Jubayer Islam Nafim

Roll- ZH-192-002
Session- 22-23
Leather Processing- II (LE-201)

INSTITUTE OF LEATHER
ENGINEERING AND
TECHNOLOGY, UNIVERSITY
OF DHAKA
Submited to Prof. Dr. Sobur Ahmed
The structure of Chrome complex
According to Werner even when to judge by the valence number, the combining power of certain atoms is exhausted, they
s�ll possess in most cases the power of par�cipa�ng further in the construc�on of complex molecules with the forma�on
of very definite atomic linkages.” This extra valence above the primary valence commonly known, is defined as auxiliary or
secondary valance.

Chromium in the chromic state is trivalent and therefore, chromic chloride should be Cr CI3, but normal chromic chloride
is Cr Cl3.6H20. How do these six water molecules then remain atached to chromium? According to Werner they remain
atached by auxiliary valence. (The number of such monodented groups which an atom can hold by means of auxiliary
valance is called co- ordina�on number and the central atom together with its co- ordinated groups is called a complex
which func�ons as a unit.) The value of the co-ordina�on number varies from two to twelve, in most cases, and for
chromium it is six. The co-ordina�on number for an atom depends upon the space available around it.

In normal chromic chloride, thus the chlorine atoms are atached to normal chromic chloride, thus the chlorine atoms are
atached to chromium by primary valence forming electrovalent linkages whereas the six water molecules are atached by
secondary valence and these can be differen�ated by pu�ng a third bracket as follows:

The three chlorine atoms have received from chromium one electron each to from the electrovalent linkage- a linkage
which is a scaler quan�ty and therefore has no direc�on or magnitude. The three chlorine atoms can therefore ionize and
can be precipitated by silver nitrate.

On the other hand, each of the six water molecules has shared with chromium a pair of electrons forming co-ordinate
linkage which being a vector quan�ty has definite magnitude and direc�on. These water molecules are not therefore so
easy to detach from chromium. (Cr 6H20)+++ is thus complex and acts as a unit. When the violet solu�on of chromic
chloride is heated, the solu�on turns green. Due to the supplied heat one water molecule of the complex gets replaced by
chlorine atom with the forma�on of another type of Chlorine called β-form. To do this, one chlorine atom, out of the three
has given back one electron which it received from chromium previously.
The chrome complex, thus, loses one of its posi�ve charges and the chlorine atom inside the third bracket or complex
forms co-ordinate linkage with chromium. This chlorine cannot therefore ionize, nor can it be precipitated by silver nitrate.
This chlorine is thus inac�ve as far as chemical reac�on is concerned and can be called masked. From β-Chromic chloride
therefore only two chlorine, outside the complex, can be precipitated by AgNO3 solu�on. Further hea�ng will convert β-
Chromic chloride to γ-chromic chloride from which only one chlorine can be precipitated by silver nitrate.

There are another four more possible type of chromium chloride, whose forma�on may occur in the presence of
hydrochloric acid and sodium chloride, whereby all complexly held water molecules may finally be displaced.

We thus see that chromium chloride may exist in three different forms ca�onic, non-ionic, and anionic. Basic chromium
compounds which are used for tanning can be ca�onic, anionic or nonionic, but their tanning behavior will be different.

Ca�onic chrome complex: Mono-chloro penta-aquo chromic chloride (α, β and γ form of chrome complex)

Anionic chrome complex: Sodium-hexachloromiate

Nonionic chrome complex: trichloro-triaquo-chromium.

Basic chrome complex:

The number of OH group held by basic chrome compound is termed as basicity. Only basic chromium compounds have
tanning power and a non-basic chromium compound can become basic by hydrolysis. Chrome compounds containing no
complexly held water do not get hydrolyzed and therefore Werner, Pfeiffer etc. regarded the hydrolysis as that of water
removal from the complexly held water groups, as follows: -

The above concept shows that during the process of hydrolysis acid is liberated because of which the pH of chrome liquor
goes down. This hydrolysis can be accelerated by the addi�on of alkali and by dilu�on.
Olation, Polymerization and Oxolation
Ola�on: Ola�on can be defined as linking of one hydroxyl group by two adjacent chromium atoms. The hydroxyl group is
linked up with one chromium by primary valence, and with next chromium by secondary valence, thus: Cr___OH------Cr.
This olated OH group cannot be �trated through acid like unolated one. Ola�on is favored by heat, �me and increasing
concentra�on. Ola�on can linkup more than two chromium compounds and increase total molecular weight of compound.
But that doesn't mean there is a direct rela�onship between molecular weight of compound and the degree of ola�on.

