SURFACE PHENOMENA

Surface phenomena are processes on the interface between bulk phases. The layer properties
depend directly on the properties of volume phases and on the character of phase’s interaction.

Free energy of liquid surface. Surface Tension.

Let us consider a pure solvent and let us discuss the difference between state of molecule in the
volume of solvent and on the surface layer of it (Fig.6).

Fig.6. State of solvent’s molecule in the volume of solvent and in the surface layer of it.

The attraction forces of the surrounding molecules act on the every molecule of solvent. For a
solvent molecule situated in the volume these forces act equally in all the spatial directions and
therefore they compensate each other. On the surface of phase, forces affecting the molecule
don’t compensate. Molecules on interface have the excess of potential energy and the excessive
potential energy appears. The non-compensated attraction forces that act in the direction towards
inside of liquid cause the so called free surface energy (Gs) of liquid: Gs = σ×S, where S – is
the liquid surface (m2), σ–is called the surface tension of the liquid.

According to the second thermodynamic low surface processes may proceed spontaneously if
G is decreased. Consequently either surface tension or area may be decreased.

Surface tension  is measured as the value of the excessive Gibbs’s energy by the unit of
interface area: σ = Gs/S,

Surface tension is equal to the work which is needed to form the unit of interface area.

The value of surface tension may be demonstrated by the form of drops (Fig.7). In general, the
more surface tension the more molecule interaction in interface (drop form is closer to sphere).

Fig.7. Comparison drop form and surface tension values:

σ(mercury) = 436 mJ/m2, σ( water ) = 72 mJ/m2, σ(oil ) = 18 mJ/m2

Factors influencing surface tension.

Surface tension depends on: temperature, nature of substance, pressure and concentration.

a) At the increasing of temperature  decreases and at critical or boiling point comes

to zero.
b) The higher the polarity and the density of medium, the higher the surface tension
value: like example, water surface tension is 72,75 mJ/m2, mercury surface tension is 471,6
mJ/m2
2
Normal blood surface tension value is 46,0 – 47,0 mJ/m
c) Surface tension is decreased at pressure increasing.
d) Concentration can change it in any direction, according to the special
classification of substance.
Surface activity and surface active substances (Fig.8).

If the soluble substance decreases the surface tension it is named surface-active substance
(SAS - surfactant). Examples: alcohols, bile acids, proteins.

If the soluble substance slightly increases the surface tension it is named surface-inactive
substance (SIS). Examples: inorganic salts, acids and bases.

If the soluble substance doesn’t change the surface tension it is named surface non-active
substance (SNS). Examples: saccharose, glycine.

Fig.8. Surface tension vs concentration curves for different types of substance

The ability of soluble substances change the surface tension is named surface activity. Surface
activity is the first derivative of surface tension by concentration with negative sign

d
g
Traube’s Rule dC

The surface activity increases in 3 to 3,5 times at prolongation of carbon chain at one methylene
(CH2-) group. (Fig.9)
Fig.9. Comparison Surface activity of carbonic acids

Usage of SAS in medicine

Cationic and anionic SAS are used in surgery as antiseptic agents. For example quaternary
ammonia salts have in 300 time’s greater antimicrobial activity than phenol. Anionic and
cationic SAS with the alkyl radical from С8 till С14 have the high antiphage activity.

SAS antimicrobial activity is connected with their influence on the cell membrane permeability
and their inhibiting affection on the bacterial enzyme systems.

Sorption

The spontaneous heterogenic process of substance uptake from the surroundings by liquid or
solid phases is called sorption. Reverse process is called desorption. Uptaking substance is
named sorbent. Uptaked substance is named sorbate.

Types of sorption

1. Adsorption is the process in the interface

2. Absorption is the process in the bulk of solution
Adsorption

Adsorption depends on:

1. Concentration of dissolved substance;

2. Nature of substance – like example, for carbonic acids adsorption is increased
with chain length growth (Fig.10);

Fig.10. Dependence adsorption by chain length growth.

 3. Temperature - adsorption is the exothermic process, and desorption is the
endothermic process. Therefore by La-Chatelier’s principle at temperature increasing adsorption
decreases and desorption increases.
Dependence of adsorption on the solute equilibrium concentration at constant temperature is
named adsorption isotherm.

d C
Gibbs adsorption equation

where

dC RT
Г – adsorption, mol/m2;

σ – surface tension;

С – solute concentration, mol/L;

R – universal gas constant, J/mol×K;

Т – temperature, K.

One more classification of Adsorption process

Physical

 small energy of interaction: 4 – 40 kJ/mol by van der Waals forces

 reversible
 Example in organism: products of protein putrefactions absorbs on the cellulose
fibers in the bowels.
Chemical (chemosorption)

 Greater energy of interaction: 40 - 400 kJ/mol by chemical reaction

 irreversible
 Example in organism: pariental digestion by the enzymes adsorbed on the
glycocalyx villi, enzyme-substrate interaction, hormonal regulation, formation of body-antibody
complexes.
Langmuir’s theory

1) Adsorption takes place not at full surface but only on the heterogeneities which are called
adsorptive centers.

2) One center is occupied only by one molecule.

3) There is molecule «life time» in the center and after finishing this time molecule desorbs

Langmuir’s isotherm (Fig.11)

Fig.11. Langmuir’s isotherm: I – linear adsorption, II – non-linear adsorption, III – limiting
adsorption.

Usage of adsorption in medicine

Adsorption therapy is used for elimination of toxic compounds and metabolites from gastro-
intestinal tract. Adsorbents: aluminum hydroxide, aluminum phosphate, magnesium oxide are
used as antacid drugs. Activated carbon is administered at meteorism and different types of
poisoning.

Extracorporeal adsorption therapy is an effective method to remove unbound

radioimmunoconjugates from the bloodstream and reduce the nonspecific radiation exposure of
normal tissues.

Hemosorption is removal of toxins or metabolites from the circulation by the passing of blood,
within a suitable extracorporeal circuit, over semipermeable microcapsules containing
adsorbents (e.g., activated charcoal) or other adsorbents (e.g., various resins, albumin-conjugated
agarose).