Explain the surface tension phenomena

Describe measurement methods

Effects of temperature & concentration on surface tension
Surface tension

A measurement of the cohesive energy present at an interface.

Molecules of a liquid attract each other. Interactions of a bulk molecule of a liquid
are balanced by an equal attractive force in all directions.
Molecules on the surface of a liquid experience an imbalance of forces.
Surface tension is (gamma), unit: dyne/cm or N/m.

Thermodynamic definition

Mechanical work to increase a surface = , reversible = +

, Gibbs =

the surface area of = spontaneous (G<0).

increase surface area certain needed energy, as it is, non-spontaneous (G>0).
Spontaneous (or non-spontaneous) calculation = change in the surface area is
precisely the surface tension.

Surface tension origins

Liquids adopt shapes that minimize their surface area, to ensure the largest fraction
of molecules is in the bulk, and thus surrounded by similar molecules.
It is also to ensures that smallest fraction of molecules lies at the surface, and in
contact with dissimilar molecules
Water droplets are round; a sphere has the smallest surface-to-volume ratio.
Liquid rearranges itself into a lowest energy conformation
Those molecules at the surface have no neighbors above them; attractive forces
between them grow stronger.
Force acting to pierce the surface must overcome this to minimize surface area
Strength of this surface tension depends on preference of liquid molecules to be
adjacent = intermolecular forces within liquid & liquid and the air.
Examples: insect walking on water, floating a needle, washing with hot water

Interfacial tension

Interface- boundary between phases that exist together.

Should be classified into 2 adjacent phases; solid, liquid, or gaseous state.
One phase is gas; the term is surface tension.

Capillarity

Ability of a liquid to flow in narrow spaces without help of, and in opposition to,
external forces like gravity.
Examples: paper towels absorb through capillarity, burning a candle, the melted wax
rises up the, blood is pumped throughout the body, which distributes blood in the
smallest blood vessels.

Formation of drops

Occurs when mass of liquid is stretched.

Water from faucet gain mass until stretched to where surface tension can no longer
bind it to the faucet.
It then separates and surface tension forms the drop into a sphere.
Water running from the faucet, break up into drops during its fall - gravity stretching
the stream, and surface tension then pinching it into spheres

Contact angle

Drop of liquid on a solid surface; the edge forms a

defined angle (depends on material properties of
liquid & solid)
Contact angle determine relationship between liquidsolid surface tension & liquid-gas surface tension.
Surface tension gas-liquid interface
Solid surface - such as the walls of a container interface curves up or down near that surface;
Concave or convex shape (meniscus).
Convex (contact angle > 90), the cos term is (-), liquid-solid surface tension +.
Concave (contact angle < 90), the cos term is +, liquid-solid surface tension -.
Wetting examples: drops on a window, dispersing a powder in a milk

Surface tension measurement methods

Capillary rise
A capillary tube immersed in a liquid that wets glass.
Wetting inner wall of the capillary, surface of the liquid
.
To its surface, liquid must rise within the capillary
again wet and again the liquid rises.
Process stops when force of surface tension acting =
force due to the column of liquid acting downward.
Most liquid, = 1, =

Wilhelmy plate
A thin plate (platinum/iridium) is used &
dipped into the liquid.
Vessel with liquid is gradually lowered and the
force measured by the balance at the point of
detachment F is noted.
=

, L:wetted length of plate

Ring method
The force required to detach a ring from a
surface/interface.
Measured from the arm of a balance / using the
torsion wire arrangement (du Nouy tensiometer)
Platinum ring probe is often used
The surface/interfacial tension: inner rad, ) outter
rad, R rings radius, F pull on ring

2( + )

// =

Drop-volume & drop-weight

Liquids drop can detached themselves from the tip of a narrow tube that
mounted vertically
Mass/volumes are measured
Point of detachment, surface tension: m=drops mass,
V=drops volume, r=tubes radius, =correction factor

Correction factor required because on detachment:

-Drop does not completely leave the tip
-Surface tension forces seldom exactly vertical

Effect of temperature on surface tension

= 0 1

T n
Tc

log = log0 + n log 1

T
Tc

Tc : Critical temperature the temperature which gas and liquid

phases cannot distinguish
n: is an empirical factor, whose value is 11/9 for organic liquids
o : Surface tension of liquid at 25C
Effect of solute concentration on surface tension

Solutes effects on surface tension depending on their structure (on water):

Surface tension, inorganic salts
Surface tension progressively, alcohols
Surface tension and, once a minimum is reached, no more effect: surfactants

Gibbs isotherm
is surface activity = excess solute / area of the surface over what would be
present if the bulk concentration prevailed all the way to the surface. Units =
mol/m2. C is concentration of the substance in the bulk solution, R is gas
constant &T temperature.
Only be applied to ideal (very dilute) solutions with 2 components.

Surface activity = unequal distribution of a solute surface and body of a solution.

amount of solute/cm2 in the surface in excess to that in the bulk, C: concentration

of the solution, T= absolute temperature
If this rate is + ( increase with C), -, solution body solute > surface

(-) expulsion of solute from the surface; (+) adsorption of solute from the solution
by the surface

Coefficient of spreading

- Coefficient of spreading B on the surface of A. It is difference between the

adhesion work (work to separate one liquid from another) and cohesion work (work
to pull a column of pure liquid apart).
Adhesion work: Wa = a + b AB
Cohesion work: Wcb = 2B

=
= a + b AB 2B
= a b AB

SBA +, liquid B spread on the surface of A (oil on water)

SBA -, liquid B remain as a drop on the surface of A.