Polymeriza�on: The molecular weight of chrome complexes can also be increased by polymeriza�on. The difference
between ola�on and polymeriza�on is that water is eliminated during ola�on but not during polymeriza�on with the
forma�on of a very big complex having less water solubility. The tanning property of chrome complex is largely dependent
on its size, as small par�cles do not have tanning proper�es and on the other hand, large colloidal par�cles do not
penetrate the collagen fibers.

Oxola�on: The olated chrome compounds are con�nuously heated more acid is found to be liberated and the-chrome
complexes become more stable than olated compounds due to oxygen bridge between the two chromium atoms; Thus Cr-
0-Cr. This is called oxola�on and the compounds oxolated compounds.

Linkage of chrome compound by forming ring: The acid groups, organic and inorganic, present in the chrome liquor also
play significant role and two or more chromium atoms may be linked up, some�mes with ring forma�on, by these groups.
For example, sulphate, formate, acetate and other forms of organic acid can form stable six membered between two
chrome compound already joined by hydroxyl group.

Oxalates, tartarates etc. which have maximum power of penetra�on into the chrome complexes can form stable five
membered rings including only one chromium atom. Malonate forms a stable six membered ring. Salts like succinate,
fumarate, adipate, suberate, phthalate, etc. where two carboxyl groups are separated by several CH, groups can also
increase the molecular size of the complex. Mono olated chrome compounds are unstable unless they are reinforced by
stable ring structure.

Recent work suggests that the stability of chrome complex is mainly

due to ring forma�on like figure 1. It is also suggested that when sulphate is added to 33% basic ca�onic chrome liquor
and the solu�on is boiled, the complex in it enlarges like figure 2.

Fig. 1 Fig. 2:

When the size of the complex increases it cannot remain suspended in solu�on-and ul�mately gets precipitated.

Masking:
Masking is conven�onally defined as: the modifica�on of metal complexes, by replacing aquo ligands with other less labile
ligands – the purpose is to render the complex less suscep�ble to addi�onal complexing reac�ons, including precipita�on.

Example: Sodium formate, Formic acid i.e. organic acids and their salts.

Organic acids penetrate into chrome complex, lowering the tanning power of liquor. The penetra�ng power of organic
radicals is more than the inorganic ones. The penetra�ng power of different radical are shown below,

Chloride< sulphate< acetate< formate< oxalate

The Principle and Effect of Masking in Chrome Tanning:

Masking agents radicals which have penetrated into the chrome complex behave differently as if they have been kept
under mask. Chlorine outside the complex can be precipitated by AgNO3, solu�on but such precipita�on of chlorine is not
possible if it is inside the chrome complex. The acid radicals Inside the chrome complex are atached to chromium through
co-ordinate valencies, whereas the acid radicals outside are atached to chromium through electrovalent linkage. Such
Penetra�on of acid radicals into the chrome complex is called masking. Since masking reduces the tanning power of
chromium complex more chromium gets fixed to collagen to inac�ve all the reac�ve sites of the later. So, masked chrome
liquor gives fullness to leather due to bigger fixa�on of chromium. There is no risk of case hardening with masked chrome
liquor, rather the chromium is uniformly distributed in the leather, and the grain become smooth and fine. Over masking
makes the chrome complex totally inac�ve and hence, it cannot tan at all. The effect of masking is given below:

1. Since the chrome tanning reac�on depends on crea�ng carboxyl complexes with collagen carboxyl groups,
modifying the complexes by including other carboxyls as ligands reduces the number of reac�on sites available to
the collagen, so the reac�vity of the chromium (III) is reduced. Reducing the number of complexa�on reac�on
 sites is that the concentra�on of hydroxyl ions required to precipitate the salt is increased, in other words, the pH
of precipita�on is raised. This means that the system can be made more reac�ve by raising the pH, to increase the
availability of reac�on sites on collagen, avoiding precipita�ng the chrome.
2. The colour of the chrome complex is altered by the ligands in the molecule and this affects the colour struck in
the wet blue leather.
3. It changes the composi�on of chrome compound by conver�ng it from ca�onic to firstly non-ionic and then
anionic form.
4. Due to masking, the number of reac�on sites available for the carboxylic group of collagen reduced as a result it
reduces the rate of fixa�on and increases the rate of penetra�on.
5. It changes the shrinkage temperature and other quality like fullness, feel of leather.
6. Since the masking agents are typically anionic, they reduce the charge on the complex, thereby reducing the ini�al
affinity of the chrome complex for collagen carboxyls.

