THE THEORY OF DYEING

Assignment By Professor : Yasir Ansari

Name :
Ahmer Adnan Baloch
Colour Perception
We see colour with the sensors in the retina of the eye called rods and
cones. The rods are sensitive to low light and the cones, which require a greater
intensity of light, are sensitive to colour. The message is passed to the optic nerve
and then on to the brain.

We see colour because of the Rods and Cones in our eyes:

There are about 12million rods and about 6 to 7 million cones, in the human eye.

Rods are more sensitive than the cones but they are not sensitive to
colour, they perceive images as black, white and different shades of grey. More
than one thousand times as sensitive, the rods respond better to blue but very
little to red light.

Each cone contains one of three pigments sensitive to either RED GREEN
or BLUE.

Each pigment absorbs a particular wavelength of colour. There are short

wavelength cones that absorb blue light, middle wavelength cones that absorb
green light, and long wavelength cones that absorb red light.

When we observe a colour that has a wavelength between that of the

primary colours red, green and blue, combinations of the cones are stimulated. An
example could be that yellow light stimulates cones that are sensitive to red and
to green light. The result is that we can detect light of all colours in the visible
spectrum.

People who suffer colour blindness have less numbers of particular cones
than normal, so they get colours confused.

If we lose our eye sight, the body adapts and receives colour rays through
the skin. It takes time for the body to adapt, but it has been shown that people
who are blind, can differentiate between different colours.

The eye picks up colour and light by the Rods and Cones. It is the Cones
that detect Colour. Each cone contains one of three pigments sensitive to either
RED GREEN or BLUE.
Dye
A dye can generally be described as a colored substance that has an
affinity to the substrate to which it is being applied. The dye is generally applied in
an aqueous solution, and may require a mordant to improve the fastness of the
dye on the fiber.
Auxochrome
This is a group of atoms attached to a chromophorewhich modifies the ability of
that chromophore to absorb light. Example-OH , - NH2, Aldehydes.

An auxochrome is a functional group of atoms with nonbonded electrons which,

when attached to a chromophore, alters both the wavelength and intensity of
absorption. If these groups are in direct conjugation with the pi-system of the
chromophore, they may increase the wavelength at which the light is absorbed
and as a result intensify the absorption. A feature of these auxochromes is the
presence of at least one lone pair of electrons which can be viewed as extending
the conjugated system by resonance.

It increases the color of any organic compound. For example, benzene does not
display color as it does not have any chromophore but nitrobenzene is pale yellow
color because of the presence of nitro group. Para-hydroxynitrobenzene exhibits
a deep yellow color. Here an auxochrome (-OH) is conjugated with the
chromophore -NO2. Similar behavior is happens in azo benzene (red color) but
para-hydroxy azobenzene is dark red color.

There are mainly two types of auxochromes-

1. Acidic -COOH, -OH, -SO3H

2. Basic -NHR, -NR2, -NH2

The presence of an auxochrome in the chromogen molecule is essential to make a

dye. However, if an auxochrome is present in the meta position to the
chromophore, it does not affect the colour.

An auxochrome is known as a compound that produces red shift as it increases

the wavelength of absorption therefore moving closer to infrared light.
Chromophore
A chromophore is part (or moiety) of a molecule responsible for its color.

When a molecule absorbs certain wavelengths of visible light and transmits or

reflects others, the molecule has a color. A chromophore is a region in a molecule
where the energy difference between two different molecular orbitals falls within
the range of the visible spectrum. Visible light that hits the chromophore can thus
be absorbed by exciting an electron from its ground state into an excited state.

In biological molecules that serve to capture or detect light energy, the

chromophore is the moiety that causes a conformational change of the molecule
when hit by light.

Chromophores almost always arise in one of two formsconjugated pi systems or

resonating systems. and metal complexes.[contradiction]

In the former, the energy levels that the electrons jump between are extended pi
orbitals created by a series of alternating single and double bonds, often in
aromatic systems. Common examples include retinal (used in the eye to detect
light), various food colorings, fabric dyes (azo compounds), lycopene, -carotene,
and anthocyanins.

The metal complex chromophores arise from the splitting of d-orbitals by binding
of a transition metal to ligands. Examples of such chromophores can be seen in
chlorophyll (used by plants for photosynthesis), hemoglobin, hemocyanin, and
colorful minerals such as malachite and amethyst.

