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Sam Hay, CHEM10111, LM1 workshop 1

• Chemical concepts

• What is maer?
• Anything that occupies space and has mass
• Comprised of atoms and molecules

• 3 kinds of maer:
• Element (1 type of atom, e.g. hydrogen, helium, oxygen)
• Compound (2+ di+erent atoms bonded together, e.g. water, glucose, protein X)
• Mixture (2+ di+erent atoms or molecules not bonded, e.g. air, blood, dirt)

• NB: Molecules are atoms connected by bonds

• Some are compounds (e.g. H2O)
• Others are not compounds (e.g. O2)
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Sam Hay, CHEM10111, LM1 workshop 1

hp://[Link]

hps://[Link]
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Sam Hay, CHEM10111, LM1 workshop 1

• Elements have unique chemical symbols.

• H, hydrogen
• C, carbon
• N, nitrogen
• O, oxygen
• Na, sodium
• Fe, iron

• Compounds have non-unique names.

Numbers give stoichiometries, metals are hps://[Link]
named 6rst
• H 2O
• FeS2
• C2H6O
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Sam Hay, CHEM10111, LM1 workshop 1

• Di+erent elements have di+erent proper9es

• Physical state
• Reac9vity, etc.

• Dalton’s Atomic Theory (largely) explains this:

• Elements are made up of atoms, which are indivisible and can neither be
created nor destroyed.
• The atoms of a given element are iden9cal and have the same mass and
fundamental chemical proper9es.
• Atoms of di+erent elements combine with one another in simple whole
numbers to give molecules.
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Sam Hay, CHEM10111, LM1 workshop 1

• Brief history of Atomic Theory:

• Dalton, Manchester 1803: complete descrip9on of maer in terms of atoms

• Goldstein, Germany 1886: discovers proton
• Tompson, Manchester 1897: discovers the electron
• Chadwick, Cambridge 1932: discovers neutron

• Rutherford, Manchester 1911: 1st model of the atom and (re)discovers the proton
• Bohr, UK and Demark 1913: Adds electrons to Rutherford’s model

• Atom has small posi9vely charged nucleus

• Electrons orbit the nucleus
• Only certain orbitals allowed (they are quan9sed)
• Energy required to move to outer orbitals
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Sam Hay, CHEM10111, LM1 workshop 1

• Atoms are made of:

Protons Neutrons Electrons

Mass 1 1 1/1840

Charge +1 0 -1

Location in Orbitals
Nucleus Nucleus
atom (‘shells’)
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Sam Hay, CHEM10111, LM1 workshop 1

• In an atom:
6

C
12.011

• Number of PROTONS = number of ELECTRONS atomic number (z)

• Charge = 0
• This value is called the Atomic number (z)
• An atom can gain or lose electrons to form an
ION mass number (A)

• Mass = number of PROTONS + NEUTRONS

• This is called the mass number (A)
• Has units of Daltons (Da)

• Can also represent atoms by e.g.:

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Sam Hay, CHEM10111, LM1 workshop 1

• Why is the mass not an integer?

• Isotopes:
• Atoms of the same element with di+erent numbers of neutrons

• e.g. Carbon has 3 natural isotopes:

• 12C 6 PROTONS + 6 NEUTRONS
• 13C 6 PROTONS + 7 NEUTRONS
• 14C 6 PROTONS + 8 NEUTRONS

• Natural abundance:
• 12C 98.9%
• 13C 1.1%
• 14C 1ppt (but radioac9ve so rela9vely easily measured)
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Sam Hay, CHEM10111, LM1 workshop 1

• Ions?

• In a neutral atom (charge = 0) the number of PROTONS = number of ELECTRONS

• It is possible to add or remove electrons so the number of PROTONS ≠ ELECTRONS
• The resul9ng ION will have a resul9ng charge, which balances the number of gained/lost electrons

• A CATION is created when 1 or more electrons is removed:

• e.g. Na → Na+ + e-
• e.g. Mg → Mg2+ + 2e-

• An ANION is created when 1 or more electrons is added:

• e.g. Cl + e- → Cl-
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Sam Hay, CHEM10111, LM1 workshop 2

• Electronic Structure (in a post QM world):

• Atoms have discrete energy levels, n
• Numbered, with 1 closest to nucleus
• Progressively increase in energy from n = 1, 2, 3,…
• Discrete number of electrons found per energy level:
• n = 1, 2 electrons
• n = 2, 8 electrons n=1
• n = 3, 18 electrons
n=2
• Energy levels subdivided into atomic orbitals n=3
• Electrons found in these orbitals
• Orbital have complex shapes describing electron wavefuncon
• (Have to invoke QM wave par9cle duality to describe electrons)
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Sam Hay, CHEM10111, LM1 workshop 2

• Orbital proper9es (shape) depend on n

• n = 1, s orbitals
• n = 2, s + p orbitals
• n = 3, s + p + d orbitals

• s orbitals:
• Spherically symmetrical
• Electrons can get close to the nucleus
• Higher energy level (n), larger the size of the s orbital n=1 n=2

• p orbitals:
• Shape is bi-lobed
• Have zero probability at the centre (i.e. at nucleus); electrons further from
nucleus
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Sam Hay, CHEM10111, LM1 workshop 2

• Orbitals can have more than one orienta9on:

• s orbitals are spherical , so only one in each energy level.
• Each energy level (n ≥ 2) has 3 x p orbitals.
• Each energy level (n ≥ 3) has 5 x d orbitals.

