Chapter I: GENERAL CHEMISTRY

Kim Anh NGUYEN, BPharm, PhD

nkimanh@uhsvnu.edu.vn
 Outline
• Atoms
• Chemical bonds
• Chemical equilibria in aqueous solutions
• Dissolution of electrolytes
• Redox reactions
• Metal complexes
Atoms
 Atomic Theory of Matter
“All matter is composed of small
particles called atoms”

Ancient Greek “átomos” = “indivisible”

• A compound is a type of matter

composed of atoms of two or more
John Dalton (1766–1844)
elements chemically combined in
fixed proportions
• A chemical reaction consists of the
rearrangement of the atoms present
in the reacting substances to give
new chemical combinations
The identity of an element

Atomic number (Z)

the number of protons

Mass number (A)

the total number of
protons and neutrons
 Isotopes
Atoms whose nuclei have the same atomic number but
different mass numbers

Carbon-11: artificial radioactive isotope

Atomic mass

Atomic mass  Mass number

(mass of the protons and neutrons)

The SI unit of mass is the kilogram

 Atomic mass
Atomic mass is often expressed in the non-SI unit dalton
(Da) or atomic mass unit (amu)

1 amu = 1/12 of the mass of a free carbon-12 atom

Relative atomic mass (atomic weight): ratio of

the mass of the atom to the atomic mass unit
 Standard atomic weight
The weighted arithmetic mean of the relative atomic
masses of all isotopes of that element weighted by each
isotope's abundance on Earth.

Example: Calculate the standard atomic weight of Cl?

https://www.degruyter.com/document/doi/10.1515/pac-2019-0603/html
 Structure of Atoms
Rutherford‘s model (planetary model)

Most of the mass of the atom

(> 99.95%) is concentrated in
a positively charged nucleus,
around which the negatively
charged electrons move.
The nucleus occupies only a
very small portion of the
space of the atom.
 Structure of Atoms
Bohr’s model (for hydrogen)
An electron can have only
specific energy values
(energy levels) in an atom.

The energy of an electron:

ℜ: Rydberg constant
When n inscreases, h : Planck constant
the electron’s energy increases. c : speed of light in vacuum
n : energy levels (1,2,3…)
 Structure of Atoms
Bohr’s model (for hydrogen)
 Structure of Atoms
Bohr’s model (for hydrogen)

The emission of light: an electron

undergoes a transition from an
upper to lower energy level.

Atomic Emission Spectra

flames of Li & Na

Emission spectrum of hydrogen

 Structure of Atoms
Bohr’s model (for hydrogen)

Bohr’s theory established the concept of atomic

energy levels and explained the atomic spectrum
of hydrogen.

It was unsuccessful in accounting for the details

of atomic structure and in predicting energy
levels for atoms other than hydrogen.
 Structure of Atoms
(quantum mechanics)
Wave-particle duality of submicroscopic particles

Schrödinger’s equation
The probability of finding the particle
(electron) within a region of space

Erwin Schrödinger
Hydrogen atom (1887 – 1961)
 Structure of Atoms
(quantum mechanics)
Atomic radius
The maximum in the radial distribution function of the
outer shell of the atom

Argon has a radius Argon atom

of … pm
 Structure of Atoms
Atomic orbitals
The regions of space where there is high probability
(>95%) of finding the electrons.
s orbitals: Spherical shape
 Structure of Atoms
Atomic orbitals p orbitals: Two lobes arranged
along a straight line

Three p orbitals in each p

subshell are set at right
angles to each other
 Structure of Atoms
Atomic orbitals d orbitals: Complicated shapes

From the 3rd shell

Five d orbitals in
each d subshell
 Structure of Atoms
Atomic orbitals
https://www.youtube.com/watch?v=8ROHpZ0A70I&ab_channel=TED-Ed
 Electron configuration
A particular distribution of electrons
into shells and subshells
Shells n=1 n=2 n=3 n=4
Subshells 1s 2s 2p 3s 3p 3d 4s 4p 4d 4f
Number of orbitals in 1 1 3 1 3 5 1 3 5 7
subshells
Maximum number of 2 2 6 2 6 10 2 6 10 1
electrons in subshells 4
Maximum number of 2 8 18 32
electrons in shells
 Electron configuration
Orbital diagram
A diagram to show how the orbitals of a subshell are
occupied by electrons

Example: Boron atom (Z = 5): 1s22s22p1

 Electron configuration
Increasing order of electron
energy in subshells:
 Electron configuration

Pauli exclusion principle: An orbital can hold at most two

electrons, and only if the electrons have opposite spins.
 Electron configuration
Hund’s rule: the lowest-energy arrangement of electrons
in a subshell is obtained by putting electrons into
separate orbitals of the subshell with the same spin
before pairing electrons.