A common motif in biochemistry is chromophores consisting of four pyrrole

rings. These come in two types:

* the pyrroles form an open chain, no metalphytochrome, phycobilin, bilirubin

* the pyrroles form a ring (porphyrin), with a metal in the centerheme, chlorophyll

Color abstractions
The foundations of pre-20th-century color theory were built around pure or ideal
colors, characterized by sensory experiences rather than attributes of the physical
world. This has led to a number of inaccuracies in traditional color theory
principles that are not always remedied in modern formulations.[citation needed]

The most important problem has been a confusion between the behavior of light
mixtures, called additive color, and the behavior of paint or ink or dye or pigment
mixtures, called subtractive color. This problem arises because the absorption of
light by material substances follows different rules from the perception of light by
the eye.
A second problem has been the failure to describe the very important effects of
strong luminance (lightness) contrasts in the appearance of surface colors (such
as paints or inks) as opposed to light colors; colorssuch as grays, browns or
ochres cannot appear in light mixtures. Thus, a strong lightness contrast between
a mid valued yellow paint and a surrounding bright white makes the yellow appear
to be green or brown, while a strong brightness contrast between a rainbow and
the surrounding sky makes the yellow in a rainbow appear to be a fainter yellow or
white.

A third problem has been the tendency to describe color effects holistically or
categorically, for example as a contrast between yellowand blueconceived as
generic colors, when most color effects are due to contrasts on three relative
attributes that define all colors:

1. lightness (light vs. dark, or white vs. black),

2. saturation (intense vs. dull), and
3. hue (e.g., red, orange, yellow, green, blue or purple).

Thus, the visual impact of yellowvs. bluehues in visual design depends on the
relative lightness and intensity of the hues.

These confusions are partly historical, and arose in scientific uncertainty about
color perception that was not resolved until the late 19th century, when the artistic
notions were already entrenched. However they also arise from the attempt to
describe the highly contextual and flexible behavior of color perception in terms
of abstract color sensations that can be generated equivalently by any visual
media.

Many historical color theorists have assumed that three pure primary colors can
mix all possible colors, and that any failure of specific paints or inks to match this
ideal performance is due to the impurity or imperfection of the colorants. In
reality, only imaginary primary colors used in colorimetry can mixor quantify all
visible (perceptually possible) colors; but to do this the colors are defined as lying
outside the range of visible colorsthey cannot be seen. Any three real primary
colors of light, paint or ink can mix only a limited range of colors, called a gamut,
which is always smaller (contains fewer colors) than the full range of colors
humans can perceive.
Dyes In Solution
At some stage in all dyeing processes the color chemicals for sorption by
the goods must be in the finest state of subdivision possible, which is
monomolecular, i.e., single molecules or molecular ions which can be negatively
or positively charged (anions or cations
respectively). The molecular ions are almost always dissolved in water, but for an
exception, refer to the upcoming sections on disperse dyes and their application
by continuous dyeing methods:

By contrast, dispersions of even the most finely ground pigment contain

particles which are gross, compared with the size of dye molecules or ions, and
they do not diffuse into fibers.
Dyes are exposed to fibers by the circulation of dye bath and fiber relative to one
another. Given the right conditions, the molecules or ions can make their way
through the water to the fiber surfaces, down pores, cracks and fissures in the
fiber surfaces, and ultimately between the polymer molecules, becoming
distributed in the fiber itself. But these dye solutions are not as simple as they
might seem.

Aggregation
In the case of dyes for cellulose, the finest state of subdivision has the color
bearing chemicals in the form of anions, written Dye', each with its accompanying
number (n) of sodium cations, n Na*, foroverall electrical neutrality; i.e., equal
numbers of positive and negative charges. Here n represents the number of
negative charges perdye anion and is usually between two and four. When dye
solutions are dilute and the concentrations of salts (electrolytes) are low these
anions are the principle form of the dye. However; as the con-centrations of
dissolved dye and electrolyte are increased, the an-ions become attracted to one
another by weak forces, known as vander Waals forces, forming aggregates or
larger clusters. ln extreme cases these may grow large enough to become
insoluble and then the aggregate is actually precipitated out of the water. Dye
manufacturers rely on this phenomenon to salt out water soluble soliddye from its
concentrated solutions by the addition of salt.Although it is the single dye-anion
which does the dyeing, this anion is often accompanied in solution by a reservoir
of soluble dye-ion to dye-ion aggregates. These are in a state of dynamic equilib-
rium with the single dye-anion and will break down again if dye bath conditions
become right. This situation can be written:

The arrows indicate a process capable of going both ways, and sub-script m on
the left hand side of the equation is the number of dyeions in the aggregate, the
value of which is unknown in most cases.Aggregation is reduced as the
temperature increases, while thesolubility of most dyes increases.

