Mst.

Sharmin Aktar
Lecturer
Dept: Leather Engineering
NEUTRALIZATION ILET, DU

Neutralization
Chrome tanned leather are always acid when they leave the tan liquors. This acidity is further
increased due to hydrolysis of the chrome compounds when the chrome tanned leathers are aged
after tanning. This can be expressed by a most simple chemical equation as follows:
4 Cr (OH) SO4 + H2O Cr4 (OH)6 (SO4)3 + H2SO4
33% 50% basic
The acid present in the chrome tanned leathers can broadly he classified under the following
heads:
a) Free acid
b) Protein bound acid
c) Acid present inside the co-ordination sphere of chrome complex
d) Acid fixed up with the chrome complex by primary valence.
During neutralisation the free and protein bound acids are efficiently removed either by repeated
washing with water or by chemical treatment. If these acids are not removed the next important
finishing operations like dyeing, fatliquoring etc. cannot be properly performed.

Objectives
 To remove the unwanted acid from chrome tanning
 To make the leather suitable for further treatment

Effect of neutralization on dyeing

Chrome tanned leathers are generally dyed with acid or direct dyes. Basic dyes do not react with
chrome tanned leathers unless the latter is mordanted. For simplicity therefore we shall avoid its
discussion. Both acid and direct dyes are sodium or potassium salts of certain colored acids.
When these dyes are dissolved into water a part of them ionize into their basic and acidic
fractions as represented below:
x Na x- + Na+
These negatively charged acid fraction x - , of the dyes react with the positively charged groups of
the protein and thus color is imparted to the leathers. Chrome tanned leathers are positively
charged due to its high acidity and therefore if they are direct immersed into an acid or direct dye
solution, without going through the neutralization operation, the available positive charges of the
leather will immediately react with the negatively charged dye molecules. The acidity of an
unneutralised leather is always un-uniform and therefore may cause uneven dyeing if directly
immersed into a dye bath.
On the other hand, over-neutralized leathers have practically no positive charges to react with. It
is therefore almost impossible to dye an over-neutralized leather with acid or direct dye. Proper
neutralization of leather is therefore necessary for ideal dyeing.

Effect of neutralization on fatliquoring

After dyeing the chrome tanned leathers are fatliquored generally with an anionic oil-in water
emulsion. According to the ideal condition of fatliquoring the negatively charged fat droplets
should penetrate into the leather upto a certain depth and break down there due to the
neutralization of their negative charges by the positive charges of the protein. The oil present
inside these droplets thus spread over the fiber surfaces and lubricate the latter. For ideal
condition the distribution of oil in chrome upper leather should not be uniform throughout its
thickness. The percentage of oil should be maximum at the grain and flesh sides and should
decrease as the middle layer is approached. To achieve this ideal condition of fatiquoring the
chrome tanned leathers should be properly neutralized. If chrome tanned leather are not
neutralized and put into an anionic oil-in-water emulsion the oil droplets will break down on the
leather surfaces due to the neutralization of negative charges of the oil droplets by the positive
charges present at the surface of the leathers. In that case oil will not penetrate inside the leather,
rather, the oil will be deposited on the surface making the leather greasy in feel and appearance.
On the other hand if leathers are over-neutralized the oil droplets will penetrate upto the middle
layers of the leathers which will therefore become soft, loose and flaccid.

The most important neutralizing agents

Strong product
1. Sodium carbonate (soda), borax: Products of this category are seldom used, possibly in
combination with mild products. Used in small quantities their neutralizing action is only
superficial. Larger amounts result in good penetration, however with over-neutralization of the
grain zone and a simultaneous detanning effect.
Mild products
2. Sodium hydrogen carbonate:
One of the most frequently used products. It is important that a float and dissolving temperature
of <38°C be observed in order to avoid soda formation. Over-neutralization is possible if large
amounts are used.
3. Ammonium bicarbonate:
Rapidly penetrating product. Very suitable for leathers of dense texture (pig leather, reptiles)
4. Sodium formate:
Mild neutralizing effect with low pH value. Over-neutralization is not possible. Mostly used in
conjunction with sodium hydrogen carbonate.
5. Calcium formate:
Mild neutralizing effect with no risk of over-neutralization. Formation of calcium sulphate can
cause trouble and may produce stains.
6. Sodium acetate:
Mild neutralizing effect with low pH value and bleaching of the chrome tanning color towards
blue. Over neutralization is not possible. Very suitable for pale leathers and aluminium- tanned
leathers.
7. Sodium sulphite:
Mild neutralizing effect with uniform penetrative power, without over neutralization. Due to
formation of sulphite complexes the chrome tanning color is intensified towards green.
8. Sodium thiosulphate:
Large amounts are required. Bleaching of the tanning color is obtained by deposition of colloidal
sulphur. Is therefore used for white and pale leathers.
9. Sodium aluminium silicate:
Besides a mild neutralizing action this has the added effect of aluminium silicate retanning,
which improves fullness and firmness of grain.
10. Polyphosphates:
Mild, penetrative neutralizing agent without risk of over neutralization. Often used in
combination with sodium bicarbonate.