Example:
Carbon atom (Z = 6) with the ground-
state configuration 1s22s22p2.
Three possible orbital diagrams are
given. Which one is correct?
 Electron configuration
Exercise 1: Which of the following orbital diagrams or
electron configurations are possible?

Exercise 2: Write the electron configuration and

orbital diagram of P (Z = 15)
 Valence electrons

Valence shell = outermost shell

Valence electrons

• Valence electrons are involved in chemical reactions

• Similarities among the valence shells
 similarities of the chemical properties (groups in the
periodic table).
 A tabular arrangement of elements in rows and columns,
highlighting the regular repetition of properties of the elements
 Vertical column contains elements with the same number of
outermost shell electrons

Elements in the same column tend to have similar chemical properties

Chemical Bonding
 IONIC BONDS
A chemical bond formed by the electrostatic attraction
between positive and negative ions

noble-gas configurations

Na+ is surrounded by six Cl−,

and every Cl− by six Na+
 IONIC BONDS

Coulomb’s law
The potential energy obtained in bringing two charges
Q1 and Q2, initially far apart, up to a distance r apart is
directly proportional to the product of the charges and
inversely proportional to the distance between them

E: potential energy
k: 8.99 × 109 J.m/C2
+e: 1.602 × 10-19 C
(J) -e: - 1.602 × 10-19 C
r: distance between the
nuclei of the ions (m)
 IONIC BONDS

Coulomb’s law
Calculate the energy obtained when the a Na+ ion
and a Cl- ion come together to a distance of 282 pm.

The energy is released

kJ/mol ?
 COVALENT BONDS
Covalent bond: a chemical bond formed by the sharing
of a pair of electrons between two atoms

• As the atoms approach, the electrons are attracted

simultaneously by the positive charges of the two
nuclei, holding the atoms together.
• As the atoms get close enough, the repulsion of the
nuclei becomes larger than the attraction of electrons
for nuclei.
 COVALENT BONDS

The distance between nuclei at the minimum

energy is called the bond length
 THE OCTET RULE

Atoms in molecules tend to have eight electrons in their

valence shells.

Lewis Formula

(A formula using dots to represent valence electrons)

 THE OCTET RULE: EXCEPTIONS

• Molecules with an atom having < 8 valence electrons

• Molecules with an atom having > 8 valence electrons

From the third period on, the

elements also have d orbitals,
which may be used in bonding
sp3d hybridation
 MULTIPLE BONDS

A double bond is a covalent bond in which two pairs of

electrons are shared by two atoms.

A triple bond is a covalent bond in which three pairs of

electrons are shared by two atoms.
 POLAR COVALENT BONDS

-

Electronegativity of O, Cl, C, H: 3.5; 3.0; 2.5; 2.1

 COORDINATE COVALENT BONDS
A bond formed when both electrons of the bond are
donated by one atom
 BOND STRENGTH and BOND LENGTH
The bond (dissociation) energy for a diatomic molecule:
the standard enthalpy change for the reaction:
 BOND STRENGTH and BOND LENGTH

Bond Bond Energies (kJ/mol)

H-F 569
H-Cl 432
H-Br 370
H-I 295

When one atom bonds to various atoms in a group,

the bond strength typically decreases as we move
down the group (the bond length is proportional to
the atomic radius)
 BOND STRENGTH and BOND LENGTH

the bond strength increases, the bond length decreases

 BOND STRENGTH and BOND LENGTH

Triple bonds are stronger and shorter than double bonds and
single bonds between the same two atoms
Chemical equilibria in aqueous solutions
 REVERSIBLE REACTIONS
Many reactions never result in complete conversion of
reactants to products.

Reversible reactions proceed to a state of chemical

equilibrium in which the ratio of concentrations of reactants
and products is constant. 47
 REVERSIBLE REACTIONS

The amounts of reactants and products are constant

because the rates of the forward and reverse reactions
are exactly the same.

48
 EQUILIBRIUM CONSTANT

Equilibrium constant expressions describe the concentration

relationships among reactants and products at equilibrium.