Chemical Potential
The concept of chemical potential is introduced to help explainthe transfer of
direct dyes or other anionic chemicals from thedyebath to the fiber, particularly in
the presence of an excess of oppositely charged ions such as the sodium cation,
Na*, which is introduced by the addition of simple sodium salts. Chemical
potential is analogous to electrical potential or temperature. In all three cases,
when there are two masses at different po-tentials (or temperatures) and they are
brought into contact, someof the potential will be transferred from the mass at the
higher potential to that at the lower potential. If the potential of dye dissolvedin a
dyebath in contact with the fiber is higher than that of the dyein the fiber; then
dyeing or sorption will take place. If the reverse istrue, stripping or desorption of
dye will take place. When dye in the dyebath and dye in the fiber are at the same
chemical potential,there will be no net transfer of dye, even though the system will
bein dynamic equilibrium, with dye ions constantly entering and leaving the fiber
at the same rate.
For a given dye solution in water let the concentration of dye-anions and sodium
cations be written [Dye]s and [Na*]s, where thesquare brackets denote
concentration and subscript s indicates ionsin solution. Physical chemists
express these concentrations in terms of gram molecules or gram ions per liter-
but that does not changethe argument, only specifies the units in a more scientific
wayIn hot dilute dyebaths, where aggregation is of least concem, the chemical
potential of the solution is related to the product:

As tl1is product increases, so does the chemical potential of the solution. Notice
that the concentration of the sodium ion is raised tothe power n making it
relatively more important the higher the value of n. Increasing the sodium ion
concentration by adding sodium salts to this dye solution will also increase the
product and therefore the chemical potential of the solution.In an anionic dyeing
situation, as with all cellulose dyeing, rais-ing the chemical potential of the
dyebath by adding salt will havethe effect of driving the dye from the higher
potential and into thefiber where the chemical potential will also increase until it
reaches.

Solubility Product

In saturated dye solutions-i.e., in pure dye solutions in which nomore dye will
dissolve the product is called the solubility product:
 Adding more sodium ions by add-ing salt to such solutions would cause the
product to increase andto exceed the solubility product. To overcome this
tendency somesolid dye will be precipitated out (salted out) of solution thereby
reducing the concentration of dye-ion in solution and readjusting the product. If
the salt concentration is high enough, only a small amount of dye anion can be
present in the solution without it being salted out.It should now be apparent that
the addition of simple sodiumsalts to solutions of the sodium salts of color
bearing anions willlower the attraction of the anion for the waten and the anion
will tryto leave the water for any available, alternative location-for ex-ample the
fiber.

The Fiber-Water Boundary

All fibers when immersed in water acquire a negative electrical po-tential in the
immediate vicinity of the surface. This potential is con-sidered to be effective over
a longer range than atomic dimensions.The origin and nature of the negative
surface potential of fibers inwater; its relationship to streaming potential, zeta
potential, the Stemlayer; the diffuse layer, the Dorman and Gouy-Chapman models
ofthe diffuse layers are all beyond the scope of this work, but can eas-ily be
found.It is mainly important to recognize that such a nega-tive potential will offer
resistance to the approach of similarlycharged ions such as the dye anion, just as
the north pole of a magnet will resist the approach of the north pole of another
magnet.

charged ions such as the dye anion, just as the north pole of a mag-net will resist
the approach of the north pole of another magnet.Negative potential at fiber
surfaces will be attractive to oppositely charged ions or cations, which is why so
many fiber surfaces can be stained by basic (cationic) dyes.The negative potential
of the fiber is masked (or swamped) bythe presence in the dyebath of high
concentrations of such electro-lytes as salt, with its many sodium and chloride
ions; and the elec-trolyte simultaneously raises the chemical potential of the dye
insolution. As a result, the effectiveness of the potential barrier to re-sist dye
moving to the fiber surface is doubly diminished by thepresence of simple,
soluble salts. The situation is further improvedby stirring the dyebath to provide a
good flow of solution across thefiber surfaces. This can be seen as eroding the
boundary layer inwhich the negative potential is effective.

