CHEM 355 SURFACE CHEMISTRY AND PHASE EQUILIBRIA

Richard Tia, Ph.D.

 SURFACE AND INTERFACIAL PHENOMENA

Surface/interface:
•Boundary between a material and its surrounding environment.
•The physical boundaries of a condensed phase ( solid or liquid)

Interface: Boundary between two condensed phases

Surface: Boundary between a condensed phase and a gaseous phase

What is special about surfaces/interfaces: 

•The periodic monotone of bulk electronic and structural properties comes to an end at the surface of a
material.

•The atoms at the surface show unique properties that are different from those of atoms in bulk because of
unbalanced forces of attraction - residual forces.

• While atoms in the bulk of a solid are happily bonded in all

directions to their neighbours, bonds at the surface often remain
unsaturated leading to reconstructions, enhanced chemical
reactivity, and interesting electronic properties.
Atoms and molecules at surfaces/interfaces have different bonding environments than those in the bulk of a
material
This gives rise to a range of phenomena at surfaces/interfaces, such as adsorption, surface/interfacial tension
etc

Surface chemistry therefore deals with a study of phenomena that occurs at surfaces or interfaces, such as
adsorption, surface tension, formation of colloids, electrode processes, corrosion etc and has applications in
scientific research and in industry such as heterogeneous catalyst technology, chromatography,
semiconductor-based technology, medical technology, anticorrosion and lubricant technology, and
nanotechnology.
 ADSORPTION

Adsorption is the process in which atoms, ions or molecules from a substance (gas, liquid or dissolved solid)
adhere to the surface of another substance.

Involves the preferential partitioning of substances from the gaseous, liquid or solution phase onto the
surface of a solid substrate.

The increase in the concentration of a substance at the interface

of a condensed phase and a liquid or gaseous layer owing to the
operation of surface forces. - IUPAC

The substance is separated from one phase and accumulated or

concentrated at the surface of the adsorbing substance.

The adsorbing phase is the adsorbent, and the material concentrated or

adsorbed at the surface of that phase is the adsorbate.
The process of adsorption arises due to presence of unbalanced or residual forces at the surface of
the liquid or solid phase.

These unbalanced residual forces have tendency to attract and retain the molecular species with
which it comes in contact with the surface.

Adsorption is essentially a surface phenomenon.

Adsorption is different from Absorption.

•Absorption means uniform distribution of the substance

throughout the bulk
•Adsorption essentially happens at the surface of the
substance.

•When both Adsorption and Absorption processes take

place simultaneously, the process is called sorption.
The exact nature of the binding depends on whether the adsorption is physical (physisorption) or chemical
(chemisorption).

Physical adsorption(physisorption) – the forces of attraction between adsorbate particles and adsorbent are
van der Waal’s forces. Can easily be reversed by heating or decreasing pressure;

Chemical adsorption (chemisorption) – chemical bonds are formed between adsorbate particles and
adsorbent.
Important Applications of Adsorption
→ Production of High Vacuum
→ Gas Masks
→ Humidity Control
→ Clarification of Sugar
→ Chromatographic Analysis
→ Heterogeneous Catalysis
→ Adsorption Indicators
→ Removal of hardness of water
Production of High Vacuum
Gas Masks
Clarification of Sugar
Chromatographic separation
Heterogeneous Catalysis
There are four steps in the catalysis of the reaction C 2H4 + H2⟶C2H6 by nickel.

(a)Hydrogen is adsorbed on the surface, breaking the H–H bonds and forming Ni–H bonds.

(b)Ethylene is adsorbed on the surface, breaking the π-bond and forming Ni–C bonds.

(c)Atoms diffuse across the surface and form new C–H bonds when they collide.

(d) C2H6 molecules escape from the nickel surface (desorb), thus they should not be strongly
attracted to nickel.
 THERMODYNAMICS OF ADSORPTION

Except for special cases,

Hence adsorption of a gas on a surface is always an exothermic process.

 ADSORPTION ISOTHERMS

Adsorption isotherm: a graphical representation of the relationship between the bulk activity of adsorbate and
the amount adsorbed at constant temperature.