[C]𝑐 [D]𝑑
𝐾𝑒𝑞 =
[A]𝑎 [B]𝑏

[A], [B], [C], [D]: molar concentrations if A, B, C, D represent

dissolved solutes
a, b, c, d: whole numbers required to balance the equation

equilibrium constants are unitless 49

 EQUILIBRIUM CONSTANT

[C]𝑐 [D]𝑑
𝐾𝑒𝑞 =
[A]𝑎 [B]𝑏

Products

Concentration
Concentration

Reactants

Products
Reactants

Time

Keq provides no information about the reaction rate.

(HOW MUCH, NOT HOW FAST) 50
 EQUILIBRIUM CONSTANT
Heterogeneous Equilibria
• Homogeneous equilibria: all the components are in solution
• Heterogeneous equilibria: involves two phases

(s) (aq) (aq)

The “concentration” of a pure solid/liquid (undissolved) is unity.

When any amount of the solid is already present, adding more

solid does not bring about a shift in the equilibrium
51
 MANIPULATING EQUILIBRIUM CONSTANTS

Stepwise and overall Keq

The Keq for a reaction that is the sum of two or more reactions is
equal to the product of the Keq for the individual reactions.
[Ag NH3 + ൧
𝐾1 =
Ag + NH3
[Ag NH3 2 + ൧
𝐾2 =
Ag NH3 + NH3

+ + +
[Ag NH3 ൧ [ Ag NH3 2 ൧ [ Ag NH3 2 ൧
𝐾3 = 𝐾1 × 𝐾2 = +
× +
=
Ag NH3 Ag NH3 NH3 Ag + NH3 2
52
 MANIPULATING EQUILIBRIUM CONSTANTS

Keq of the reverse reaction

[Ag NH3 2 + ൧
𝐾3 =
Ag + NH3 2

Ag + NH3 2
𝐾4 = 𝐾3 −1 = +
[Ag NH3 2
൧

53
 LE CHÂTELIER’S PRINCIPLE

The position of chemical equilibrium

always shifts in a direction that tends to
relieve the effect of an applied stress.

French chemist
Henry-Louise Le Châtelier
(1850–1936)

54
 LE CHÂTELIER’S PRINCIPLE

Concentrations
Introducing an additional amount of a reactant/product
to the reaction mixture
 A shift in equilibrium in the direction that tends to
use up the added substance.

Addition of Fe2+ to the solution at equilibrium

 the reaction shifts to the left

Changes in concentrations do not affect the equilibrium constant.

55
 LE CHÂTELIER’S PRINCIPLE
Temperature
• An increase in the temperature of a system  A shift in
equilibrium in the direction that tends to absorb heat

• A decrease in the temperature of a system  A shift in

equilibrium in the direction that tends to release heat

Increase in the temperature

 the reaction shifts to the left

All equilibrium constants are temperature-dependent 56

 LE CHÂTELIER’S PRINCIPLE

Pressure

• An increase in the pressure on a system  A shift in

equilibrium in the direction producing less gas molecules

• A decrease in the pressure on a system  A shift in

equilibrium in the direction producing more gas molecules

Decrease in the pressure on the system favors decomposition

of NO2 into NO and O2  restore the pressure.

All equilibrium constants are temperature dependent 57

TYPES OF EQUILIBRIA IN AQUEOUS SOLUTIONS

• Acid-base dissociation
• Solubility/Precipitation reactions
• Complex formation
• Reduction-oxidation

58
DISSOLUTION AND DISSOCIATION
 SOLUTIONS

Solutions = homogeneous mixtures

Solvent: the component that is present in the greatest quantity

Solutes: other solution components, “dissolved” in the solvent
liquid / gaseous / solid solutions

60
 DISSOLUTION
A substance (solute) dissolves into a solvent and forms a solution.

Interactions (intermolecular forces) between solute particles - solvent

 Each molecule/ion of the solute separates from each other,
surrounded by solvent molecules and enters the solution.
This process is called solvation or hydration (when solvent = water)

Glucose(s) Glucose(aq)

61
 DISSOCIATION

When an ionic compound dissolves, forming cations

and anions, this process is referred to as dissociation.
62
Clustering of water dipoles around the surface of the ionic crystal
If these ion–dipole forces of attraction > the interionic forces of
attraction in the crystal, dissolution-dissociation will occur.
 Formation of hydrated ions in solution 63
 DISSOCIATION CONSTANT
• Compounds that dissociate completely: strong electrolytes
• Compounds that dissolve but dissociate partially: weak electrolytes

H3 O+ [CH3 COO− ]
𝐾𝑎 = (the acid dissociation constant)
[CH3 COOH]

NH4 + [OH− ] (the base dissociation constant)

𝐾𝑏 =
[NH3 ]

64
DISSOCIATION CONSTANT

65
 SOLUBILITY EQUILIBRIA

The solution is saturated when the

rates of dissolution and
crystallization become equal.

