Chemistry

Contents

Contents ...................................................................................................................... 1
Chapter 1 ..................................................................................................................... 6
Electrons in Atoms ...................................................................................................... 6
1.1. Introduction .................................................................................................. 6
1.2. New Atomic Models ....................................................................................... 9
1.3. Quantum Mechanics ................................................................................... 12
1.4. Multielectron atoms .................................................................................... 17
Chapter 2 ................................................................................................................... 18
The Periodic Table and Atomic Properties ............................................................... 18
2.1. Discovery of the Periodic Table ................................................................... 18
2.2. Periodicity of the oxidation numbers .......................................................... 18
2.3. Sizes of Atoms and Ions .............................................................................. 19
2.4. Slater rules for Zeff ....................................................................................... 19
2.5. Penetration and Screening.......................................................................... 20
2.6. Ionisation energy – Endothermic................................................................ 21
2.7. Electron Affinity – Exothermic ................................................................... 23
2.8. Magnetic Properties .................................................................................... 23
2.9. Terminology................................................................................................. 23
Chapter 8 ................................................................................................................... 24
Thermochemistry ...................................................................................................... 24
8.1. Introduction ................................................................................................. 24
8.2. Heat and Work ............................................................................................ 24
8.3. First Law of Thermodynamics .................................................................... 26
8.4. Enthalpy ...................................................................................................... 26
8.5. State functions ............................................................................................ 28
8.6. Heat of reaction ........................................................................................... 28
8.7. Types of processes ....................................................................................... 28
8.8. Calorimetry ................................................................................................. 29
8.9. Laws of thermochemistry............................................................................ 29
8.10. Types of enthalpy changes....................................................................... 29
8.11. Enthalpy and bond energy ...................................................................... 30

1
Chapter 3 ................................................................................................................... 31
The Ionic Bond........................................................................................................... 31
3.1. Definition of ionic bond ............................................................................... 31
3.2. Properties of ionic compounds .................................................................... 31
3.3. Lattice Energy, U ........................................................................................ 31
3.3.1. Born-Landé Equation – Theoretical determination of U .................... 32
3.3.2. Born-Haber Cycle – Experimental determination of U....................... 34
3.4. Properties of ionic solids ............................................................................. 35
3.4.1. Electrical conductivity ......................................................................... 35
3.4.2. Hardness .............................................................................................. 35
3.4.3. Melting point ........................................................................................ 35
3.4.4. Solubility .............................................................................................. 35
3.5. Ionic liquids ................................................................................................. 36
3.6. Ionic conductors........................................................................................... 37
Chapter 4 ................................................................................................................... 38
Covalent bond ............................................................................................................ 38
4.1. Definition of covalent bond ......................................................................... 38
4.2. Lewis model ................................................................................................. 38
4.2.1. Octet rule .............................................................................................. 38
4.2.2. Lewis structures ................................................................................... 38
4.2.3. Multiple bonds...................................................................................... 39
4.2.4. Hypervalent molecules – Expanded octet............................................ 39
4.2.5. Hypovalent molecules – Incomplete octet ........................................... 39
4.2.6. Formal charges ..................................................................................... 39
4.2.7. Procedure for writing Lewis structures ............................................... 40
4.2.8. Resonance ............................................................................................. 40
4.3. VSPER Model .............................................................................................. 40
4.3.1. Lone pairs ............................................................................................. 41
4.3.2. Electronegativity .................................................................................. 41
4.3.3. Multiple bonds...................................................................................... 41
4.4. Valance bond theory .................................................................................... 42
4.4.1. Hybridisation........................................................................................ 42
4.5. Molecular orbital theory.............................................................................. 42
4.5.1. MO energy level diagrams ................................................................... 44
4.6. Benzene molecule ........................................................................................ 46

2
Chapter 5 ................................................................................................................... 49
Intermolecular forces ................................................................................................ 49
5.1. Bond polarity ............................................................................................... 49
5.1.1. Dipole moment ..................................................................................... 49
5.1.2. Percentage of ionic character ............................................................... 49
5.1.3. Electronegativity scales ....................................................................... 50
5.1.4. Pauling’s equation and Hannay-Smith’s equation .............................. 50
5.2. Covalent solids ............................................................................................ 51
5.3. Van der Waals forces................................................................................... 51
5.3.1. Dipole – dipole interactions ................................................................. 51
5.3.2. Dipole – induced dipole interactions.................................................... 52
5.3.3. Induced dipole – induced dipole interactions ...................................... 52
5.4. Hydrogen bonds ........................................................................................... 52
Chapter 6 ................................................................................................................... 53
Metallic bond ............................................................................................................. 53
6.1. The electron sea model ................................................................................ 53
6.2. Band theory ................................................................................................. 53
6.3. Properties of metals .................................................................................... 55
6.4. Semiconductors ........................................................................................... 55
6.4.1. Extrinsic/compound semiconductors ................................................... 56
6.5. Diodes .......................................................................................................... 57
6.5.1. Forward bias ........................................................................................ 57
6.5.2. Reverse bias.......................................................................................... 57
6.6. Conducting polymers................................................................................... 58
6.7. Superconductivity ....................................................................................... 58
6.7.1. Meissner effect ..................................................................................... 58
Chapter 9 ................................................................................................................... 59
Principles of Chemical Equilibrium .......................................................................... 59
9.1. Equilibria..................................................................................................... 59
9.1.1. Dynamic equilibria ............................................................................... 59
9.1.2. The equilibrium law ............................................................................. 59
9.1.3. Homogeneous equilibria....................................................................... 60
9.1.4. Heterogeneous equilibria ..................................................................... 60
9.2. Calculating Kc ............................................................................................. 60
9.3. Equilibrium constant for gases, Kp ............................................................. 61

3
 9.4. Relationship between Kc and Kp ................................................................. 62
9.5. What does an equilibrium constant tell us? ............................................... 62
9.6. Reaction Quotient ....................................................................................... 63
9.7. Le Chatelier’s Principle............................................................................... 63
9.7.1. Temperature ......................................................................................... 64
9.7.2. Pressure ................................................................................................ 64
9.7.3. Concentration ....................................................................................... 64
9.7.4. Catalysts............................................................................................... 64
9.8. Application of rates and equilibrium .......................................................... 64
Chapter 10 ................................................................................................................. 65
Spontaneous change .................................................................................................. 65
10.1. Meaning of spontaneous change.............................................................. 65
10.2. Entropy .................................................................................................... 65
10.3. Entropy change in a phase transition ..................................................... 66
10.4. Third law of thermodynamics.................................................................. 66
10.5. Second law of thermodynamics ............................................................... 67
10.6. Gibbs free energy ..................................................................................... 67
10.7. Equilibrium .............................................................................................. 68
10.8. Temperature and Gibbs free energy ....................................................... 69
Chapter 11 ................................................................................................................. 70
Acids-Base Equilibria ................................................................................................ 70
11.1. Arrhenius theory...................................................................................... 70
11.2. Brønsted-Lowry theory of acids and bases.............................................. 70
11.3. Self-ionisation of water ............................................................................ 71
11.4. pH Scale ................................................................................................... 71
11.5. Strong and weak acids and bases ............................................................ 72
11.6. Polyprotic acids ........................................................................................ 73
11.7. Measuring pH .......................................................................................... 73
11.7.1. pH meter ........................................................................................... 73
11.7.2. Indicators .......................................................................................... 74
11.8. Buffer solutions........................................................................................ 74
11.8.1. The Henderson-Hasselbach Equation .............................................. 74
11.9. Neutralization reaction and titration curves .......................................... 75

4
Chapter 12 ................................................................................................................. 77
Electrochemistry ....................................................................................................... 77
12.1. Introduction ............................................................................................. 77
12.2. Balancing equations ................................................................................ 78
12.3. Electrochemical cells ............................................................................... 79
12.4. Standard electrode potentials ................................................................. 80
12.5. Work ......................................................................................................... 81
12.6. Nernst Equation ...................................................................................... 82
12.7. Batteries................................................................................................... 82
12.7.1. Alkaline cell ...................................................................................... 83
12.7.2. Leclanché dry cell ............................................................................. 84
12.7.3. Silver-zinc cell ................................................................................... 84
12.7.4. Lead-acid cell .................................................................................... 85
12.7.5. Nickel-cadmium cell ......................................................................... 86
12.7.6. Lithium-ion battery .......................................................................... 87
12.7.7. Fuel cell............................................................................................. 88
12.8. Corrosion .................................................................................................. 88
12.9. Electrolysis............................................................................................... 89

5
Chapter 1

Electrons in Atoms

1.1. Introduction

Law of conservation of mass – Lavoisier (1774)

“The mass of substances in a closed system will remain constant, not matter what
process are acting inside the system.”

This is the first experimental law in chemistry and means the matter can change
form, however, cannot be created or destroyed.

Law of definite proportions – Proust (1799)

“A chemical compound always contains exactly the same proportion of elements as

mass.”

This law is equivalent to the law of constant composition.

Law of multiple proportions – Dalton (1803)

“If two elements form more than a single compound, the masses of one element
combined with the fixed mass of the second are in the ratio of small whole
numbers.”

Atomic number, Z: Number of protons.

Mass number, A: Number of protons + neutrons.

6
Isotopes: Atoms with the same number of protons, but different number of
neutrons.

Atomic mass of the element: The average value of the isotopic mass of the isotopes
of a given element bearing in mind the percentage of the isotope’s natural
abundances.

Mole: The amount of substance that contains the same number of elemental
entities that the number of atoms of carbon-12 that are exactly contained in 12g of
pure carbon-12.

The number of elemental entities contains in one mole is known as the Avogadro
constant:
𝑁𝐴 = 6.022 × 1023

The crisis of the Rutherford’s atomic model

• The model explains the discoveries in relation to the structure of the atom.
• The model is unstable according to some physics principles.
o If the electrons do not move: they should collapse into the nucleus.
o If the electrons are moving: they should emit radiation and get ever
closer to the nucleus.

What is a spectrum?

The decomposition of an electromagnetic radiation into its different wavelengths.

Types of spectra:

• Continuous
• Line → atomic spectra

Balmer’s Formula

In 1885, Johann Balmer derived the equation for hydrogen’s line spectrum,
through trial and error.
1 1
𝜈 = 3.2881 × 1015 ( 2 − 2 )
2 𝑛

7
Rydberg’s Formula

Rydberg’s formula is a generalization of Balmer’s formula.

The visible spectrum of hydrogen is only a part of the hydrogen spectrum:

Far IR: Pfund

IR: Brackett
Close IR: Paschen
Visible: Balmer
UV: Lyman
1 1 1
𝑣̅ = = 𝑅∞ ∙ ( 2 − 2 )
𝜆 𝑛𝑖 𝑛𝑗

Rydberg’s constant in different units:

RH is Rydberg’s constant for hydrogen.

𝑒 4 𝑚𝑒
𝑅∞ =
8𝜀0 ℎ3 𝑐
𝑅∞ = 1.0968 × 107 𝑚−1

𝑅∞ 𝑐 = 3.2898 × 1015 𝑠 −1

𝑅∞ ℎ𝑐 = 2.1799 × 10−18 𝐽

Relation between Balmer’s and Rydberg’s equations

Balmer’s equation with wavenumber, instead of frequency:

𝑐 1 1
𝜈= = 3.2881 × 1015 ( 2 − 2 )
𝜆 2 𝑛
1 3.2881 × 1015 1 1
𝜈̅ = = ( 2 − 2)
𝜆 299 792 458 2 𝑛
1 1 1
𝜈̅ = = 1.0968 × 107 ( 2 − 2 )
𝜆 2 𝑛
1 1 1
𝜈̅ = = 𝑅∞ · ( 2 − 2 )
𝜆 2 𝑛
Balmer’s equation is Rydberg’s equation for the Balmer’s series in hydrogen’s
spectrum.

8
 1.2. New Atomic Models
The Blackbody Radiation

A black body is an ideal physical body that absorbs all incident electromagnetic
radiation, regardless of frequency or angle of incidence.

Rayleigh-Jeans Law

Rayleigh-Jeans law agrees with experimental data for long wavelengths, but it
predicts and energy output that diverges toward infinity at shorter wavelengths.
This is known as the ultraviolet catastrophe.

The energy density, 𝜌:

8𝜋𝑘𝑇
𝜌=
𝜆4
Planck’s Law

The Planck Law gives a distribution that

peaks at a certain wavelength. The peak
shifts to shorter wavelength with higher
temperature and shifts to the longer
wavelength with lower temperatures.
8𝜋 𝜀
𝜌= 4
( 𝜀 )
𝜆 𝑒 ⁄𝑘𝑇 − 1

Photoelectric effect
Heinrich Hertz, 1888: Light striking the surface of certain metals causes ejection of
electrons. If the frequency of the light striking the metal is greater than the
threshold frequency, 𝜈, electrons are ejected.

• The number of ejected electrons depends on the light intensity.

• The kinetic energy of the ejected electrons depends on the frequency of light
emitted.

Einstein’s solution:
𝐸𝛾 = 𝜙 + 𝐸𝑘
1
ℎ𝜈 = ℎ𝜈𝑜 + 𝑚𝑣 2
2
Light is not a wave, but a collection of discrete
wave packets (photons).
𝐸𝑘
𝑉𝑠 = → 𝐸𝑘 = 𝑒𝑉𝑠
𝑒
ℎ𝜈 = ℎ𝜈𝑜 + 𝑒𝑉𝑠
ℎ
Potential needed to stop the electrons emitted: 𝑉𝑠 = 𝑒 (𝑣 − 𝑣𝑜 )
9
Bohr’s Model of the Atom

Niels Bohr attempted to explain the atomic spectra using Planck’s quantum theory.

First Bohr’s Postulate

• The atom has a nucleus that contains the positive charge and the greatest
part of the mass of the system.
• The electron moves in circular orbits about the nucleus with the motion
following classical physics.

In order to equilibrate the system, the electrostatic force (Fe) should be equal to the
centripetal force (Fc):
𝑘 · 𝑍 · 𝑒2 𝑚 · 𝑣2 𝑘 · 𝑍 · 𝑒2 2
𝑘 · 𝑍 · 𝑒2
𝐹𝑒 = 𝐹𝑐 = = → 𝑟 = → 𝑣 =
𝑟2 𝑟 𝑚 · 𝑣2 𝑚·𝑟

Second Bohr’s Postulate

• The electron has only a fixed set of allowed orbits called stationary states.
As long as the electron remains in a given orbit, its energy is constant, and
no energy is emitted.
• The angular momentum of the electron is quantized and can have values
ℎ
equal to: 𝑛 2𝜋.

𝑝=𝑚·𝑣
𝑙 = 𝑟 × 𝑝 = 𝑟 × (𝑚 · 𝑣)
ℎ
𝑚·𝑣·𝑟 =𝑛· =𝑛·ℏ
2𝜋
ℏ2
𝑟= · 𝑛2
𝑘 · 𝑚 · 𝑍 · 𝑒2
ℏ2 4𝜋𝜀0 ℏ2 ℎ2 𝜀0
𝑎0 = = 2 =
𝑘𝑚𝑒 2 𝑒 𝑚 𝜋𝑚𝑒 2
1
𝑟 = 𝑛2 𝑎0 ·
𝑍
Where 𝑎0 is Bohr’s radius

The energy of the electron in each orbit:

1 𝑘 · 𝑍 · 𝑒2
𝐸 = 𝐸𝑐 + 𝐸𝑝 = 𝑚𝑣 2 −
2 𝑟
𝑘 · 𝑍 · 𝑒2 𝑘 2 · 𝑚 · 𝑍2 · 𝑒 4 1
𝐸=− =− · 2
2𝑟 2 · ℏ2 𝑛
𝑅∞ ℎ𝑐 2
𝐸=− ·𝑍
𝑛2

10
Third Bohr’s Postulate
• An electron can pass only from one allowed orbit to another. In such
transitions, fixed discrete quantities of energy (quanta) are involved – either
adsorbed or emitted.
The difference in energy between two orbits is then:
𝑘 2 𝑚𝑍 2 𝑒 4 1 1 1 1
Δ𝐸 = 2
· ( 2 − 2 ) = 𝑅∞ ℎ𝑐 · ( 2 − 2 )
2ℏ 𝑛𝑖 𝑛𝑗 𝑛𝑖 𝑛𝑗

𝐸 = ℎ𝜈

ℎ𝑐 𝑘 2 𝑚𝑍 2 𝑒 4 1 1
ℎ𝜈 = = 2
· ( 2 − 2)
𝜆 2ℏ 𝑛𝑖 𝑛𝑗

1 2𝜋 2 𝑚𝑍 2 𝑒 4 𝑘 2 1 1
𝜈̅ = = · ( − )
𝜆 ℎ3 𝑐 𝑛𝑖2 𝑛𝑗2

The last formula is Rydberg’s formula (where 𝑛𝑖 < 𝑛𝑗 ):

1 1 1
𝑣̅ = = 𝑅∞ ∙ ( 2 − 2 )
𝜆 𝑛𝑖 𝑛𝑗

The Zeeman Effect – NMR Spectroscopy splitting

In 1896, Pieter Zeeman, studying the interactions between magnetism and light,
found that:
• The spectral lines are split in the presence of a magnetic field.
• The split was proportional to the applied magnetic field.