• p orbitals
• Have same shape, but are orthogonal.
• Energy is the same (called degenerate)

• d orbitals
• Have more complex shapes
• Energies not all degenerate
• Outside the scope of CHEM10111
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Sam Hay, CHEM10111, LM1 workshop 2

• Each orbital contains 2 electrons with di+erent spin (spin up and spin down).

Energy Atomic orbitals Total # of # of shell

Level (n) allowed orbitals electrons

1 s 1 2

2 s, p 1+3 8

3 s, p, (d) 1 + 3 (+ 5) 8 (18)

hps://[Link]/
wiki/Electron_con6gura9on
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Sam Hay, CHEM10111, LM1 workshop 2

• Where are the electrons (e-) located?

• n=1 1s orbital 2 e-

• n=2 2s orbital 2 e-
2px orbital (x) 2 e-
2py orbital (y) 2 e- 6 e- in 2p orbitals
2pz orbital (z) 2 e-

• n=3 3s orbital 2 e-
3p orbitals (3) 6 e-
3d orbitals (5) 10 e-
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Sam Hay, CHEM10111, LM1 workshop 2

• To understand atomic electronic structure (and therefore an atom’s proper9es, e.g.

for bonding) we must consider orbital energies.

• For hydrogen (1 e- system) these can be shown as:

Con9nuum

n=4
Energy 3s, 3p (3px 3py 3pz), 3d (3dz2, 3dxz, 3dyz, 3dxy, 3dx2-y2)
n=3
En
n=2 2s, 2p (2px 2py 2pz)

n=1 1s
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Sam Hay, CHEM10111, LM1 workshop 2

• For larger elements with >1 electron, the energy levels are split
• 2s e- are closer to the nucleus than 2p e-
• so 2s e- shield 2p e- from stabilising e+ect of the posi9ve nucleus
• Similar argument for other orbitals, but gets more complicated

3d
3s 3p
n=3
Energy
n=2 2p
En 2s

n=1 1s
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Sam Hay, CHEM10111, LM1 workshop 3

• Determine the electronic con6gura9on and draw orbital energy diagrams using Hund’s rule and the
Pauli exclusion principle

• How do we 6ll this up with electrons?

3d
3s 3p
n=3
Energy
n=2 2p
En 2s

n=1 1s
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Sam Hay, CHEM10111, LM1 workshop 3

• Electrons occupy orbitals

• Orbitals are 6lled according to the AuSau (building-up) principle, which makes use of:
• Hund’s rule
• Pauli exclusion principle

• Hund’s rule
• Orbitals are 6lled in order of energy, with the lowest in energy 6lled 6rst:
• Fill in order of 1s, 2s, 2p, 3s, etc…
• For a set of degenerate orbitals (e.g. px, py, pz):
• Add a single electron to each orbital before pairing
• The single electrons should have parallel spins (denoted by an arrow)

• Pauli exclusion principle

• An orbital can hold up to 2 electrons, but they must have opposite spins (one up, one down)
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Sam Hay, CHEM10111, LM1 workshop 3

• Wri9ng electronic structures:

• This representa9on shows the main energy level (n), the type/ shape of the orbital (s or p) and the
electron occupancy.
No. of e-
Value in orbital
of n 1s1
Type of
Orbital (s, p, d…)
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Sam Hay, CHEM10111, LM1 workshop 3

• Example: Silicon
• Atomic number = 14
• Electronic con6gura9on = 1s2 2s2 2p6 3s2 3p2 = [Ne] 3s2 3p2

n=3
Energy
n=2
En

n=1
• Noble gases (He, Ne, Ar, etc.) have complete electron con"guraon (full shell)
• [He] is shorthand for 1s2
• [Ne] is shorthand for 1s2 2s2 2p6
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Sam Hay, CHEM10111, LM1 workshop 3

• Organisa9on of periodic table corresponds to orbital 6lling

• Atomic electronic con6gura9ons determines trends across periods and down groups

Group
I II III IV V VI VII VIII
P1 H He
(1s1) (1s2)
P 2 Li Be B C N O F Ne
Period

[He]2s1 [He]2s2 [He]2s22p1 [He]2s22p2 [He]2s22p3 [He]2s22p4 [He]2s22p5 [He]2s22p6

P 3 Na Mg Al Si P S Cl Ar
[Ne]3s1 [Ne]3s2 [Ne]3s23p1 [Ne]3s23p2 [Ne]3s23p3 [Ne]3s23p4 [Ne]3s23p5 [Ne]3s23p6

s block hps://[Link]
p block
Transion metals + f block
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Sam Hay, CHEM10111, LM1 workshop 3

• Trends across (the 6rst 3 rows of) the periodic table:

• Valence electrons:
• Members of the same Group (I, II, etc) have same number of outer shell (valence) electrons
• Valence electrons determine bonding and reac9vity, so members of the same group have
similar behaviour

• Electronega9vity:
• Increases from boom leW to top right
• F is the most electronega9ve, Cs and Fr are the least electronega9ve
• Important ones for later: O > N > C

• Van der Waals / atomic radius:

• Increases as you move down each group (more electrons)
• Decreases as you move from leW to right (electron contracon)
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