell
• n=2 principal quantum shell consists of shells electrons
(n=)
one s sub-shell and one p sub-shell.
1 s 2
Thus, carries a maximum of 8
2 s and p 2+6=5
electrons.
s, p and
• n=3 principal quantum shell consists of 3 2+6+10=18
d
one s sub-shell, one p sub-shell and
one d sub-shell. Thus, carries a
maximum of 18 electrons.

The sub-shells for the four principal quantum shells are given in the figure below.
The electrons fill up the sub-shells in increasing order of energy in each sub-shell.
Until the atomic number of 18 (Argon), the shells are filled in order: 1s, 2s, 2p, 3s
and 3p. For potassium (atomic number 19), the electron fill up the 4s sub-shell
rather than 3d sub-shell. This is because the energy of 4s orbital is less than that of
3d orbital.

Figure 6: Principal quantum shells and sub-

shells
AQA A-Level Chemistry 3.1.1 Atomic structure

H. Atomic orbitals
An atomic orbital is the region of space around the nucleus that can be occupied
by one or two electrons. Each quantum sub-shells is made of one or more atomic
orbitals. The number of atomic orbitals for each sub shell is given in the table
below:
Maximum
Sub- Number of
number of
shell atomic orbitals
electrons
s 1 2
p 3 6
d 5 10
f 7 14

Each orbital is a three-dimensional structure. A s-orbital has a spherical shape. All

s-orbitals have the same shape but the energy of 2s orbital is greater than that in
1s orbital and so on.

Figure 7: Shape of s-orbitals

A p-orbital has a lobe like structure as shown in figure 4. There are three 2p orbitals
and each of them have the same structure but each of them is aligned in x, y and z
axis. Hence, the naming of these orbitals are 2px, 2py and 2pz. The shape of 3p
orbitals is similar to that of 2p orbitals.

Figure 8: Shape of p-
AQA A-Level Chemistry 3.1.1 Atomic structure

I. Electron configurations
The electron configuration of an element denotes the number of electrons in each
sub shell in order. For example, helium has 2 electrons which are filled in the 1s
orbital. The electron configuration is written as:
electron configuration of He=1s2
where 1 represents the principal quantum number, s represents the sub-shell and 2
represents the number of electrons in 1s sub-shell.
Similarly, electron configuration of nitrogen (atomic number=7) is written as:
electron configuration of N=1s22s22p3
The electron configurations up to atomic number of 36 is required. There are few
points to be noted:
• The electrons fill the 4s sub-shell before filling up the 3d sub-shell.
For example:
Potassium has atomic number of 19
electron configuration of K=1s22s22p63s23p64s1
Calcium has atomic number of 20
electron configuration of Ca=1s22s22p63s23p64s2
• The electrons fill up 3d sub shell after filling up 4s sub shell. For example:
Scandium has atomic number of 21
electron configuration of Sc=1s 22s22p63s23p64s23d1
Some exceptions to this pattern are Chromium (atomic number=24) and
copper (atomic number=29). It can be noted that 4s shell is filled with only one
electron for these two elements.
electron configuration of Cr=1s22s22p63s23p63d54s1
electron configuration of Cu=1s22s22p63s23p63d104s1
AQA A-Level Chemistry 3.1.1 Atomic structure

J. Filling of orbitals
The shells are filled in the increasing order of energy levels. The order in which the
electrons are filled is shown in figure below.

Figure 9: Filling up of sub-shells

Filling up of orbitals in an element is expressed by placing arrows in boxes. Arrows
denote the electrons. The direction in which the arrow points, denotes the spin of
electron. An electron rotates in its own axis in either clockwise or anti-clockwise
direction. In an orbital, electrons rotate in opposite directions, and hence, have
opposite spins.

Electrons are negatively charged. As like charges repel each other, electrons
occupy separate orbitals if possible. Only when the all orbitals of a sub shell are
filled with one electron, the electrons are paired in those orbitals. The paired
electrons always have opposite spins to minimise repulsions.