Bohr-Sommerfeld Model
The Zeeman effect was explained by Sommerfeld assuming the electrons where in
elliptic orbits and introducing two new quantum numbers.
• l: angular momentum quantum number
• m: magnetic quantum number

Quantum numbers:
1) Principal quantum number, n = 1, 2, 3, 4, …
2) Angular quantum number, l = 0, 1, 2, 3, …, n-1
o l=0→s
o l=1→p
o l=2→d
o l=3→f
3) Magnetic quantum number, m = -l to +l

Electron spin
A beam of neutral atoms in the presence of a magnetic field splits into two beams.
This shows the presence of a new quantum number: spin.

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Pauli Exclusion Principle
In 1925 Wolfgang Pauli postulated the exclusion principle: “In an atom two
electrons cannot have the same four quantum numbers.”

1.3. Quantum Mechanics

Heisenberg’s Uncertainty Principle: Pairs of physical properties, such as position

(x) and momentum (p), cannot be simultaneously known to arbitrarily high
precision. That is, the more precisely one property is measured, the less precisely
the other can be measured.
ℎ
Δ𝑥Δ𝑝 ≥
4𝜋

Wave-particle duality: Louis De Broglie stated that as light can have particle-like
properties, matter can have wave-like properties.
Erwin Schrödinger showed that the wave functions of a quantum mechanical
system can be obtained solving the equation:

̂ Ψi = 𝐸𝑖 Ψ𝑖
𝐻
𝐻 = 𝐻𝑎𝑚𝑖𝑙𝑡𝑜𝑛𝑖𝑎𝑛 𝑜𝑝𝑒𝑟𝑎𝑡𝑜𝑟 (Operator)
̂
𝐸𝑖 = 𝐸𝑛𝑒𝑟𝑔𝑦 𝑜𝑓 𝑡ℎ𝑒 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛 (Observable)
Ψ𝑖 = 𝑊𝑎𝑣𝑒𝑓𝑢𝑛𝑐𝑡𝑖𝑜𝑛

Principles:
• The information about a quantum system can be obtained from function Ψ
that is called the wavefunction. The state of a system is associated to that
function.
• Each observable is related with an operator. If the system is in a certain
state defined by Ψ, the value of the observable 𝑎𝑖 can be determined by
using the operator A on the function Ψ.
• The function Ψ has no physical meaning but its square modulus |Ψ|2 is a
probability distribution function. For a differential volume Ψ 2 𝑑𝑥 is related
with the probability of finding the system (for instance one particle) in this
volume. From this postulate it can be found that (normalization condition):

+∞
∫ |Ψ|2 𝑑𝑥 = 1
−∞

12
Particle in a Box
The particle in a box model helps us see the origin of the quantization of energy.

̂ Ψ = 𝐸Ψ
𝐻

ℏ2 2
̂=−
𝐻 ∇ +𝑉
2𝑚

𝜕2 𝜕2 𝜕2
∇2 = + +
𝜕𝑥 2 𝜕𝑦 2 𝜕𝑧 2

As we are in 1D:
2
𝜕2
∇ = 2
𝜕𝑥

ℏ2 𝜕 2
(− · + 𝑉) Ψ = 𝐸Ψ
2𝑚 𝜕𝑥 2

ℏ2 𝜕 2
𝐸Ψ + · Ψ − 𝑉Ψ = 0
2𝑚 𝜕𝑥 2

ℏ2 𝜕 2
· Ψ + (E − V)Ψ = 0
2𝑚 𝜕𝑥 2

Outside the box: 𝑉 = ∞

(𝐸 − 𝑉)Ψ = (𝐸 − ∞)Ψ = −∞Ψ

ℏ2 𝜕 2
· Ψ = ∞Ψ
2𝑚 𝜕𝑥 2

𝜕2
Ψ = ∞Ψ
𝜕𝑥 2

Ψ=0

13
Inside the box: 𝑉 = 0
(𝐸 − 𝑉)Ψ = (𝐸 − 0)Ψ = 𝐸Ψ

ℏ2 𝜕 2
· Ψ + EΨ = 0
2𝑚 𝜕𝑥 2

𝜕2 2m
2
Ψ = −E 2 Ψ
𝜕𝑥 ℏ

Finally:
2 𝑛𝜋
Ψ = √ sin 𝑥
𝐿 𝐿

𝑛 2 ℎ2
𝐸=
8𝑚𝐿2

Example:
What is the energy difference between the ground state and the first excited state
of an electron contained in a one-dimensional box 1.00 × 102 pm long? Calculate the
wavelength of the photon that could excite the electron from the ground state to the
first excited state.
ℎ2
𝐸1 = (12 )
8𝑚𝐿2

ℎ2
𝐸2 = (22 )
8𝑚𝐿2
3ℎ2
Δ𝐸 = 𝐸2 − 𝐸1 =
8𝑚𝐿2
−34 )2
3(6.626 × 10
Δ𝐸 = = 1.81 × 10−17 𝐽
8(9.109 × 10−31 )(1.00 × 10−10 )2

ℎ𝑐
𝐸 = ℎ𝜈 =
𝜆

Schrödinger Equation

The Schrödinger equation in spherical polar coordinates:

1 𝜕 2 𝜕Ψ 1 𝜕2Ψ 1 𝜕 𝜕Ψ 2𝜇
2
· (𝑟 · ) + 2 2
· 2
+ 2 2
· (sin 𝜃 · ) + 2 (𝐸 − 𝑉) · Ψ = 0
𝑟 𝜕𝑟 𝜕𝑟 𝑟 · sin 𝜃 𝜕𝜙 𝑟 · sin 𝜃 𝜕𝜃 𝜕𝜃 ℏ

The solutions to the equation are in the general form:

Ψ(𝑟, 𝜙, 𝜃) = 𝑅(𝑟) · 𝑌(𝜙, 𝜃)

R(r) is the radial wavefunction.

Y(φ, θ) is the angular wavefunction.

14
Plotting Orbital Angular Wave Functions
An angular wave function can be described as 𝑌(𝜃, 𝜑).
Example:
1
3 2
𝑌(𝑝𝑥 ) = ( ) sin 𝜃 cos 𝜑
4𝜋

‘xy’ plane:
1
3 2
𝜃 = 90° → sin 90 = 1 → 𝑌(𝑝𝑥 ) = ( ) cos 𝜑
4𝜋
‘xz’ plane:
1
3 2
𝜑 = 0° → cos 0 = 1 → 𝑌(𝑝𝑥 ) = ( ) sin 𝜃
4𝜋
‘zy’ plane (Nodal plane):
𝜑 = 90° → cos 90 = 0 → 𝑌(𝑝𝑥 ) = 0

1
3 2
𝑌(𝑝𝑦 ) = ( ) sin 𝜃 sin 𝜑
4𝜋

‘xy’ plane:
1
3 2
𝜃 = 90° → sin 90 = 1 → 𝑌(𝑝𝑦 ) = ( ) sin 𝜑
4𝜋
‘xz’ plane (Nodal plane):
𝜑 = 0° → sin 0 = 0 → 𝑌(𝑝𝑦 ) = 0
‘zy’ plane:
1
3 2
𝜑 = 90° → sin 90 = 1 → 𝑌(𝑝𝑦 ) = ( ) sin 𝜃
4𝜋

1
3 2
𝑌(𝑝𝑧 ) = ( ) cos 𝜃
4𝜋

‘xy’ plane (Nodal plane):

𝜃 = 90° → cos 90 = 0 → 𝑌(𝑝𝑧 ) = 0
‘xz’ plane:
1
3 2
𝜑 = 0° → 𝑌(𝑝𝑧 ) = ( ) cos 𝜃
4𝜋
‘zy’ plane:
1
3 2
𝜑 = 90° → 𝑌(𝑝𝑧 ) = ( ) cos 𝜃
4𝜋
Start to measure 𝜑 from x.
Start to measure 𝜃 from z.

15
Orbitals

Orbitals can be defined in two ways, depending on whether the electron is treated
as a wave or as a particle.
• Electron as a particle:
Mathematical description of the probability of finding the electron in the space.
• Electron as a wave:
Mathematical description of the region of space with a high electronic charge
density.

Solution to Schrödinger Equation

The different solutions to the Schrödinger equation determine the different shapes
of the orbitals. For example, the angular part of the s does not depend on θ or φ
therefore the s orbital is a sphere.

Radial Distribution Function, P(r)

The radial distribution function provides the probability of finding an electron at a

given distance from the nucleus.

𝑃(𝑟) = 𝑟 2 𝑅2 (𝑟)

Where R(r) is the radial component of the wave function.

Conclusions:

• The probability of finding the electron very close to the nucleus is very
small, because in this region r2 is very small.
• The maximum of the radial distribution curve corresponds to the distanc to
the nucleus where it is more likely to find the electron.
• The distance of the electron to the nucleus in the maximum of the radial
distribution curves in those that only have one maximum (1s, 2p, 3d…) is
exactly equal to the radius of the corresponding orbit calculated by the Bohr
𝑛 2 𝑎𝑜
theory ( 𝑍
).
• On average, the 2s electron is located further from the nucleus than the 1s,
hence 2s will have a greater energy.
• The total probability of finding the electron near the nucleus, for the same
“n” value, decreases with increasing “l”. (Penetration ability).

16
 1.4. Multielectron atoms

Effective nuclear charge: The net positive nuclear charge felt by the electrons due
to shielding effects.
𝑍𝑒𝑓𝑓 = 𝑍 − 𝜎
𝑍𝑒𝑓𝑓 → Effective nuclear charge
𝑍 → Atomic number
𝜎 → shielding constant

Minimum Energy Principle – Aufbau Principle

Electrons occupy orbitals in a way that minimizes the energy of the atom.

Hund’s Rule of Maximum Multiplicity

When orbitals of identical energy are available (degenerated orbitals) electrons
initially occupy these orbitals singly.

Degenerated orbitals: Orbitals with the same energy.

17
Chapter 2

The Periodic Table and Atomic Properties

2.1. Discovery of the Periodic Table

In 1869, Dimitri Mendeleev and Lothar Meyer proposed the periodic law:
“When elements are arranged in order of increasing atomic mass, certain sets of
properties recur periodically.”

Mendeleev placed certain elements out of the order of increasing atomic mass to
get them into the proper group of his Periodic Table. He assumed this was because
of errors in atomic masses.

Henry G.J. Moseley used a mathematical relation to predict the existence of new
elements. Moseley’s law states that “The square root of the frequency of the
emitted x-rays is proportional to the atomic number.”:

√𝜈 ∝ 𝑍
Moseley’s law:
𝜈 = 𝐴(𝑍 − 𝑏)2

𝜈 → emission frequency

𝐴, 𝑏 → constants

𝑍 → atomic number

2.2. Periodicity of the oxidation numbers

18
2.3. Sizes of Atoms and Ions
Atomic radius is hard to define, as the electron charge density is extended to
infinity. Therefore, the effective atomic radius ( 95% of the electron density) is
used.

Types of atomic radius:

• Covalent radius
• Metallic radius
• Ionic radius

Atomic radius depends on the position of an element in the periodic table, as it

depends on the value of n and the effective nuclear charge.

Ionic radius

The radius of cations (+) is less than the radius of neutral atoms because they have
the same atomic number, but less electrons therefore there is less electrostatic
repulsion and the outer electron is attracted with a greater force to the nucleus.

The radius of anions (-) is greater than the radius of neutral atoms because they
have the same atomic number, but more electrons therefore there is more
electrostatic repulsion and the outer electron is less attracted to the nucleus.

2.4. Slater rules for Zeff

𝑍𝑒𝑓𝑓 = 𝑍 − 𝜎

𝑍𝑒𝑓𝑓 → Effective nuclear charge

𝑍 → Atomic number
𝜎 → shielding constant

Slater rules:

The amount of nuclear charge felt by an e- depends on the orbital it is located and
on the number of electrons located in between that electron and the nucleus:

• If the considered e- is in an “ns” or “np” orbital:

o All the electrons in “ns” and “np” orbitals with the same value of “n”
contribute with s = 0.35 (for n = 1, s = 0.30)
o All the electrons in orbitals with (n – 1) contribute with s = 0.85
o All the electrons in orbitals with a principal quantum number  n – 2
contribute with s = 1
• If the considered e- is in an “nd” or “nf” orbital.
o All the electrons in the same “nd” or “nf” orbitals contribute with s =
0.35
o All the rest of electrons contribute with s = 1
19
Ni (Z = 28)

1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 3𝑑8 4𝑠 2

𝜎 = (1 · 0.35) + (16 · 0.85) + (10 · 1) = 23.95

𝑍𝑒𝑓𝑓 = 28 − 23.95 = 4.05

Ni2+ (Z = 28)

1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 3𝑑8

𝜎 = (0.35 · 7) + (18 · 1) = 20.45
𝑍𝑒𝑓𝑓 = 28 − 20.45 = 7.55

2.5. Penetration and Screening

Penetration: Estimation of how close an electron gets to the nucleus.

Penetration describes the proximity to which an electron can approach to the

nucleus. In a multi-electron system, electron penetration is defined by an electron's
relative electron density (probability density) near the nucleus of an atom.
Penetration depends on the shell (n) and subshell (l). For example, we see that
since a 2s electron has more electron density near the nucleus than a 2p electron, it
is penetrating the nucleus of the atom more than the 2p electron.

Electrons which experience greater penetration experience stronger attraction to

the nucleus, less shielding, and therefore experience a larger effective nuclear
charge, but shield other electrons more effectively.
The effective nuclear charge increases from left to right and increases from top to
bottom on the periodic table.

Within the same shell value (n), the penetrating power of an electron follows this
trend in subshells (l):

s>p>d>f

Screening/Shielding: Reflects how an outer electron is blocked from the nuclear

charge by inner electrons.

Atomic radius increases down a group

The atomic radius increases down a group because the value of the principal
quantum number (n) increases. Therefore, the outer electron is further away from
the nucleus.

20
Atomic radius decreases along the period
The size of the atoms decreases along the period because the atomic number
increases, and the shielding remains almost constant. As the value of Z increases
by 1 the value of the shielding constant increases by 0.35. Therefore, the overall
increase in 𝑍𝑒𝑓𝑓 is 0.65 and consequently the electrons are attracted with a greater
force to the nucleus. This means the atomic radius decreases.

Atomic radius remains almost constant in the transition metals

The effective nuclear charge remains almost constant (increases by 0.15) in the
transition metals, therefore the attraction of the outer electron to the nucleus is
also almost constant. As a consequence, the atomic radius of transition metals
remains nearly constant.

Sc (Z = 21)

1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 4𝑠 2 3𝑑1

𝜎 = (1 · 0.35) + (9 · 0.85) + (10 · 1) = 18
𝑍𝑒𝑓𝑓 = 21 − 18 = 3

Ti (Z = 22)

1𝑠 2 2𝑠 2 2𝑝6 3𝑠 2 3𝑝6 4𝑠 2 3𝑑2

𝜎 = (1 · 0.35) + (10 · 0.85) + (10 · 1) = 18.85
𝑍𝑒𝑓𝑓 = 22 − 18.85 = 3.15

V (Z = 23)

1𝑠 2 2𝑠 2 2𝑝6 3𝑠 3 3𝑝6 4𝑠 2 3𝑑3

𝜎 = (1 · 0.35) + (11 · 0.85) + (10 · 1) = 19.7
𝑍𝑒𝑓𝑓 = 23 − 19.7 = 3.3

2.6. Ionisation energy – Endothermic

The energy needed to remove one electron from a gaseous atom.

𝐴(𝑔) → 𝐴+ (𝑔) + 𝑒 − 𝐸𝑖 = +100 𝑘𝐽 𝑚𝑜𝑙 −1

A lower ionisation energy means it is easier to remove an electron, therefore the

atom has a greater metallic character. Whereas, a higher ionisation energy means
it is harder to remove an electron therefore the atom has less metallic character.

Ionisation energy increases across the period and up the group.

21
The nth ionization energy refers to the amount of energy required to remove an
electron from the species with a charge of (n – 1). For example, the first three
ionization energies are defined as follows:

• 1st ionization energy

𝐴(𝑔) → 𝐴+ (𝑔) + 𝑒 −

• 2nd ionization energy

𝐴+ (𝑔) → 𝐴2+ (𝑔) + 𝑒 −

• 3rd ionization energy

𝐴2+ (𝑔) → 𝐴3+ (𝑔) + 𝑒 −

When electrons are removed from a lower shell, the value of the ionisation energy
increases drastically. This is because an electron is removed from a stable full
shell, making it less stable.

22
2.7. Electron Affinity – Exothermic
The energy released when an electron is absorbed by a gaseous.

𝐴(𝑔) + 𝑒 − → 𝐴− (𝑔) 𝐸𝑎 = −100 𝑘𝐽 𝑚𝑜𝑙 −1

The electron affinity increases across the period and up the group, which means it
becomes more negative. However, electron affinity presents a large number of
anomalies such as B, N, O and F.

A lower electron affinity (absolute value) means less energy is released when the
atom absorbs an electron, therefore there is a greater metallic character.