The concentration of a
saturated solution is called the
solubility of the solute in the
given solvent, at a given
temperature.

66
 SOLUBILITY-PRODUCT CONSTANT
Calculation of solubility A slightly soluble substance has a definite
solubility at a given temperature.

Example: The Ksp of AgCl at 25 oC is 1.0 × 10-10.

Calculate the concentrations of Ag+ and Cl− in a saturated solution
of AgCl, and the solubility of AgCl.

When AgCl dissociates, equal amounts of Ag+ and Cl- are formed.
Let s represent the molar solubility of AgCl.
𝐾𝑠𝑝 = Ag + . [Cl− ]
s s s (M)

Ag + = Cl− = 𝑠 = 𝐾𝑠𝑝 = 1.0 × 10−10 = 1.0 × 10−5 (𝑀)

67
 SOLUBILITY-PRODUCT CONSTANT
Calculation of solubility The solubility product must be
exceeded for precipitation to occur.

Example: What must be the concentration of added Ag+ to just

start precipitation of AgCl in a 1.0 × 10−3 M solution of NaCl?

Precipitation: [Ag+].[Cl-]> Ksp AgCl

 Ag + . (1.0 × 10−3 ) > 1.0 × 10−10

1.0 × 10−10
 Ag + >
1.0 × 10−3

 Ag + > 1.0 × 10−7 (𝑀)

68
Redox reactions
 REDOX REACTIONS
A reduction–oxidation reaction (redox reaction) occurs
between a reducing and an oxidizing agent

(Ox1 is reduced to Red1, and Red2 is oxidized to Ox2)

• A reducing agent will tend to give up (an) electron(s)

and be oxidized to a higher oxidation state.
• An oxidizing agent will tend to take on (an) electron(s)
and be reduced to a lower oxidation state

70
 REDOX REACTIONS

A redox reaction can be written as two half-reactions.

• Oxidation: electron donating half-reaction
• Reduction: electron accepting half-reaction

half reactions

71
 GALVANIC CELLS

The half reactions take place in separate locations (half cells).

Galvanic (voltaic) cells: electrochemical cells in which

spontaneous redox reactions produce electricity.
72
 GALVANIC CELLS

• Anode: the electrode at which oxidation occurs

• Cathode: the electrode at which reduction occurs
• Salt bridge: allows ion transfer between the half cells

73
Reactivity series of metals

74
E0 (V)

75
 ELECTRODE POTENTIAL - CELL POTENTIAL
Electrode potential: the tendency of the ions to take on
electrons (reduction potentials.)

Cell potential: the difference between the potentials of

the two electrodes. 𝐸 = 𝐸 −𝐸
𝑐𝑒𝑙𝑙 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 𝑎𝑛𝑜𝑑𝑒

Standard cell potential: the cell potential measured under

standard conditions (a = 1 for solutions, 1 atm for gases, at
25°C). 0 0 0
𝐸 𝑐𝑒𝑙𝑙 = 𝐸 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 −𝐸 𝑎𝑛𝑜𝑑𝑒

Cell potential is always positive.

76
ELECTRODE POTENTIAL - CELL POTENTIAL

𝐸 0 𝑐𝑒𝑙𝑙 = 𝐸 0 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸 0 𝑎𝑛𝑜𝑑𝑒

= 𝐸 0 𝐶𝑢2+ /𝐶𝑢 − 𝐸 0 𝑍𝑛2+ /𝑍𝑛

= 0.34 𝑉 − −0.76 𝑉

= 1.10 𝑉 77
E0 (V)

78
 THE STANDARD HYDROGEN ELECTRODE

No method can determine the absolute electrode potentials,

because all voltage-measuring devices determine only difference
in potentials between two electrodes. (𝐸𝑐𝑒𝑙𝑙 = 𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 − 𝐸𝑎𝑛𝑜𝑑𝑒 )

Relative electrode potentials, measured versus a common

reference electrode: the standard hydrogen electrode

𝐸𝐻 + /𝐻2 = 0.000 𝑉 = 𝐸𝑎𝑛𝑜𝑑𝑒

𝐸𝑐𝑎𝑡ℎ𝑜𝑑𝑒 = 𝐸𝑐𝑒𝑙𝑙

79
 THE NERNST EQUATION
• determination of potential under
non-standard conditions.
• relationships between potential
and concentrations of the species.