Figure 10: Filling up of orbitals

AQA A-Level Chemistry 3.1.1 Atomic structure

K. Electron configurations and periodic table

The periodic table can be divided into four blocks: s-block, p-block, d-block and
f-block.
• s-block: Hydrogen, Helium, Group 1, group 2 elements and helium have
outermost electrons in s-shell
• p-block: Group 3 to 18 (except He) have outermost electrons in p-shell
• d-block: Elements that have outermost electrons in d-shell. These elements
are also called as transition elements.
• f-block: Elements that have outermost electrons in f-shell.

Figure 11: Blocks of periodic table

L. Electron configurations of ions

Positive ions are formed when atoms lose electrons. For s-block elements,
electrons are lost from the outermost s-shell. For example: electron configuration of
Calcium is 1s22s22p63s23p64s2. Calcium loses two electrons and forms Ca2+.

Electron configuration of Ca2+=1s22s22p63s23p6

The configuration of Ca2+ is similar to that of Argon (Atomic number =18) which is a
noble gas.
Negative ions are formed when atoms gain electrons. For example: electron
configuration of oxygen is 1s22s22p4. Oxygen gains two electrons and forms O 2-.

Electron configuration of O2-=1s22s22p6

The configuration of O2- is similar to that of Neon (Atomic number =10) which is a
noble gas.
AQA A-Level Chemistry 3.1.1 Atomic structure

M. Electronic configurations of period 2 and 3 elements

The pattern in electronic configuration of period 2 and period 3 elements are shown in
the table below.

Element Electronic Element Electronic

(Period 2) configuration (Period 3) configuration
Li [He]2s1 Na [Ne]3s1
Be [He]2s2 Mg [Ne]3s2
B [He]2s22p1 Al [Ne]3s23p1
C [He]2s22p2 Si [Ne]3s23p2
N [He]2s22p3 P [Ne]3s23p3
O [He]2s22p4 S [Ne]3s23p4
F [He]2s22p5 Cl [Ne]3s23p5
Ne [He]2s22p6 Ar [Ne]3s23p6

N. Electronic configuration of d-block elements

Transition element is a d-block element that forms one or more stable ions
with an incomplete d sub-shell. The electronic configuration of d block
elements of period 4 is given in the table below.

Element Atomic number Electronic configuration

Scandium (Sc) 21 [Ar]3d14s2

Titanium (Ti) 22 [Ar]3d24s2
Vanadium (V) 23 [Ar]3d34s2
Chromium (Cr) 24 [Ar]3d54s1
Manganese (Mn) 25 [Ar]3d54s2
Iron (Fe) 26 [Ar]3d64s2
Cobalt (Co) 27 [Ar]3d74s2
Nickel (Ni) 28 [Ar]3d84s2
Copper (Cu) 29 [Ar]3d104s1
Zinc (Zn) 30 [Ar]3d104s2
AQA A-Level Chemistry 3.1.1 Atomic structure

O. Periodic trends in ionisation energy

First ionisation energy of an element is the energy required to remove one electron
from each atom in one mole of atoms of an element in its gaseous state to form
gaseous 1+ ions. It is measured in kJ/mol.
X(g)→X+(g)+e-
The ionisation energy generally increases across a period and decreases down the
group. Factors that affect the ionisation energy are:
• Size of nuclear charge
Across the period towards right, the number of protons and electrons increases and
the force of attraction between nucleus and electrons increases. Hence, more energy
is required to remove electron from the outermost shell. Ionisation energy increases
with increase in atomic number.
• Distance of valence electrons from the nucleus
As the distance of valence electrons increases from the nucleus, the force of attraction
gets weaker and hence, ionisation energy decreases.
• Shielding of inner electrons
As the number of filled electron shells between the valence electrons and the nucleus
increases, the ionisation energy decreases. The inner electrons reduce the force of
attraction as they repel the valence electrons.
The ionisation energies decrease down the group because the valence electrons are
shielded by the filled orbitals. The distance between the valence electrons and nucleus
also increases down the group, making it easy to remove valence electron.
The ionisation energy of elements of period 3 are given in the table below. This trend is
also applicable for period 2.

