PHYSICAL

CHEMISTRY
SURFACE TENSION
General definition

j
(
\
,
G
A
P T ,
where G is the Gibbs free energy and
A is the area.
Pressure drop across a spherical surface
(Young-Laplace equation)
P
R

2
where R is the radius of the sphere
Surface enthalpy
H T
T
P

j
(
\
,

Temperature dependence
(Katayama-Guggenheim equation)

j
(
,
\
,
( 0
1
T
T
C
n
where
0
and n are empirical param-
eters of a given liquid, and T
C
is the
critical temperature. For organic com-
pounds, n = 11/9.
ADSORPTION
Definitions
Adsorption is a process whereby a gas
or liquid (adsorbate) accumulates on the
surface of a solid or liquid (adsorbent) to
form a molecular or atomic film. In con-
trast, absorption is a process whereby a
gas, liquid or solid diffuses into a liquid
or solid to form a solution.
Physisorption is used when the adsor-
bate is physically bound to the adsor-
bate through weak bonds, such as van
der Waals forces. Chemisorption is used
when the adsorbate is chemically bound
to the adsorbate, such as through cova-
lent bonds.
Surfactants, or surface-active agents,
are wetting agents that lower the sur-
face tension of a liquid by lowering the
interfacial tension between two liquids.
Surfactants are typically long molecules
composed of a hydrocarbon tail and a
polar head. Surfactants can be classified
according to the charge of the head:
Anionic surfactants have negatively
charged groups (such as sulfate, sulfo-
nate or carboxylate)
Cationic surfactants have positively-
charged groups (such as quaternary
ammonium ions)
Zwitterionic surfactants have a polar
head with both positively and nega-
tively charged groups.
Nonionic surfactants don't have any
charged group for the polar head. Ex-
amples of non-ionic surfactants are alkyl
poly(ethylene oxide) and fatty alcohols.
Above a certain surfactant concentra-
tion, called the critical micelle con-
centration, the surfactant molecules
form spherical-shaped aggregates in
solution. In water, for example, the
hydrocarbon tail assemble together to
form an oil-like droplet with the polar
heads forming an outer shell (dia-
gram). The presence of micelles is what
enables detergent solutions to dissolve
oils and fats.
ADSORPTION ISOTHERMS
Gibbs adsorption isotherm
d kT d c
i
i
i
ln
where k is the Boltzmann constant
T is the temperature, in Kelvin

i
is the surface concentration of ith
component
c
i
is the bulk concentration of the ith
component
Langmuir adsorption isotherm

i
i
i
i
c
B c

+
where B is an empirical constant. This
classical equation is useful for describ-
ing the adsorption of molecules onto a
solid surface to form a monolayer. For
multilayer adsorption, the BET isotherm
is used:
BET (Brunauer, Emmett and Teller)
adsorption isotherm

i
i
i i
i i
i
i
i
i
K p
K p
p
P
p
P

+
j
(
,
\
,
(
,

,
,
]
]
]
]

j
(
,
\
,
(
,

,
,
]
]
]
]
1 1
where K
i
is a constant, p
i
is the pressure
of the adsorbable component i, and P
i
its vapor pressure. Other isotherms of
importance include:
Henry adsorption isotherm

i
i
i
c
B

where B is an empirical constant.
Freundlich adsorption isotherm

i
F
i
F
m
c
B

j
(
,
\
,
(
where
F
, B
F
and m are empirical
constants.
NOMENCLATURE
A Area
B Empirical constant for adsorption
isotherms
c
i
Bulk concentration of i
th
component
G Gibbs free energy
H Enthalpy
k Boltzmann constant
K
i
Equilibrium constant
n An empirical constant in the rela-
tion describiong the temperature
dependence of surface tension
n
i
Number of adsorbed molecules or
atoms on a surface (n
i
=
i
A)
P Pressure
p
i
Pressure of i
th
component
R Radius of a spherical surface, such
as a bubble or meniscus
T Temperature
Tc Critical temperature

i
Surface concentration of i
th
compo-
nent

i
Surface concentration of i
th
compo-
nent at large concentrations

F
An empirical parameter of the
Freundlich isotherm
Surface tension

o
Surface tension of pure solvent

References
1. Levine, I., Physical Chemistry, 2nd ed., Mc-
Graw Hill Book Co., N.Y., 1983, pp. 342365.
2. Perry, R.H. and Green, D.W., Perrys Chemical
Engineers Handbook, 7th ed., McGraw Hill
Book Co., N.Y., p. 16-1213.
3. Danov, K.D. and others, Equilibrium and Dy-
namics of Surfactant Adsorption Monolayers
and Thin Liquid Films, Handbook of Deter-
gents, Part A: Properties, M.Dekker, N.Y., pp.
303418, 1999.