2.8. Magnetic Properties

Electrons have a charge and a property called spin, therefore as they are
essentially spinning charges, they induce a magnetic field. As a consequence, they
are affected in the presence of an external magnetic field.
In a diamagnetic atom or ion all electrons are paired, and the individual magnetic
effects cancel out.

A paramagnetic atom or ion has unpaired electrons, and the individual magnetic
effects do not cancel out. The unpaired electrons possess a magnetic moment that
causes the atom or ion to be attracted to an external magnetic field. The more the
unpaired electrons are present, the stronger is this attraction.

2.9. Terminology
Monovalent ion: 1+/- ion.
Divalent ion: 2 +/- ion.
Trivalent ion: 3 +/- ion

23
Chapter 8

Thermochemistry

8.1. Introduction
System: The part of the universe chosen to study.

Surroundings: The part of the universe outside the system.

Types of system:

• Open: Exchange of matter and energy between the system and the
surroundings.
• Closed: Exchange of energy only between the system and the surroundings.
• Isolated: No exchange between system and surroundings.

8.2. Heat and Work

Heat

Heat: The energy transferred between a system and the surroundings as a result of
temperature difference.

The quantity of heat required to change the temperature of a substance depends

on:

• Temperature change
• Quantity of substance
• Nature of the substance

Calorie (cal): The quantity of heat required to change the temperature of one gram
of water by one degree Celsius. The SI unit for heat is simply the basic SI energy
unit, the joule (J).

1 cal = 4.184 J

Heat capacity (C): The quantity of heat required to change the temperature of a
system by one degree.

Specific heat (c): the quantity of heat required to change the temperature of one
gram of the substance by one degree Celsius.

Molar heat capacity: The quantity of heat required to change the temperature of
one mole of the substance by one degree Celsius.

24
Specific heat of water between 0 and 100 ºC is approximately:

1.00 𝑐𝑎𝑙 𝑔−1 °𝐶 −1 = 4.184 𝐽 𝑔−1 ℃−1

𝑄 = 𝑚𝑐Δ𝑇 = 𝐶Δ𝑇

Where Δ𝑇 = 𝑇𝑓 − 𝑇𝑖

• When there is a decrease in temperature, Q is positive. Therefore, the

system absorbs heat. Endothermic.
• When there is an increase in temperature, Q is negative. Therefore, the
system releases heat. Exothermic.

𝑄𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 + 𝑄𝑟𝑒𝑙𝑒𝑎𝑠𝑒𝑑 = 0

𝑄𝑎𝑏𝑠𝑜𝑟𝑏𝑒𝑑 = −𝑄𝑟𝑒𝑙𝑒𝑎𝑠𝑒𝑑

Work

Work can be exchanged between the system and the surroundings in several ways:

• Mechanical processes:
o Change of position in a gravitational field.
o Changes in velocity.
o Change of the volume.
• Electrical work

In chemistry: Work involving expansion or compression → Pressure – Volume

work.

Definition of work:
𝑉2
𝑑𝑊 = − 𝑝 𝑑𝑉 → 𝑊 = − ∫ 𝑝 𝑑𝑉
𝑉1

For a discrete pressure increase (minimum work):

𝑉2
𝑊 = − ∫ 𝑝 𝑑𝑉 = −𝑝𝑒𝑥𝑡𝑒𝑟𝑛𝑎𝑙 · Δ𝑉
𝑉1

𝑝𝑒𝑥𝑡𝑒𝑟𝑛𝑎𝑙 = 𝑝𝑓

For a continuous pressure increase (maximum work):

𝑉2 𝑉2
𝑛𝑅𝑇 𝑉2
𝑊 = − ∫ 𝑝 · 𝑑𝑉 = − ∫ 𝑑𝑉 = −𝑛𝑅𝑇 · ln
𝑉1 𝑉1 𝑉 𝑉1

• When a gas expands, Δ𝑉 is positive and the work is negative. Work done by
the system.
• When a gas contracts, Δ𝑉 is negative and the work is positive. Work done on
the system.

25
 8.3. First Law of Thermodynamics
Internal energy: The total energy contained in a system.

It includes:

• Translational kinetic energy

• Energy of molecular rotations and vibrations
• Potential energy in chemical bonds
• Energy of electrons in atoms
𝑛

𝐸 = ∑ 𝐸𝑖
𝑖=1

First law of thermodynamics (principle of conservation of energy):

Δ𝑈 = 𝑄 + 𝑊; 𝑑𝑈 = 𝛿𝑄 + 𝛿𝑊

For isolated systems: Δ𝑈 = 0 therefore 𝑄 + 𝑊 = 0.

At a constant volume (isochoric process):

𝛥𝑈 = 𝑄 + 𝑊

Δ𝑈 = 𝑄 − 𝑃 𝑑𝑉

As volume is constant 𝑑𝑉 = 0:

Δ𝑈 = 𝑄𝑉

𝑄𝑉 is heat at a constant volume.

𝑄 = 𝐶𝑉 Δ𝑇

Therefore, the heat capacity at a constant volume is:

𝑄
( ) = 𝐶𝑉
𝛥𝑇 𝑉

The specific heat capacity at a constant volume is therefore:

𝐶𝑉
𝑐𝑉 =
𝑚
𝑄 = 𝑚𝑐Δ𝑇 = 𝑚𝑐𝑉 Δ𝑇 = 𝑄𝑉

8.4. Enthalpy
The enthalpy is the heat at a constant pressure (isobaric process).

Δ𝑈 = 𝑄 + 𝑊 = 𝑄𝑃 − 𝑝Δ𝑉

𝑄𝑃 = Δ𝑈 + 𝑝Δ𝑉 → 𝑄𝑃 = Δ𝐻

𝐻 = 𝑈 + 𝑝𝑉
26
Change in enthalpy:

𝛥𝐻 = 𝐻𝑓 − 𝐻𝑖 = (𝑈𝑓 + 𝑃𝑓 𝑉𝑓 ) − (𝑈𝑖 + 𝑃𝑖 𝑉𝑖 )

𝛥𝐻 = (𝑈𝑓 − 𝑈𝑖 ) + (𝑃𝑓 𝑉𝑓 − 𝑃𝑖 𝑉𝑖 )

𝛥𝐻 = 𝛥𝑈 + 𝛥(𝑃𝑉)

As the process takes places at constant pressure:

𝑃𝑓 = 𝑃𝑖 = 𝑃 → 𝛥𝐻 = 𝛥𝑈 + 𝑃𝛥𝑉

The heat capacity at a constant pressure is:

𝐻
( ) = 𝐶𝑃
Δ𝑇 𝑃

Therefore, the specific heat capacity at constant pressure is:

𝐶𝑃
𝑐𝑃 =
𝑚
𝑄 = 𝑚𝑐Δ𝑇 = 𝑚𝑐𝑃 Δ𝑇 = 𝑄𝑃

Relation of 𝑄𝑉 and 𝑄𝑃 (gases)

Δ𝐻 = Δ𝑈 + 𝑃Δ𝑉

𝑃𝑉 = 𝑛𝑅𝑇

For constant temperature and pressure (isobaric and isothermal process):

𝑃Δ𝑉 = Δ𝑛𝑅𝑇

Δ𝐻 = Δ𝑈 + Δ𝑛𝑅𝑇

Relation of 𝑄𝑉 and 𝑄𝑃 (solids and liquids)

If the pressure is constant, the change in volume in solids and liquids is very small,
therefore:

𝑄𝑉 ≅ 𝑄𝑃

Δ𝑈 ≅ Δ𝐻

Characteristics of Δ𝐻

• Δ𝐻 is an extensive property. This means that if the system is divided into

subsystems, the sum of the induvial enthalpies will be equal to the enthalpy
of the original system.
• Δ𝐻 changes sign when the process is reversed.

27
 8.5. State functions
The property of a system that depends only on the current state of the system, not
on the way in which the system acquired that state (independent of path). State
functions are also called point functions. The opposite to point functions are path
functions or process functions. Process functions depend on the path.
State functions:

• Internal energy, U
• Pressure, P
• Volume, V

Not state functions:

• Work, W
• Heat, Q

8.6. Heat of reaction

In a chemical reaction there is a change in the chemical energy of the system. The
system gains or losses heat.

Heat of reaction, Q: Quantity of heat exchanged between a system and its

surroundings when a chemical reaction occurs within the system at constant
temperature.

Exothermic reaction: The chemical energy is converted into thermal energy.

• In an isolated system: Produces a temperature increase.

• In a non-isolated system: Gives off heat to the surroundings.

Endothermic reaction: The thermal energy is converted into chemical energy.

• In an isolated system: Produces a temperature decrease.

• In a non-isolated system: Gives a gain of heat from the surroundings.

8.7. Types of processes

Isothermal process:

An isothermal process occurs with no temperature change. In this type of process

Δ𝑈 = 0 and Δ𝑇 = 0 but 𝑄 ≠ 0.

Adiabatic process:

An adiabatic process occurs when there is no exchange of heat with the

surroundings.

28
 8.8. Calorimetry
A calorimeter is a device used to measure heat changes. A type of calorimeter is the
calorimeter bomb, which is treated as an isolated system. Therefore:

Δ𝑈 = 𝑄 + 𝑊 = 0

W = 0 as Δ𝑉 = 0

Δ𝑈 = 𝑄

𝑄𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 + 𝑄𝑐𝑎𝑙𝑜𝑟𝑖𝑚𝑒𝑡𝑒𝑟 = 0

Where 𝑄𝑐𝑎𝑙𝑜𝑟𝑖𝑚𝑒𝑡𝑒𝑟 = 𝑄𝑟𝑒𝑐𝑖𝑝𝑖𝑒𝑛𝑡 + 𝑄𝑤𝑎𝑡𝑒𝑟 + ⋯

𝑄𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 + 𝑄𝑤𝑎𝑡𝑒𝑟 + 𝑄𝑟𝑒𝑐𝑖𝑝𝑖𝑒𝑛𝑡 = 0

𝑄𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 + 𝑚𝑤𝑎𝑡𝑒𝑟 · 𝑐𝑤𝑎𝑡𝑒𝑟 · Δ𝑇 + 𝐾 · Δ𝑇 = 0

Where K is the constant of the calorimeter

8.9. Laws of thermochemistry

Lavoisier and Laplace’s law: ”The energy change accompanying any transformation
is equal and opposite to energy change accompanying the reverse process.”

Hess’ law: ”The energy change accompanying any transformation is the same
whether the process occurs in one step or many steps.”

8.10. Types of enthalpy changes

Standard state: The pure element or compound at a pressure of 1 bar (100 kPa)
and at the temperature of interest (298 K).

Standard enthalpy of reaction: The enthalpy change of a reaction in which all

reactants and products are in their standard states.

Standard enthalpy of formation: The enthalpy change that occurs in the formation
of one mole of a substance in the standard state from the reference forms of the
elements in their standard states.

The standard enthalpy of formation of a pure element in its standard state is 0.

Δ𝐻𝑟𝑜 = ∑ vP Δ𝐻𝑓𝑜 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑜𝑠) − ∑ vr Δ𝐻𝑓𝑜 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

Where 𝑣𝑝 and 𝑣𝑟 are the stoichiometric coefficients.

29
 8.11. Enthalpy and bond energy
Bond energy: Energy necessary to break a certain chemical bond. It is usually
referred to one mole of bonds.

Δ𝐻𝑟𝑜 = ∑ 𝐻 (𝑏𝑜𝑛𝑑𝑠 𝑏𝑟𝑜𝑘𝑒𝑛) − ∑ 𝐻 (𝑏𝑜𝑛𝑑𝑠 𝑓𝑜𝑟𝑚𝑒𝑑)

30
Chapter 3

The Ionic Bond

3.1. Definition of ionic bond

A type of chemical bond that involves a metal and a non-metal (or polyatomic ions)
through electrostatic attraction.

A large number of atoms for an ionic solid and not pairs of anion and cation. Each
anion is surrounded by as many cations as possible and viceversa.

Characteristics of an ionic bond:

• The electrons are completely localized in the ions (anions and cations).
• The bond does not have directional preference.

3.2. Properties of ionic compounds

• Ionic compounds have strong electrostatic bonds between particles. As a
result, they generally have very high melting and boiling points.
• Solid ionic compounds cannot conduct electricity because there are no
mobile ions or electrons present in the lattice. When the ionic compounds
are dissolved in a liquid or molten, they can conduct electricity with the
mobile ions.
• They are usually appreciably soluble in other polar solvents such as
alcohols, acetone and dimethyl sulfoxide as well. Ionic compounds do not
tend to dissolve in non-polar solvents such as diethyl ether or hexane.

3.3. Lattice Energy, U

The lattice energy of an ionic solid is a measure of the strength of bonds in that
ionic compound. It is usually defined as the enthalpy of formation of the ionic
compound from gaseous ions and as such is invariably exothermic.

𝑀+ (𝑔) + 𝑋 − (𝑔) → 𝑀𝑋(𝑠)

31
 3.3.1. Born-Landé Equation – Theoretical determination of U
The main interaction between ions is the electrostatic attraction force. However,
there are other interactions such as the repulsive force between electrons and the
repulsive force between nuclei.

Energy of one interaction (electrostatic potential energy):

𝑍+ 𝑍− 𝑒 2
𝐸=𝑘
𝑑
1
Where 𝑘 =
4𝜋𝜀0

If the ions have the same charge, the energy is positive and if they have different
charge, the energy is negative.

When the crystal is formed the total energy of the interaction is:

|𝑍+ ||𝑍− |𝑒 2 2 |𝑍+ ||𝑍− |𝑒 2 2 |𝑍+ ||𝑍− |𝑒 2 2 |𝑍+ ||𝑍− |𝑒 2 2

𝐸𝑎 = − + − + +⋯
4𝜋𝜀0 𝑑 4𝜋𝜀0 2𝑑 4𝜋𝜀0 3𝑑 4𝜋𝜀0 4𝑑

|𝑍+ ||𝑍− |𝑒 2 1 1 1 |𝑍+ ||𝑍− |𝑒 2

𝐸𝑎 = − [1 − + − + ⋯ ] = − · 2 ln 2
4𝜋𝜀0 𝑑 2 3 4 4𝜋𝜀0 𝑑

For one mole of solid:

|𝑍+ ||𝑍− |𝑒 2
𝐸𝑎 = −𝑁𝐴 · 2 ln 2
4𝜋𝜀0 𝑑

Where 2 ln 2 is the Madelung constant.

32
The Madelung constant depends on the structure of the solid and the relative
position of the ions in the solid.

For a three-dimensional crystal:

|𝑍+ ||𝑍− |𝑒 2
𝐸𝑎 = −𝑁𝐴 𝐴
4𝜋𝜀0 𝑑

The value of d is calculated by adding the radius of the anion and the radius of the
cation.

Additionally to the electrostatic attraction between the ions, there is repulsion

between electrons. The repulsion increases quickly as the distance decreases. The
energy (Er) is a destabilization energy.

The equilibrium between the two contributions stabilizes the finals structure:

𝑈 = 𝐸𝑎 + 𝐸𝑟

|𝑍+ ||𝑍− |𝑒 2 𝐵
𝑈 = −𝑁𝐴 𝐴+ 𝑛
4𝜋𝜀0 𝑑 𝑑

Minimizing the energy with respect to the distance:

𝛿𝑈 |𝑍+ ||𝑍− |𝑒 2 𝑛𝐵
= 𝑁𝐴 2
𝐴 − 𝑛+1 = 0
𝛿𝑑 4𝜋𝜀0 𝑑 𝑑

𝐴𝑁𝐴 |𝑍+ ||𝑍− |𝑒 2 𝑑𝑛−1

𝐵=
4𝜋𝜀0 𝑛

Final Born-Landé equation:

𝐴𝑁𝐴 |𝑍+ ||𝑍− |𝑒 2 1

𝑈=− (1 − )
4𝜋𝜀0 𝑑 𝑛

Where:

𝐴 = 𝑀𝑎𝑑𝑒𝑙𝑢𝑛𝑔 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

𝑛 = 𝐵𝑜𝑟𝑛 𝑒𝑥𝑝𝑜𝑛𝑒𝑛𝑡, A number between 5 and 12, dependent upon the electronic
configuration of the closed shell ions.

𝑑 = 𝑟+ + 𝑟−

33
 3.3.2. Born-Haber Cycle – Experimental determination of U
The value for the lattice enthalpy cannot be calculated directly in the laboratory,
therefore Hess’ law is used to find its value experimentally.

The Born-Haber cycle is based on the processes that can be done on the lab:

1. Standard enthalpy of formation: The enthalpy change when one mole of a

compound is formed from its elements in standard states under standard
conditions.
2. Standard enthalpy of sublimation: The enthalpy change that accompanies
the sublimation of one mole of solid. This can also be considered as the
enthalpy change of atomisation.
3. Standard enthalpy of dissociation: The enthalpy change that accompanies
the dissociation of one mole of molecules. This can also be considered as the
enthalpy of atomisation.
4. Ionization energy: The enthalpy change when one mole of gaseous 1+ ions is
formed from one mole of gaseous atoms.
5. Electron affinity: The enthalpy change when one mole of gaseous 1- ions is
formed from one mole of gaseous atoms.

