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THE PHYSICAL CHEMISTRY

OF DYEING AND TANNING
GENERAL INTRODUCTION
Published on 01 January 1954. Downloaded by Tufts University on 28/10/2014 14:03:03.

BY SIR ERICRIDEAL
Chemistry Department, King’s College, London, W.C.2
Received 8th September, 1953

It was a happy thought of the committee responsible for initiating this Dis-
cussion of the Faraday Society in their decision to hold the meeting in this city
of Leeds. The contributions made in the past and being made by workers here
are recognized all over the world as of outstanding importance If one were to
cavil at all at the efforts of the committee, one might suggest that the range of
the Discussion is truly enormous. The subject-matter of dyes and dyeing, even
for one particular class of dyestuff and one textile mzterial, is already very great
and presents many unsolved problems, whilst the addition of the equally
complicated subject of tanning is indeed piling Pelion on Ossa. I suppose
the fiindamental questions which are to be asked are : “ how, in any particular
casc, is the dye combined with the fibre?”, “what are the conditions of
equilibrium? ” and, finally, “ what governs the rate of dyeing ? ”
The intcraction of a dye with a fibre may, as we see in this Discussion, vary
from salt formation with wool to a simple solution mechanism for non-ionic
dyes in polyethylene teraphthalate. In the former case we note that the free
energy change in the conversion of the protons of the acid dye combining to
form a covalent linkage with the carboxyl groups of the wool side-chains is one
of the major factors to be considered; the dye anions must likewise penetrate
to prcserve electric neutrality. We may consider the equilibrium between thc
wool phase and the aqueous medium to be defined by a Donnan distribution with
fixed protons and mobile dye anions or that both cation and anion occupy local-
ized sites and that the equilibrium is governed by a Langmuir equilibrium. If
this latter is true, we must assume that thcre is only one type of site, that there
is no interaction between neighbours and that the ions are not mobile. The diffi-
culty associated with the method of treating the system as a Donnan equilibrium
is that the thermodynamic relationships give us merely the activities of the two
phases whilst we are interested in the quantities in each phase. Clearly some
method is required for defining the volume of the wool phase before we can obtain
all the information we desire. In addition, the assumption that the anions are
virtually free within the wool phase, being present merely to justify electro-neutrality,
is scarcely in accordance with the facts. Not only do various anions vary in inter-
action energy with the wool sites but, as we note, the resolution of optically active
anions by adsorption on wool is confirmatory proof that anion sitcs are more
than sites for simple electrostatic bonding. In the treatment of localizcd sitcs,
the prcmises on which an exact theory can be based are as yet somewhat un-
certain. For example, we have reason to believe that certain of the keto amino
groups in the polypeptide chain can, under suitable conditions, function as sites.
Wc are likewise confronted with problems in the other extreme case whcre the
simple assumption of a Nernst partition law can be regarded as the basic con-
trolling factor in the uptake of dye. Wc note, for example, how rapidly the
9
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10 GENERAL INTRODUCTION

activity of a dye may change in the presence of a salt, how many dyes arc in cffect
not simple monomers in solution but, as the concentration rises or on the addi-
tion of salts, aggregated forms build up; dimers or even more complex micelles
make their appearance. Again the concept of solution in the fibrous material
is not a clear one. We recognize in the majority of synthetic fibres ordered and
less ordered domains. That there is a melting range rather than a melting point
is a recognition that we cannot divide the domains into simple crystallites and
amorphous regions. Since relatively large entropy changes are involved in the
Published on 01 January 1954. Downloaded by Tufts University on 28/10/2014 14:03:03.

passage of the dye from the aqueous into the non-aqueous phase; differences of
this kind may well affect the partition coefficient in different regions of the fibre.
We must also note that in aqueous phase the mechanism of solution, i.e. dis-
persion or peptization of the dye by water involves not only a reduction of the
dipolar cohesive forces but frequently polar interaction and frequently hydrogen
bonding at specific points on the dye molecule. Must we not invoke similar
considerations in the fibrous phase ? Here the adlineated macromolecules may
well give rise to adlineation of the dye molecule. Instances of dichroism in
dyeing immediately come to mind, as will be seen from the papers being com-
municated. Equally complex are the factors which govern the rate of dyeing.