- the amount of adsorbate on the adsorbent as a function of its pressure (if gas) or concentration (if liquid) at
constant temperature.
 LANGMUIR’S ADSORPTION ISOTHERM

The Langmuir adsorption model:

-assumes monolayer adsorption on a homogeneous surface.

-explains adsorption by assuming an adsorbate behaves as an ideal gas at isothermal conditions.

The adsorbent is assumed to be an ideal solid surface composed of series of distinct sites capable of binding
the adsorbate.
POSTULATES
1. Adsorption takes place only at specific localized sites on the surface and the saturation coverage
corresponds to complete occupancy of these sites.

2. Each site can accommodate one and only one molecule or atom and a constant amount of heat energy is
released during this process.

3. The surface is energetically homogeneous, and there is no interaction between neighbouring adsorbed
molecules or ions.

4. There are no phase transitions.

5. Dynamic equilibrium exists between adsorbed gaseous molecules and the free gaseous molecules. That
is, the rate of condensation is equal to the rate of evaporation after a sufficient time of adsorption.
Let θ be the fraction of surface occupied by adsorbed molecule at any time.

Then the rate of evaporation of gas from the surface is proportional to θ

Rate of condensation of molecule on the surface is proportional to the fraction of surface available (1 – θ)
and the pressure (striking force).
At equilibrium the rate of condensation equals the rate of evaporation:
From Equation 4, two limiting cases can be identified:
LIMITATIONS OF LANGMUIR’S ISOTHERM

1.The gases do not behave ideally

2.It fails at high temperatures

3.Multi-layer adsorption of gases is possible.

4.The adsorbent surface is not uniform throughout.

5.The adsorbent and adsorbate may chemically interact in few cases.

 FREUNDLICH’S ADSORPTION ISOTHERM

In 1909, Freundlich gave an empirical expression representing the isothermal variation of adsorption of a
quantity of gas adsorbed by unit mass of solid adsorbent with pressure. This expression can be applied to both
gases and solutions.

x is the amount of substance adsorbed by m g of adsorbent at pressure P or concentration C. k and n are

constants for any given concentration.
LIMITATIONS OF FREUNDLICH’S ISOTHERM

1.Freundlich’s isotherm is purely empirical and has no theoretical basis.

2.The equation is valid only up to a certain pressure and is invalid at high pressure.

3.The constants k and n are not temperature independent, they vary with temperature.

4.Freundlich’s adsorption isotherm fails when the concentration of the adsorbate is very high.
 BRUNAUER-EMMERT-TELLER (BET) ADSORPTION ISOTHERM

- an extension of the Langmuir theory, which is a theory for monolayer molecular adsorption, to multilayer
adsorption with the following hypothesis:

1.Gas molecules physically adsorb on a solid in layers infinitely,

2. There is no interaction between each adsorption layer and
3. The Langmuir theory can be applied to each layer.

V = total volume of gas adsorbed per unit area or mass

Vm = volume of a gas adsorbed per unit mass when the surface is covered by a unimolecular layer.
P = the pressure at any time
P° = the saturated vapour pressure.
A plot of f/V(1- f) against f gives a straight line with

Combining equations (2) and (4)

CLASSIFICATION OF ADSORPTION ISOTHERMS
 Adsorption with dissociation

In some cases there is evidence that the substance being adsorbed is dissociated upon adsorption.
E.g. in the adsorption of H2 on the surface of many metals, the H2 molecules are dissociated into atoms,
each of which occupy the surface sites.
From (3)
 COMPETITIVE ADSORPTION
For competitive adsorption of two molecules A and B which:

(i) are both adsorbed molecularly and

(ii) compete for the same adsorption sites,

then the Langmuir model can be used to derive a modified adsorption isotherm.

The fraction of surface covered by molecules of type A is θA and that of type B is θB, then the fraction of bare

surface is 1−θA− θB.

For the molecule A
For the molecule B
The same approach yields

Substituting this result into (4)

Eqns (6) and (7) show that the fraction of surface covered by one
substance is reduced if the amount of the other substance is
increased. This is due to the competition between A and B for a
limited number of surface sites.
 CHEMICAL REACTIONS ON
Surfaces reactions are reactions in which at least one of the steps of the reaction mechanism is the adsorption
SURFACES
of one or more reactants.