The advantages of masking agents:

1. The pickling of the pelt can be very light.

2. Tannage is quicker.
3. Tannage is straight forward and no adjustment of basicity is needed.
4. Considerable saving on the amount of Cr2O3 required for sa�sfactory tannage and beter exhaus�on of tan bath.
5. Produc�on of leather of higher chrome content, fuller, flunk and more even substance.
6. Achieved desired effect on finness of the grain, fullness of feel and exhaus�on of the chrome liquor from tanning
bath.

The disadvantages of masking agents:

1. Too much masking makes the liquor inac�ve and unsuitable for tanning.
2. Excessive masking reduces the dyeing proper�es of leather specially with anionic dyes like acidic dyes.
3. It will make the process costly.

In prac�ce, therefore, 0.3 to 0.5 mole of masking agent per mole of Cr2O3 is normally used during pickling. To prepare
masked chrome liquor, the unmasked chrome liquor is first prepared and then the required amount of masking agents,
dissolved in minimum quan�ty of water, is added with vigorous s�rring. The liquor is then allowed to stand for a week.
Thus, masked liquor is obtained.

Figure: masking of organic acids.

Method of Chrome Tanning:

Chromium is the best of inorganic tanning material known so far. More than 90% of mineral tanned leathers of today are
chrome tanned. The tanning procedure for chrome tanning can be of two types.
 1. Double bath
2. Single bath

Double Bath Tanning:

In this process of tanning, the bated or unbated pelts which might not have been pickled, is agitated in a mixture of
dichromate, acid and salt. The chromic acid formed by the ac�on of acid on dichromate penetrates into the pelt and gets
uniformly distributed throughout the cross sec�on. The salt prevents the unwanted swelling. Chromic acid impregnated
pelts are then transferred to the second bath containing reducing agent like sodium thiosulphate with acid. The chromic
acid gets reduced by sulfurous acid and basic chromium compounds are formed inside the skin which tan the leather. The
tanned skin has greenish-blue colour.

Reac�ons:

1. In first bath, Na2Cr2O7 + H2SO4 = Na2SO4 + H2Cr2O7

2. In second bath:

It can be assumed that under the normal condi�ons of two bath tanning, equa�on (a) cons�tutes from 30 to 40 percent
of the total reac�on, (b) 10 to 20 percent and (c) 50 percent.

The double tanning is done in three steps.

1. First bath or chroming

2. Dipping and
3. Second bath or reduc�on

First bath or chroming:

In this bath, pelts are treated with chromic acid prepared by adding acid, especially hydrochloric acid (HCl), to a solu�on
of dichromate. Here 5 to 7 percent dichromate (experimentally 6%) on the skin weight and half of this quan�ty of
hydrochloric acid are employed. Pelt absorbs the chromic acid from the liquor but not the dichromate.

Na2Cr2O7 + HCl = NaCl + H2Cr2O7

Dipping:

If a�er the first bath opera�on, the chromed pelts are directly put into the reduc�on bath there is every possibility of
diffusion of the chromic acid (bleedings) from the skin into the second bath. To prevent this an intermediate process called
dipping is followed. In this opera�on the chromed pelts are dipped one by one into a dilute acid solu�on of hypo. The
chromic acid at the surface only gets chance for reduc�on and is fixed to the pelt surface. This type of surface tanned pelt
does not bleed in the second bath.
Second bath or reducing:

In this bath the chromic acid present in the chromed pelt is reduced and the basic chromium formed inside the pelt get
fixed. The bath is prepared with hypo and acid. The quan��es of hypo, acid and water in this bath are very important and
the quality of the tanned leather depends largely on them. For every 100 lbs of pelt, if 6 percent dichromate in the first
bath is applied then use 20 lbs hypo, 300 lbs water and approximately 8 lbs of hydrochloric acid (33%). The acid should be
used in instalments. The temperature of the bath should be maintained within the range 55° to 60°F.