Neutralization with Syntans

When chrome leathers are neutralized with mild alkalis like borax, sodium bicarbonate or similar
materials, the leather tends to become loose. This looseness is specially noticed in softy leathers,
which require heavy neutralization. But customers demand softy leathers that are not loose and
show a fine break when folded grain side in. The production of such leathers is not at all possible
with the ordinary method of neutralization even with mild alkalis. Neutralization with sodium or
potassium salts of organic acids also cannot be of much help. The looseness of leather is caused
by the voids between corium minor and major and unless these empty spaces are filled with
some suitable material, leathers with a fine break cannot be manufactured. These voids can be
filed with resins or natural tannins, but in that case the leather will lack the desired softness
unless a heavy dose of fatliquor is used.
A neutralizing type of syntan has solved this problem. To understand the neutralizing effect of a
syntan, one must know what neutralization actually is. Neutralization does not mean the removal
of acid from chrome leather and does not say anything about pH control. Neutralization is
actually a process to control the electric charges present on the leather surface. If the surface
charges are controlled without affecting the acid or pH of chrome leather, then that also should
be called neutralization.
Neutralizing syntans are such synthetic tanning materials. It is not always necessary that the
neutralizing syntans should have a high pH. These may be slightly alkaline, neutral or even
acidic. These syntans control the surface cationic charges by reacting with the basic amino
groups of leather.
These syntans fix to the leather and fill the voids between corium major and minor and thus give
extra fullness to the leather and make the latter free from looseness. Moreover, these syntans,
being light colored tanning materials, suppress the blue color of chrome leather making the latter
suitable for the manufacture of light-colored leathers. Thus, neuralization with syntans also
performs the function of impregnation and bleaching at the same time.
The chrome blue can also be neutralized with hypo. It showed better silky grain than leathers
neutralized with mild alkalis.
The neutralizing syntans which are sodium salts of weak organic acids, give the neutralizing
effect.

Parameters of neutralization
1. Float length
With float coefficients of 0.5-2 depending on type of leather, thickness and type of vessel. A
washing or rinsing bath should take place after deacidification in order to remove the salts that
have formed.
2. Temperature
Carried out in a range of 30-40ºC. < 38ºC if sodium hydrogen carbonate is used.
3. Intensity
Depends on the type of leather to be produced. Neutralization of the entire cross section is
required for soft leathers mostly in the upper pH range of 5.0-6.0. For firm upper leathers the pH
range is between 4.2-5.0. The outer zones are neutralized in the higher pH range, the inner zones
are only slightly neutralized. Leathers which tend to develop a loose grain should always be
treated in the lower pH range.
4. Duration
About 30 minutes to2 hours depending on the thickness of leather and texture, type of
neutralizing agent and type or leather to be produced.

Possible defects
1. Inadequate deacidification
If the middle zone of the cross-section remains un-neutralized problems may arise in subsequent
processing A
a) Astringent retanning agents diffuse only with difficulty into this zone.
b) Fat emulsions crack in this zone and cause smudging and fat stains.
c) In the leather the free acid migrates into the outer zone, causing corrosion at metal parts
of final products. Fatty spew may also occur to a great extent
2. Over-neutralization
Results in detanning of the grain zone and thus in loose grain, strawy, brittle grain or in
unfavorable cases even crackiness of the grain. Furthermore, may lead to uneven, pale and thin
dyeings.

Controls of de-acidification
Operational:
Cut off a small piece of leather, if possible from a section of dense texture. Then let an 0.1 %
indicator solution of bromocresol green (dissolved in 50 % alcohol) drip onto the cross-section.
The change of color indicates the progressive depth of penetration of the neutralizing agent and
the pH value on the leather.
Transition interval of bromocresol green:
Yellow = pH 3.4 and below
Yellow-green = pH 4.0
Green = pH 4.5
Blue-green = pH 5.0
Blue = pH 5.4 and above
The following indicators can be used for ranges below and above the mentioned values:
Bromophenol blue = pH 3.0 – 4.6 (yellow-blue)
Bromocresol purple = pH 5.2 – 6.8 (yellow-purple-red)
Bromothymol blue = pH 6.0-7.6 (yellow-blue)
Ideal condition of neutralization for chrome upper leather
According to the ideal condition of neutralization for proper dyeing and fatliquoring the leather
surface of the neutralized leather should be electrically neutral and the acidity should increase as
the middle layer is approached. During cationic chrome tanning chrome complex react with the
carboxyl group of the protein and therefore the isoelectric point of the chrome tanned protein is
always higher than the limed protein. This is of course true only when the cationic chrome liquor
is free from excessive masking salt. The isoelectric point of limed collagen is nearly 4.7 and this
value is shifted within the range of 5.0 to 6.0 due to such chrome tanning. The surface of chrome
tanned leather will therefore be electrically neutral if the pH value are kept within this range i.e.
within 5.0 to 6.0.
From the theoretical point of view, a leather is considerd properly neutralized when its surface is
at the isoelectric point of chromed collagen and the middle layer is at a pH value 4.4 to 5.3.