UNIMOLECULAR REACTIONS

- at sufficiently high concentration of A, the rate is independent of concentration of A (zero order kinetics).

- An example of this type of behaviour is the decomposition of NH3 into N2 and H2 on a tungsten surface.
 BIMOLECULAR REACTIONS

• Langmuir – Hinshelwood mechanism

• Eley – Rideal mechanism

LANGMUIR – HINSHELWOOD MECHANISM

This mechanism proposes that both molecules are adsorbed and the adsorbed molecules undergo a
bimolecular reaction:
 The maximum rate corresponds to the presence of the maximum number of A and B pairs on the surface.

The physical explanation of the fall-off in the rate at high concentration of A is that one reactant displaces
the other as its concentration is increased.

The rate law is complex and there is no clear order with respect to any of the reactants.
The rate law is complex and there is no clear order with respect to any of the reactants.

Special Cases:

Thus the reaction is first-order with respect to the

reactants and second order overall.

The order is 1 with respect to B and -1 with

respect to A. The higher the concentration of A,
the slower the reaction goes, in this case A
The order is 1 with respect to B. There are two
inhibits the reaction.
extreme possibilities of this:
Reactions that follow the Langmuir – Hinshelwood mechanism:

1.2 CO + O2 → 2 CO2 on platinum catalyst.

2.CO + 2 H2 → CH3OH on ZnO catalyst.

3.C2H4 + H2 → C2H6 on copper catalyst.

 ELEY – RIDEAL MECHANISM

Only one of the molecules adsorbs and the other reacts with it directly from the gas phase, without adsorbing:

At low concentrations of A, the order is one with respect to A. At

high concentrations of A, the order is one with respect to A
Reactions that follow the Eley – Rideal mechanism:

1.2 CO + O2 (adsorbed) → H2COH2

2.CO2 + H2 (ads) → H2O + CO

3.NH3 + 3/2 O2 (ads) → N2 + 3 H2O on platinum catalyst.

4.C2H2 + H2 (ads) → C2H4 on nickel or iron catalysts.

 SURFACE AND INTERFACIAL TENSION
 Intermolecular interactions in a liquid lower the internal energy.

 Molecules at the surface of the liquid experience fewer interactions from other liquid phase molecules
compared with molecules in the bulk phase
- have a higher average energy than molecules in the bulk liquid phase.

 It requires work to increase the area of the liquid-vapour interface since such an increase means fewer
molecules in the bulk liquid phase and more in the surface layer.

 Positive work is required to increase the area of an interface between two phases.

 Liquids tend to assume a configuration of a minimum surface area.

 Thus an isolated drop of liquid is spherical, since a sphere is the three-dimensional shape with a
minimum ratio of surface area to volume.
- The number of molecules in the interface is proportional to A
The Katayama-Guggenheim equation
The ‘miracle’ of surface tension: The ‘Jesus’ lizard walking on water
 SURFACTANTS

Substances that, when present at low concentration in a system, has the property of adsorbing onto the
surfaces or interfaces of the system and of altering to a marked degree the surface or interfacial free energies
of the surfaces (or interfaces).

The interfacial free energy is the minimum amount of work required to

create that interface.

The interfacial free energy per unit area is what we measure when
we determine the interfacial tension between two phases.

It is the minimum amount of work required to create a unit area of the interface or to expand it by a unit area.

Work is required to bring a molecule from the interior to the surface.

The interfacial or surface tension is also a measure of the difference in nature of the two phases meeting at
the interface (or surface). The greater the dissimilarity in their natures, the greater the interfacial (or surface)
tension between them.
A surfactant is therefore a substance that at low concentrations
adsorbs at some or all of the interfaces in the system and
significantly changes the amount of work required to expand
those interfaces.
Surfactants have a characteristic molecular structure consisting of a structural group that has very little
attraction for the solvent, known as a lyophobic group, together with a group that has strong attraction for the
solvent, called the lyophilic group - amphipathic structure.
At the interface between two condensed phases, the dissimilar molecules in the adjacent layers facing each
other across the interface have potential energies different from those in their respective phases.

minimum work required to create the interface

The lyophobic portion of the surfactant has two functions in surface tension reduction:

(1)to produce spontaneous adsorption of surfactant molecules at the surface and

(2) to increase interaction across the interface between adsorbed surfactant molecules there and the
molecules in the adjacent phase.