FIG. 1.-Direct dyes on cotton, 60" C , as function of l / n , where n is number of

passages of dye liquor through fibre in 10 min (recalc. from data of Fern).

Recently Dr. Davies and I have been looking at a few of these and the results
we have obtained in several cases are rather surprising.
THERATE OF DYEING.-Many studies have been made of the rates of diffusion
of dyes within sheets of Cellophane or within textile fibres. Apart, however,
from the diffusion within the solid, there are two other processes, which in practice
may well be rate-controlling. The first of these is the diffusion of the dye through
the aqueous layer in contact with the solid surface. With plane surfaces there is
a layer of liquid, effectively unstirred for slow flow rates, this layer being of the
order 0.01-0*1mm thick. Stirring of the solution more vigorously will, of course,
reduce the thickness 6 of this unstirred layer, while in the unstirred solution a
value (about 0-5 mm) determined by thermal convection is attained. Diffusion
through layers of this order of thickness may be a slower process than any of the
other diffusive steps in attaining dyeing equilibrium. As we stir more rapidly,
the layers not only become thinner: it also may become possible for the eddies
which accompany turbulent flow to approach more closely to the interface.1
Fig. 1 shows the data of Fern recalculated to show how the rate of circulation
of dye-liquor influences the rate of dyeing. If we try to extrapolate the curves
to infinite r d e of stirring (zero l / n ) we see that, although further measurements
in the fast stirring region are clearly required, the major part of the barrier to
diflusion arises from the aqueous phase adjacent to the fibres.
Fig. 2 shows the effect for the same dye on a Cellophane sheet and on a piece
of cotton. The stirring rate is clearly much more important for the fibrous material
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SIR E R I C R I D E A L 11
than for the sheet of Cellophane, on account of the liquid being less easily moved
between the fibres ; the unstirred layers therefore increase rapidly in thickness
at low stirring rates.
These effects can be represented, in the simpler cases, in terms of the Reynolds
number of the system. This quantity, defined by pvZ/y (where p = density of
liquid ; v = velocity of liquid relative to solid ; 7 = viscosity ; I = character-
istic length), is a measure of the turbulence of the system. At low values of the
Reynolds number (denoted hereafter by Re) viscous forces predominate : at
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larger values the forces of inertia predominate, and the flow pattern becomes
very different. If Z is very small, we may see that Re is likely to be small under
all conditions, but if 1 is large, the flow will be turbulent except at the lowest
velocities. As a first approximation, one may show that 6 = Z/(Re)*, or, if the
rate of dyeing is limited by the transport across the unstirred layer of thickness 6
(and is therefore proportional to 1/8), the rate of transfer of dye is proportional
to (Re)a/l, Z being the dimension of the fibre in the direction of flow. This applies

(Slo
ads3

(fml
b *-I--
Ce//ophane
" C
adsorphobn
fast
// (sh-iiy f a t e ) Slow
slirring sttcrtnq

if Re is large. Thus the rate of dyeing of a Cellophane slab should vary as the
square root of the velocity of flow past it, i.e. rate cc 770.5 for this effect. If there
is also a barrier within the cellulose, we may write : l/rate = const. u-o*~+const.
The linearity is satisfactory (fig. 3), though it clearly requires testing over a wider
range of conditions. The plot is derived assuming the additivity of the resistances
to diffusion in a Cellophane sheet, and the intercept on the ordinate axis gives the
resistance to diffusion due to factors other than those associated with the un-
stirred aqueous layer. The empirical findings of Brunner (1904) and of McBain
(1922) that 8~0.67is constant can also be used to recalculate the data for Cello-
phane, but these experiments do not. allow us to make any exact evaluation of the
exponent, as the range of velocities is not great enough.
Recent work on turbulent flow at liquid-liquid interfaces in investigations of
mass transfer 2 has suggested the following equation,
K (densitylviscosity) = const. (Re)O*67- 10,
if the viscosity of the second phase is high. Here K is the mass transfer coefficient.
We may note that the exponent is higher than the values of 0.5 and 0.67 quoted
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12 GENERAL INTRODUCTION

above. The meaning of the constant is not clear as yet, except that for appreci-
able transfer to occur (across the " unstirred " layer) a certain critical stirring rate
must apparently be reached.
In the dyeing process the mass of small fibres in close proximity complicates
severely the exact treatment of diffusion rates through the aqueous phase. The
data for the different dyes (fig. 1 and 2) are not spread over a sufficient range of
stirring speeds for any exact mathematical treatment to be possible, but at high
rates of stirring (or of circulation of the dye liquor) an exponent n of about - 0.5
Published on 01 January 1954. Downloaded by Tufts University on 28/10/2014 14:03:03.