Single Bath Tanning:

The basic principle for both single bath and double bath processes are the same and the difference lies with the fact that
in double bath method chromic acid gets reduced inside the pelt whereas in single bath already reduced chrome liquor is
used for tanning. In this tanning procedure, the chrome liquor can be made by sodium or potassium dichromate or by
chrome alum.

From chrome alum: When chrome liquor is made from chrome alum, acid is not required and only by adding calculated
amount of alkali the liquor is made ready. Chrome alum solu�on (cold) is violet in color due to the presence of Cr(H2O)6+++
ions which on ageing gets basified, and olated and acquire tanning property and to accelerate this, alkali is added. Chrome
alum solu�on prepared hot is green and contains strongly olated chromium compounds and free sulphuric acid. Asvar
tanning proper�es are concerned, the com liquor prepared from hot and cold chrome alum solu�on are quite different
and produce lather of different characteris�cs.

From dichromate solu�on: Chrome liquor is also made from dichromate and in that case the later is dissolved in minimum
quan�ty of water in a lead lined vessel and then required quan�ty of sulphuric acid is added. The chromic acid thus formed
is then reacted with reducing agents with vigorous s�rring. Generally, glucose or molasses is used as a reducing agents but
other substances like hypo, saw dust, fleshing or glue, glycine, formaldehyde, alcohol, oxalic acid, unsaturated fatly acid,
etc. can also be used. When SO2 is passed through dichromate solu�on without acid, a 33% basic liquor is produced. Such
liquor is called self-basified liquor.

K2Cr2O7 + 3SO2 + H2O  2Cr(OH)SO4 + K2SO4

The Mechanism of Chrome Tanning:

The mechanism of chrome tanning can be explained by two steps. First is the penetra�on of chrome compound and the
second is the fixa�on of chrome to the collagen protein.

In first step, the chrome complexes are treated with acid and masking agent so that they can easily penetrate inside the
pelt and uniformly distribute. They help to lower the affinity of chrome complexes toward collagen, facilita�ng greater
penetra�on. Here the rate of penetra�on is greater than the rate of fixa�on. Otherwise, there can be seen precipita�on
and fixa�on toward surface only.

In the second step, the pH of chrome liquor is increased by adding base such as sodium bicarbonate (mainly in
basifica�on step of tanning). As a result, the chrome complexes are started to get basified and this basified chrome
complex has the poten�al to crosslink with the carboxyl group of collagen fibres. The chrome compound which has
previously reacted with sulphate, formate (masking agents) are now get basified so that they can from crosslink with the
carboxylic group of collagen fibres.
Basifica�on: Cr3+ + OH-  [Cr---OH]2+

Addi�on of sulphate: [Cr---OH]2+ + SO4 2-  [SO4----Cr-----OH]0

Masking agent reac�on: [SO4----Cr-----OH]0 + Formate  [OH----Cr-----Formate]+ + SO4 2-

This form of chrome (III) can form extended polynuclear structures with hydroxyl, oxo, and sulfato bridges. These bridges
can be replaced by the carboxyl groups of collagen, which act as ligands and coordinate with the chromium ions. The
whole thing can be explained in three steps shown below,

1. Crosslinking
2. Ola�on
3. Oxala�on

Crosslinking: According to Gustavson, the carboxylate ion of collagen fiber form coordinated bond with the collagen
complex. The cross-linking occurs mainly at the pH range of 3.5–4.5, where the carboxyl groups are ionized and the
chromium complex is soluble.

Ola�on and Oxala�on: A�er ge�ng atached to carboxylic group, due to increase in pH and ageing the chrome complex
starts to involve in ola�on and oxola�on where the SO4 2- displaced by OH group and mul�ple chrome compound get
atached and form a chain. The chain link neighboring collagen fibers and strengthen the crosslink. They lock the fibers
and insure the stability and strength of the collagen protein. The higher the hydrothermal stability, the more cross-linked
the collagen is. The cross-linking can also affect the physical proper�es of the leather, such as its strength, flexibility, and
appearance.

[Note: the above mechanism of chrome tanning is based on the co-ordina�on theory of chrome complex, which is more
stablished than any other theory. But there is s�ll some ongoing cri�cism like direct crosslinking would disrupt the helical
structure of collagen and reduce its flexibility but that doesn’t happen. So further research is needed on this field of
knowledge.]