CHEE2940 Lecture 12 - Surface Chemistry

CHEE2940: Particle Processing

Lecture 12: Colloid & Surface Chemistry I

This Lecture Covers

Introduction to colloid and surface chemistry Surface energy and surface tension

Measurement of surface energy and surface tension

12.1 INTRODUCTION

WHAT ARE THE COLLOIDS?

• .Are objects in the size range of approx. 1 nm

(10-9 m) to 10 microns (10 x 10-6 m). • Can be particles, droplets, bubbles,

macromolecules, flocs, etc.

• Examples: aerosols (inhaler), cement, soil, paint, pesticides.

• Processes: food, pharmaceuticals, ore flotation, water treatment.

COLLOID SCIENCE

• Colloid science deals with colloids.

• Is an interdisciplinary subject, with some prominent areas of physics (e.g. van der

Waals interaction) and physical chemistry (e.g. adsorption).

SURFACE/INTERFACE SCIENCE

• It deals with surfaces (solid-gas, fluid-gas) and interfaces (more general term).

• Focuses on atoms, molecules, and

phenomena occurring at the interface (e.g., surface oxidation, surface forces).

THE LINK BETWEEN COLLOID AND INTERFACE SCIENCE • Features of colloidal systems:

o Large surface-area-to-volume ratio. o For a sphere, 2 3 surface area 6 volume / 6 D D D

π

π

o Surface properties (e.g., adsorption &

o Surface forces are greater in magnitude than body forces.

o Amount of chemicals for surface coverage and modification can be quite small.

• Surface science is closely linked with colloid science.

o Colloid science is inevitably part of surface science.

o The reverse does not necessarily hold.

TOPICS TO BE COVERED IN CHEE 2940

• Surface/Interface characterisation (surface tension, surface energy, hydrophobicity,

wettability, surface charge, etc.)

• Surface properties (adsorption & surfactants). • Surface and colloid forces (van der Waals

forces, electric double layer forces, and non-DLVO forces).

12.2 SURFACE ENERGY AND TENSION

SURFACE ENERGY

• Additional energy associated with the creation of a surface – due to the higher energy state of unfulfilled bonds at the surfaces.

Attractive force holding atoms and molecules together

Individual atom (in solids) or molecule (in liquids)

Extra energy due to these unfilled (broken) bonds

• Surface energy of polar (ionic) substances is

very high (They are soluble in or wetted by water)

Ionic crystal of NaCl salt. Each atom has six nearest neighbors, with cubic (BCC) geometry. The cubic shape of salt (NaCl) crystals is due to the regular arrangement

There are two basic cubic crystal structures: - Body centred cubic (BCC) structure and - Faced centred cubic (FCC) structure.

In the BCC structures, there is one atom at

each corner of the cubic unit cell and one atom in the cell centre. Atom touch along the body

In the FCC structures, there is one atom at

each corner, one atom in each face, and the atoms touch along the face diagonal.

NaCl crystals: Salt has the BBC structure but halite (a NaCl mineral) has the FCC structure.

• Surface energy of apolar substances is low (e.g., graphite – van der Waals bonding,

layering structure – we can use pencils to write on paper)

10 12 10 11 10 10

0001

Space lattice with structured layers (left) and crystal (right) of diamond

Carbon forms

- graphite (layered structures, water repellent) - diamond (hexagonal structures, heavy)

• Chemical bonding (revision from chemistry) o Ionic bonding:

- Electrons are completely transferred from one atom to another.

- Positively and negatively charged ions are formed.

- The oppositely charged ions are attracted to each other by electrostatic forces which are the basis of the ionic bond.

- Example: NaCl

Na (left) loses its one valence electron to Cl (right), producing Na+ (left) and Cl- (right).

- Features of ionic bonds & compounds:

* Ionic bonds form between metals and non-metals

* Ionic compounds dissolve easily in water and other polar solvents.

* Ionic compounds tend to form crystalline solids with high melting temperatures.

o Covalent bonding:

- Occurs when atoms share electrons. - The atoms have a similar tendency for

electrons (generally to gain electrons). - Commonly occurs between non-metals. - Examples: H₂, O₂, H₂O.

- Two sub-types of covalent bonds

* Non-Polar Covalent Bonding: formed when the bonding electrons are equally shared, e.g. H₂.