The function of the lyophilic group is to provide strong interaction between the molecules of surfactant at
the interface and the molecules of solvent.
 PHASE EQUILIBRIA

A phase of a system is a chemically and physically distinct portion of the system.

If a system is uniform throughout, both in chemical composition and physical state, the system is said to be
homogenous or to consist of only one phase.

A system consisting of more than one phase is called heterogeneous

All gases are miscible in all proportions – one phase system

Two totally miscible liquids - One phase system

A solution of sodium chloride in water – One phase system

A flask of liquid benzene in contact with benzene vapour and air - a

two-phase system;

If we add a measure of sucrose (practically insoluble in benzene), a

three-phase system: a solid, a liquid and a vapour phase.
- A constituent of a system is any chemical species (an ion or a molecule) that is present.
- A mixture of ethanol and water has two constituents; a solution of sodium chloride in water has three
constituents: water, Na+ ions and Cl- ions.
• A component of a system is a chemically independent constituent of the system. The number of
components in a system is the minimum number of independent species necessary to define the
composition of all the phases present in the system.

- Pure water is a one-component system, because we need only the species H 2O to specify its
composition.

- A mixture of ethanol and water is a two-component system: we need the species H 2O and

C2H5OH to specify its components.

- An aqueous solution of sodium chloride has two components because, by charge balance, the
number of Na+ ions must be the same as the number of Cl - ions.
CaCO3(s) CaO(s) + CO2(g)
phase 1 phase 2 phase 3
The number of components = number of constituents – number of reactions
= 3-1
=2
- The number of degrees of freedom (or variance) of a system is the number of intensive variables that
can be changed independently without disturbing the number of phases in equilibrium.

In a single-component, single-phase system, the temperature and pressure may be changed independently
without changing the number of phases. So the variance is 2 (i.e. the system is bivariant).

-On the other hand, if two phases are in equilibrium (a liquid and its vapour) in a single-component
system, the temperature (or pressure) can be changed at will but the change in temperature (or pressure)
demands an accompanying change in pressure (or temperature) to preserve the number of phases in
equilibrium. That is, the variance of the system has fallen to 1.
GENERAL EQUILIBRIUM THEORY: THE CHEMICAL POTENTIAL

G = G(P, T, ni), U = U(V, T, ni­)

dG = -SdT + VdP for any system of constant composition, i.e. when all the dn i = 0
Components can be transferred across the phase boundaries in this system, but no mass can enter or leave
the system as a whole.
 THE GIBBS PHASE RULE
- The number of degrees of freedom is equal to the number of intensive variables required to describe a
system, minus the number that cannot be independently varied.
- The state of a system containing P phases and C components is specified if we specify the temperature,
the pressure and the mole fractions of each component in each phase.
- We can specify the composition of a phase by giving the mole fractions of C-1 components.

- The total number of composition variables is P(C-1).

- The total number of intensive variables is P(C-1) + 2.

- At equilibrium, the chemical potential of a component J must be the same in every phase:
μJ (α) = μJ (β) = …………….. for P phases

Thus, the total number of restrictions is C(P-1).

The total number of degrees of freedom = Total number of Total number of

– restraining conditions
intensive variables
:. F = P(C-1) + 2 – C(P-1)

=C-P+2
 One component phase diagram

C = 1 and F = 3 – P
TC = Vaporization Curve
TA = Sublimation Curve
TB: Fusion Curve
 Two component phase diagram

C = 2 and F = 4 – P
NOBEL INTERLUDE
THE PHYSICS PRIZE
 Three component phase diagram

C = 3 and F = 5 – P
 The Physical Chemistry of Solutions

A solution is a homogeneous mixture; a one-phase system with more than one component.