The Physical Dye-Fiber Bond

One of the most poorly understood phenomena in dyeing is thehigh substantivity
of direct clye anions and the anions of vat andsulfur dye leuco compounds for
cellulose, and the causes of the physical dye-fiber bond. The anions from
dissolved reactive dyesand azoic coupling components have less substantivity
charged ions such as the dye anion, just as the north pole of a mag-net will resist
the approach of the north pole of another magnet.
Negative potential at fiber surfaces will be attractive to oppositelycharged ions or
cations, which is why so many fiber surfaces can bestained by basic (cationic)
dyes.The negative potential of the fiber is masked (or swamped) bythe presence in
the dyebath of high concentrations of such electro-lytes as salt, with its many
sodium and chloride ions; and the elec-trolyte simultaneously raises the chemical
potential of the dye insolution. As a result, the effectiveness of the potential
barrier to re-sist dye moving to the fiber surface is doubly diminished by
thepresence of simple, soluble salts. The situation is further improvedby stirring
the dyebath to provide a good flow of solution across thefiber surfaces. This can
be seen as eroding the boundary layer in which the negative potential is effective.

The Physical Dye-Fiber Bond

One of the most poorly understood phenomena in dyeing is thehigh substantivity
of direct dye anions and the anions of vat andsulfur dye leuco compounds for
cellulose, and the causes of the physical dye-fiber bond. The anions from
dissolved reactive dyesand azoic coupling components have less substantivity It
has been suggested that for substantivity direct dye anions should be long and
linear; but some substantive dyes are neither.Most direct and vat dye anions are
essentially planar and rather large. Hydrogen bonding has been suggested as the
source of the attraction, but there is evidence that cellulose is so strongly hydro-
gen bonded to water that preferential hydrogen bonding to theamino, hydroxy or
other groups present within direct dyes seemsquite improbable.The most likely
cause of substantivity appears to be the combina-tion of relatively weak forces,
including the same short range vander Waals forces which contribute to the
association of dye-ions with one another in the form of aggregates, either in
solution or after the single dye-ions have passed across the potential barrier and
have reached the fiber-water surface boundary Such tendencies to ag-gregate
have been mentioned earliel; and certainly would be en-hanced by some
combination of planarity length and linearity of dye anions, all of which favor such
dye-ion to dye-ion association.

It has been suggested that for substantivity direct dye anion sshould be long and
linear; but some substantive dyes are neither.Most direct and vat dye anions are
essentially planar and ratherlarge. Hydrogen bonding has been suggested as the
source of the attraction, but there is evidence that cellulose is so strongly hydro-
gen bonded to water that preferential hydrogen bonding to the amino, hydroxy or
other groups present within direct dyes seems quite improbable.

The most likely cause of substantivity appears to be the combina-tion of relatively

weak forces, including the same short range vander Waals forces which
contribute to the association of dye-ions withone another in the form of
aggregates, either in solution or after the single dye-ions have passed across the
potential barrier and have reached the fiber-water surface boundary Such
tendencies to ag-gregate have been mentioned earliel; and certainly would be en-
hanced by some combination of planarity length and linearity ofdye anions, all of
which favor such dye-ion to dye-ion association.
Diffusion Into the Fiber
Once the dye molecule, ion or other color bearing species (let us callit simply dye)
has become associated with the fiber surfaces, thenext stage in the dyeing
process is the diffusion of the dye from thesurfaces and into the fiber. This
diffusion of dye into the fiber is acomplex subject to treat mathematically and
much work has beenconfined to studying the simpler cases of polymer films and
indi-vidual fibers with more or less circular cross sections. Even
then,experimental studies of dye diffusion are potentially difficult.For a succinct
discussion of the relationship between the dye dif-fusion coefficient, D,
temperature and the denier of the fibers, seethe Dyeing Primer. The diffusion
coefficient varies with, and can besensitive to, increases in temperature. It can be
shown that practicaldyeing rates for cylindrical fibers of known radius, r, are
related to the fractions D/ri and D / denier.

What dyers need to be aware of is that when the dye has reached the surface of
the fiber it has not finished its journey The dyeing process is not over until dye
has diffused from the surface and to-wards the center of the fiber to give a more
uniform distribution within the fiber. This situation can be summarized by means
of a figure, which strictly speaking relates only to dyes of highSubstantivity
applied at a relatively low percentage on the weightof the goods (%owg). Fig. 1.3
shows the concentration of dye at dif-ferent locations within the fiber. An early
stage of dyeing is indi-cated in Fig 1.3., curve a, which shows a high
concentration of dyeat the fiber-dyebath boundary [Dye]!, where the squared
brackets indicate concentration and subscript f means in the fiber. There is a
small tailing out of dye toward the center of the fiber some distance away As the
dyeing process continues, curve b, the progression of dye into the fiber
continues, the larger concentration of dye at thesurface diminishes and in the
final stages of dyeing, Fig. 1.3, curvec, the distribution of dye throughout the fiber
is essentially uniform.The relative velocity of surface sorption of dye and its
subsequent diffusion into the fiber will determine the actual shapes of the ra-dial
concentration profiles for the dye.

