SURFACE PHENOMENA IN

SOLUTIONS OF BIOLOGICAL
IMPORTANCE
 Surface molecular phenomena
• The surface of separation between two phases
of a substance (liquid and a gas in which the
vapors of the liquid itself can be found) or
between two immiscible liquids = an elastic
membrane-
 own structure
 specific properties
 Surface molecular phenomena
• Surface layer = the thin layer at the free
surface of a liquid in contact with a gas of a
thickness equal to the radius of the sphere of
molecular interaction
• Sphere of molecular interaction = the space
where cohesive forces act for a specific
molecule
 Surface molecular phenomena
• Cohesive force = molecular forces of
attraction manifesting on a molecule from the
surrounding molecules.
• Molecular beam = distance at which
intermolecular forces of attraction occur
(approximately 1 nm).
 Surface molecular phenomena

Within liquid mass R=0

>>>>>QUASI-STATIONARY EQUILIBRIUM

>>>>>MINIMUM INTERACTION POTENTIAL ENERGY

 Surface molecular phenomena
atmosferă

sfera de acţiune
lichid
moleculară

a) b) c)

Fig.1 Poziţiile sferelor de acţiune moleculară pentru diferite molecule

 Surface molecular phenomena
• Liquid surface layer having a thickness equal to
the radius of the sphere of molecular action =
surface layer.
• Since all molecules in the surface layer are
subject to a resultant force oriented towards the
fluid volume, the surface layer presses on the
remaining of the fluid =
• tension elastic membrane.
• The pressure exerted by the surface layer on the
unit area is called internal pressure.
 Surface molecular phenomena
Surface layer – all molecules participating in
determining the internal pressure
Example
• The thickness of the surface layer of the water
surface – 0,05 mm
• Internal pressure - 170.000 atm

>>>>> LIQUIDS ARE INCOMPRESSIBLE

 Effects of surface tension
• Formation of spherical
droplets. Surface tension
gives them a quasi-
spherical form, because
the sphere has the
smallest surface area:
volume ratio
>>>SURFACE LAYER = elastic
membrane tending to
decrease the surface.
 Effects of surface tension
• The floating of objects denser than water
occurs when the object is not wet and its
weight is small enough to be offset by the
forces arising from the surface tension.
 Effects of surface tension
• Oil/water separation is caused by a difference
in the surface tension of different liquids.
 Surface tension force

• To maintain a membrane stretched in static

equilibrium, at its edge there must be a force F,
tangent to the liquid surface and normal to the
surface edge = surface tension force.
 Surface tension force
F≈l
•  

• σ = coefficient of proportionality,
named coefficient of surface tension,
• F=σl  
Coefficient of surface tension:
•  

 F
l
 Surface tension force
• Thus, to increase the free surface area of a
liquid mass with a quantity ΔA, a work (L)
quantity is needed.

•  This work is transformed in potential energy.

 Surface tension force
A rectangular liquid membrane
stretched over a rigid frame of height l,
mobile height and negligible mass

• In order to determine the work needed to increase the

surface area of a liquid membrane by an amount ΔA, the
mobile side of the membrane is shifting on a distance ΔS,
under the action of an external force F
•  Membrane stretching is a quasi-static process.
 Surface tension force
L  F  S F  l
L    l  S
L    A
E    A
E
 
A
 Coefficient of surface tension

E
 F
l
 
A
Coefficient of surface tension
Depends on fluid nature
Surface tension of different fluids in contact with air
mN/m.
Fluid Temperature °C Surface tension
Acetic acid 20 27.6
Water 20 72,8

Gasoline 20 28,8
Aceton 20 23.7
Diethyl ether 20 17.0
Ethanol 20 22.27
Glycerin 20 63
Isopropanol 20 21.7
Mercury 15 487
Methanol 20 22.6
Olive oil 20 32,1
 Coefficient of surface tension
Depends on solutions concentration.
Solvates may have effects on surface tension depending
on their structure:
• Reduced or no effect such as sugar
• Increased surface tension, as inorganic salts
• Progressive decrease in surface tension as the alcohols
• Decrease in the surface tension up to a point beyond
which, they have no longer any effect, such as
surfactants
[

Coefficient of surface tension

Depends on solutions concentration
Surface tension of different fluids in contact with air
mN/m
Temperature°
Fluid Surface tension
C
Acetic acid 20 27.6
Acetic acid (40.1%) + water 30 40.68
Acetic acid (10.0%) + water 30 54.56
Ethanol 20 22.27
Ethanol (40%) + water 25 29.63
Ethanol (11,1%) + water 25 46.03
Sodium chloride  6.0M aqueous
20 82.55
solution
Sucrose (55%) + water 20 76.45
Water 20 72.8
 Coefficient of surface tension
Depends on temperature
• The general tendency is that surface tension decreases with
increasing temperature, reaching a value of 0 at the critical
temperature.
• There are some empirical equations that make the connection
between surface tension and temperature:
• Eötvös rule 3/ 2
 V  k (T  T )
c

