Dyeing Theory

• How a given dye is taken up by a particular textile fibre or

• The mechanism of dyeing

Developments
• Dufay – 1737 – developed theory based on physical chemical
principles
• 1930 - use of spectrophotometric methods to determine the
concentration of adsorbed dye
 Commonly used terms
• Adsorption - refers to the spontaneous accumulation of solute
molecules (dye molecules) at an interface (solid/liquid such as
fibre/dyebath).
• Adsorption arises due to forces of interaction operating between the
adsorbate (dye molecule) and the adsorbent surface (textile fibre)
• Absorption - when a species from one phase becomes evenly distributed
throughout the bulk of another phase.
• The term sorption covers both adsorption and absorption.
• The amount of dye adsorbed by fibres at equilibrium - Df [units: g kg−1, mol kg−1]
• The amount of dye in solution – Ds [units: g l−1; mol l−1]
• Saturation value of dyeuptake on fibre, S [units: g kg−1, mol kg−1]
• Dyeing absorption isotherms
Approaches to study the mechanism of dyeing
(1) at equilibrium (thermodynamics of dyeing)
(2) before equilibrium is attained (kinetics of dyeing)

Relationship between kinetics of dyeing and thermodynamics of dyeing

• Two phases are involved – Fibre phase and aqueous phase
• In dyeing, dye molecules move or diffuse through the aqueous phase
(i.e. the dyebath) to the fibre phase
• Then they diffuse and accumulate within the water-filled, swollen
substrate
• The kinetics of dyeing considers the rate at which dyeing proceeds
and therefore, concerns the rate at which the dye diffuses in both the
aqueous phase and fibre phase
• This is commonly depicted in terms of a rate of dyeing curve
• A rate of dyeing plot depicts the amount of dye adsorbed by the fibre,
Df, as a function of dyeing time, t.
• Thermodynamics considers the dyeing process only when it has reached
equilibrium and is commonly depicted in terms of an equilibrium
adsorption curve
• It is not concerned with the rate at which dyeing occurs
• Thermodynamics of dyeing relates to truly reversible dyeing systems at
equilibrium
• However, not all dyeing systems display such thermodynamic reversibility
• Examples – Oxidation of the leuco forms of sulphur and vat dyes
• Coupling of azoic coupling components
• Mordant dyeing
• Formation of covalent dye–fibre bonds in the case of reactive dyes
• Fully reversible dyeing systems from a thermodynamic perspective
include:
• Disperse dyes on PES
• Direct dyes on cellulosic fibres
• Acid dyes on wool and PA fibres
• Basic dyes on PAN
When undyed fibre is immersed in an aqueous
dyebath, dye uptake commences
• In the initial stages, dyeing proceeds relatively rapidly and, thereafter, the
rate of dye uptake gradually decreases and becomes constant
• At this stage, an equilibrium state has been achieved in which dye
molecules continue to be exchanged between the fibre phase and aqueous
phase
• The rate of adsorption of the dye onto the fibre from the dyebath is equal
to the rate of desorption of dye from the fibre to the dyebath
• When equilibrium dye uptake is achieved, then a plot of Df and Ds provides
a single point on the equilibrium adsorption curve
• Repetition using higher amounts of dye, but identical application
conditions (i.e. pH, temperature, electrolyte concentration, etc.) provides
additional rate of dyeing curves
When these points are connected, the shape of the plot is
indicative of the mechanism of dye adsorption
• In the curve shown previously, the equilibrium adsorption curve is
called adsorption isotherm, since it was undertaken at constant
temperature
• The shape of the curve implies a Langmuir mechanism
• It means the substrate contains a limited number of sites at which
dye adsorption occurs
• This is denoted by the saturation value of the fibre, S.
• Several types of dyeing adsorption isotherms exist
 Thermodynamics
• In essence, thermodynamics is concerned with heat and its
transformation into mechanical work
• It considers interrelations between heat, work and energy
• And also the ways in which a particular system exchanges heat, energy
and matter with another system and with its surroundings
• Thermodynamics describes and correlates macroscopic properties of
substances (e.g. the pressure exerted by a gas)
• Without going into microscopic aspects (e.g. the kinetic theory of gases)
• It can predict differences between an initial and a final state of a change
• However, it cannot predict rate of change
 Thermodynamics of Dyeing
• The purpose of studying the thermodynamics of dye adsorption is to
elucidate the mechanism by which dye adsorption occurs (?)
• To provide a quantitative measure of the tendency of the dye to pass
from the solution phase to the fibre phase
• Since thermodynamics considers dyeuptake at equilibrium – it means
no further increase in dye uptake by the fibre occurs
This can be done in two ways
• Carrying out dyeing till dyeuptake becomes constant, irrespective of
time.
• Or, a dyed fibre is immersed in an blank aqueous bath and desorption
is allowed to proceed until no further loss of dye from the dyed fibre
occurs, irrespective of time.
• Thermodynamics of dyeing applies to reversible dyeing systems at
equilibrium
• → In case of a truly reversible dyeing system, the results obtained by
dye adsorption to equilibrium and dye desorption to equilibrium
should result in identical equilibrium behaviour.