The rate of this diffusion process within the fiber might be quite slow and will vary
widely from dye to dye. There is no agitation within the dyebath which can
possibly affect the rate of diffusioninside the fiber which for all practical purposes
behaves as if it werea flexible, solid rod. Dyeing, as far as exhaustion of the
dyebath a flexible, solid rod.

Dyeing, as far as exhaustion of the dyeb at his concerned, may be over long
before the dye is uniformlydistributed throughout the fiber; which is why there is
some confusion between the terms the end of the dyeing and true dyeing
equilibrium.
For those who wish to stop the dyeing as soon as the dyebath isat its maximum
exhaustion, notethere are some material draw backs to having the dye on the
outer surfaces of the fiber as opposed touniformly throughout the fiber. The first
one relates to the fastness properties of the resulting dyeing. If the dye is on or
near the fiber surface then the ease with which it is lost to any subsequent wet or
abrasive processes is much increased. More surprising perhaps; a fiber, with a
fixed amount of color distributed in it, looks darker incolor the more uniformly that
color is distributed. Consequently those content to stop the dyeing when the dye
is merely distributed just within the fiber surface, overlook the possibility of an
increased color yield, which will result as the dye diffuses (albeit slowly) into the
fiber to become more uniform. Another benefit of uniform distribution of dye is
that the lightfastness of the resulting dyeing is greaterThe property of having a
fiber with most of the dye distrib-uted at the outer surfaces is called ring dyeing.
Ring dyeing has thedisadvantages mentioned, but it is quite common, particularly
incontinuous dyeing. Do not confuse this with ring dyed yarns!Bearing in mind
the behavior of dye solutions, the fiber-waterboundary and the nature of the dye-
fiber bond detailed above, twodifferent but complementary pictures of the overall
dyeing processfor anions on cellulose will now be introduced. One represents di-
rect dyeing graphically The other describes an arithmetical modelfor dyeing in
general, which is applicable to cellulose dyeing. Their usefulness derives from
their relative simplicity

ThermodynamicsEquilibrium; Extent of Dyeing

These areplotted against the concentrations of dye left in the bath at that time,
[Dye]. Subscript e refers to the end of the dyeing, or close to equi-librium. These
points lie on a continuous, smooth curve covering avery wide range of dye
concentrations. This continuous curve iscalled a sorption isotherm. In the case of
dyes for cellulose theseisothenns curve gradually towards the x-axis, but never
quite leveloff. This behavior describes what are known as Freundlich
isotherms.The Freundlich Isotherm is governed by the empirical relation-ship:

Here the power n is a value of no theoretical significance (empiri-cal); n is less

than 1 but greater than 0, and k is a proportionality constant.

Freundlich Sorption Isotherm

There are several implications to such Freuncllich isotherms:

The partition or substantivity coefficient, K, which equals the concentration of

dye in the fiber at the end of the dyeing (grams pergram) divided by the
concentration of the dye in the solution atthe end of the dyeing (grams per gram)
can be represented by the fractions:
From the gradient of the dotted lines drawn on Fig. 1.4b it can beseen that the
substantivity coefficient K is not a true constant and gradually falls off as the
amount of dye added to the dyebath ini-tially (or left in the dyebathfinally)
increases. The importance of Kwill be discussed later, but it is related to the
percentage exhaustion of the dyebath, %E. The drop in exhaustion with increasing
depth of shade is well known to dyers, who expect less exhaustion from dyeings
of heavy depths. To counteract the loss of exhaustion, it isusual to alter the
dyebath conditions by adding increasingly moreand more salt as the depth of
shade increases, to drive more dye
onto the fiber:

The Freundlich isotherrns reflect the loss of activity or chemicaleffectiveness,

of the dye in solution with increasing concentra-tion, perhaps due to
aggregation.

The Freundlich isotherms can also reflect the fact that the fibersurface, on
which the dye molecules are initially absorbed, is het-erogeneous. Some of
the locations, which get filled first, are more interactive with dye than those
which are filled later.

They are usually indicative of nonionic, or relatively weak bond-ing

possibilities between dye and fiber, which has already beenmentioned.