5.0-6.0 4.7-5.0 4.4-4.7 4.2-4.4 4.4-4.7 4.7-5.0 5.0-6.0

Leather thickness

Due to electrical neutrality the oil droplets cannot break down on the surfaces of the leathers but
penetrate upto certain deph where the positive charges of acid-protein help them to break down.
Similarly the negatively charged dye molecules do not immediately react with the electrically
neutral leather surface and thus get time to be uniformly distributed throughout the entire leather
surface. The uniformly distributed dye molecules then fix up to the leather surface as free acid
from the inner layers gradually and uniformly comes out there.

Role of the isoelectric point

The concept of an isoelectric point in proteins can be defined as follows:

∑ f i [NH 2]
i
IEP=
∑ f j [COOH ]
j
There are two points, relating to isoelectric point and its particular relevance to post tanning, that
are very important and worth emphasizing:
1. IEP is a point on the pH scale, so it does not change with changing pH of the system. The
IEP of collagen is the same whether it is in the limed state or in the pickled state. The
importance of this point is that the isoelectric point can only be changed if there is a
chemical change that alters availability of active groups.
In the context of charge on leather, care must be taken in ascribing the influence of
charged reagents. For example, treating collagen with cationic chromium (III) species
may be regarded as altering the IEP, because it may introduce positive charge. Whilst the
introduction of charge is true notably, the charge can be lost by treatments other than pH
change. From this point of view, the charge is immaterial as far as the IEP is concerned,
although the binding of chromium (III) clearly impacts on the IEP, by removing some
carboxyl function from the IEP determining ratio.
2. The charge on collagen is determined by the relative values of the IEP and the pH. If the
pH is higher than the IEP, the collagen is negatively charged, and if the pH is lower than
the IEP, the collagen is positively charged. Moreover, the further the pH is from the IEP,
the greater the charge. The clear consequence is the effect on the affinity of reagents that
rely on charge for fixation to the leather. This can be modelled as shown in Figure 1,
which also shows the effect of moving the isoelectric point.
From the model in Figure 1, it can be seen that the effects of moving the isoelectric point are as
follows:
 Change to higher IEP: at any pH value the charge on the protein/leather is either less
negative or more positive, depending on which side of the IEP is considered.
 Change to lower IEP: at any pH value the charge on the protein/leather is either less
positive or more negative, depending on which side of the IEP is considered.
The effects of charge on an electrostatic reaction can be understood from the simple relationship:
Rate ∞ [reagent charge]a [substrate charge]b
where the rate refers to the rate of the fixation reaction, which will be controlled by the
magnitudes of the charges, because they determine the degree of attraction. Clearly, if the
charges are different, the affinity is favored: this results in fast uptake, with a limitation on the
degree to which the reagent can penetrate the substrate. In contrast, if the charges are the same,
the affinity is disfavored: the reaction is slowed, because of the availability of reaction sites, so
penetration is favored. The measurement of the magnitude of the charge on leather is not easy.
Attempts have been made to use charged dyes to determine charge interactions, but not with
much success. In the context of processing, the best we can do currently is to estimate the overall
effect of the accumulation of change. In native collagen, charge as a function of pH will reflect
the swelling curve, since there is some cause and effect. The swelling is also influenced by
osmosis and lyotropy, and may even be controlled by those mechanisms, depending on the
specific conditions in solution.

increasingly positive charge zero charge increasingly negative charge

0 14
lower IEP IEP higher IEP

increasing affinity of anionic reagents decreasing affinity of anionic reagents

=more efficient uptake = less efficient uptake
=more surface reaction = better penetration
=less surface uniformity = more surface uniformity

decreasing affinity of cationic reagents increasing affinity of cationic reagents

=less efficient uptake =more efficient uptake
=better penetration =more surface reaction
=more surface uniformity =less surface uniformity

Fig- 1 : Relationship between pH and charge, governed by the isoelectric point