Desorption of C.I. Reactive Black 5 from

an activated alumina-supported iron
oxide composite as a function of pH
Adsorption and desorption of C.I. Disperse red 19 on CA at 80oC
 Equilibrium of C.I. Direct Blue 1 on CV sheet

• The adsorption process for direct dyes on cellulosic substrates is entirely

reversible
• When a dyed fibre/sheet is placed in dilute aqueous electrolyte solution, dye
desorbs from the substrate until an equilibrium is established
• The partition of the dye between the substrate and solution is approximately
identical to that observed when the same quantity of dye is applied to the
undyed fibre from a bath of similar electrolyte concentration
At equilibrium

• The following equation describes the distribution of dye in two

phases

• Higher the value of K (partition coefficient), greater is the transfer of

dye in fibre
Adsorption
• Typically, adsorbent surfaces are physically and chemically
heterogeneous (textile fibre surfaces)
• Two broad types of adsorption phenomena exist:
• Physical adsorption (physisorption) and
• Chemisorption (chemical adsorption)
• In physical adsorption, the forces of interaction involved include van
der Waals forces, electrostatic force (e.g. ion–ion, ion–dipole and H-
bonds
• Chemisorption involves the formation of a chemical reaction between
the adsorbate and specific locations within the surface (i.e. active
sites)
Adsorption Isotherms
• Experimental isotherms generally correspond to one of six types
• The first five types were proposed by Brunauer, Deming, Deming and
Teller in 1940
• Also known as the BDDT classification
• The last (type VI) was added later (in 1985)
• At sufficiently low fractional surface coverage (occupancy) of
adsorbate, θ, the isotherms reduce to a linear form (in the majority of
cases)
• i.e. amount adsorbed α relative pressure, P/Po
• In the case of dyeing equilibria, the most commonly encountered
adsorption isotherms are the partition isotherm (Nernst isotherm),
Langmuir isotherm and Freundlich isotherm
Types of adsorption isotherm commonly encountered in dyeing
Partition Isotherm (Nernst isotherm)
• It is typically displayed for the adsorption of disperse dyes on
hydrophobic fibres such as PES and CTA
• A linear relationship exists between [D]f and [D]s
• The constant K is the distribution coefficient or partition coefficient
• The point at which the horizontal line begins denotes the saturation
value, Ss of the dye in solution
• It represents the maximum aqueous solubility of the dye
• As the addition of dye to a dyebath in excess of Ss does not change
the amount of dissolved dye, the amount of dye adsorbed by the
fibre, [D]f, remains constant
(1)
Langmuir Isotherm
• This model is typically obtained for the adsorption of anionic dyes (acid dyes) on
wool, silk and PA fibres, as well as basic dyes on PAN fibres.
• Dye adsorption is considered to occur at a limited number of sites within the fibre
• Assumption – all the sites are equivalent, there is no interaction between either
the sites or dye molecules that occupy sites and when a dye molecule occupies
an adsorption site, that site is incapable of further adsorption.
• When all such sites have been occupied by dye molecules, the fibre is considered
saturated
• This is referred to as the fibre saturation value, Sf
• At equilibrium, the rate of adsorption of dye onto the fibre = dye desorption from
the fibre
• The rate of dye adsorption depends on dissolved dye concentration [D]s and the
occupancy of the adsorption sites in the fibre, Sf − D f

• The rate of desorption depends on the amount of dye in the fibre, [D]f
At equilibrium (2)
Or
Where K=K2/K1 (3)
Or (4)

Or (5)

A plot of 1/Df and 1/Ds will give a line with slope of 1/KDf and an
intercept of 1/Sf
• At low amounts of dye, the Langmuir isotherm in Eq. 3 resembles that
of the Nernst isotherm (Eq. 1)
Alternative Langmuir plots
Freundlich Isotherm
• Freundlich isotherms describes the adsorption of direct dyes on
cotton and other cellulosic fibres.