Here, V is the molar volume of the substance,  TC  is the critical
temperature  and  k is a constant valid for almost all substances k =
2.1 x 10−7. [J K−1 mol-2/3]  For water,  V = 18 ml/mol and TC = 374 °C
can be used.
 Coefficient of surface tension
Surface tension of different fluids in contact with air
mN/m
Fluid Temperature °C Surface tension
Water 0 75.64
Water 20 72.80
Water 25 71.97
Water 50 67.91
Water 100 58.85
 Coefficient of surface tension
• If fluids that come in contact have the same
surface tension as the air >>>, they get mixed
E.g.: Water – Alcohol

• There are substances that are able to reduce

the surface tension = tensioactive substance
E.g.: Alcohols, organic acids, detergents
 Coefficient of surface tension
• The coefficient of surface tension of come
biological fluids t=200C; (mN/m)
• Serum 64-65
• Urine 66-70
• Bile 48
• Milk 50
• Lymph 65
 Contact phenomena between liquids and solids

Contact angle and interfacial tension

• Surface tension is not just a property of the fluid, but a
property of the fluid interface with another environment.
• If a fluid is in a container, than at the outside of the
interface between fluid / air at the above surface, there is
also an interface between the fluid and the container walls.
• The surface tension between fluid and air is usually higher
than the surface tension from the contact with the container
walls.
• Where two surfaces meet, their geometry must be in such
a way as all forces be in a state of balance.
CONTACT ANGLES
Contact angles
 Contact angles
Its vertical component should exactly cancel the
force fls  .

θ = is the contact angle

 a concave meniscus has a contact angle less
than 90°, the fluid wash vessel walls = lyophilic
 and a convex meniscus has a contact angle
higher than 90 °
 Contact phenomena
• A solid can be lyophilic in relation to a liquid
and lyophobic compared to other liquid.

Example
Water wets the glass and does not wet the
paraffin.
Mercury does not wet the glass but it does
wet a clean iron surface.
 Capillarity phenomena
• Capillarity is the ability of a porous material
or of a tube to draw up a liquid ↔
intermolecular adhesion forces between the
liquid and solid are stronger than the
intermolecular cohesion forces within the fluid.
Remark!
• Capilarity can induce an upward movement of
the water, contrary to the downward one,
induced by gravitation.
Capillarity phenomena

m  g    l  cos 
 V  g    l  cos 
2
    r  h  g    2    r  cos 
2    cos 
h
rg
 Adsorption
• In physics, adsorption is the pehnomenon of
retaining the molecules of a fluid substance
on the surface of a liquid or solid.
• There are solid-gas adsorption, liquid-gas and
liquid-liquid.  
• Intensity adsorption degree is directly
proportional to pressure and inversely
proportional to the temperature at which there is
the adsorbent-adsorbate interface.
 Adsorption
• Adsorption can be:
• physical, physical adsorption, when
adsorption is due to the action of
Van der Waals forces of attraction between
the molecules of adsorbent and adsorbate.
• Chemical, chemisorption, phenomenon in
which the gas is kept at surface by the
chemical forces specific to the substances
involved.
 Adsorption-interactions
• Nature of adsorbent
• Nature of adsorbate
• Size of the contact area – the adsorbent power of a body increases by
dividing it in very small fragments
• Temperature
• Surface tension
• Substance concentration – if C is the concentration of the nonadsorbate
substance and c, the concentration of the adsorbent substance, adsorption
occurs until equilibrium is reached between the two concentrations
(Freundich relationship), where K and n are constants that depend on the
nature of bodies.
1/ n
c  K C
• Area electrical load – selective adsorption
• Electrical load of the adsorbate particle - selective adsorption
 Adsorption-effect
Orients the surface molecules
Change the structure of the adsorbate
molecules
Chemical properties are changed

Remark!
This explains the increasing speed of some
chemical reactions at the level of the
adsorption surface.
 Adsorption-applications
• Activated carbon with increased porosity is
internally administered in gastro-intestinal disorders
in order to adsorb the secretions and the harmful
substances in the digestive tube.
• The attraction force of all substances depends, both
on the area of the internal surface and of the
pores distribution. The surface area is decisive for
the degree of activation, pore distribution
determines accessibility. If the pores are too small,
the components with large molecules cannot pass.