34
 3.4. Properties of ionic solids
3.4.1. Electrical conductivity
In solid state are usually insulators

• Valence electrons on the ions (no mobile electrons)

• Ions in fixed positions in the solid (no mobile ions)

When the ionic compounds are molten, they can conduct electricity as the ions are
mobile.

When the ionic compounds are dissolved in polar solvents, they can conduct
electricity as the ions are mobile.

Conductivity is the inverse of resistivity:

1
𝜎=
𝜌

The units of conductivity are siemens per metre (S/m).

3.4.2. Hardness
Hardness is related with the attractive cohesion force in the ionic structure.

Mohs Scale

The Mohs scale of mineral hardness is based on the ability of one natural sample of
matter to scratch another. This value is related with the absolute value of the
lattice energy. Th Mohs scale ranges from 1 to 10, with diamond being the hardest
with a value of 10 and talc being the softest with a value of 1.

3.4.3. Melting point

The melting point of a substance is the temperature at which it changes state from
solid to liquid at atmospheric pressure. At the melting point the solid and liquid
phase exist in equilibrium.

The melting point can also be considered as the temperature at which the ions
leave the fixed positions they occupy in the crystal and adopt the mobility
characteristic of a liquid.

The melting point increases as the absolute value of the lattice energy increases

3.4.4. Solubility
Standard enthalpy change of solution (∆𝐻𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝜃
): The enthalpy change when one
mole of an ionic substance dissolves in water to give a solution of infinite dilution
under standard conditions.

35
Standard enthalpy change of hydration (Δ𝐻ℎ𝑦𝑑𝑟𝑎𝑡𝑖𝑜𝑛
𝜃
): The enthalpy change when
one mole of gaseous ions dissolve in sufficient water to give an infinitely dilute
solution under standard conditions.

Standard enthalpy change of solvation (𝛥𝐻𝑠𝑜𝑙𝑣𝑎𝑡𝑖𝑜𝑛

𝜃
): The enthalpy change when one
mole of gaseous ions dissolve in a solvent (other than water) to give a solution of
infinite dilution.

For a solvent other than water:

Δ𝐻𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = −𝑈 + Δ𝐻𝑠𝑜𝑙𝑣𝑎𝑡𝑖𝑜𝑛

For water only:

𝛥𝐻𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = −𝑈 + 𝛥𝐻ℎ𝑦𝑑𝑟𝑎𝑡𝑖𝑜𝑛

Hess’ cycle:
Δ𝐻𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝑀𝑋(𝑠) → 𝑀 + (𝑎𝑞) + 𝑋 − (𝑎𝑞)

U Δ𝐻𝑠𝑜𝑙𝑣𝑎𝑡𝑖𝑜𝑛

𝑀+ (𝑔) + 𝑋 − (𝑔)
Sodium and potassium salts are soluble in water because they have relatively
small lattice energies. Magnesium and aluminium salts are often much less soluble
because it takes more energy to separate the positive and negative ions in these
salts. NaOH, for example, is very soluble in water, but Mg(OH)2 dissolves in water
only to the extent of 0.009 g/L, and Al(OH)3 is essentially insoluble in water.

Solvation/hydration: The process by which water/solvent molecules surround the

ions forming ion-dipole bonds and dissolving the ionic solid.

3.5. Ionic liquids

An ionic liquid (IL) is a salt in the liquid state. In some contexts, the term has been
restricted to salts whose melting points is below some arbitrary temperature, such
as 100°C. Many of the IL are liquids at room temperature. While ordinary liquids
such as water and gasoline are predominantly made of electrically neutral
molecules, ILs are largely made of ions.

36
Examples:

1-Butyl-3-methylimidazolium hexafluorophosphate, also known as BMIM-PF6:

3.6. Ionic conductors

Ionic conductors, also known as solid electrolytes and superionic conductors, are
materials that act as solid state ion conductors and are used primarily in solid
oxide fuel cells. As solid electrolytes they conduct due to the movement of ions
through voids, or empty crystallographic positions, in their crystal lattice structure.
The most commonly used solid electrolyte is yttria-stabilized zirconia, YSZ. In
these compounds one component of the structure, the cation or the anion, is
essentially free to move throughout the structure, acting as charge carrier.

Type of conducting ion.:

• Cationic conductors where the carriers are Li+, Na+, K+, Ag+, Cu+, Tl+,
Pb2+, H+(or H3O+, or NH4+)
• Anionic conductors where the carriers are F-or O2-.

37
Chapter 4

Covalent bond

4.1. Definition of covalent bond

A covalent bond is the union of atoms with high and similar electron affinity by
sharing valence electrons.

Models to explain the covalent bond:

• Lewis’s model: Complete the valence shell (noble gas configuration) by

sharing electrons.
• The VSPER model (VSEPR = Valence-Shell Electron-Pair Repulsion Theory): The
spatial disposition of the valence shell e- to minimize the electron repulsion
give us the geometry of the molecule.
• Valence bond theory: The bond electrons occupy the space where the valence
orbitals overlap.
• Molecular orbital theory: New molecular orbitals are formed by the
combination of atomic orbitals.

4.2. Lewis model

The Lewis model is the first approximation to the study of the covalent bond.

In the union of two hydrogen atoms to form the H2 molecule:

• The bond is formed by sharing both electrons between the nuclei.

• The electrons are under the influence of both nuclei and are localized mostly
between them.

4.2.1. Octet rule

Pairing of electrons leads to a noble gas configuration. If all the electrons are
paired the atoms have a large stability.

4.2.2. Lewis structures

• Establish a distribution of the electrons around the atoms.
• Do not give information about the molecular geometry or to the bond
energy.
• Is a simple model to represent bonds in compounds.

38
4.2.3. Multiple bonds
Some elements share more than a pair of electrons, such as:

• Two pairs → Double bond (Diatomic oxygen)

• Three pairs → Triple bond (Diatomic nitrogen)

4.2.4. Hypervalent molecules – Expanded octet

The elements of the third period and beyond have accessible empty d orbitals.
Therefore, they may have more than 8 electrons in the valance shell and can form
more bonds.

Examples:

Phosphorus pentachloride, PCl5

Sulphur hexafluoride, SF6

4.2.5. Hypovalent molecules – Incomplete octet

Some elements form molecules with an incomplete octet, which means less than
eight electrons in the valance shell.

Example:

Boron trichloride, BCl3

4.2.6. Formal charges

Formal charges are apparent charges on certain atoms in a Lewis structure that
appear when atoms have not contributed equal number of electrons to the covalent
bonds.

To calculate formal charges:

• Count lone pair electrons as belonging entirely to the atoms on which they
are found.
• Divide bond pairs equally between the bonded atoms.

𝐹𝐶 = −(𝑓𝑖𝑛𝑎𝑙𝑒 − 𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑒 )

Example:

NH4+

Formal charge in N:

𝐹𝐶 = −(4 − 5) = +1

Formal charge in H:

𝐹𝐶 = −(1 − 1) = 0
39
4.2.7. Procedure for writing Lewis structures
1) Determine the stoichiometric formula.
2) Count the total number of valence electrons in the structure.
a. Add the valence electrons for all the atoms in the molecule.
b. If the molecule would be charged, add one electron for each negative
charge and discount one electron for each positive charge.
3) Draw a skeletal structure placing two electrons (one single bond) between
the central atom and each of the terminal atoms.
4) Distribute the rest of the electrons starting with the atoms with higher
electron affinity until the octets are complete.
5) Place the remaining electrons (if any) on the central atom.
6) Calculate Formal Charges.
a. Count lone-pair electrons as belonging entirely to the atoms on which
they are found.
b. Divide bond-pair electrons equally between the bonded atoms.
7) Formal charges should be as low as possible: establish double bonds among
the central and the peripheral atoms until the lowest formal charge
possible.
8) Elements of the second period cannot have more than 8 electrons

4.2.8. Resonance
Resonance is a way of describing delocalized electrons within certain molecules or
polyatomic ions where the bonding cannot be expressed by one single Lewis
structure.

Example:

• Perchlorate ion, 𝐶𝑙𝑂4−

• Ozone, 𝑂3

4.3. VSPER Model

The VSPER model allows to calculate the molecular geometry from the Lewis
structures.

Electron pairs repel to each other, whether they are bond pairs or lone pairs.
Electrons pairs assume orientations around an atom to minimize repulsions and
maximise separation.

• The bond pairs are placed between the atoms and their location determine
the position of the bond.
• The lone pairs are located in a certain atom, but they also occupy a zone in
the space.
• Multiple bonds occupy the same region in the space and are geometrically
analogous to a single pair.

40
4.3.1. Lone pairs
Lone pairs belong to one atom only, instead of being shares between two atoms like
bonding pairs. Therefore, lone pairs occupy more space and cause a larger
repulsion.

The repulsion lone pair-lone pair is greater than the repulsion lone pair-bonding
pair, which is greater than the repulsion bonding pair-bonding pair.

4.3.2. Electronegativity
If the external atoms are more electronegative than the internal atoms, the
electrons are more attracted towards the external atoms. This causes a lower
electrostatic repulsion between groups of electrons.

4.3.3. Multiple bonds

There is larger electron density in multiple bonds than in single bonds, therefore
the repulsion multiple bond-single bond is greater t the repulsion single bond-
single bond.

41
4.4. Valance bond theory
The formation of the covalent bond as the overlapping of the valance shell atomic
orbitals.

The inner shell electrons and non-bonding pairs are located in the corresponding
atoms. However, bonding electrons are localized in the atomic orbitals overlapping
region. This causes a constructive interference of the atomic wavefunction, higher
electronic density and higher attraction between nucleus and electrons.
P orbitals have positive and negative lobes. The overlap of two positive lobes,
causes constructive interference and the overlap of a negative and a positive lobe
causes destructive interference.

Sigma bond (σ): End-to-end overlap (frontal) of orbitals along the straight line
joining the nuclei of bonded atoms. Electron density is found between the nuclei of
the bonding atoms.

Pi bond (π): Side-to-side overlap (lateral) of p orbitals, producing a high electron

density above and below the line joining the bonded atoms.

4.4.1. Hybridisation
Hybridisation is the linear combination of atomic orbitals. The number of hybrid
orbitals equals the total number of atomic orbitals that are combined.

“sp” → 2 directions 180º (linear)

“sp2” → 3 directions 120º (trigonal planar)

“sp3” → 4 directions 109.5º (tetrahedral)

“sp3d” → 5 directions 120º + 90º + 180º (trigonal bipyramidal)

“sp3d2” → 6 directions (octahedral)

4.5. Molecular orbital theory

The atomic orbitals combine to give a new group of orbitals that belong to the
molecule. This type of orbitals are called molecular orbitals.

A molecular orbital (MO) can be described as a mathematical function describing

the wave-like behaviour of an electron in a molecule.

• The number of molecular orbitals formed is equal to the number of atomic

orbitals combined.
• One of the two molecular orbitals formed when two atomic orbitals are
combines is a bonding molecular orbital at a lower energy that the original
atomic orbitals. The other is an anti-bonding molecular orbital at higher
energy.
• In the ground state configuration, electrons enter the lowest energy
molecular orbitals available.
42
 • The maximum number of electrons in each molecular orbital is two due to
Pauli’s exclusion principle.
• In the ground state configuration, electrons enter the molecular orbitals of
identical energy singly before they pair up (Hund’s rule).

A linear combination of atomic orbitals or LCAO is a quantum superposition of

atomic orbitals and a technique for calculating molecular orbitals in quantum
chemistry. LCAO allows to obtain a wave function that can explain the covalent
bond:

• The atomic orbitals should have a similar energy.

• The atomic orbitals should overlap significantly.
• The atomic orbitals should have a suitable symmetry.

When atomic orbitals interact, the resulting molecular orbital can be of two types:

1. Bonding MOs:

Bonding interactions between atomic orbitals are constructive (in-phase)

interactions. (Addition of orbitals)

Bonding MOs are lower in energy than the atomic orbitals that combine to produce
them.

2. Antibonding MOs:

Antibonding interactions between atomic orbitals are destructive (out-of-phase)

interactions, with a nodal plane where the wavefunction of the antibonding orbital
is zero between the two interacting atoms. (Subtraction of orbitals)

Antibonding MOs are higher in energy than the atomic orbitals that combine to
produce them.

43
Bond order: Half of the difference between the number of antibonding and bonding
electrons.
𝑛º 𝑏𝑜𝑛𝑑𝑖𝑛𝑔 𝑒 − − 𝑛º 𝑎𝑛𝑡𝑖𝑏𝑜𝑛𝑑𝑖𝑛𝑔 𝑒 −
𝑏𝑜𝑛𝑑 𝑜𝑟𝑑𝑒𝑟 =
2

4.5.1. MO energy level diagrams

Homonuclear diatomic molecules:

Bond order: 0.5 1 0.5 0

44
 The example in the left is common for
homonuclear molecules with an atomic
number greater than 7. For example, O2
and F2

However, homonuclear diatomic

molecules with an atomic number less
than or equal to 7, have a the π bonding
molecular orbitals with lower energy
than the σ bonding molecular orbitals.

8−4
𝐵𝑜𝑛𝑑 𝑜𝑟𝑑𝑒𝑟 = =2
2
Single bond: Bond order = 1

Double bond: Bond order = 2

Triple bond: Bond order = 3

A greater bond order means a greater stability.

MO for 2p orbitals:

45
Heteronuclear diatomic molecules:

Atoms with higher electronegativity have lower energy, therefore are placed lower
in the diagram. This is because the lone pairs of electrons are more stable in more
electronegative atoms, making this atoms lower in energy.

4.6. Benzene molecule

Benzene is the basis of aromatic compounds or arenes. Benzene is a colourless
liquid with a characteristic smell and molecular formula: C6H6. Benzene has
boiling temperature of 80 ºC and melting temperature of 6 ºC. It was first isolated
in 1825 by Michael Faraday.

Hydrocarbons (Contain only C and H)

Aromatic: Aliphatic:
Contains a benzene Contains no benzene
ring. ring.

Benzene’s formula suggests it is very unsaturated, therefore chemists proposed a

series of aliphatic hydrocarbons with the formula C6H6. The predicted properties of
these substances did not match the experimental observations with benzene.
Benzene is very unreactive, whereas the proposed compounds reacted quite easily.
In addition, an unsaturated compound usually undergoes addition reactions
whereas benzene undergoes substitution reactions.

46
Kekulé structure of benzene

In 1865, Friedrich August Kekulé proposed a cyclic structure for benzene:

However, this structure failed in three ways:

1. As the proposed structure contains double bonds, it is expected that benzene

would undergo addition reactions. However, benzene undergoes substitution
reactions, therefore proving an error in the structure.
2. Double bonds and single bonds have different lengths. The C=C is 0.134 nm
whereas the C-C bond is 0.154 nm. If benzene had alternating double and
single bonds, it should have an irregular shape. Instead benzene is a regular
hexagon with bond lengths of 0.139 nm, in between the length of a double
and a single bond.
3. The theoretical thermochemistry data for Kekulé’s model does not match
with the experimental data.

The expected value for the enthalpy change of the hydrogenation of benzene
(assuming benzene is cyclohexa-1,3,5-triene) is -360 kJ mol-1. However, the actual
value is -208 kJ mol-1. The difference of 152 kJ mol-1 is called the delocalisation
energy or resonance energy and means the real structure of benzene is 152 kJ mol-1
more stable than the Kekulé structure.

The electrostatic potential maps and the electron density maps show benzene is a
symmetrical regular hexagon, with an angle of 120º and equal length bond angles.
These maps (as well as x-ray diffraction) show benzene is not cyclohexa-1,3,5-
triene.

Pauling’s model of benzene

In 1931, due to the accumulation of evidence against Kekulé’s model, Linus

Pauling proposed a new model. He proposed benzene was in a state between two
Kekulé structures. This is called resonance hybrid.

47
In this structure, each bond in the ring is in between a single and a double bond.
Therefore, Pauling’s model explained the data of the electron density maps and the
x-ray diffraction. It could also explain the thermochemistry problems, as the
resonance hybrid is in a lower energy state than either of the two Kekulé
structures.

Orbital model of benzene

Benzene is built from hydrogen atoms (1s1) and carbon atoms (1s2 2s2 2p2). Each
carbon atom has to join to three other atoms (one hydrogen and two carbons) and
doesn’t have enough unpaired electrons to form the required number of bonds.
Therefore, a sp2 hybrid orbital forms.

The three sp2 hybrid orbitals form the three σ bonds (one with hydrogen and two
with carbon). The remaining p-orbitals of each carbon lie all on the same axis and
therefore overlap side-to-side, forming three π bonds. This causes the formation of
a region of high electron density above and below the carbon ring. This region of
high electron density contains 6 delocalised electrons in a π system or three
molecular orbitals.
This model of the structure of benzene explains the regular hexagon shape of
benzene, as the delocalisation of electrons means there are no alternating double
and single bonds. The delocalisation also explains the stability of benzene, because
the more delocalisation the more stable the molecule is.

LUMO: Lowest Unoccupied Molecular Orbital

HOMO: Highest Occupied Molecular Orbital

48
Chapter 5

Intermolecular forces

5.1. Bond polarity

When two atoms are different, they have different affinity for the electrons of the
bond and then there may be a separation of charge and an electric dipole moment
appears.