As more and more dye is added to a dye bath, more and more dye will
continue to go onto the fiber. There is, of course, a practical limit as to how
much dye may be put on any fiber; and this is dictated by the cost
effectiveness of the change in color obtained by increasing the dye bath
concentration. Above this limit further dye additions merely cause a gradual
loss of brightness andgradual change of hue accompanied by diminished
wetfastness properties.

Note:

Recently several authors 3 have fitted direct dyeing datato Langmuir isotherms
rather than tothe traditional Freundlich isotherm. Neither isotherm is ideal.
Thesimple Langmuir isotlierrn implies a saturation value for dye on thefiber,
which single direct dyes do not appear to have, even though(within a practical
range) isotherms for individual dyes in directdye mixtures do seem to fit well to
Langmuirequations.The em-pirical Frenmdlich isotherm can be shown to be
unsuitable for kinetic modeling of the dyeing process.

Substantivity and Partition Coefficients

By rearranging we can bring the two rate constants onto the same side of the
equation, and they can be combined into a numeri-cal constant, K, provided the
concentration of dye in both solutionand fiber are in the same units-e.g., grams
per gram-in which case the units cancel out.

K is known as the substantivity or partition coefficient shown inFig. 1.4b, and is a

measure of the extent to which dye prefers thefiber to the dye bath in the
particular dyebath conditions.

Liquor Ratio and Exhaustion

The partition or substantivity coefficient, K, can be used as a simpletool to
demonstrate the general nature of the relationship betweensubstantivity; liquor-
to-goods ratio, L, and percent exhaustion at theend of the dyeing, %E. The percent
exhaustion at any time duringthe dyeing is the percent of dye initially present in
the dyebath whichhas left the dyebath for the fiber. The percent exhaustion at the
endof the dyeing is of obvious importance to a dyer since it reflects howefficiently
dye has been transferred from the bath to the fiber. Per-centage exhaustion can
be written:

The equation is useful in showing the effect of varying liquorratios upon

exhaustion, and the general magnitude of K, or the ex-tent to which dye prefers
the fiber over the dyebath.'5
For a particular dyeing, exhaustion might be 90%-i.e. %E=90,when dyed in the
plant at a 10:1 liquor-to-goods ratio, L=l0. Putting these values in Eq. 1.12, K must
be equal to 9for the equation tobalance. But, at a 25:1 liquor ratio-e.g., in the
laboratory when K=90and L=25, %E=78.3. This is a substantial loss of color yield,
and color literally down the drain.

The model confirms what experienced dyehouses already know.Plant

dyeings at lower liquor ratios give higher color yields than laboratory dyeings at
higher liquor ratios. It is well known that thedye content of laboratory formulations
may have to be reduced bythe plant to give the same shades as those dyed in the
laboratory Tobring plant and laboratory dyeings of cellulosic fibers closer
together,the laboratory may elect to use larger amounts of electrolyte (salt)in an
attempt to parallel plant dyeings and achieve higher exhaus-tion levels. If the
relationship between plant and laboratory dyeingsis well understood, color
recipes or dye formulations from the labo-ratory reproduce well in the plant.To
have a dyeing with 95% exhaustion at a liquor ratio of 10:1,requires that K=190.
The substantivity coefficient had to more thandouble from 9to 19to improve the
percentage exhaustion by 5%,from 90% to 95%.In the case of the substantivity of
anionic dyes for cellulosic fiber,it is truly remarkable that forces so poorly
understood can cause thedyes to prefer cellulose to water by such large margins.
Fick's Laws of Diffusion
Diffusion is the mechanism by which components of a mixture are
transported around the mixture by means of random molecular (Brownian) motion
(cf. permeationthe ability of a diffusant to pass through a body - dependent on
both the diffusion coefficient, D, and the solubility coefficient, S, ie, permeability
coefficient, P = D.S). Flynn et al. cite Berthalot as postulating, at the beginning of
the nineteenth century, that the flow of mass by diffusion (ie, the flux), across a
plane, was proportional to the concentration gradient of the diffusant across that
plane.

In the mid-1800's, Fick introduced two differential equations that quantified the
above statement for the case of transport through thin membranes. Fick's First
Law states that the flux, J, of a component of concentration, C, across a
membrane of unit area, in a predefined plane, is proportional to the concentration
differential across that plane (see note), and is expressed by:

Equation for Fick's First Law

Fick's Second Law states that the rate of change of concentration in a volume
element of a membrane, within the diffusional field, is proportional to the rate of
change of concentration gradient at that point in the field, as given by:

Equation for Fick's Second Law

where t = time.