* Polar Covalent Bonding: formed when electrons are unequally shared between two atoms, e.g. H₂O.

- Features of covalent bonds & compounds: * Covalent bonds form between non-metals. * Covalent compounds have low solubility in water and other polar solvents.

* Covalent compounds can form various substances (crystalline solids, liquids and gases).

SURFACE and INTERFACIAL TENSIONS • Is the surface (interfacial) energy of the

air-liquid (air-liquid-air-liquid) interface.

• Is also equal to the force (per unit length)

acting parallel to the surface which tends to cause the surface area to contract.

• For fluid-liquid interfaces, interfacial energy and surface tension are two different names for the same thing.

• Units:

o For surface/interfacial energy:

2 2

J N m N

Surface energy = = =

m m m

⋅

o For surface/interfacial tension:

N Surface tension =

• Examples: Interface tension Liquid Water Surface tension Liquid Air

12.3 MEASUREMENT OF INTERFACE ENERGY AND TENSION

• Measurement of surface and interfacial tension is easy.

• Precise measurement of surface and

interfacial energy between the solid and fluid phases can be problematic because solid

surfaces are not morphologically and chemically uniform.

• The measurement principle is based on the fact that the system of interfaces always

minimises its free energy (surface energy and potential energy).

o Examples:

- Small bubbles and droplets are spherical (Of the objects with the same volume, sphere

- Contact angle between a solid and a liquid surface presents the geometry with the

lowest surface energy. γ_wa Air Mineral Water γwm γma θ

MEASUREMENT OF SURFACE and INTERFACIAL TENSIONS

1) Capillary Rise Method

It uses the rise of the liquid up in a narrow capillary. Laplace pressure: P 2 R

γ

γ

θ

θ

Hydrostatic pressure:

ρ

ρ

g … acceleration due to gravity Balancing the pressure gives

2 gh R

γ ρ

ρ

γ

θ

Meniscus corrections: 1 ... 2 3 ghr r h

ρ

γ

It comes from the exact solution to Young-Laplace Equation:

(

)

(

)

ρ

γ

where the primes describe the derivatives with respect to the radial coordinate x.

Differential Capillary Rise Method for

eliminating reference to the flat surface of the liquid reservoir. 1 1 2 2 2 2 gh r gh r

ρ

ρ

γ

(

)

ρ

γ

2) Wilhelmy Plate Method

- A fully wetted plate is suspended from the balance and dips into the liquid.

- The maximum wetting force is measured by detaching the plate from the liquid.

Balancing the wetting force, the measured detaching force, and the plate weight gives

det 1

plate perimeter cos

F G

γ

θ

− =

For a fully wetted plate

θ

If a liquid with known surface tension is used as a reference, we obtain det det, ref ref F G F G

γ γ

3) du Noüy Ring Method

It’s similar to the Wilhelmy method. A ring is used.

det 4 F R

γ

β

π

β

3) Drop-Volume and Drop-Weight Methods

- Drops of the liquid are allowed to

detach themselves slowly from the tip of a vertically mounted narrow tube.

- Either their weight (m) or volume (V) is measured. 2 2 mg V g r r

ρ

γ

φ

φ

π

π

5) Pendant (sessile) Drop (Bubble) Shape Methods

Sessile drop sitting on a solid surface

Pendant drop captured to the end of a needle

The shapes are photographed, digitised, and

fitted with the Young-Laplace equation to obtain the surface (interfacial) tension.

6) Oscillating Jet Method (Adamson)

- A liquid jet emerging from a nozzle is

unstable and oscillates about its preferred circular cross section.

- Surface tension is calculated from the jet dimensions (obtained photographically).

- Suitable for measuring the dynamic surface tension (at very short times – 0.01 s).

7) Maximum Bubble Pressure Method (Adamson)

- The pressure versus time is measured. - The pressure curves passes through a

maximum where the bubble radius is equal to the capillary radius – hemispherical shape.

max hyd

p p

r

γ

- Dynamic surface tension is calculated by dividing

MEASUREMENT OF SURFACE ENERGY • The contact angle,

θ

• Minimising the free energy gives

γla Air Solid Liquid γ_sa θ γ_ls = cos sa ls la

γ

γ

γ

θ

- Surface tension is measured - State equation links the

solid-related energies (WA Neuman)

( )

f

γ

γ

• Possible hysteresis of contact angle

Contact angles between a drop and a titled surface