The covalent bond of a homonuclear molecule has no displacement of charge,

whereas the covalent bond of a heteronuclear molecule has a partial displacement
of charge. Ionic bonds have a total displacement of charge.

5.1.1. Dipole moment

𝜇⃗ = 𝑞 · 𝑑⃗

𝜇⃗ = dipole moment

𝑑⃗ = displacement vector

The displacement vector points from the negative to the positive charge.

The magnitude of the dipole moment is:

𝜇 = |𝜇⃗| = 𝑞𝑑

Units:

• Cm
• eÅ = 1.602 × 10−29 𝐶 𝑚
• Debye (D) = 3.33 × 10−30 𝐶 𝑚

5.1.2. Percentage of ionic character

The percentage of ionic character is the amount of a compound’ s ionic and covalent
character.
𝜇𝑒
%𝐼𝐶 = × 100
𝜇𝑡

𝜇𝑒 = experimental dipole moment

𝜇𝑡 = theoretical dipole moment

The theoretical dipole moment is calculated assuming total separation of charge

(ionic bond).

49
 5.1.3. Electronegativity scales
When two atoms of a different element bond by means of a covalent bond the
shared electron density can be attracted differently by each atom.

Hence, electronegativity (χ) can be defined as the ability of an atom to attract the
electron density of the covalent bonds it can form.
There are several scales of electronegativity:

• Pauling scale

Pauling scale is based on the increment of the energy of a heteronuclear covalent

bond when compared with the energy of the related homonuclear covalent bonds.
1
𝐷𝐴−𝐵 = (𝐷𝐴−𝐴 + 𝐷𝐵−𝐵 ) + 23.06 𝑘𝑐𝑎𝑙 (𝜒𝐴 − 𝜒𝐵 )2
2
Pauling scale is a relative scale therefore it establishes fluorine as a reference
(𝜒 = 4.00).

• Mulliken scale

Robert S. Mulliken proposed that the arithmetic mean of the first ionization energy
(𝐸𝑖 ) and the electron affinity (𝐸𝑒𝑎 ) should be a measure of the tendency of an atom
to attract electrons.
𝐼 + 𝐸𝐴
𝜒=
2
• Allred scale

Electronegativity should be related to the charge experienced by an electron on the

"surface" of an atom: The higher the charge per unit area of atomic surface the
greater the tendency of that atom to attract electrons.
𝑍𝑒𝑓𝑓
𝜒 = 3590 2 + 0.744
𝑟𝑐𝑜𝑣

• Sanderson scale

5.1.4. Pauling’s equation and Hannay-Smith’s equation

The value of percentage ionic character can be estimated from the difference in
electronegativity. Given two atoms A and B:
Δ𝜒 = 𝜒𝐴 − 𝜒𝐵

Pauling equation:
1
(Δ𝜒)2
𝐼𝐶% = (1 − 𝑒 −4 ) × 100

Hannay-Smith equation, for 0 < Δ𝜒 < 2:

𝐼𝐶% = 16Δ𝜒 + 3.5(Δ𝜒)2

50
 5.2. Covalent solids
Three dimensional solids:

Examples:

• Diamond, C
• Silicon carbide, SiC
• Boron nitride, BN
• Quartz, SiO2
• Alumina, Al2O3
• Rutile, TiO2

Laminar solids (2D):

• Graphite, C

In graphite, the carbon atoms form three bonds with other carbon atoms, therefore
hybridize sp2. The remaining p orbital contains one electron which is delocalised
across the structure, hence graphite is good electrical conductor.
The covalent bonds are formed in a hexagonal 2D structure. The bonds between the
layers are not covalent bonds, but intermolecular forces (London dispersion forces).

• Lead (II) oxide, PbO

Chain solids (1D):

• Silicon disulphide, SiS2

• Black phosphorus, P

5.3. Van der Waals forces

5.3.1. Dipole – dipole interactions
Dipole-dipole interactions (also called Keesom interactions) are electrostatic
interactions between permanent dipoles in molecules.

The interaction depends on the dipole moment, μ, as stated by Keesom’s formula:

2𝜇4
𝐸𝐾 = −
3𝑅6 𝑘𝑇
Dipole – dipole interactions have an energy of 50 – 200 kJ/mol, therefore are the
strongest of the Van der Waals forces. They are observed in molecules with
permanent dipoles such as:

• Ammonia
• Water
• Acetone
• HCl

51
 5.3.2. Dipole – induced dipole interactions
Dipole – induced dipole interactions (also called Debye forces) appear from the
induction (also known as polarization), which is the attractive interaction between
a permanent dipole on one molecule and an induced dipole on another. The energy
of dipole – induced dipole interactions is 1 – 10 kJ/mol.

The induced dipole moment is directly proportional to the electric field:

𝜇𝑖 = 𝛼𝐸

Where 𝛼 is the polarizability.

The energy in dipole – induced dipole interactions are described by the Debye’s
formula:

2𝛼𝜇4
𝐸𝐷 = − 6
𝑅

5.3.3. Induced dipole – induced dipole interactions

The induced dipole – induced dipole force (also called London dispersion force) is
caused by correlated movements of the electrons in interacting molecules. The
electrons, which belong to different molecules, start "feeling" and avoiding each
other at the short intermolecular distances, which is frequently described as
formation of "instantaneous dipoles" that attract each other. The energy of the
London dispersion forces is less than 5 kJ/mol, therefore are the weakest of the
Van der Waals forces.

The interaction energy in London dispersion forces is:

3𝐼𝛼 2
𝐸𝐿 = −
4𝑅 6
Where I is the ionisation energy.

5.4. Hydrogen bonds

A hydrogen bond is the attractive interaction of a hydrogen atom with an
electronegative atom, such as nitrogen, oxygen and fluorine, that comes from
another molecule or chemical group. The hydrogen must be covalently bonded to
another electronegative atom to create the bond. The energy of a hydrogen bond is
4 – 120 kJ/mol.

They are observed in:

• Water
• DNA (Between the bases)

52
Chapter 6

Metallic bond

6.1. The electron sea model

According to the electron sea model (also called electron gas model or Drude’s
model),

• The metal atoms lose their valance shell electrons readily and can form a
group of positively charged ions.
• The positively charged metal ions are arranged in a definite geometric
shape.
• This array of positively charged is submerged in the sea of freely moving
electrons.
• Due to smaller ionization energy, the valance electrons of the metal are not
held by the nucleus firmly and the electrons can move freely.
• The mobile electrons move around the group of metal ions freely similar to
the free movement of sea water or any gas.

Metallic solids:

• Equivalent positions
• Bond not directional

Covalent solids:

• Equivalent positions
• Directional bond

Ionic solids:

• Non-equivalent positions
• Bond not directional

6.2. Band theory

The electron sea model predicts the bond strength of metallic bonds increases as
the number of valance electrons increase, therefore the melting point of the metal
should increase. However, this is not observed experimentally, hence a new theory
must be proposed.

The filled molecular orbitals compose the valance band.

The unfilled molecular orbitals compose the conduction band.

53
The electrons of a single, isolated atom occupy atomic orbitals each of which has a
discrete energy level. When two or more atoms join together to form into a
molecule, their atomic orbitals overlap. The Pauli exclusion principle dictates that
no two electrons can have the same quantum numbers in a molecule. So if two
identical atoms combine to form a diatomic molecule, each atomic orbital splits into
two molecular orbitals of different energy, allowing the electrons in the former
atomic orbitals to occupy the new orbital structure without any having the same
energy.

Similarly if a large number N of identical atoms come together to form a solid, such
as a crystal lattice, the atoms' atomic orbitals overlap. Since the Pauli exclusion
principle dictates that no two electrons in the solid have the same quantum
numbers, each atomic orbital splits into N discrete molecular orbitals, each with a
different energy. Since the number of atoms in a macroscopic piece of solid is a very
large number (N~1022) the number of orbitals is very large and thus they are very
closely spaced in energy (of the order of 10−22 eV). The energy of adjacent levels is
so close together that they can be considered as a continuum, an energy band.

Each type of orbital can give rise to its own band, the electronic structure of a solid
usually consists of a series of bands. The electronic structure of a bulk structure is
referred as the band structure.

This model predicts:

• Bonding becomes stronger as the number of valance electrons increases, and

the bonding orbitals are increasingly populated.
• Past the middle elements of the transition metals, the bond becomes weaker
as electrons fill antibonding orbitals.

Strong bonds between atoms lead to metals with higher melting and boiling points,
greater hardness, …

54
 • In some metals the valance band is only partially filled therefore serves as a
conduction band (outlined in black).
• In other metals, the valance band is full, but a conduction band overlaps it.
• In a semiconductor, the valance band is full, and the conduction band is
empty. However, the energy gap between them is small enough for electrons
to make the transitions between them acquiring thermal energy.
• In an insulator, the valance band is filled, and the conduction band is
empty. The energy gap is too large for electrons to make transitions
therefore insulators do not conduct electricity.

6.3. Properties of metals

Metals:

• Metals are malleable and ductile

• Have very high boiling and melting points
• Are good conductors of electricity
• Are good thermal conductors.

6.4. Semiconductors
The electrical conductivity depends on the number of electrons that are promoted
across the gap (the number of electrons increase as temperature increases and
hence the conductivity increases).

55
Types of semiconductors:

• Intrinsic semiconductors: Semiconduction is a property of the band

structure of the pure material.
• Compound semiconductors: A semiconductor with charge carriers that are
present as a result of the replacement of some atoms by dopant atoms.

6.4.1. Extrinsic/compound semiconductors

An extrinsic semiconductor is one that has been doped. Doping involves
incorporating a trace element or chemical called a doping agent during the
manufacture of the semiconductor. The purpose of doping is giving the
semiconductor different electrical properties from the pure semiconductor crystal.

In an extrinsic semiconductor, these foreign dopant atoms in the crystal lattice

provide most of the charge carriers, that carry electric current through the crystal.
The doping agents used are of two types, resulting in two types of extrinsic
semiconductors.

n-types semiconductors

An electron donor dopant is an atom which, when incorporated in the crystal,

releases a mobile conduction electron into the crystal lattice. An extrinsic
semiconductor which has been doped with electron donor atoms is called an n-type
semiconductor, because the majority of charge carriers in the crystal are negative
electrons.

The addition of pentavalent impurities such as antimony, arsenic or phosphorous

contributes free electrons, greatly increasing the conductivity of the intrinsic
semiconductors. Phosphorous may be added by diffusion of phosphine gas (PH3).

p-types semiconductors

An electron acceptor dopant is an atom which accepts an electron from the lattice,
creating a vacancy called a hole, which can move through the crystal like a
positively charged particle. An extrinsic semiconductor which has been doped with
electron acceptor atoms is called a p-type semiconductor, because the majority of
charge carriers in the crystal are positive holes.

The addition of trivalent impurities such as boron, aluminium or gallium to an

intrinsic semiconductor creates deficiencies of valence electrons, called "holes". It is
typical to use B2H6 gas to diffuse boron into the silicon material.

56
 6.5. Diodes
Joining a piece of n-type silicon to a piece of p-type silicon produces a p-n junction.
As the n-type silicon contains excess electrons and the p-type silicon contains
excess holes, some of the extra electrons will diffuse across the junction into the
holes. This causes that either side of the junction will get normal silicon forming
again and since ordinary silicon does not conduct electricity, nor does the junction.
This produces a barrier between the n-type and the p-type semiconductors, called a
depletion zone. When this occurs the p-n junction is at equilibrium.

6.5.1. Forward bias

In forward bias, the p-type is connected with the positive terminal and the n-type is
connected with the negative terminal of the battery.

The holes in the p-type region and the electrons in the n-type region are pushed
toward the junction and start to neutralize the depletion zone, reducing its width.
The positive potential applied to the p-type material repels the holes, while the
negative potential applied to the n-type material repels the electrons.
As the p-n junction width has decreased the electrons and holes are able to move
across the junction, so a current flows.

6.5.2. Reverse bias

Connecting the p-type region to the negative terminal of the battery and the n-type
region to the positive terminal corresponds to reverse bias.

Because the p-type material is now connected to the negative terminal of the power
supply, the 'holes' in the p-type material are pulled away from the junction, leaving
behind charged ions and causing the width of the depletion region to increase.
Likewise, because the n-type region is connected to the positive terminal, the
electrons are pulled away from the junction, with similar effect. This increases the
voltage barrier causing a high resistance to the flow of charge carriers, thus
allowing minimal electric current to cross the p–n junction. The increase in
resistance of the p–n junction results in the junction behaving as an insulator.

57
 6.6. Conducting polymers
A conducting polymer is an organic polymer that conducts electricity. The first
conductive polymer was poly(acetylene) doped with halogens, which had almost the
electrical conductivity of a poor metal.

Conjugated polymers are organic macromolecules that are characterized by a

backbone chain of alternating double- and single-bonds. Their overlapping p-
orbitals create a system of delocalised π-electrons, which can result in interesting
and useful optical and electronic properties.

6.7. Superconductivity
Superconductivity is a phenomenon of exactly zero electrical resistance occurring
in certain materials, called superconductors, when cooled below a characteristic
critical temperature. Superconductivity is also characterized by the Meissner
effect, which involves the ejection of any magnetic flux lines form the interior of the
superconductor.

The electrical resistivity of a metallic conductor decreases gradually as

temperature decreases. However, in ordinary conductor such as copper, this
decrease is limited by impurities and other defects. Even near absolute zero, a real
sample of copper shows some resistance. Instead in a superconductor the resistance
falls to zero below its critical temperature, which means an electric current flowing
in a loop of superconducting wire can persist indefinitely with no power supply.

6.7.1. Meissner effect

The Meissner effect is the expulsion of a magnetic field from a superconductor
during its transition to the superconducting state.

The samples, in the presence of an applied magnetic

field, were cooled below their superconducting
transition temperature, whereupon the samples
cancelled nearly all interior magnetic fields. They
detected this effect only indirectly because the
magnetic flux is conserved by a superconductor:
when the interior field decreases, the exterior field
increases. The experiment demonstrated for the
first time that superconductors were more than just
perfect conductors and provided a uniquely defining
property of the superconductor state.

58
Chapter 9

Principles of Chemical Equilibrium

9.1. Equilibria
9.1.1. Dynamic equilibria
Dynamic equilibrium: An equilibrium in which the rate of the forward reaction is
equal to the rate of the backward reaction.

If a reversible reaction is carried out in a closed container so that the reactants and
products cannot escape, a state of dynamic equilibrium can be established.
𝐴+𝐵 ⇌𝐶+𝐷

The state is an equilibrium because:

• The rates of the forward and reverse reaction are the same.

• The net concentrations of the components of the reaction mixture remain

constant.

It is not necessary that the concentration of products and reactants is equal, only
the rates of reaction must be exactly the same.

9.1.2. The equilibrium law

At equilibrium the ratio of the concentrations of products and reactants is constant.
The ratio value is called the equilibrium constant, Kc. The c in Kc, means
concentrations are used to calculate the value. It is always the same for a
particular reaction under fixed conditions.
𝑎𝐴 + 𝑏𝐵 ⇌ 𝑐𝐶 + 𝑑𝐷
[𝐶]𝑐 [𝐷]𝑑
𝐾𝑐 =
[𝐴]𝑎 [𝐵]𝑏

The equilibrium constant of the backward reaction is the reciprocal of the

equilibrium constant for the forward reaction.
1
𝐾𝑐′ =
𝐾𝑐
The units of the equilibrium constant vary like the units for the rate constant. Unit
are not required when the number of moles of reactants equals the number of
moles of products, as they cancel each other. Instead, when the number of moles of
reactants are not the number of moles of products the units for Kc are required.
Solids are not included in the Kc expression and water is only included when it is a
product.

59
 9.1.3. Homogeneous equilibria
A homogeneous equilibrium has everything present in the same phase. The usual
examples include reactions where everything is a gas, or everything is present in
the same solution.

Example:
2𝑆𝑂2 (𝑔) + 𝑂2 (𝑔) ⇌ 𝑆𝑂3 (𝑔)
[𝑆𝑂3 ]
𝐾𝑐 =
[𝑆𝑂2 ][𝑂2 ]

9.1.4. Heterogeneous equilibria

A heterogeneous equilibrium has substances present in more than one phase. The
usual examples include reactions involving solids and gases, or solids and liquids.

Example:
𝐶𝑎𝑂(𝑠) + 𝑆𝑂2 (𝑔) ⇌ 𝐶𝑎𝑆𝑂3 (𝑠)
1
𝐾𝑐 =
[𝑆𝑂2 (𝑔)]

Solids and liquids are not included in the expressions as their concentrations are
constant. This is because the concentration of a solid and a liquid is its density
which is constant, so it is not added to the equilibrium expression.

9.2. Calculating Kc
Moles of reactant at equilibrium = initial moles – moles reacted

Moles of product at equilibrium = initial moles + moles formed

The volume is not taken into account if the number of moles of reactants is equal to
the number of moles of products as they cancel out.

