Assignment No.

2
Name : Sana Iqbal Sahi
Roll No : 03
MS chemistry (2nd semester)
Course Title: industrial process chemistry
Course code : chem-534

Topic:
Masking agents in chrome tanning

Submitted by:
Dr. Omer javed

GCWUS
 Masking agent in chrome
tanning

Masking agents in chrome tanning:

Introduction:

Leather products are prepared from animal skin, and they are commonly used to produce daily
necessities, such as clothing, footwear and decoration. Leather tanning is an essential step to
convert raw skin into leather, and endows the leather with satisfactory mechanical strengths and
high resistance to heat, chemicals and putrefaction. Specifically, leather tanning is a process
which improves the dispersion and fixation of collagen fibers via abundant crosslinking networks
between the tanning agent and –NH2/–COOH groups in the collagen matrix. Tanning leather
using chrome salt (Cr (III)) is the traditional and most used approach worldwide. However, as a
human carcinogen is generated from the oxidation of Cr ( III) to Cr(VI), chrome salts are
becoming increasingly restricted due to stricter environmental regulations and health concerns.

The most common tanning agents used in the U. S. is trivalent chromium and vegetable tannins
extracted from specific tree barks. Alum, syntans (man-made chemicals), formaldehyde,
glutaraldehyde, and heavy oils are other tanning agents.

Masking agents are of major significance, and the type of leather produced depends very
strongly on which complexing agents are present. These tend to slow down the tanning action.
A masking agent is a reagent used in chemical analysis which reacts with chemical species that
may interfere in the analysis. In sports a masking agent is used to hide or prevent detection of a
banned substance or illegal drug like anabolic steroids or stimulants.

In order to penetrate into fibrous structure of the hide and skin, the chromium complex must be
small. This may be obtained by a low PH and low basicity chromium salt. When penetration has
been achieved a higher ph is required; this liberates the carboxyl groups of the collagen and
leaves them free for coordination, and helps in the formation of oLo and oxo polynuclear
chromium complexes. When the chrome tanning has been achieved and the skin is more resistant
to heat, and temperature may be raised.The uptake of chromium from tanning bath under normal
conditions of tanning is of the order of 40-70% of used chromium. It is now possible to increase
the absorption levels of chromium in the tanning bath. These strategies include (a) changing
conditions of tanning such as mechanical action, time, float length, pH and temperature.

Increasing collagen reactivity is mainly depending on increasing the number of carboxylic

groups on the amino acid side chains, which provide more sites for cross-linking with chromium
salts and increasing exhaustion. On the other hand, chrome masking is defined as the
incorporation of certain reactive groups into chrome tannin complexes to enhance the chrome
penetration rate and permit basification to higher PH.

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 Masking agent in chrome
tanning

Masking agents in chrome tanning:

 Formate masking
 acetate masking
 Phathalate masking.
 oxalic acid masking
 Ascorbic acid as a potential masking agent

Formate masking:

In chrome tanning, it is known that the chromium may be complexed or "masked" with an
organic acid such as formic or acetic acid to increase the pH at which hydrated chromium oxide
begins to precipitate from the basic chromium sulfate to above the pH at which the carboxyl
groups of the hide collagen begin to ionize and become more receptive to attachment of the
chrome complex. Thus, it is known that chrome tanning should begin at a fairly low pH (for
example, below about 3.0) to permit the rapid penetration of chrome through the pickled hide,
and the tanning should be finished at a higher pH such that the chrome can combine with the
collagen and form hydrated chromium oxide-sulfate cross-linked microstructures which provide
the stabilized condition in the hide known as "tanning".

