Chuong 1. GIOI THIEU CHUNG VE HOA HỌC BE MAT TIEP XUC- TTTMai (part 2) -HV

CHAPTER 1
INTRODUCTION:
SURFACE & INTERFACE
SCIENCE (part 2)
Trần Thụy Tuyết Mai
P.113B2 – Physical-Chemistry & Analytic Division – CHEM. ENG.
tuyetmai@hcmut.edu.vn HCMUT-VNU 11
Heterogeneous interfaces
• Molecular interactions
• Classification of interfacial surface
• Solid-solid interface
• Solid-liquid interface
• Gas-solid interface
• Liquid-liquid interface
tuyetmai@hcmut.edu.vn 2
Molecular Interactions
• Molecular interactions are attractive or repulsive
forces between molecules and between non-bonded atoms.
• Molecular interactions are also known as noncovalent interactions,
intermolecular interactions (tương tác liên phân tử), non-bonding
interactions, noncovalent forces & intermolecular forces (lực liên
phân tử).
• Molecular Interactions are between molecules, and between atoms
that are not linked by bonds.
• Molecular interactions include cohesive, adhesive & repulsive forces
between molecules.
• Noncovalent interactions
Non-covalent interactions are weak interactions between atoms
or molecules where no chemical reaction takes place. Because
no formation or breaking of chemical bonds is induced, non-
covalent interactions are often called non-bonded interactions.
The non-covalent interactions (~20 kJ/mole) include hydrogen
bond, van der Waals interaction, ionic interactions and
hydrophobic interactions.
Noncovalent interactions are individually weak but
collectively strong.
tuyetmai@hcmut.edu.vn Molecular Interactions 4

Hydrophobic interactions
• When hydrophobic interactions occur, van der Waals interactions
take place between nonpolar compounds and some specific
changes in water structure. Once the molecules come closer to
each other, the number of water particles in contact with them
decreases. Moreover, these structural changes significantly
contribute to free energy.
• Hydrophobic interactions are categorized as solvent-induced
interactions. Hydrophobicity could be characterized by the free
energy of association or alternatively by changes in the free
energy as a function of the distance between a pair of nonpolar
molecules in an aqueous solution.
tuyetmai@hcmut.edu.vn Molecular Interactions 5
Ion-ion interactions (intermolecular

forces, lực liên kết liên phân tử) would be
the attractive force felt between two
oppositely charged ions, that aren't How protein changes shape to allow polar heads (blue)
bonded together yet. to interact with water while non-polar hydrophobic
groups (red) do not interact with the water.
Ionic bonding (intramolecular force, lực
liên kết nội phân tử) is within one
compound, like the bonding of Na+ and
Cl-.
Molecular Interactions
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Modules_(Physical_and_Theoretical_Chemistry)/Physical_Properties_of_Matter/Atomic_an
tuyetmai@hcmut.edu.vn d_Molecular_Properties/Intermolecular_Forces/Hydrophobic_Interactions#:~:text=Hydrophobic%20interactions%20describe%20the%20relations,example%20of%20this%20particular%20interaction. 6
Molecular Interactions for gas-gas
* At low P, the molecules are so far apart for most of the
time that the intermolecular forces play no significant
role è perfect gas.
*At moderate P, (the average separation is only a few
molecular diameters, the attractive forces dominate
* At high P, when the average separation of the
molecules is small, the repulsive forces dominate and
the gas can be expected to be less compressible because
now the forces help to drive the molecules apart.
ü Repulsive forces between molecules assist expansion
ü Attractive forces assist compression.
Fig. The variation of the potential energy of two molecules on their separation. High
positive potential energy (at very small separations) indicates that the interactions b/w
them are strongly repulsive at these distances. At intermediate separations, where the
potential energy is negative, the attractive interactions dominate. At large separations
tuyetmai@hcmut.edu.vn
(on the right) the potential energy is zero and there is no interaction b/w the molecules 9
Molecular interactions in liquids