The phase may be solid, liquid, or gas.

xi ≡ ni/ntot ci ≡ ni/V ρi ≡ mi/V

Since V of a solution depends on T and P, the concentrations c i change with changing T and P. Mole
fractions and molalities are independent of T and P.
 PARTIAL MOLAR QUANTITIES

- a thermodynamic quantity which indicates how an extensive property of a solution or mixture varies with
changes in the molar composition of the mixture at constant temperature and pressure.

-the contribution a particular component of a sample makes to the total quantity of sample.

-Eg. the partial molar volume is the contribution to the volume that a component in a sample makes to the
total volume of the sample

V ≠ V* unless solution is ideal!

Addition of 50.0 cm3 of water to 50.0 cm3 of ethanol at 20 °C and 1 atm gives a solution whose volume is
only 96.5 cm3 at 20°C and 1 atm.

The difference between V of the solution and V* results from:

(a) differences between intermolecular forces in the solution and those in the pure components;

(b) differences between the packing of molecules in the solution and the packing in the pure components,
due to differences in sizes and shapes of the molecules being mixed.
 IDEAL SOLUTIONS

- An ideal solution is a solution that has physical properties linearly related to the properties of the pure
components.

- The interactions between molecules of solute and solvent are the same as those between the molecules of
each substance by itself.

- An ideal solution is therefore a solution where the molecules of the various species are so similar to one
another that replacing molecules of one species with molecules of another will not change the spatial
structure or intermolecular interaction energy in the solution.

- Ideal solutions obey Raoult’s law

 RAOULT’S LAW (FRANÇOIS-MARIE RAOULT, 1882)

- At any given temperature for a particular solid or liquid, there is a pressure at which the vapour formed
above the substance is in dynamic equilibrium with its liquid or solid form - vapour pressure of the
substance at that temperature.

-At equilibrium, the rate at which the solid or liquid

evaporates is equal to the rate that the gas is condensing
back to its original form. This pressure is constant
regardless of how much of the substance is present.

-The vapour pressure of an ideal solution is dependent on

the vapour pressure of each chemical component and the
mole fraction of the component present in the solution.

At equilibrium,
This law is strictly valid only under the assumption that intermolecular forces between unlike molecules are
equal to those between similar molecules: the conditions of an ideal solution.

The molecular origin of Raoult’s law is the effect of the solute on the entropy of the solution.
For an ideal solution (when Raoult’s law is obeyed), a plot of vapour pressure against mole fraction yields a
straight line.

This is nearly true for the benzene and toluene mixture at 40 oC.
Ideal and Non-Ideal Solutions and Raoult’s Law
 A mixture of carbon disulphide and
A mixture of trichloromethane (chloroform) and dimethoxymethane or benzene and methanol show
acetone shows a negative deviation from ideal a positive deviation from ideal behaviour
behaviour (Raoult’s law) at 35 oC, indicating that the indicating that the polar and non-polar molecules
two different molecules prefer each other’s company prefer the company of their own kind.
to their own.
 HENRY’S LAW (WILLIAM HENRY, 1803)

The solubility of a gas in a liquid depends on temperature, the partial pressure of the gas over the liquid, the
nature of the solvent and the nature of the gas.

Henry's law states that at a constant temperature, the amount of a given gas that dissolves in a given type and
volume of liquid is directly proportional to the partial pressure of that gas in equilibrium with that liquid.

The solubility of a gas in a liquid is directly proportional to the partial pressure of the gas above the liquid.

Henry’s law holds only for dilute solutions and low gas pressures.

- A bottle of carbonated drinks.

-Bends in deep sea diving

 Colligative Properties

- properties of a solution that depend mainly on the relative numbers of particles of solvent and solute
molecules and not on the detailed properties of the molecules themselves.

- referred to as statistical properties because they can be understood solely on the basis of counting the
relative numbers of particles in a solution.

Examples of colligative properties of solutions are:

1.Vapour pressure depression

2. Boiling point elevation

3. Freezing point depression

4.Osmotic pressure
Boiling Point Elevation and Freezing Point Depression
 Osmotic Pressure

(a) A dilute solution of glucose in water is placed in the right arm of a U-tube, and the left arm is filled to
the same height with pure water; a semipermeable membrane separates the two arms. Because the flow
of pure solvent through the membrane from left to right (from pure water to the solution) is greater than
the flow of solvent in the reverse direction, the level of liquid in the right tube rises.