Example:
The reaction for the formation of hydrogen iodide dos not go to completion but
reaches an equilibrium:
𝐻2 (𝑔) + 𝐼2 (𝑔) ⇌ 2𝐻𝐼(𝑔)

A mixture of 1.9 mol of H2 and 1.9 mol of I2 was prepared and allowed to reach
equilibrium in a closed vessel on 250 cm3 capacity. The resulting equilibrium
mixture was found to contain 3.0 mol of HI.

Calculate the value of Kc.

60
 H2 I2 HI
Initial 1.9 1.9 0
Change -1.5 -1.5 +3.0
At equilibria 0.4 0.4 3.0
Concentration 1.6 1.6 12

[𝐻𝐼(𝑔)]2 (12)2
𝐾𝑐 = = = 56.25
[𝐻2 (𝑔)][𝐼2 (𝑔)] (1.6)(1.6)

No units as:

nº moles of reactants = nº moles of products

9.3. Equilibrium constant for gases, Kp

In the calculation of the equilibrium constant it is more convenient to use partial
pressures when dealing with gases.

When calculating the equilibrium constant using pressure two values must be
used: partial pressure and mole fraction.

The mole fraction, xi, of a gas is the fraction of the total number of moles of gas
present:
𝑛𝑖
𝑥𝑖 =
𝑛𝑡𝑜𝑡𝑎𝑙
The total number of moles is the sum of the moles at equilibrium and the sum of all
the mole fractions must always be 1.0. In a gas the proportion by volume is always
the same as the proportion by moles or mole fraction.
In a vessel containing a mixture of gases, the partial pressure of one gas is the
pressure it would exert if it occupied the vessel alone.
𝑝𝑖 = 𝑥𝑖 ∙ 𝑝
𝑝𝑖 → 𝑝𝑎𝑟𝑡𝑖𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒
𝑥𝑖 → 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛
𝑝 → 𝑡𝑜𝑡𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒

When dealing with partial pressures the unit of pressure is irrelevant as it is a

ratio. It may be atm (atmosphere), Pa (Pascal) or mmHg (millimetre of mercury).
𝑎𝐴(𝑔) + 𝑏𝐵(𝑔) ⇌ 𝑐𝐶(𝑔) + 𝑑𝐷(𝑔)
𝑐 𝑑
𝑝(𝐶(𝑔)) 𝑝(𝐷(𝑔)) 𝑃𝐶𝑐 · 𝑃𝐷𝑑
𝐾𝑝 = =
𝑎
𝑝(𝐴(𝑔)) 𝑝(𝐵(𝑔))
𝑏
𝑃𝐴𝑎 · 𝑃𝐵𝑏

61
Calculating Kp

Example:

In an experiment, 1.0 mol of hydrogen and 1.0 mol of iodine were allowed to reach
equilibrium at 698 K.
𝐻2 (𝑔) + 𝐼2 (𝑔) ⇌ 2𝐻𝐼(𝑔)

At equilibrium, 80% of the hydrogen was converted to hydrogen iodide at total

pressure of 1.1 atm.

Calculate the value of Kp.

H2 I2 HI
Initial 1 1 0
Change -0.4 -0.4 +0.8
At equilibrium 0.6 0.6 0.8
Mole fraction (x) 0.6/2=0.3 0.6/2=0.3 0.8/2=0.4
Partial pressure 0.3·1.1=0.33atm 0.3·1.1=0.33atm 0.4·1.1=0.44atm
(p)
2
𝑝(𝐻𝐼(𝑔)) (0.44)2
𝐾𝑝 = = = 1.78
𝑝(𝐻2 (𝑔))𝑝(𝐼2 (𝑔)) (0.33)(0.33)

9.4. Relationship between Kc and Kp

𝐾𝑝 = 𝐾𝑐 (𝑅𝑇)𝑛

𝑅 → 𝐺𝑎𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡, 8.31 𝐽 𝐾 −1 𝑚𝑜𝑙 −1

𝑇 → 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒, 𝐾
𝑛 → 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑜𝑛 𝑡ℎ𝑒 𝑟𝑖𝑔ℎ𝑡 ℎ𝑎𝑛𝑑 𝑠𝑖𝑑𝑒
𝑚𝑖𝑛𝑢𝑠 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠 𝑜𝑛 𝑡ℎ𝑒 𝑙𝑒𝑓𝑡 ℎ𝑎𝑛𝑑 𝑠𝑖𝑑𝑒

9.5. What does an equilibrium constant tell us?

The equilibrium constant of a reaction is how far a reaction proceeds to completion.
When the value of K is very small, it means the denominator must be very large
compared to the numerator, therefore at equilibrium there are much more moles of
reactants than products. Instead, if the value of K is very big then the numerator
must be very large compared to the denominator so there are much more moles of
products than reactants at equilibrium.

62
 Value of K Extent of reaction Example
Very large Reaction proceeds almost
to completion leaving
K > 1 x 1010 very small amount of C (s) + O2 (g) ↔ CO2 (g)
reactants at equilibrium.
K≈1 Concentrations of 2BrCl ↔ Br2 + Cl2
reactants and products
are nearly the same at (In CCl4 solution)
equilibrium.
Very small Reaction hardly occurs,
producing very small
K < 1 x 10-10 quantities of products at 2HBr(g) ↔ H2(g) + Br2(g)
equilibrium.

The term position of equilibrium refers to the magnitude of the equilibrium

constant. When K is very large the position of equilibrium lies to the right-hand
side of the equation and when the value of K is very small the position of
equilibrium is said to lie to the left-hand side of the equation. The value of K tells
nothing about the rate of reaction.

9.6. Reaction Quotient

The reaction quotient, 𝑄𝑐 , is an expression for the equilibrium constant when the
system has not reached equilibrium (non-equilibrium conditions). The reaction
quotient provides information about the position of equilibrium of the system.

Given the reaction:

𝑎𝐴 + 𝑏𝐵 ⇌ 𝑐𝐶 + 𝑑𝐷
[𝐴]𝑎 [𝐵]𝑏
𝑄𝑐 =
[𝐶]𝑐 [𝐷]𝑑

If 𝑄𝑐 = 𝐾𝑐 : The reaction is at equilibrium.

If 𝑄𝑐 < 𝐾𝑐 : The reaction moves to the right.

If 𝑄𝑐 > 𝐾𝑐 : The reaction moves to the left.

9.7. Le Chatelier’s Principle

“When a system at equilibrium is subjected to change in concentration,
temperature or pressure, then the system readjusts to counteract the effect of the
applied change and a new equilibrium is established.”

63
 9.7.1. Temperature
Increasing the temperature of a reaction causes a shift towards the endothermic
reaction, in order to decreases the temperature. Decreasing the temperature of a
reaction causes a shift towards the exothermic reaction, in order to increase the
temperature.

9.7.2. Pressure
Increasing the pressure of a gaseous reaction causes a shift towards the side with
fewer gas molecules. Decreasing the pressure causes a shift towards the side with
the larger number of gas molecules.

If the number of moles of gas is the same on both sides, changing the pressure will
have no effect on the position of the equilibrium.

9.7.3. Concentration
Increasing the concentration of a substance will cause the reaction to move in the
direction that uses up the added substance. Decreasing the concentration of a
substance will cause the reaction to move in the direction that replaces the
removed substance.

9.7.4. Catalysts
Catalysts only affect the rate of reaction but do not affect the equilibrium position
of a reaction. when adding a catalyst both the forward and backward reaction
speed up so there is no overall change in the equilibrium position.

9.8. Application of rates and equilibrium

Important industrial reversible reactions:

Haber process – Manufacture of ammonia:

𝑁2 (𝑔) + 3𝐻2 (𝑔) ⇌ 2𝑁𝐻3 (𝑔)

Contact process – Manufacturing sulphuric acid

2𝑆𝑂2 (𝑔) + 𝑂2 ⇌ 2𝑆𝑂3 (𝑔)

Esterification
𝐶𝐻3 𝐶𝑂𝑂𝐶2 𝐻5 (𝑙) + 𝐻2 𝑂(𝑙) ⇌ 𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑙) + 𝐶2 𝐻5 𝑂𝐻(𝑙)

64
Chapter 10

Spontaneous change

10.1. Meaning of spontaneous change

Spontaneous process: A process that occurs in a system by itself. Once started, no
action from outside the system (external action) is necessary to make the process
continue.

Non-spontaneous process: A process that will not occur unless some external action
is continuously applied.

Properties of spontaneity:

• If a process is spontaneous, the reverse process is non-spontaneous.

• Both spontaneous and non-spontaneous processes are possible, but only
spontaneous processes will occur without intervention. Non-spontaneous
processes require the system to be acted on by an external agent.
• Some spontaneous processes occur very slowly, and others occur rather
rapidly. Spontaneous does not mean fast.

Usually spontaneous process are exothermic process, however there are exceptions
therefore a new variable is required to describe the spontaneity of a reaction.

10.2. Entropy
Entropy is a state function which is related to the number of possible
arrangements of the particles in energy levels available in a system.

The Boltzmann equation

At microscopic level the entropy is related with the number of microstates of a
system. The larger the number of arrangements (i.e. microstates) of the particles
(atoms, molecules, ions) in a particular state of the system, the greater the entropy
of the system.
𝑆 = 𝑘 ln 𝑊

Where S is the entropy, k is Boltzmann’s constant and W is the number of

microstates.

Microstate: The particular way in which particles are distributed amongst the
states.

65
At macroscopic level the entropy is related with the reversible heat divided by the
temperature:
𝑄𝑟𝑒𝑣
Δ𝑆 =
𝑇
Where 𝑞𝑟𝑒𝑣 is the reversible heat.

Qualitative predictions of entropy change

Entropy increases:

• Increase of the number of microscopic particles.

• Increase of the space available for them.
• Increase of the particles accessibility to the microscopic energy levels of the
system.

Processes that generally result in an increase in entropy

• Pure liquids or solutions formed from solids.

• Gases formed from either solids or liquids.
• Solution of solids.
• Increase of temperature of a substance.
• Increase of the number of molecules of gas as a result of a chemical reaction.

10.3. Entropy change in a phase transition

At the equilibrium between two phases (phase transition), the heat exchange can
be done reversely:
𝑄𝑟𝑒𝑣
Δ𝑆 =
𝑇
𝑄𝑟𝑒𝑣 = Δ𝐻𝑡𝑟𝑎𝑛𝑠
Δ𝐻𝑡𝑟𝑎𝑛𝑠
Δ𝑆 =
𝑇𝑡𝑟𝑎𝑛𝑠

10.4. Third law of thermodynamics

The third law of thermodynamics states that:

“The entropy of a pure perfect crystal at 0 K is zero.”

Standard molar entropy. 𝑆 𝑜 : The absolute entropy of one mol of a substance in its
standard state.

The changes in entropy in a reaction can be calculated from the standard molar
entropy of reactants and products:

𝑜 𝑜
Δ𝑆 = ∑ 𝑆𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∑ 𝑆𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

66
We have always to consider two changes in entropy:

• Changes in the entropy of the system

• Changes in the entropy of the surroundings

10.5. Second law of thermodynamics

The second law of thermodynamics states that:
Δ𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + Δ𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 > 0

All spontaneous processes produce an increase in the entropy of the universe.

In a process with only P-V work, at constant T and P, the heating effect
experienced by surroundings is opposite to that of the system, then:

𝑄𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = −(𝑄𝑠𝑦𝑠𝑡𝑒𝑚 )𝑝 = −Δ𝐻𝑠𝑦𝑠𝑡𝑒𝑚

The quantity of heat will produce only an infinitesimal change in the surroundings
(reversible changes) and we can write:
𝑄𝑟𝑒𝑣 Δ𝐻𝑠𝑦𝑠𝑡𝑒𝑚
Δ𝐻𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔𝑠 = =−
𝑇 𝑇

10.6. Gibbs free energy

Substituting the value of the enthalpy change of the surroundings in the previous
equation:
Δ𝐻
Δ𝑆 = Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚 −
𝑇
𝑇Δ𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 𝑇Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚 − Δ𝐻

−𝑇Δ𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = Δ𝐻𝑠𝑦𝑠𝑡𝑒𝑚 − 𝑇Δ𝑆𝑠𝑦𝑠𝑡𝑒𝑚

A new thermodynamic value is defined:

𝐺 = 𝐻 − 𝑇𝑆

For a process at a constant T:

Δ𝐺 = Δ𝐻 − 𝑇Δ𝑆

The Gibbs free energy is a state function and the terms apply to measurements on
the system.

Δ𝐺 < 0 → Spontaneous process

Δ𝐺 > 0 → Non-spontaneous process

67
Standard Gibbs free energy:
Δ𝐺 𝑜 = Δ𝐻 𝑜 − 𝑇Δ𝑆 𝑜

Δ𝐺 𝑜 = ∑ Δ𝐺𝑓𝑜 (𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − ∑ Δ𝐺𝑓𝑜 (𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

The standard free energy of formation, Δ𝐺𝑓𝑜 :

The change in free energy for a reaction in which a substance in its standard state
is formed from its elements in reference forms in their standard states.

• The standard free energies of formation of the elements in its physical form
and the reference standard state (P = 1 bar) are zero.
• ΔG of reverse processes are equal but opposite in sign.
• ΔG for an overall process can be obtained by adding the values of ΔG for the
individual steps.

10.7. Equilibrium
For Δ𝑇 = 0: Thermal equilibrium: the temperature does not change.

For Δ𝑃𝑉 = 0: Mechanical equilibrium: the pressure does not change.

For Δ𝐺 𝑜 = 0: Chemical equilibrium: the reaction does not progress no change in the
chemical composition.

𝑑𝐺 = 𝑉 𝑑𝑃
𝑃 𝑃
𝑛𝑅𝑇 𝑃
Δ𝐺 = ∫ 𝑉 𝑑𝑃 = ∫ 𝑑𝑃 = 𝑛𝑅𝑇 ln ( )
1 1 𝑃 1
𝑃
Δ𝐺 = 𝐺 − 𝐺 𝑜 = 𝑛𝑅𝑇 ln ( )
1
For the reaction:
𝐻2 (𝑔) + 𝐼2 (𝑔) ⇌ 2𝐻𝐼(𝑔)

𝑜
𝑃𝐻𝐼 𝑃𝐻 𝑃𝐼
Δ𝐺𝑟𝑒𝑎𝑐𝑡 = 2 (𝐺𝐻𝐼 + 𝑛𝑅𝑇 ln ( )) − (𝐺𝐻𝑜2 + 𝑛𝑅𝑇 ln ( 2 ) + 𝐺𝐼𝑜2 + 𝑛𝑅𝑇 ln ( 2 ))
1 1 1

𝑜
𝑃𝐻𝐼 𝑃𝐻 𝑃𝐼
= 2𝐺𝐻𝐼 − 𝐺𝐻𝑜2 − 𝐺𝐼𝑜2 + 2𝑛𝑅𝑇 ln ( ) − 𝑛𝑅𝑇 ln ( 2 ) − 𝑛𝑅𝑇 ln ( 2 )
1 1 1

𝑜
𝑃𝐻𝐼 2 𝑃𝐻 𝑃𝐼
= Δ𝐺𝑟𝑒𝑎𝑐𝑡 + 𝑛𝑅𝑇 ln ( ) − 𝑛𝑅𝑇 ln ( 2 ) − 𝑛𝑅𝑇 ln ( 2 )
1 1 1

o
𝑃𝐻𝐼 2 𝑃𝐻 𝑃𝐼
= ΔG𝑟𝑒𝑎𝑐𝑡 + 𝑛𝑅𝑇 (ln ( ) − ln ( 2 ) − ln ( 2 ))
1 1 1

68
 𝑃 2
( 𝐻𝐼 )
𝑜
= Δ𝐺𝑟𝑒𝑎𝑐𝑡 + 𝑛𝑅𝑇 ln ( 1 )
𝑃𝐻2 𝑃𝐼2
( 1 )( 1 )

𝑜
= Δ𝐺𝑟𝑒𝑎𝑐𝑡 + 𝑛𝑅𝑇 ln 𝑄𝑝

In the equilibrium:
Δ𝐺𝑟𝑒𝑎𝑐𝑡 = 0
𝑜
0 = Δ𝐺𝑟𝑒𝑎𝑐𝑡 + 𝑛𝑅𝑇 ln 𝐾𝑝
𝑜
Δ𝐺𝑟𝑒𝑎𝑐𝑡 = −𝑛𝑅𝑇 ln 𝐾𝑝

10.8. Temperature and Gibbs free energy

For a given reaction:
Δ𝐺 𝑜 = Δ𝐻 𝑜 − 𝑇Δ𝑆 𝑜
Δ𝐺 𝑜 = −𝑅𝑇 ln 𝐾𝑝

Rearranging the equation:

Δ𝐺 𝑜 𝑇Δ𝑆 𝑜 − Δ𝐻 𝑜 Δ𝑆 𝑜 Δ𝐻 𝑜
ln 𝐾𝑝 = − = = −
𝑅𝑇 𝑅𝑇 𝑅 𝑅𝑇
Given two equivalent reactions, at different temperatures, with equilibrium
constants 𝐾𝑝1 and 𝐾𝑝2 :
𝐾𝑝 Δ𝑆 𝑜 Δ𝐻 𝑜 Δ𝑆 𝑜 Δ𝐻 𝑜 Δ𝐻 𝑜 Δ𝐻 𝑜 Δ𝐻 𝑜 1 1
1
ln =( − )−( − )= − = ( − )
𝐾𝑝2 𝑅 𝑅𝑇1 𝑅 𝑅𝑇2 𝑅𝑇2 𝑅𝑇1 𝑅 𝑇2 𝑇1

Van’t Hoff Equation:

𝐾𝑝1 Δ𝐻 𝑜 1 1
ln =− ( − )
𝐾𝑝2 𝑅 𝑇1 𝑇2

𝑦 = 𝑚𝑥 + 𝑐
−Δ𝐻 𝑜 1 Δ𝑆 𝑜
ln 𝐾𝑝 = · +
𝑅 𝑇 𝑅
1
𝑦 = ln 𝐾𝑝 , 𝑥 =
𝑇

Assuming Δ𝑆 𝑜 and Δ𝐻 𝑜 do
not vary significantly with
temperature.