First ionisation
Period 3 element
energy (kJ/mol)
sodium (Na) 494
magnesium (Mg) 736
aluminium (Al) 577
silicon (Si) 786
phosphorus (P) 1060
sulfur (S) 1000
chlorine (Cl) 1260
argon (Ar) 1520
Figure 12: Periodic trends in ionisation
energy
AQA A-Level Chemistry 3.1.1 Atomic structure

Generally, the first ionisation energy across the period increases towards right due to
increase in atomic number which makes it difficult to remove an electron. There are
small dips across the period between Magnesium and Aluminium, and between
Phosphorous and Sulphur. These dips are also found in period 2 between Beryllium
and Boron, and Nitrogen and Oxygen.
Aluminium has one electron in its 3p orbital. It requires less energy to remove one
electron from p-shell when compared to that of Magnesium. This is due to shielding of
valence electrons in 3p orbital by electrons in 3s orbital. In case of Mg, the shielding is
comparatively less. The electronic configuration of aluminium and magnesium are
given.

I.E1 of Al < I.E1 of Mg

In phosphorous, each 3p orbital consists of an electron. Sulphur has 2 pair of electrons

in one of the 3p orbitals. There is a force of repulsion between these paired electrons
which makes it easier to remove even though atomic number increases. Hence, the
ionisation energy of Sulphur is less than Phosphorous.

I.E1 of S < I.E1 of P

AQA A-Level Chemistry 3.1.1 Atomic structure

Second ionisation energy is the energy required to remove one electron from each ion
in one mole of ions of single positively charged ions in gaseous state to form gaseous
2+ ions.
X+(g)→X2+(g)+e-
The ionisation energies of group 2 elements are given below. The ionisation energy
decreases down the group because the outer most electrons gets further away from
nucleus and:
• Increase in the size of the atom
• Decrease in force of attraction between nucleus and valence electrons
• Increase in shielding effect of filled inner shells
Successive ionisation energy is always greater than the 1 st ionisation energy because
the electrons are removed from a positively charge ions. The ionisation energies of
group 2 elements are:

1st ionisation energy 2nd ionisation energy

Element
(kJ/mol) (kJ/mol)
Beryllium (Be) 900 1760
Magnesium (Mg) 736 1450
Calcium (Ca) 590 1150
Strontium (Sr) 548 1060
Barium (Ba) 502 966

P. Predicting electronic structure using successive ionisation energy

Successive ionisation energy is the energy required to remove one mol of electrons
from one mol of positive gaseous ions.
The successive energies are always greater than the first ionisation energy. A positive
ion is smaller than the atom and hence, the force of attraction between nucleus and the
valence electron increases.
Successive ionisation energies are used to predict the number of electrons in each
shell of an atom and the group of an element.
AQA A-Level Chemistry 3.1.1 Atomic structure

Example: Consider the graph that shows the log 10 ionisation energy versus the
number of electrons removed from magnesium,

Figure 13: log10 ionisation energy

i. Why are the first two electrons easier to remove?

ii. Why is it difficult to remove the 3rd electron when compared to the first 2
electrons?
iii. What does this graph tell about the electron configuration of magnesium?
 Solution:
iv. The outermost shell is the s-subshell. The outermost electrons have greatest
shielding from nucleus by the inner electrons. The force of attraction between the
outermost electrons and the nucleus is the least.
v. Once the second electron is removed, the size of the atom is significantly
reduced, which leads to an increase in the force of attraction between outermost
electrons and nucleus. Also, there is less shielding by inner electrons. That is why
it is difficult to remove the third electron.
vi. The outermost shell contains 2 electrons. The next shell contains 8 electrons. The
innermost shell contains 2 electrons.