• Can be rearranged to the form

Standard Affinity, Standard Heat and Standard
Entropy of Dyeing

Standard affinity of dyeing, Δμɵ, the standard heat of dyeing, ΔHɵ, and
the standard entropy of dyeing, ΔSɵ, are related as

Δμɵ =ΔHɵ −TΔSɵ

Standard Affinity of Dyeing, Δμɵ
• Substantivity refers to the attraction between a dye and a fibre that
results in the preferential adsorption of the dye onto the fibre
• % Exhaustion, which seems to be related to substantivity, is actually
dependent on dyeing conditions
• Standard affinity, Δμɵ, which is a fundamental parameter much less
dependent on dyeing variables is a better measure of substantivity
• The standard affinity provides a measure of the tendency of a dye
molecule to move from the solution phase to the fibre phase under
precise (i.e. standard) conditions of temperature, pH, electrolyte
concentration, LR, etc. (units: J mol−1; kcal mol −1)
• Affinity is the quantitative expression of substantivity
It is the difference between the chemical potential of the dye in its
standard state in the fibre and the corresponding chemical potential in
the dyebath

• Determination of the standard affinity of dyes for textile fibres

• μ is the chemical potential, R the universal gas constant and af and as

the activities of the dye in the fibre and solution phases, respectively
Gibbs Energy, G
• In thermodynamics, the maximum amount of energy that can be
extracted from a closed system to do work other than that of
expansion at constant pressure, is the Gibbs energy or free energy, G.
• In the case of a reaction, Gibbs energy is a measure of the tendency
for reaction to occur (criterion of spontaneous change)
• Free energy is a function of both enthalpy, H, and entropy, S, such
that
G=H – TS
Closed system - mass of material remains constant and there is no transfer of material to or from the
surroundings during the process
For constant volume processes, free energy is termed as Helmholtz free energy
• When an isolated system changes from a well-defined initial state to an equally
well-defined final state, the change in free energy is given by (in the case of a
constant temperature process)

∆𝑮 = 𝑮 𝒑𝒓𝒐𝒅𝒖𝒄𝒕𝒔 - 𝑮 𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕𝒔
𝒇𝒊𝒏𝒂𝒍 𝒔𝒕𝒂𝒕𝒆 𝒊𝒏𝒊𝒕𝒊𝒂𝒍 𝒔𝒕𝒂𝒕𝒆

Or ΔG=ΔH – TΔS
For a constant pressure process, free energy describes the spontaneity of
reaction (and position of equilibrium) such that:
• ΔG = negative: the process is spontaneous (i.e. moves towards equilibrium)
• ΔG = 0: the system is at equilibrium
• ΔG = positive: the process is not spontaneous (moves away from equilibrium)

Isolated system : A thermodynamic system completely enclosed by walls through which neither
energy nor matter can pass.
• The change in the free energy of a system that occurs during a reaction
can be measured under a set of given conditions.

• When the data are collected under a set of reference standard-state

conditions, the ensuing free energy of reaction is referred to as the
standard free energy, ΔGɵ,

• This is equal to the difference in free energy between products and

reactants in their standard state

• The symbol ɵ represents the standard state

ΔGɵ =ΔHɵ – TΔSɵ
Raoult's law
For a solution of two liquids, A and B, Raoult's law predicts that if no
other gases are present, then the total vapor pressure above the
solution is equal to the weighted sum of the "pure" vapor pressures of
the two components, 𝒑𝑨 and 𝒑𝑩 . Thus the total pressure above the
solution of A and B would be
𝒑 = 𝒑∗𝑨 𝒙𝑨 + 𝒑∗𝑩 𝒙𝑩
Where 𝒑∗𝑨 is the vapor pressure of the pure component 𝒑𝑨 and 𝒑∗𝑩 of
𝒑𝑩 . 𝒙𝑨 and 𝒙𝑩 are the mole fractions of the respective components.
Mathematically, Raoult's law for a single component in an ideal solution is stated as

P = xPo
Where P is the partial vapor pressure of the component i in the gaseous mixture
(above the solution), Po is the vapor pressure of the pure component i, and x is
the mole fraction of the component i in the mixture (in the solution).

