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SKIN COMPONENTS and WATER
Leather production is carried out largely in water.
Skin does not dry between the production operations. The discussion of
the character and strength of the bonds between water and skin components
therefore gains importance.
Energy of ion hydration depends on charge
and kind. For H+ approx. 176 kcal / mole ( 1156 kJ/mole
). Interaction of ions and water molecules consist of water-cation and
water-anion interactions. Absolute free energies and enthalpies of
ion hydration are greater for anions.
Ions of small radii and
multivalent ones Li+, Na+, H3O+,
Ca+, Al+3, OH-, F-
increase the viscosity of water -they show
a structure making ability .
They produce, apart from polarization, the immobilization and electrostriction
(a dielectric deformation of molecules in the external electric field proportional
to the square field intensity) of water molecules
as well as the decrease of entropy ( due to additional ordering
) in the second hydration layer .
Large monovalent
ions generally give a structure-breaking
effect (entalpy increase). K+ , NH4+,
Cl-, Br-, I-, NO3-,
IO3, ClO4- ion increase
mobility of water .
Nonpolar substances have a very strong structure forming influence
on water (only observed in the first layer of water molecules). The water
coordination number is increased to 5 and happens spontaneously. Water-water
interaction does not change but hydrocarbon-hydrocarbon interaction decreases
as hydrocarbon-water interaction is established.
Collagen -water system :
Water bound to collagen forms a kind a of chain
, parallel to the collagen molecule chain .
There are two water
molecules per tripeptide unit firmly
bound by H-bonds to the helical part of the collagen molecule(with
binding energy close to 11-12 kcal/mol = 46-50 KJ/mol). Their residence
time in their sites is about 0.1-1.0ms. This water
accounts for 35 % of collagen weight ("first hydration shell", and
a second one between 35 to 50%). The remaining part of water, in a not
strictly limited amount, which is in weak interactions with a number of
different sites, forms a multilayer with liquid-like properties .
The first kind of water does not freeze at 0C0
. The strength of H bonds between `swelling` water of collagen is
about 1-2 kcal /mol . There are no sharp limits between strongly and weakly
bound water , nor between weakly bound completely free water .
Glycosaminoglycans and water :
It has been suggested that all polar groups of gycosaminoglycans are
involved in water binding.
Swelling of hyaluronic acid is greatest .
The swelling degree decreases with the increase of ionic strength of
the NaCl soln. This may contribute to swelling on soaking.
It can be expected that the effect of gycosaminoglycans on the behaviour
of water in the skin is greater than that of collagen, since the former
are more spread out and thus more accesible. Hydration of polysaccharides
is directly dependent on the amount of -OH groups occurring in a unit.
Water permeability of skin:
The external surface of skin of land animals is permeable to liquids
to a very limited extent. There is no substantial change after the death
of the animal.
Penetration of water through skin is time proportional except for the
initial period (period necessary to reach dynamic equilibrium).
The ability of ions and non ionic substances to penetrate skin is of
great importance for the curing and soaking processes.
Molecules penetrate the skin in a passive way
-by diffusion. Three arguments speak in favour :
1) specific permeability remains unchanged even for a long time
after skin is removed from animal .
2) diffusion obeys Fick's law , an exception is Na and K ions
which are actively absorbed by the skin
Fick's law : p = r / c
p - permeability constant
r - penetration rate
c - concentration
3) Stratum corneum of epidermis is resistant to penetration and
various compounds ( ie. arrest alkyl phosphoric compounds).
Permeability of skin decreases with age; also
decreases to half its value as the temperature decrease by 10 K.
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