Molecules in liquids are held to other molecules by
intermolecular interactions, which are weaker than the
intramolecular interactions that hold the atoms together within
molecules and polyatomic ions.
Intermolecular interactions: the forces of interaction between
molecules. These forces are normally weakly attractive.
Q1. Transition phases of pure substances: intermolecular

interactions or intramolecular interactions?
Coulomb’s law & Intermolecular Forces
The potential energy ( E ) of two

oppositely charged particles
(with charges q1 and q2 )
decreases (becomes more
negative) with increasing
magnitude of charge and with
tuyetmai@hcmut.edu.vn decreasing separation ( r ) 14
Intramolecular forces (chemical bonds)
tuyetmai@hcmut.edu.vn https://sciencenotes.org/intramolecular-forces/ 16
• Q2:
Surface Tension, Viscosity, and Capillary Action: intermolecular
interactions or intramolecular interactions?
Molecular interactions in solids???
Types of Solids:
• A molecular solid is a solid that consists of atoms or molecules held together by
intermolecular forces.
• A metallic solid is a solid that consists of positive cores of atoms held together by a
surrounding “sea” of electrons (metallic bonding). è Positively charged atomic cores
are surrounded by delocalized electrons è iron, copper, and silver.
• An ionic solid is a solid that consists of cations and anions held together by the
electrical attraction of opposite charges (ionic bonds, intramolecular forces).
Examples are cesium chloride, sodium chloride, etc.
• A covalent network solid is a solid that consists of atoms held together in large
networks or chains by covalent bonds. Diamond is an example of a three-dimensional
network solid. Every carbon atom in diamond is covalently bonded to four others, so
an entire crystal might be considered an immense molecule. It is possible to have
similar two-dimensional “sheet” and one-dimensional “chain” molecules, with atoms
held together by covalent bonds.
Molecular interactions in solids
Covalence bond: Structures of diamond and graphite Diamond is a three-dimensional network solid;
every carbon atom is covalently bonded to four others. Graphite consists of sheets of carbon atoms
covalently bonded to form a hexagonal pattern of atoms; the sheets are held together by van der
Waals forces.
Solid-solid interface
• Solid-solid interfaces are broadly divided into coherent, semi-
coherent, and incoherent classes.
• A coherent interface is formed when lattice constants of two
phases are nearly identical, and all lattice planes stay
continuous across the interface.
• semi-coherent interfaces, the unequal lattice spacing of the two
phases leads to the buildup of lattice strains relieved by
defects.
• incoherent interface is formed for significant lattice mismatch
and characterized by a highly disordered structure.
• Any interface is usually characterized by its energy normalized
to the surface area (γ) and work of adhesion (Ead).
coherent semi-coherent incoherent
Schematic representation of interface: a coherent, b semi-coherent

and c incoherent; HREM images are taking from Courtesy of G.K.
tuyetmai@hcmut.edu.vn
Dey, BRC, India 28
• Any interface is usually characterized by its energy normalized

to the surface area (γ) and work of adhesion (Ead).
g = (Etot – E(1)bulk – E(2)bulk)/2S
where Etot is the total energy of the supercell with two phases and two
interfaces, Ebulk1 and Ebulk2 are the total energies of the bulk phases with the same number of
atoms as in the supercell with interfaces, and S is the area of one interface.
In contrast to surface energies, which are always positive, γ can be negative, showing that the
bonding between the different elements from the two phases is stronger than the bonding
between the same elements in one of the phases. The positive γ shows that the interface is
thermodynamically unstable, in which case the phases will tend to reduce the interface area
(for example, during annealing).
tuyetmai@hcmut.edu.vn R. Besson et al., Surfaces and Interfaces 33 (2022) 102272 29

