 Chromium complexes and their structures

From Werner’s theory, there might be seven types of chromic acid structures. Here
these are stated below:
CrCl3.H2O is a co-ordination complex where six water molecules are added as
secondary valency termed as co-ordination number and 3Cl is primary valency
The co-ordination complex acts as an atom. In Normal [Cr(H2O)6]Cl3 complex 3Cl
is attached to chromium by primary valency and H2O is attached by secondary
valency. This complex is violet in color in the solution. But when heated the
solution turned into a green color solution. The 3Cl atoms can be precipitated by
AgNO3 and simultaneously the chrome complexes lose one of their positive
charge.

Violet Color

When heated we found two types of complexes as β-chromic chloride and γ-chromic
chloride respectively.

These 3 complexes are cationic in nature . Another 4 types of complexes are formed in
the presence of NaCl

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The last 3 complexes are anionic in nature . These seven types of complexes can
be represented using SO4 in stead of Cl also.

 Phenomena of Hydrolysis, Olation, Oxolation, Polymerization

of chrome complexes

Normal salts of Chromium like CrCl3 or Cr2(SO4)3 have no tanning power. These
salts can be made of basic salt by hydrolysis. Hydrolysis of these salts are given
below:

CrCl3+ H2O Cr(OH)Cl2 + HCl

Cr2(SO4)3 + H2O Cr(OH)SO4 + H2SO4
As both reaction indicated the chrome liquor will be acidic in nature (presence of HCl
and H2SO4), we can add alkali to accelerate the hydrolysis process. The alkali can be
represented in a following way also:

 Olation: The attachment of a hydroxy (-OH) group with one chromium atom
with a primary valency and another Chromium atom with a secondary valency
(Cr-OH…..Cr) is called olation. In olation, the water group was eliminated and
a bigger molecular weight compound was produced. The mechanism of olation

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 in 33.33% basic chrome chloride is stated below:

Olation combines two or more molecules of basic chrome compounds with one
another producing a bigger molecule. Olation is affected by heating increase in
basicity or concentration etc.

 Oxolation : The formation of an Oxygen bridge between metal ion

Chromium with acid liberation is termed oxolation. Oxolated compounds can
be formed by continuous heating of olated compounds. The reaction is given
below :

Again heat

 Polymerization: The process in which the chrome compounds simply join

up by forming bigger molecules is called polymerization. The increase in the
size of the molecule of basic chrome compound can be done by both olation
and polymerization. The main difference between olation and polymerization is

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 that there is no elimination of water in the polymerization compound to the
olation process. The reaction is stated below :

Polymerization

 Masking, Principle of masking, effects of masking on chrome

tannage.

Masking: The modification of metal complexes, by replacing aqua ligands

with other less labile ligands – the purpose is to render the complex less
susceptible to additional complexing reactions, including precipitation.

It has been assumed that the function of masking is to aid chrome penetration at
the start of tanning, by reducing the reactivity of the complexes. Although such
masking can in principle be achieved with any ligand capable of creating a
complex, in the case of chrome tanning the commonest practical masking agent
is formate, usually derived from the pickling formulation, but it may be added
after a sulfuric acid pickle or the masking reaction might be conducted prior to
the tanning reaction.
The principle of using a masking agent in chromium tanning is to control and
optimize the tanning process by regulating the concentration of chromium ions
in the tanning bath. The primary masking agent used in this process is sodium
formate (HCOONa), although other substances can also serve as masking
agents.
The key reactions in chromium tanning with a masking agent involve the
formation of stable and soluble complexes between the masking agent (sodium
formate) and the toxic, hexavalent chromium ions (Cr⁶⁺) in the tanning bath.
These complexes reduce the concentration of toxic chromium in the bath,

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 making it safer for the tanning process and the environment. Here are the
reactions:
1. Hexavalent Chromium Reduction: In the presence of a reducing agent like
sodium formate, hexavalent chromium (Cr⁶⁺) is reduced to trivalent chromium
(Cr³⁺): 2Cr⁶⁺ + 3HCOO⁻ + 3H₂O → 2Cr³⁺ + 6CO₂ + 3OH⁻
2. Formation of Chromium Formate Complex: The trivalent chromium ions
(Cr³⁺) then form stable complexes with formate ions (HCOO⁻): Cr³⁺ +
3HCOO⁻ → Cr(HCOO)₃

 Effects of masking on chrome tannage

The designation of ‘complexation masking’ indicates that the net effect is to
modify the ability of the complex to react further, i.e. this conforms more to the
conventional view of masking. Comparing the effects of formate and oxalate
masking (Figure 11.20), the notional structures indicate that formate is likely to
be less able to interact with water than an aquo ligand, thereby conferring a
degree of hydrophobicity. In contrast, oxalate has the potential for effective
hydrogen bonding, because it offers only carbonyl groups for interaction with
the solvent, so the net effect is a reduction in the number of available reaction
sites and hence reduced affinity for collagen carboxyls, driven by the chelating
mechanism.