is certainly required, approaching - 1.0 as the stirring rate becomes slower and
Re is less, i.e. as the flow becomes more streamlined. This means that in the
latter circumstances the uptake of dye depends simply on the amount of liquor-
carried dye passing the fibre per second. A similar result was found by Alexander
et ai.3
At high dye concentrations, Alexander and Hudson 3 found that the dyeing
rate was controlled by the aqueous layer at low stirring speeds, but that at high
stirring rates the rate depended on diffusion through the wool itself, the transport
of dye to the surface of the fibres then exceeding the rate at which dye was removed
from the surface by diffusion into the interior of the fibre. At low concentra-
tions of Orange 11, diffusion through the aqueous layers was found to be always

FIG. 3.-Data of Neale et af. recalculated to show depcndence of reciprocal of dye

adsorbed after 5 min OR cellulose sheet on inverse square rate of velocity of dye liquor
past sheet. (Chlorazol Sky Blue FF at 90" C.)

rate-determining. The energies of activation for diffusion were 5 kcal for dyeings
in which control was by the aqueous layers, but 13 kcal for diffusion within the
fibre. This suggests that an alteration of temperature can alter the rate-deter-
mining step in the dyeing process, the hydrodynamics of the system being more
important at higher temperatures.
Besides the aqueous layers adjacent to the fibres, therc are two other possible
barriers to diffusion. If the dye is charged, e.g. carrying sulphonate groups, it
may encounter a force of electrical repulsion within a few tens of angstroms from
the surrace, due to the presence of the molecules of dye of similar electrical charge
already adsorbed there. In recent years, considerable attention has been devoted
to elucidating quantitatively the mechanism of the slow lowering of surface
tension, and in particular the action of this potential barrier, with limited success.
For exact interpretation, it is preferable to use the simplest possible systcms,
and long-chain sulphates or quaternary ammonium ions have proved uscful.
Work is at present in hand in this laboratory to evaluate exactly ihe barriers due
to diffusion and to electrical repulsion, the latter effect clearly being of importance
since a few years ago Sutherland and Rideal (unpublished) noted that salts present
even in very low concentrations greatly accelerated the rate of lowering of surface
tension, presumably by reducing the repulsive barrier. Alexander and Kitchencr
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SIR ERIC RIDEAL 13

(1950) have looked into some of the implications of potential barriers of this sort
in the dyeing process.
To pass from the adsorbed state to the interior of the fibre may also require
considerable energy. The ionized groups have to lose some of their co-ordinated
watcr, and energy must be supplied to strip this away against the attraction of
the water dipoles for the ion : that is to say, the process requires an energy of
activation. The magnitude of this interfacial barrier has never been accuractely
measured, owing to severe experimental difficulties. A preferred molecular
Published on 01 January 1954. Downloaded by Tufts University on 28/10/2014 14:03:03.

orientation may also be necessary, adding an entropy factor to the work term.
With regard to dyes the importance of this type of barrier to diffusion is still
far from clear.
We may notc in concluding that unless further research can be devised to
scparate and cstimate the magnitude of these different processes, the physical
chemistry of dyeing can never be free from empirical factors. We may con-
fidently hope that tracer techniques and further fundamental studies of the
hydrodynamics and of the adsorptive and electrical factors operating at surfaces
will prove fruitful in strengthening the foundations of the physical chemistry of
dyeing.
1 Danckwerts, I d Eng. Clzem., 1951, 43, 1460. Fern, unpublished data, quoted
by Vickerstaff, The Physical Clzemistry of Dyeing (Oliver and Boyd, 1950).
2 Lewis (A.E.R.E., Marwell), unpublished data.
3 Alexander et al., Trans. Faraday SOC., 1949, 45, 1058, 1109; Text. Res. J., 1950.
20, 203, 481.
4 cf. e.g. Bircuinshaw and Riddiford, Quart. Rev., 1952, 6, 157.