(half reaction)

Walther Nernst
𝑅𝑇 (𝑎 ) 𝑦
winner of the 1920 𝑅𝑒𝑑
Nobel Prize in Chemistry 𝐸 = 𝐸0 − 𝑙𝑛
𝑛𝐹 (𝑎𝑂𝑥 )𝑚

E: reduction potential at the specific concentrations

R: gas constant (8.3143 V C K-1 mol-1)
T: absolute temperature (Kelvin)
n: number of electrons involved in the half-reaction
F: Faraday constant (96,487 C mol−1)
80
a: activity
 THE NERNST EQUATION

For convenience, concentrations are usually used in place of activities:

𝑅𝑇 [𝑅𝑒𝑑] 𝑦
𝐸 = 𝐸0 − 𝑙𝑛
𝑛𝐹 [𝑂𝑥]𝑚

𝑦
0.05916 [𝑅𝑒𝑑]
At 25 oC: 𝐸 = 𝐸0 − 𝑙𝑜𝑔
𝑛 [𝑂𝑥]𝑚

Example: A solution is 10-3 M in Cr2O72- and 10-2 M in Cr3+. If the pH is

2.0, what is the potential of the half-reaction at 298K? (E0 = 1.33 V)
81
THE NERNST EQUATION

82
THE NERNST EQUATION

𝑅𝑇 𝑃𝐻2
𝐸 = 𝐸0 − 𝑙𝑛 + 2
2𝐹 [𝐻 ]

𝑅𝑇 1
𝐸 = 𝐸0 − 𝑙𝑛
2𝐹 [𝑆𝑛2+ ]

83
METAL COMPLEXES
 STRUCTURE
Coordination compounds (complexes)
A central metal atom/ion is surrounded by several ligands
Lewis acid Lewis bases
electron-pair receptor electron-pair donors

inner-sphere complex: the ligands are attached directly to a central metal ion
outersphere complexes: occur where cation/anion associate in solution.
 CLASSIFICATION
Ligands having only one point of attachment: monodentate
Ligands having more than one point of attachment: polydentate
• two points of attachment: bidentate
• three points of attachment: tridentate
• four points of attachment: tetradentate
…
CLASSIFICATION

87
CLASSIFICATION

Polydentate ligand
Ethylenediaminetetraacetic acid
(EDTA)

88
 CHELATES
Chelating agents (chelators): compounds capable of
binding metal ions to form complex ring-like structure
called ‘chelates’.
Chelating agents possess “ligand” binding atoms: O, N, S

Mn+

1:1

EDTA

EDTA forms a very stable, cage-like structure around the metal ion
3D STRUCTURE
The heme group
The central Fe(II) atom is liganded
to the four N atoms of the
porphyrin ring, to a His side chain
and to O2.
The six ligands are arranged at the
corners of an octahedron centered
on the Fe ion.
 COMPLEX FORMATION EQUILIBRIA

[Ag NH3 + ൧
𝐾1 =
Ag + NH3
[Ag NH3 2 + ൧
𝐾2 =
Ag NH3 + NH3

[Ag NH3 + ൧ [Ag NH3 2 + ൧ [Ag NH3 2 + ൧

𝐾3 = 𝐾1 × 𝐾2 = +
× +
=
Ag NH3 Ag NH3 NH3 Ag + NH3 2

91
 COMPLEX FORMATION EQUILIBRIA

[Ag NH3 2 + ൧
𝐾3 =
Ag + NH3 2

K3 : stability constant (Ks) or formation constant (Kf) of Ag(NH3)2+

Ag + NH3 2
𝐾4 = 𝐾3 −1 = +
[Ag NH3 2
൧

K4 : instability constant (Ki) or dissociation constant (Kd) of Ag(NH3)2+

92
 COMPLEXOMETRIC TITRATIONS

Determination of water total hardness

 Measurement of the amount of calcium and magnesium ions
dissolved in water.

Ca2+ + EDTA4- → CaEDTA2-

At pH = 10
Mg2+ + EDTA4- → MgEDTA2-

• Water samples
• Titrant: 0.01 M EDTA solution
• Ammonia pH 10.0 buffer
• Indicator: Eriochrome Black T
https://www.youtube.com/watch?v=akRcLMQUxm4&t=414s&ab_channel=chatzida 93
 EDTA solution

Water sample
 Further reading

• Fundamental concepts and chemical laws

✓ The Law of Conservation of Mass
✓ The Law of Constant Composition
✓ The Law of Multiple Proportions

https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_Chemistry_(Zumdahl_
and_Decoste)/02%3A_Atoms_Molecules_and_Ions/2.02_Fundamental_Chemical_Laws