(b) (b) At equilibrium, the pressure differential, equal to the osmotic pressure of the solution (Πsoln ),
equalizes the flow rate of solvent in both directions.

(c) (c) Applying an external pressure equal to the osmotic pressure of the original glucose solution to the
liquid in the right arm reverses the flow of solvent and restores the original situation.
A colloid is a substance in which microscopically dispersed insoluble particles are
suspended throughout another substance.

Unlike a solution, whose solute and solvent constitute only one phase, a colloid has a
dispersed phase (the suspended particles) and a continuous phase (the medium of
suspension).
A colloidal system is not a true solution but it is not suspension either because it does
not settle out like a suspension will over time.
To qualify as a colloid, the mixture must be one that does not settle or would take a
very long time to settle appreciably.
 TYPES OF
There are three types of colloids
COLLOIDS(1) hydrophilic colloids, (2) hydrophobic colloids, (3)
and association colloids.
Micelles
 PROPERTIES OF COLLOIDAL SOLUTIONS

The main properties of colloidal solutions are as follows:

(1) Physical properties

(i)Heterogeneous nature: Colloidal solutions are heterogeneous in nature. They consist of two phases; the dispersed
phase and the dispersion medium.

(ii) Stable nature: The colloidal solutions are quite stable. Their particles are in a state of motion and do not settle down at
the bottom of the container.

(iii) Filterability: Colloidal particles are readily passed through the ordinary filter papers. However they can be retained by
special filters known as ultrafilters (parchment paper).
 (2) Colligative properties

Due to formation of associated molecules, observed values of colligative properties like relative
decrease in vapour pressure, elevation in boiling point, depression in freezing point, and osmotic
pressure are smaller than expected. For a given colloidal solution the number of particles will be very
small as compared to the true solution.
 (3) Mechanical properties
(i) Brownian movement

The molecules of the dispersion medium are constantly colliding with the particles of the dispersed
phase. The dispersion medium particles are unequal, thus causing a zig-zag motion of the dispersed
phase particles. The Brownian movement explains the force of gravity acting on colloidal particles. This
helps in providing stability to colloidal sols by not allowing them to settle down.

(ii) Diffusion: The colloidal particles diffuse from higher concentration to lower concentration region.
However, due to bigger size, they diffuse at a lesser speed.

(iii) Sedimentation: The colloidal particles settle down under the influence of gravity at a very slow
rate. This phenomenon is used for determining the molecular mass of the macromolecules.
 (4) Optical properties: Tyndall effect

When light passes through a colloidal solution, its path becomes visible because of scattering of light by particles.
This is called Tyndall effect. The illuminated path of the beam is called Tyndall cone. The intensity of the scattered
light depends on the difference between the refractive indices of the dispersed phase and the dispersion medium.
The Tyndall effect confirms the heterogeneous nature of the colloidal solution.
 (5) Electrical properties
(i) Electrophoresis

Electrophoresis is the movement of colloidal particles under an applied electric field. If the particles accumulate near the negative
electrode, the charge on the particles is positive. On the other hand, if the sol particles accumulate near the positive electrode, the charge
on the particles is negative.
 APPLICATIONS OF COLLOIDS

Colloids play a very significant role in nature and in our daily life. Some of the important applications of colloids
are discussed below:

1. Foodstuffs: Many of our food stuffs are colloidal in nature. Milk, butter, whipped cream, fruit jellies, ice cream,
bread etc are all colloidal in nature. For example, milk is an emulsion of butter fat in water, stabilized by protein
(casein). Ice cream is a dispersion of colloidal ice particles in cream. Similarly, bread consists of air dispersed in
baked dough.
2. Medicines: Medicines in colloidal form are easily adsorbed by the body tissues and hence are more
effective. Therefore a large number of pharmaceutical preparations are emulsions. Halibut-liver oil,
cod-liver oil, skin ointments etc are emulsion. Antibiotics such as penicillin, streptomycin, etc are
usually injected in the body in colloidal form.
3. Smoke screen: In warfare smoke screens are used to hide the movement of troops. Smoke
screens are the colloidal dispersions of very fine particles of titanium oxide in air.