• The work of adhesion (Ead) is equal to the work required for
idealized separation of the interface into two phases with the
formation of free surfaces:
Ead= (Etot Eslab1 Eslab2)/2S
where Eslab1 and Eslab2 are the total energies of the slabs with two free surfaces for two
corresponding phases and with the same number of atoms in total as in the supercell with
interfaces. Ead should be negative, otherwise, the two combined phases are unstable with
respect to decomposition into two separate phases. In many situations, such as under
Grand canonical ensemble conditions, it is essential to consider non-stoichiometric
interfaces, such as obtained when the stoichiometry of the slab with interface is different
from the stoichiometry of constituting bulk phases. In this case, the chemical potential of
excessive or deficient elements is added to the right part of Eqs. (11) and (12). The ranges
of accessible chemical potentials are determined from the phase diagrams constructed in
chemical potential space
Coherent solid/solid interfacial energies of alloys

& immiscible liquid/liquid interfacial energies
The total Gibbs energy of the A–B system (G) (including both two bulk and
one interface phases) is expressed as follows:
Where GBI, GBII and GIF are the Gibbs energies of BI, BII and IF, respectively.
The interfacial energy (σIF) is numerically equivalent to the change of
* In a hypothetical A–B system the Gibbs energy of the system (dG) resulting from the changed
containing two bulk phases interface area (dΩ):
(named BI and BII) and an
interface (named IF).
IF is regarded as a two-atomic
layer where the composition of
each layer is identical to that of
its adjoining bulk phase at the
original state.
tuyetmai@hcmut.edu.vn Y. Liu, et al. , Calphad 65 (2019) 225–231 31

Characteristic parameters:
Solid-liquid interfaces o Wetting/contact angle: q
o Wetting degree: cosq
• The classical Young's equation.o Wetting energy: 10-3 - 10-5 cal/cm2
Young's equation is a “macroscopic” equation which does
not concern itself with the microscopic shape of the liquid
surface in the vicinity of the three-phase contact region.
E123 is the difference in total free energy of the
system when at separation distance l and at
infinite distance, per unit area of the flat region.
dAL, dAS, dASL are elements of area on the liquid-air,

substrate-air, and substrate-liquid interfaces of the
macroscopic drop.
θP is the angle that the free liquid surface makes with the
microscopically near the three-phase contact line.

tuyetmai@hcmut.edu.vn L. WHITE, Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, issue 0 (1996), 390-398 33
substrate when the liquid thickness is ≪∼ 10 Å, i.e.,
Solid-liquid interfaces
• Another model was proved by Bangham and Razouk
peSG: monolayer of adsorbate when the contact angle with the surface is zero
peLG: Langmuir-Blodgett monolayer
Fa: the force of adhesion per interface area
Balance of the forces of cohesion with the force

of adhesion at the liquid-liquid interfaces.
Liquid-liquid interface
• The surface tension directly at the interface using a Langmuir-

Blodgett trough.
• A Langmuir–Blodgett trough (LB trough) is an item of
laboratory apparatus that is used to compress monolayers of
molecules on the surface of a given subphase (usually water)
and to measure surface phenomena due to this compression.
It can also be used to deposit single or multiple monolayers on
a solid substrate.
Gas-Solid interfaces
• Langmuir model
• Freundlich mode
• BET model
• xxx

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CHAPTER 1

tuyetmai@hcmut.edu.vn Molecular Interactions 4

tuyetmai@hcmut.edu.vn Molecular Interactions 5

Ion-ion interactions (intermolecular

Molecular interactions in liquids

Q1. Transition phases of pure substances: intermolecular

Coulomb’s law & Intermolecular Forces

The potential energy ( E ) of two

Molecular interactions in solids

Schematic representation of interface: a coherent, b semi-coherent

• Any interface is usually characterized by its energy normalized

g = (Etot – E(1)bulk – E(2)bulk)/2S

tuyetmai@hcmut.edu.vn R. Besson et al., Surfaces and Interfaces 33 (2022) 102272 29

Coherent solid/solid interfacial energies of alloys

tuyetmai@hcmut.edu.vn Y. Liu, et al. , Calphad 65 (2019) 225–231 31

dAL, dAS, dASL are elements of area on the liquid-air,

microscopically near the three-phase contact line.

• Another model was proved by Bangham and Razouk

Balance of the forces of cohesion with the force

• The surface tension directly at the interface using a Langmuir-

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