69
Chapter 11

Acids-Base Equilibria

11.1. Arrhenius theory

In 1887 Arrhenius published the Theory of Ionic Dissociation, where he stated that
in aqueous solutions the substances called electrolytes exist in the form of ions.
Strong electrolytes exist only in the form of ions, whereas weak electrolytes exist
partly as ions and partly as molecules.

Acids are substances that when dissolved in water yield hydrogen ions, 𝐻 + (𝐻3 𝑂+ ).
𝐻𝐴 → 𝐻 + + 𝐴−

Bases are substances that when dissolved in water yield hydroxide ions, 𝑂𝐻 − .
𝐵𝑂𝐻 → 𝐵+ + 𝑂𝐻 −

Arrhenius theory failed to explain the basic behaviour of compounds such as

ammonia, which lack 𝑂𝐻 − group.

Examples of acids:

• Hydracids (𝐻𝐶𝑙, 𝐻𝐵𝑟, 𝐻𝐼, 𝐻2 𝑆, …)

• Oxoacids (𝐻2 𝑆𝑂4 , 𝐻3 𝑃𝑂4 , …)

Examples of bases:

• Metal hydroxides (𝑁𝑎𝑂𝐻, 𝐶𝑎(𝑂𝐻)2 , …)

• Ammonia

11.2. Brønsted-Lowry theory of acids and bases

Acid: A substance that donates a proton – proton donor.
Base: A substance that accepts a proton – proton acceptor.
𝐻𝐴 + 𝐵 → 𝐵𝐻 + + 𝐴−

Acids and bases go in pairs, for example in this case HA is the acid and 𝐴− is its
conjugate base. 𝐻𝐴 and 𝐴− are called a conjugate pair.

Some substances, such as water can act as a base or an acid.

Amphoteric substances are compounds that can act both as a base and an acid.
Their acid/base character depends on the acid/base character of the substance with
which they are confronted:

• With acids they behave as base

• With bases they behave as acids

70
 11.3. Self-ionisation of water
In the self-ionization of water (or autoionization), for each 𝐻2 𝑂 molecule that acts
as an acid, another 𝐻2 𝑂 molecule acts as a base, and hydronium (𝐻3 𝑂+) and
hydroxide (𝑂𝐻 − ) ions are formed.

𝐻2 𝑂 + 𝐻2 𝑂 ⇌ 𝐻3 𝑂+ + 𝑂𝐻 −
[𝐻3 𝑂+ ][𝑂𝐻 − ]
𝐾𝑐 =
[𝐻2 𝑂][𝐻2 𝑂]

𝐾𝑤 = 𝐾𝑐 · [𝐻2 𝑂]2 = [𝐻3 𝑂+ ][𝑂𝐻 − ] = 1 × 10−14

11.4. pH Scale
The “potential of the hydrogen ion” was defined in 1909 as the negative of the
logarithm of [H+]:
𝑝𝐻 = − log[𝐻 + ]
𝑝𝑂𝐻 = − log[𝑂𝐻 − ]
𝐾𝑤 = 1 × 10−14

− log 𝐾𝑤 = − log(1 × 10−14 )

𝑝𝐾𝑤 = 14
𝑝𝑂𝐻 + 𝑝𝐻 = 14

If we have pure water:

[𝐻 + ] = [𝑂𝐻 − ]

𝐾𝑤 = [𝐻 + ][𝑂𝐻 − ] = [𝐻 + ]2 = 1 × 10−14
[𝐻 + ] = 1 × 10−7

𝑝𝐻 = 7

If we add a base to water:

[𝐻 + ] < 1 × 10−7 → 𝑝𝐻 > 7

If we add an acid to water:

[𝐻 + ] > 1 × 10−7 → 𝑝𝐻 < 7

71
 11.5. Strong and weak acids and bases
All acids and bases do not ionize or dissociate to the same extent. This leads to the
statement that acids and bases are not all of equal strength in producing H+ and
OH- ions in solution.

Acids:

The terms "strong" and "weak" give an indication of the strength of an acid or base.

• Strong acid: The ionization of the acid goes to completion.

• Weak acid: The ionization of the acid occurs to a slight extent.

For strong acids:

𝐻𝐴 + 𝐻2 𝑂 → 𝐻3 𝑂+ + 𝐴−

For weak acids:

𝐻𝐴 + 𝐻2 𝑂 ⇌ 𝐻3 𝑂+ + 𝐴−

The equilibrium constant for this dissociation process is called the acidity constant:

[𝐻3 𝑂+ ][𝐴− ]
𝐾𝑐 =
[𝐻𝐴][𝐻2 𝑂]

[𝐻3 𝑂+ ][𝐴− ]
𝐾𝑎 = 𝐾𝑐 · [𝐻2 𝑂] =
[𝐻𝐴]

The acidity constant gives an idea of the strength of the acid, a high acidity
constant means a strong acid.

Bases:

The strength of a base is higher as the tendency to liberate the hydroxyl group is
higher and as the capacity to accept the proton is higher. The strength depends on
the polarization of the bond and the donor acid with which the base is confronted.

For strong bases:

𝐵𝑂𝐻 → 𝐵+ + 𝑂𝐻 −

For weak bases:

𝐵𝑂𝐻 ⇌ 𝐵+ + 𝑂𝐻 −

The basicity constant, is the analogous of the acidity constant for bases:

[𝐵+ ][𝑂𝐻 − ]
𝐾𝑏 =
[𝐵𝑂𝐻]

The basicity constant gives an idea of the strength of the base, a high basicity
constant means a strong base.

72
Relationship between 𝐾𝑎 and 𝐾𝑏 :

𝑁𝐻3 + 𝐻2 𝑂 ⇌ 𝑁𝐻4+ + 𝑂𝐻 −

𝑁𝐻4+ + 𝐻2 𝑂 ⇌ 𝑁𝐻3 + 𝐻3 𝑂+

[𝑁𝐻4+ ][𝑂𝐻 − ]
𝐾𝑏 =
[𝑁𝐻3 ]

[𝑁𝐻3 ][𝐻3 𝑂+ ]
𝐾𝑎 =
[𝑁𝐻4+ ]

[𝑁𝐻3 ][𝐻3 𝑂+ ] [𝑁𝐻4+ ][𝑂𝐻 − ]

𝐾𝑎 · 𝐾𝑏 = · = [𝐻3 𝑂+ ][𝑂𝐻 − ] = 𝐾𝑤
[𝑁𝐻4+ ] [𝑁𝐻3 ]

𝑝𝐾𝑎 + 𝑝𝐾𝑏 = 𝑝𝐾𝑤

11.6. Polyprotic acids

Polyprotic acids are acids which have more than one ionizable proton per molecule.

Example: Carbonic acid

First dissociation:
𝐻2 𝐶𝑂3 + 𝐻2 𝑂 ⇌ 𝐻𝐶𝑂3− + 𝐻3 𝑂+
[𝐻𝐶𝑂3− ][𝐻3 𝑂+ ]
𝐾𝑎1 =
[𝐻2 𝐶𝑂3 ]

Second dissociation:

𝐻𝐶𝑂3− + 𝐻2 𝑂 ⇌ 𝐶𝑂32− + 𝐻3 𝑂+
[𝐶𝑂32− ][𝐻3 𝑂+ ]
𝐾𝑎2 =
[𝐻𝐶𝑂3− ]

11.7. Measuring pH
11.7.1. pH meter
The pH meter measures the difference in electrical potential between a pH
electrode and a reference electrode. The glass electrode for measuring the pH has a
glass bulb specifically designed to be selective to hydrogen-ion concentration. The
magnitude of the electrochemical potential across the glass bulb is linearly related
to the pH according to the Nernst equation.

The reference electrode can be the standard hydrogen electrode, SHE, or other type
of reference electrodes.

73
 11.7.2. Indicators
An indicator is a halochromic (changes colour with pH) chemical compound added
in small amounts to a solution so the pH of the solution can be determined visually.

Examples:

• Methyl orange
• Bromothymol blue
• Litmus
• Phenolphthalein
• Methyl red

The general equation for an indicator is:

𝐻𝐼𝑛 + 𝐻2 𝑂 ⇌ 𝐼𝑛− + 𝐻3 𝑂+

𝐻𝐼𝑛 stands for the acid form of the indicator and 𝐼𝑛− for the conjugate base form of
the indicator.

The ratio of these determines the colour of the solution and connects the colour to
the pH value, by the Henderson-Hasselbach equation:

[𝐼𝑛− ]
𝑝𝐻 = 𝑝𝐾𝑎 + log
[𝐻𝐼𝑛]

11.8. Buffer solutions

A buffer solution is a solution whose pH value changes only very slightly on the
addition of small amounts of either an acid or a base.

A buffer solution requires two components:

• A component which neutralizes acids

• A component which neutralizes bases

However, these two components must not neutralize each other, therefore we
require:

• A weak acid and its conjugate base

• A weak base and its conjugate acid

11.8.1. The Henderson-Hasselbach Equation

Given a reaction
𝐻𝐴 + 𝐻2 𝑂 ⇌ 𝐴− + 𝐻3 𝑂+
[𝐴− ][𝐻3 𝑂+ ] [𝐴− ]
𝐾𝑎 = = [𝐻3 𝑂+ ]
[𝐻𝐴] [𝐻𝐴]
[𝐴− ]
− log 𝐾𝑎 = − log ([𝐻3 𝑂+ ] )
[𝐻𝐴]

74
 [𝐴− ]
− log 𝐾𝑎 = − log[𝐻3 𝑂+ ] − log
[𝐻𝐴]
[𝐴− ]
𝑝𝐾𝑎 = 𝑝𝐻 − log
[𝐻𝐴]

Therefore, the Henderson-Hasselbach equation is:

[𝐴− ]
𝑝𝐻 = 𝑝𝐾𝑎 + log
[𝐻𝐴]

Buffer capacity, 𝛽: The amount of acid or base that a buffer can neutralize before
its pH changes appreciably. Maximum buffer capacity exists when [HA] and [A-]
are large and approximately equal to each other. A more formal definition is the
quantity of strong acid or base that must be added to change the pH of one litre of
solution by one pH unit.
𝑑𝑛
𝛽=
𝑑𝑝𝐻
Where dn is the infinitesimal addition of acid or base and dpH is the infinitesimal
increase/decrease in pH.

Buffer range: The pH range over which a buffer effectively neutralizes added acids
and bases. Practically, range is 2 pH units around pKa, (1 unit on either side).

11.9. Neutralization reaction and titration curves

Neutralization reaction: A reaction between an acid and a base.
End-point: The point at which the indicator changes colour.
Equivalence point: When the two reactants are mixed in exactly the proportions
indicated by the equation.

There are two types of curves, depending on whether the acid (in burette) is added
to the base (in conical flask) or the base (in burette) is added to the acid (in conical
flask).

75
The titration curves vary depending on whether the acid and base used is weak or
strong:

• Strong acid + strong base → pH = 7

• Weak acid + strong base → pH > 7
• Strong acid + weak base → pH < 7
• Weak acid + weak base → pH ~ 7

76
Chapter 12

Electrochemistry

12.1. Introduction
Oxidation: Reduction:
• Loss of electros • Gain of electrons
• Gain of oxygen • Loss of oxygen
• Loss of hydrogen • Gain of hydrogen

Oxidation number: Charge of the atom if the bonding electrons were assigned to
the most electronegative element.

Redox half-equation: A reaction that involves the transfer of electrons.

Redox pair: The species related by only a difference in electrons inside a half-
reaction.

Reduced form: The species that is the richest in electrons.

Oxidised form: The species that is poorest in electrons.
Reductor – Reducing agent: The species that oxidises itself to reduce another
species.

Oxidant – Oxidising agent: The species that reduces itself to oxidise another
species.

Rules:

• The oxidation number for elements is zero. (for example O2, Cl2, H2, N2, Fe,
Ag, S8)
• In the mono-atomic ionic species the oxidation number is equal to the
charge of the ion.
• The oxidation number of hydrogen in metallic hydrides (AlH3, NaH, CaH2,
etc) is –1. In the rest of the hydrogen compounds its oxidation number is +1.
• The oxidation number of oxygen in its compounds is –2, exception made of
the peroxides (H2O2, Na2O2, etc) in which it is –1.
• The oxidation number of alkaline metals is +1 and the one of the earth-
alkaline is +2.
• The oxidation number of the halogens in the halide (binary salts) is –1, in
the oxygen compounds may be +1,+3,+5, or +7, exception made of the
fluorine.
• The addition of the oxidation numbers in a neutral molecule must be zero.
In an ion, must be equal to its charge.

77
 12.2. Balancing equations
Balancing method to determine the stoichiometric coefficients: the ion-electron
method.

1. Write the reaction and identify the oxidant and the reductor.
2. Separate the redox half-reactions.
3. Adjust in both half-reactions the element that changes its oxidation
number.
4. Identify if the redox reaction takes place in acid or in basic media.
5. Adjust the charges in both half-reactions with electrons.
6. Combine both half-reactions in the way that the total number of electrons
in the reaction be zero (gained electrons = lost electrons).

If acid media:

a) Adjust the defect of oxygen atoms with water molecules at the other side.
b) Adjust the excess of hydrogen atoms with H+.

If basic media:

a) Adjust the excess of oxygen with OH- (add twice the necessary).
b) Adjust the new excess of oxygen and the excess of hydrogen with water
molecules.
7. Add the possible inert species and finish the fit of the entire reaction.

Example:

1. Write the reaction and identify the oxidant and the reductor.
𝐾𝑀𝑛𝑂4 + 𝐾2 𝑆𝑂3 + 𝐻2 𝑆𝑂4 → 𝑀𝑛𝑆𝑂4 + 𝐾2 𝑆𝑂4

𝐾𝑀𝑛𝑂4 is the oxidant and 𝐾2 𝑆𝑂3 is the reductor.

2. Separate the redox half-reactions and adjust them.

𝑀𝑛𝑂4− → 𝑀𝑛2+ 𝑆𝑂32− → 𝑆𝑂42−
𝑀𝑛𝑂4− + 8𝐻 + + 5𝑒 − → 𝑀𝑛2+ + 4𝐻2 𝑂 𝑆𝑂32− + 𝐻2 𝑂 → 𝑆𝑂42− + 2𝐻 + + 2𝑒 −
3. Add the two half-reactions to cancel the number of electrons.

2𝑀𝑛𝑂4− + 6𝐻 + + 5𝑆𝑂32− → 2𝑀𝑛2+ + 3𝐻2 𝑂

4. Add the remaining ions to balance the reaction.

2𝐾𝑀𝑛𝑂4 + 3𝐻2 𝑆𝑂4 + 5𝐾2 𝑆𝑂3 → 2𝑀𝑛𝑆𝑂4 + 6𝐾2 𝑆𝑂4 + 3𝐻2 𝑂

78
 12.3. Electrochemical cells
An electrochemical cell is a device capable of either generating electrical energy
from chemical reactions or facilitating chemical reactions through the introduction
of electrical energy. There are two types of electrochemical cells: galvanic (voltaic)
cells or electrolytic cells. Galvanic cells use a spontaneous redox reaction to
generate electrical energy. Electrolytic cells use electrical energy to drive non-
spontaneous reactions.

A galvanic cell consists of two half-cells connected with a salt bridge. Simple half-
cells consist of a metal (acts as an electrode) and a solution of a compound
containing the metal (e.g. Cu and CuSO4). The two half-cells produce a small
voltage if connected into a circuit.

𝑍𝑛(𝑠)|𝑍𝑛𝑆𝑂4 (𝑎𝑞)||𝐶𝑢𝑆𝑂4 (𝑎𝑞)|𝐶𝑢

Oxidation takes place in the anode and reduction takes place in the cathode. n
Oxidation: 𝑍𝑛 → 𝑍𝑛2+ + 2𝑒 −

Reduction: 𝐶𝑢2+ + 2𝑒 − → 𝐶𝑢

The Zn has a higher tendency to oxidise than the Cu, therefore more electrons will
build up on the anode, than on the cathode. This difference causes a potential
difference between the electrodes, therefore the electrons flow from the anode to
the cathode.

Couple, 𝑀|𝑀+ : A pair of species related by a change in number of e-.