Formate-masked chrome generally requires a pH of about 3.75 to release the chrome while
acetate-masked chrome requires a pH of about 4.25. The pH adjustment, however, should be
short of that which will cause precipitation of hydrated chrome oxide since the latter does not
play a part in the tanning process and can lead to poor tanning and undesirable side effect. To
optimise the speed of the chemical penetration, masking agents (formic acid, phthalate or salts of
dicarboxylic acids for complexation of Cr3+) are sometimes introduced. Masking increases the
precipitation point of the complex. The amount of masking agent can vary from 0.5 to 1.0

Acetate masking:

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 Masking agent in chrome
tanning

Phathalate masking:

The use of sparingly soluble dicarboxylic acids, such as adipic or phthalic, as masking agents to
increase chrome exhaustion. More soluble acids, such as oxalic, malonic and maleic, are also
known to reduce chrome exhaustion

This leather is fuller, not so flat, has higher chrome content and is green in colour. Here, because
of the bidentate nature of the phthalate as a complexing agent, the chromium uptake tends to be
greater and there are more links within the individual chains

Ascorbic acid as a potential masking agent:

Trivalent chromium salts in the hydroxysulfate form are the most widely used tanning agents in
the world for the transformation of hide into leather, due to their ease of use and the quality that
the leather acquires with respect to alternative tanning agents . A typical reaction of chromium
aqua species is called olation where polynuclear complexes consisting of chains of chromium
(III) ions connected by bridging hydroxide groups are formed.

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 Masking agent in chrome
tanning

Mono- and di-basic carboxylic acids are usually added to the tanning bath as ‘masking agents’ to
control the rate of reaction and penetration of chromium (III) species into hide protein.
Coordination of masking agents enhances the penetration rate by reducing the cationic charge
and making the species less reactive to collagen. On the other hand, the addition of salts of these
agents may raise the pH of the tanning solution and thus increase the reaction rate by increasing
the reactivity of collagen. Dicarboxylates (e.g. phthalate) increase the size of the olated
complexes by cross-linking, resulting in a higher number of reaction sites per molecular ion .
The rate of reaction depends on the nature of the ligands present in the chrome complex and no
tanning will occur with very stable masking groups. As a weak di-basic acid (pK1 ¼ 4.25) and a
weak bidentate ligand, ascorbic acid could be a potential masking agent in the tanning process.
We have isolated two polynuclear chromium complexes involving sulfate and hydroxo bridges
and ligating ascorbate, as part of a continuing effort aimed at the preparation of metal ascorbate
complexes

Ascorbate may exchange water molecules around chromium in the olated complexes and as a
weak chelating ligand can also be expelled from the coordination sphere during the pH
adjustment in the tanning process. In this sense, it may function as a masking agent and the
ability of ascorbate containing olated complexes to cross-link collagen is worth exploring.

Advanced masking agent for leather tanning from stepwise degradation and oxidation of
cellulose†

An oligosaccharide-based masking agent suitable for chrome-free metal tanning was produced
from cellulose via a stepwise degradation and oxidation process.

Most of the oligosaccharides were retained in the H 2O phase. Further H2O2 oxidation of the
oligosaccharides in the H2O phase broke the glycosidic bonds, and the Mw of the
oligosaccharides substantially decreased from 3144 g mol −1 to about 600 g mol−1. Besides, –CHO

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 Masking agent in chrome
tanning

and –COOH groups were introduced via H2O2 oxidation, strengthening the surface charge
density of the oligosaccharide and improving their coordination ability with metal ions as a
consequence. Al and Zr species could competitively coordinate with the limited –COOH group
at C2 in the oxidized oligosaccharides. Then, the Al/Zr-oligosaccharides complex could easily
penetrate into leather matrix, and the collagen fibers would be well dispersed and
stabilized via crosslinking reactions between immersed Al/Zr species and the collagen fibers.
With satisfactory Ts and mechanical strength, the resultant leather exhibited great potential for
commercial use.

References:

 Jiang, Z., Xu, S., Ding, W., Gao, M., Fan, J., Hu, C., ... & Clark, J. H. (2021). Advanced
masking agent for leather tanning from stepwise degradation and oxidation of
cellulose. Green Chemistry.
 Zümreoğlu-Karan, B., Ünaleroğlu, C., & Ay, A. N. (2002). Ascorbic acid as a potential
masking agent in the tanning process. Olated chromium complexes involving ligating
ascorbate and bridging sulfate groups. Transition metal chemistry, 27(4), 437-441.
 Yao, Q., Chen, H., Huang, H., & Liu, B. (2018). Mechanism and effect of hydroxyl-
terminated dendrimer as excellent chrome exhausted agent for tanning of pickled
pelt. Journal of Cleaner Production, 202, 543-552.