Industrial applications of surface tension

Spreading of drops
Surface acting agents (soaps)
Combustion
Many chemical engineering processes (e.g. adsorption, liquid extraction)Evaporation and condensation of thin liquid films (technology now widely used in
the fast growing micro-electronics industry)
Drying of paint films
Surface waves

Definition of adsorption
Types of adsorption
Application of adsorption
Adsorption of gases by solids
Adsorption isotherms (Freundlich, Langmuir and BET)
Surface area measurement using BET
Adsorption

Process molecules diffuse from bulk of a fluid to the surface of the solid forming a
distinct adsorbed phase
Solid (adsorbent), adsorbed gas/vapor (adsorbate)
Depends on T, P, the effective surface area of solid
Molecules attach to surface physisorption & chemisorption

Application of adsorption process

Very important step in solid catalyst reaction

Common process in industry
purification (removing impurities from gas/liquid stream)
de-pollution, de-colour, de-odour
solvent recovery, trace compound enrichment
natural gas storage
A batch type & required regeneration of saturated adsorbent (ex: molecular sieve,
activated carbon, silica gel, activated alumina)
Physisorption to determine area, pore shape, pore size, size distribution of porous
solid materials (BET surface area)

Physisorption

Adsorbent and adsorbate interact relatively weakly through VanDerWaals

Physisorption of gases by solid , P or T
At favourable T & P, physisorption all surfaces
Same surface can exhibit physisorption at low T
Weak interaction forces; enthalpy of adsorption <40kJ/mol; physisorption not
affect structure/texture of the adsorbent
Desorption is vice versa.
Adsorption isotherm done at LN2 temperature (77.5K, 1atm). Plot of gas adsorbed
as volume Va at 0C and 1atm (STP) vs. P/Po(Po =vapor pressure)

Chemisorption

Chemical bonds between adsorbent and adsorbate

Chemisorption interaction >>> physisorption
40 kJ/mol < heat of adsorption < 800kJ/mol
Adsorbing gas / vapor molecule splits into atoms, radicals / ions forming a chemical
bond with the adsorption site. Sharing of electrons between gas & solid surface
formation of a surface compound.
O2 chemisorbed on charcoal application of heat and vacuum result in CO
desorption instead of O2
At favourable T & P, chemisorption only certain surface sites
Chemisorption , T
Same surface can exhibit chemisorption at high T
Example: N2 chemisorption on Fe at 800oC to form iron nitride but physis orption at
LN2 temperatures.

Adsorption process

Adsorbent: Solid that provides surface for adsorption

Adsorbate: Gas/Liquid to be absorbed on liquid
Surface coverage, (0~1)

Exothermic (in special cases dissociated adsorption = endothermic)

Heat of chemisorption = magnitude of reaction heat
Heat of physisorption = magnitude of condensation heat

Adsorption of gases by solids

Good adsorbent (solid) large surface area for given mass

Ex: silica gel, charcoals
These solid have very porous structure & can take up appreciable volume of gases
Extent of adsorption can be enhanced activating adsorbents in various ways
Example: Heating to high temperature in vacuum or air (involves distilling out
hydrocarbon impurities from adsorbent and expose to larger free surface for
possible adsorption).
Chemical treatment of the adsorbent (impregnation)

Factors affecting adsorption

Nature of adsorbent
Adsorption in general increases with Tcr & boiling point of gas
Surface area of adsorbent adsorption
Mw of adsorbate , adsorption
Adsorption isotherms

Isotherm equations

Langmuir

Assumptions:
a) ideal gas
b) monolayer adsorption
c) uniform solid surface (heat of adsorption does not vary
with coverage)
d) adsorbed molecules dont interact with one another
e) adsorption is localized

= +

< Straight line

Established logic picture of adsorption process

Mostly fits many adsorption system
Assumption by Langmuir not in all situations, causing
Solid surface is heterogeneous, heat of adsorption not a contant
at different
Physisorption of gas molecules on solid surface can be >1

Freundlich

BET (Brunauer-Emmett-Teller)

Many physical adsorption isotherms like types II and III, that the adsorption doesnt
complete the first layer (monolayer) before it continues to stack on the subsequent layer
(thus the S-shape of types II and III isotherms)
Assumptions:
a) Same like Langmuir but with multi-layer adsorption
b) Heat of adsorption of additional layer = latent heat of condensation based on rate of
adsorption=rate of desorption for each layer of adsorption

P - equilibrium pressure
P0 - saturated vapour pressure of the adsorbed gas at the temperature
P/P0 - relative pressure
V - volume of adsorbed gas / kg adsorbent
Vm - volume of monolayer adsorbed gas per kg adsorbent
c - constant associated with adsorption heat and condensation heat

BET fits well all known adsorption isotherms observed (types I-V) for various types of
solids, but with fundamental defect in the theory as assumptions made (no
interaction between adsorbed molecules, surface homogeneity and liquefaction heat
for all subsequent layers being equal).

BET and other isotherms, gives accurate adsorption isotherm within restricted
pressure range. At very low (P/P0<0.05) and high relative pressure (P/P0>0.35) it
becomes less applicable.

BET isotherm provided the first applicable means of accurate determination of the
surface area of a solid.

Many new developments provide accurate for a specific system under specific
conditions in relation to the theory of adsorption isotherm.