Masking changes any or all the properties of chrome liquor as well as leather.
I. Composition of chrome compound .
II. pH of the chrome liquor .
III. The electrical migration of chrome compound.
IV. The ability of the liquor to resist precipitation when alkali is added
V. Changes the chrome fixation by the collagen

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VI. Changes the shrinkage temperature and other quality like feel, fullness of the
leather etc.

 Method Of Chrome Tannage and Mechanism of Chrome

Tanning:
The use of chromium(III) salts is currently the most common method of tanning:
perhaps 90% of the world’s output of leather in tanned in this way. The basis of the
chrome tanning reaction is the matching of the reactivity of the chromium(III) salt
with the reactivity of the collagen

Chrome tannage: The hydrophilicity/hydrophobicity of chrome-tanned leather can be

controlled by the way in which the tannage is conducted. In this case the parameters
can be set to obtain the maximum hydrophobic nature, i.e. slowest rate of change of
pH and temperature, within the constraints of the processing time.
Chromium(III) salts are stable in the range pH 2-4, where the basicity changes, but at
higher values, they will precipitate. This can be modeled in the following way, using
empirical formulae:

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The processing time for the chrome tanning reaction itself is typically less than 24
hours. Chrome tanning confers high hydrothermal stability; a shrinkage temperature
of 110’C is easily attainable. Chrome tanning alters the structure of the collagen in
only a small way: the usual chrome content of fully tanned leather is 4% Cr2O3.
Chromium(III) can act as a mordant (fixing agent for dyes) and its pale color allows
bright deep and pastel shades (even though the base color of the leather is pale blue).
The chrome tanning reaction is the creation of covalent complexes between collagen
carboxyl groups, specifically the ionized carboxylate groups and the chromium(III)
molecular ions. In this way, the reaction is no different from making any other
carboxylate complex, such as acetate or oxalate, although tanners tend to think of the
reaction as the fixation of chrome onto collagen.
The trivalent chromium ions (Cr³⁺) react with the collagen, which is the primary
structural protein in the hide or skin. This reaction forms stable and insoluble
complexes between the chromium ions and the collagen fibers. The reaction can be
represented as follows:
Cr³⁺ + Collagen → Complexed Collagen-Chromium
The complex collagen-chromium structures create stable cross-links within the
collagen fibers, effectively "tanning" the hide or skin. These cross-links make the
leather more resistant to microbial attack, decay, and enzymatic degradation.
Rechroming: The process begins by rechroming the prepared hides or skins with a
tanning solution containing trivalent chromium. During this step, hexavalent
chromium (Cr⁶⁺) is typically reduced to trivalent chromium (Cr³⁺) through the
addition of a reducing agent, such as sodium bisulfite or sodium metabisulfite.
2Cr⁶⁺ + 3SO₃²⁻ + 3H₂O → 2Cr³⁺ + 3SO₄²⁻ + 6H⁺

➢Principle of single bath chrome tanning process

The single bath chrome liquor is generally prepared from sodium and potassium
dichromate or chrome alum.
The original process was used chrome alum, Cr2(SO4)3•K2SO4.24H20, applied as
the acidic salt, typically giving a pH of almost 2 in solution. Following penetration at

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that pH, when the collagen is unreactive, the system is basified to pH 4, with alkalis
such as NaOH or Na2CO3 to fix the chrome to the collagen.
Cr2(SO4)3•K2SO4•241-120 Na2CO3 = 2Cr(OH)SO4 +Na2S04+ K2SO4+ CO2+
23H2O
In actual practice, the liquor is made according to the following recipe
•Chrome alum : Hot water = 1:5 is taken in a wooden vat
•Required content of soda ash dissolved in water in a ratio 1:10
•Then dissolved soda ash was added slowly to the chrome alum solution while stirring
thoroughly.
Chrome alum 100 parts
Soda ash 10.6 parts
Total water 600 parts

➢Principle of double bath chrome tanning process

The process was conducted in two steps:
The pelts is saturated by chromic acid in the first bath, then it is removed, usually to
stand overnight. At this time there is no reaction, because Cr(VI) salts do not complex
with protein.
Na2Cr207 + H2SO4 —> Na2SO4 + H2Cr2O7
Next, the pelt is immersed in a second bath, containing a solution of a reducing agent
and enough alkali to ensure the final pH reaches at least 4. The chromic acid gets
reduced by the sulfurous acid and basic chromium compounds are formed inside the
skin which tan later. The tanned skin has a greenish-blue color.
In 1972 stiasny and B. M. Das jointly studied the reactions. According to them, the
following reactions take place:
(a)H2Cr2O7 + 2H2SO4 + 3Na2S2O3 —> 2Cr(OH)SO4 + Na2SO4 + 3S +2H20
(b)4H2Cr2O7 +5H2SO4 +3Na2S2O3 —> 8Cr(OH)SO4 + Na2SO4 +5H20
(c)H2Cr2O7 + 5H2SO4+6Na2S203 —> 2Cr(OH)SO4 + Na2SO4 + 3Na2S5O6
+5H20

References:
Antony D. Covington -Tanning Chemistry: The Science of Leather
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Dutta S.S. – An Introduction to the Principle of Leather Manufacture
https://www.scribd.com/document/438859582/Chrome-tanning-LE-1-Compatibility-Mode
https://chat.openai.com

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