79
 12.4. Standard electrode potentials
The standard electrode potential is the tendency for a reduction process to occur at
an electrode. It is the electromotive force of a cell built of two electrodes:

• On the left-hand side is the standard hydrogen electrode (SHE).

• On the right-hand side is the electrode the potential of which is being
defined.

It is impossible to find the electrode potentials for individual half-cells. We have to

measure the emf of a cell and attribute part of this to each electrode reaction. To
make sure that all the electrode potentials we use are measured in the same way,
we choose to use a reference electrode to compare measurements against – we call
this a reference half-cell. The reference half-cell is used to measure all other
electrode potentials. It is assigned an electrode potential of 0V under standard
conditions (1 atm, 298 K and 1M).

The reference half-cell used in practice is the standard hydrogen electrode (SHE).
This consists of a hydrogen gas at 1 atm pressure and 298 K, bubbling around a
platinum electrode in 1 M H+ solution. The symbol used for the standard electrode
potential is 𝐸 𝑜 . The reaction which occurs in the half-cell is:
2𝐻 + (𝑎𝑞) + 2𝑒 − ⇌ 𝐻2 (𝑔) 𝐸𝑜 = 0 𝑉

80
To measure the standard electrode potential of another half-cell (e.g. Cu (s)|Cu2+
(aq)), we need to connect this half-cell to a standard hydrogen half-cell under
standard conditions.

Standard electrode potentials refer to the half-reaction as a reduction. 𝐸 𝑜 values

therefore reflect the ability of the reactant to act as an oxidising agent.

• The most powerful reducing agents will be found at the most negative end of
the series on the right (i.e. the one with the lower oxidation number).
• The most powerful oxidising agents will be found at the most positive end of
the series on the left (i.e. the one with the higher oxidation number).

Standard cell potential: The potential difference in a cell formed from two standard
electrodes.
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒
𝑜 𝑜 𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 + 𝐸𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛

12.5. Work
When a redox reaction takes place in a galvanic cell, a work is being done:
𝑊 = 𝑞𝑉 = 𝑧𝐹𝐸𝑐𝑒𝑙𝑙

Where z is the number of electrons and F is Faraday’s constant (𝐹 = 96485 𝐶 𝑚𝑜𝑙 −1 )

The Faraday, F, is the charge of one mole of electrons and is found by multiplying
Avogadro’s constant and the elementary charge:

𝐹 = 𝑁𝐴 𝑒 = (6.022 × 1023 )(1.6 × 10−19 ) = 96 485 𝐶 𝑚𝑜𝑙 −1

Therefore, the total charge is found by multiplying F and z. The potential

difference in the reaction is equal to 𝐸𝑐𝑒𝑙𝑙 .

𝐺 = 𝐻 − 𝑇𝑆
𝑑𝐺 = 𝑑𝐻 − 𝑆𝑑𝑇 − 𝑇𝑑𝑆 = 𝑑𝑈 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇𝑑𝑆 − 𝑆𝑑𝑇 =
𝑑𝑞
= 𝑑𝑞 − 𝑃𝑑𝑉 − 𝑑𝑊 + 𝑃𝑑𝑉 + 𝑉𝑑𝑃 − 𝑇 − 𝑆𝑑𝑇
𝑇
= 𝑉𝑑𝑃 − 𝑆𝑑𝑇 − 𝑑𝑊

If P and T are constant, then:

𝑑𝐺 = −𝑑𝑊
𝑑𝐺 = −𝑧𝐹𝐸𝑐𝑒𝑙𝑙

If it is in standard conditions:
𝑜
Δ𝐺 𝑜 = −𝑧𝐹𝐸𝑐𝑒𝑙𝑙
81
As a consequence of the formula proved above, we can use 𝐸𝑐𝑒𝑙𝑙
𝑜
to determine if a
reaction is spontaneous or not.

A reaction is considered spontaneous when Δ𝐺 < 0 → 𝐸𝑐𝑒𝑙𝑙

𝑜
>0

• Spontaneous: 𝐸𝑐𝑒𝑙𝑙
𝑜
>0
• Equilibrium: 𝐸𝑐𝑒𝑙𝑙 = 0
𝑜

• Non-spontaneous: 𝐸𝑐𝑒𝑙𝑙
𝑜
<0

12.6. Nernst Equation

The Nernst equation is an equation that relates the reduction potential of an
electrochemical reaction to the standard electrode potential of the chemical species
undergoing reduction and oxidation.
Δ𝐺 = Δ𝐺 𝑜 + 𝑅𝑇 ln 𝑄
𝑜
−𝑧𝐹𝐸𝑐𝑒𝑙𝑙 = −𝑧𝐹𝐸𝑐𝑒𝑙𝑙 + 𝑅𝑇 ln 𝑄

𝑜
𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − ln 𝑄
𝑧𝐹
Converting into a logarithm of base 10 and simplifying, we obtain:

𝑜
0.0592 𝑉
𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑒𝑙𝑙 − log 𝑄
𝑧
If the reaction is at equilibrium, then we obtain the expression:

𝑜
𝑅𝑇
𝐸𝑐𝑒𝑙𝑙 = ln 𝐾
𝑧𝐹
𝑄=𝐾
{
𝐸𝑐𝑒𝑙𝑙 = 0

12.7. Batteries
There are two types of cells: primary and secondary. Primary cells are non-
rechargeable and secondary cells are rechargeable. Cells are closed systems.

Primary cells are non-rechargeable, because the reaction carried out inside it is
non-reversible. Whereas secondary cells are rechargeable because the reaction
inside it can be reversed, by passing electricity, through the cell (charging).

Another type of cell is a flow battery or fuel cell. A fuel cell is an electrochemical
cell that converts the chemical energy from a fuel into electricity through an
electrochemical reaction. Examples of fuel cells are the hydrogen fuel cell, the
methanol fuel cell or the ethanol fuel cell. Fuels cells are open systems – reactants
flow in and products flow out.

82
 12.7.1. Alkaline cell
An alkaline cell is a type of non-rechargeable cell (primary cell) with manganese
dioxide and zinc electrodes

Oxidation:
𝑍𝑛(𝑠) + 2𝑂𝐻 − (𝑎𝑞) → 𝑍𝑛(𝑂𝐻)2 (𝑠) + 2𝑒 −

Reduction:
3𝑀𝑛𝑂2 (𝑠) + 𝐻2 𝑂(𝑙) + 2𝑒 − → 𝑀𝑛2 𝑂3 (𝑠) + 2𝑂𝐻 − (𝑎𝑞)

Overall reaction:
3𝑀𝑛𝑂2 (𝑠) + 𝑍𝑛(𝑠) + 𝐻2 𝑂(𝑙) → 𝑀𝑛2 𝑂3 (𝑠) + 𝑍𝑛(𝑂𝐻)2 (𝑠)

Cell:

𝑍𝑛(𝑠)|𝑍𝑛2+ (𝑠)||𝑀𝑛𝑂2 (𝑠)|𝑀𝑛2 𝑂3 (𝑠)

𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸 𝑜 (𝑀𝑛𝑂2 |𝑀𝑛2 𝑂3) − 𝐸 𝑜 (𝑍𝑛2+ |𝑍𝑛)

83
 12.7.2. Leclanché dry cell
The Leclanché dry cell is a non-rechargeable (primary cell) with zinc and
manganese dioxide electrodes in a ammonium chloride electrolyte.

Oxidation:
𝑍𝑛(𝑠) → 𝑍𝑛2+ (𝑎𝑞) + 2𝑒 −

Reduction:
2𝑀𝑛𝑂2 (𝑠) + 𝐻2 𝑂(𝑙) + 2𝑒 − → 𝑀𝑛2 𝑂3 (𝑠) + 2𝑂𝐻 −

Acid/base reaction:
𝑁𝐻4+ (𝑎𝑞) + 𝑂𝐻 − (𝑎𝑞) → 𝑁𝐻3 (𝑔) + 𝐻2 𝑂(𝑙)

Precipitation reaction:

𝑁𝐻3 (𝑔) + 𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑙 − (𝑎𝑞) → [𝑍𝑛(𝑁𝐻3 )2 ]𝐶𝑙2 (𝑠)

Overall reaction:
𝑍𝑛(𝑠) + 2𝑀𝑛𝑂2 (𝑠) + 𝐻2 𝑂(𝑙)
→ 𝑍𝑛2+ (𝑎𝑞) + 𝑀𝑛2 𝑂3 (𝑠) + 2𝑂𝐻 − (𝑎𝑞)

Cell:

𝑍𝑛(𝑠)|𝑍𝑛2+ (𝑎𝑞)||𝑀𝑛𝑂2 (𝑠)|𝑀𝑛2 𝑂3 (𝑠)

𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸 𝑜 (𝑀𝑛𝑂2 |𝑀𝑛2 𝑂3) − 𝐸 𝑜 (𝑍𝑛2+ |𝑍𝑛)

12.7.3. Silver-zinc cell

A silver-zinc battery is a type of rechargeable battery (secondary cell) with silver
oxide and zinc oxide as electrodes and an alkaline electrolyte.

Oxidation:
𝑍𝑛(𝑠) + 2𝑂𝐻 − (𝑎𝑞) → 𝑍𝑛𝑂(𝑠) + 𝐻2 𝑂(𝑙) + 2𝑒 −

Reduction:
𝐴𝑔2 𝑂(𝑠) + 𝐻2 𝑂(𝑙) + 2𝑒 − → 2𝐴𝑔(𝑠) + 2𝑂𝐻 − (𝑎𝑞)

Overall reaction:
𝑍𝑛(𝑠) + 𝐴𝑔2 𝑂(𝑠) → 𝑍𝑛𝑂(𝑠) + 2𝐴𝑔(𝑠)

Cell:
𝑍𝑛(𝑠)|𝑍𝑛𝑂(𝑠)||𝐾𝑎𝑂𝐻||𝐴𝑔2 𝑂(𝑠)|𝐴𝑔(𝑠)
𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸 𝑜 (𝐴𝑔2 𝑂|𝐴𝑔) − 𝐸 𝑜 (𝑍𝑛𝑂|𝑍𝑛) = 1.8 𝑉

84
 12.7.4. Lead-acid cell
A lead-acid cell is a type of rechargeable cell (secondary cell) with lead and lead
oxide electrodes in sulphuric acid.

Oxidation:
𝑃𝑏(𝑠) + 𝐻2 𝑆𝑂4 (𝑎𝑞) → 𝑃𝑏𝑆𝑂4 (𝑎𝑞) + 2𝐻 + (𝑎𝑞) + 2𝑒 −

Reduction:
𝑃𝑏𝑂2 (𝑠) + 𝐻2 𝑆𝑂4 (𝑎𝑞) + 2𝐻 + (𝑎𝑞) + 2𝑒 − → 𝑃𝑏𝑆𝑂4 (𝑎𝑞) + 2𝐻2 𝑂(𝑙)

Overall equation:
𝑃𝑏(𝑠) + 𝑃𝑏𝑂(𝑠) + 2𝐻2 𝑆𝑂4 (𝑎𝑞) ⇌ 2𝑃𝑏𝑆𝑂4 (𝑎𝑞) + 2𝐻2 𝑂(𝑙)

Cell:

𝑃𝑏(𝑠)|𝑃𝑏 2+ (𝑎𝑞)||𝑃𝑏𝑂2 (𝑠)|𝑃𝑏 2+ (𝑎𝑞)

𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸 𝑜 (𝑃𝑏𝑂2 |𝑃𝑏 2+) − 𝐸 𝑜 (𝑃𝑏 2+|𝑃𝑏) = 1.71 − (−0.28) = 2.02 𝑉

85
 12.7.5. Nickel-cadmium cell
The nickel-cadmium cell is a type of rechargeable battery (secondary cell) using
nickel oxide hydroxide and metallic cadmium as electrodes.

Oxidation:
𝐶𝑑(𝑠) + 2𝑂𝐻 − (𝑎𝑞) → 𝐶𝑑(𝑂𝐻)2 (𝑠) + 2𝑒 −

Reduction:
2𝑁𝑖𝑂(𝑂𝐻)(𝑠) + 2𝐻2 𝑂(𝑙) + 2𝑒 − → 2𝑁𝑖(𝑂𝐻)2 (𝑠) + 2𝑂𝐻 − (𝑎𝑞)

Overall reaction:
𝐶𝑑(𝑠) + 2𝑁𝑖𝑂(𝑂𝐻)(𝑠) + 2𝐻2 𝑂(𝑙) → 2𝑁𝑖(𝑂𝐻)2 (𝑠) + 𝐶𝑑(𝑂𝐻)2 (𝑠)
Cell:

𝐶𝑑(𝑠)|𝐶𝑑2+ (𝑠)||𝑁𝑖𝑂(𝑂𝐻)(𝑠)|𝑁𝑖 2+ (𝑠)

𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸 𝑜 (𝑁𝑖𝑂(𝑂𝐻)|𝑁𝑖 2+ ) − 𝐸 𝑜 (𝐶𝑑2+ |𝐶𝑑)

86
 12.7.6. Lithium-ion battery
A lithium-ion battery is a type of rechargeable cell (secondary cell) with lithium
cobalt oxide and graphite electrodes.

Oxidation:
𝐿𝑖𝐶𝑜𝑂2 (𝑠) ⇌ 𝐶𝑜𝑂2 (𝑠) + 𝐿𝑖 + (𝑎𝑞) + 𝑒 −

Reduction:
𝐶(𝑠) + 𝐿𝑖 + (𝑎𝑞) + 𝑒 − ⇌ 𝐿𝑖𝐶(𝑠)

Overall equation:
𝐿𝑖𝐶𝑜𝑂2 (𝑠) + 𝐶(𝑠) ⇌ 𝐶𝑜𝑂2 (𝑠) + 𝐿𝑖𝐶(𝑠)

Cell:
𝐿𝑖𝐶𝑜𝑂2 (𝑠)|𝐿𝑖 + (𝑎𝑞)||𝐿𝑖 + (𝑎𝑞)|𝐿𝑖𝐶(𝑠)
𝑜
𝐸𝑐𝑒𝑙𝑙 = 𝐸 𝑜 (𝐿𝑖 + |𝐿𝑖𝐶) − 𝐸 𝑜 (𝐿𝑖𝐶𝑜𝑂2 |𝐿𝑖 + )

87
 12.7.7. Fuel cell
A fuel cell is an electrochemical cell that converts
the chemical energy from a fuel into electricity
through an electrochemical reaction. Examples of
fuel cells are the hydrogen fuel cell, the methanol
fuel cell or the ethanol fuel cell. Fuels cells are
open systems – reactants flow in and products
flow out.

At the anode:
𝐻2 (𝑔) + 2𝑂𝐻 − (𝑎𝑞) → 2𝐻2 𝑂(𝑙) + 2𝑒 −

At the cathode:
𝑂2 (𝑔) + 2𝐻2 𝑂(𝑙) + 4𝑒 − → 4𝑂𝐻 − (𝑎𝑞)

Overall equation:
2𝐻2 (𝑔) + 𝑂2 (𝑔) → 2𝐻2 𝑂(𝑙)

12.8. Corrosion
Corrosion is a natural process, which converts a refined metal to a more
chemically-stable form, such as its oxide. It is the gradual destruction of materials
(usually metals) by chemical and/or electrochemical reaction with their
environment.

Neutral solution:
𝑂2 (𝑔) + 𝐻2 𝑂(𝑙) + 4𝑒 − → 4𝑂𝐻 − (𝑎𝑞)
2𝐹𝑒(𝑠) → 2𝐹𝑒 2+ (𝑎𝑞) + 4𝑒 −

Overall:

2𝐹𝑒(𝑠) + 𝑂2 (𝑔) + 2𝐻2 𝑂(𝑙) → 2𝐹𝑒 2+ (𝑎𝑞) + 4𝑂𝐻 − (𝑎𝑞)

Acidic solution:
𝑂2 (𝑔) + 4𝐻 + (𝑎𝑞) + 4𝑒 − → 4𝐻2 𝑂(𝑙)

2𝐹𝑒(𝑠) → 2𝐹𝑒 2+ (𝑎𝑞) + 4𝑒 −

Overall:

2𝐹𝑒(𝑠) + 𝑂2 (𝑔) + 4𝐻 + (𝑎𝑞) → 2𝐹𝑒 2+ + 4𝐻2 𝑂(𝑙)

In order to protect metal from corrosion, magnesium sacrificial anodes are used.
They are small cylindrical bars of magnesium attached to the steel ship, which
provide cathodic protection against corrosion.

88
 12.9. Electrolysis
A galvanic or voltaic cell is used to generate electricity from chemical reactions, by
converting chemical energy into electrical energy. However, electrolytic cells use
electricity to carry out non-spontaneous chemical reactions, by converting electrical
energy into chemical energy.

Voltaic cell:

𝑍𝑛(𝑠) + 𝐶𝑢2+ (𝑎𝑞) → 𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑢(𝑠) 𝐸 𝑜 = 1.103 𝑉

Electrolytic cell:

𝑍𝑛2+ (𝑎𝑞) + 𝐶𝑢(𝑠) → 𝑍𝑛(𝑠) + 𝐶𝑢2+ (𝑎𝑞) 𝐸 𝑜 = −1.103 𝑉

89