If a non-volatile solute (zero vapor pressure) is dissolved into a solvent to form an

ideal solution, the vapor pressure of the final solution will be lower than that of the
solvent.

The decrease in vapor pressure is directly proportional to the mole fraction of

solute in an ideal solution.
• For an ideal solution or the solvent in a dilute, non-ideal solution, the
vapour pressure of the solvent is related to the mole fraction of the
solvent, x, (Raoult’s law)
P = xPo
• In the case of two solutions of vapour pressures P1 and P2, where P1 =
x1Po and P2 = x2Po, the difference in free energy for the solvent in the
two solutions, for 1 mol of solvent:

• Assuming that the standard state is the pure solvent, taking x1 as

unity as the standard state, denoted by Gɵ, and x2 = x, then
ΔG=G−Gɵ = RT ln x
or G=Gɵ +RT ln x
For molar concentrations - G=Gɵ +RT ln c
where Gɵ is the free energy per mole of solute (assuming ideal conditions) at a
concentration of 1 mol.
Activity Coefficients
• In an ideal solution, the interactions between molecules are equivalent
and, therefore, the amount of the species present in solution can be
expressed in terms of concentration, c
• However, this situation applies only in the case of very dilute solutions
• In case of more concentrated solutions, due to interactions between the
molecules and their surroundings, deviations from ideality occur
• Hence recourse must be made to the use of the activity, a, of the species
rather than its concentration
• Hence, activity coefficients are thermodynamic parameters that are used to
account for deviations from ideal behaviour displayed by interacting
molecules in solution
The relationship between activity and concentration is, a = cf
• where a is the activity, c concentration and f the activity coefficient
• Generally, f → 1 as c → 0 so that in very dilute solutions, the system
approximates to being ideal and activity can be equated to concentration
(i.e. a = c)
• [all above equations for Gibbs energy are applicable only to extremely
dilute solutions]
• Thus, for non-ideal solutions, such as typical dye solutions, the equation is
modified as
G= Gɵ + RT ln a
• Where a is the activity of the solute and Gɵ the standard free energy per mole when the
activity is unity (a = 1) and the solute is in its standard state under defined conditions

For f > 1 and f < 1, substance shows positive and negative deviation from Raoult's law, respectively.
A positive deviation implies that substance is more volatile.
 Chemical Potential

The chemical potential (partial molar free energy), μ, of a component

describes the extent to which the Gibbs energy, G, of the system
changes in response to the addition of a very small amount of the
component at constant temperature and pressure, and when the
amount of other species remains constant

μ is a form of potential energy that can be absorbed or released during a chemical reaction or phase
transition.
• In a thermodynamically closed system, the mass of material remains constant and
there is no transfer of material to or from the surroundings during the process.
• A dyeing process is an example of a closed system.
• When in a process, material is exchanged, consumed and produced, it is
considered open
• Example - heterogeneous systems, they comprise of two or more phases that
display varying composition and mass
• A dyeing process is heterogeneous system as it contains two phases, the solid
fibre phase and the aqueous dyebath phase, which are in intimate contact
• As such the whole dyeing process is a closed system but the dyebath and fibre
components constitute open systems
• Both the dyebath and fibre phases undergo changes: the amount of dye in the
dyebath phase falls as dye molecules are adsorbed onto the fibre and, in the fibre
phase, the amount of dye increases as dye molecules are adsorbed.
 Intensive and extensive variables
• A thermodynamic system can have either intensive or extensive
variables
• For intensive variables (temperature, density and viscosity), the value
of the variable is independent of the mass and/or quantity of material
in the system
• In contrast, an extensive variable (volume, heat capacity and mass) is
dependent upon the mass and/or amount of material in the system
• An intensive variable can be obtained by division of an extensive
variable
• Example - heat capacity, Cp, is an extensive variable, heat capacity per
gram, Cp/m, is an intensive variable
Gibbs energy, G, is an extensive variable that depends on the state of the system
under consideration (temperature, T, pressure, P, the amount of other species
present, ni, nj, etc.) can be expressed as where f represents a particular function.
G=f (T,P,ni,nj,… )

• Extensive variable G can be changed to the Intensive variable, μ, by

division of G by the amount of the species i present in the system
• Assumption – the solution contains species i, j, etc. and all other
species (except i) and T, P are constant
• Then
Since G is a thermodynamic function, then so too is μ and, therefore, it
can be used in the place of G,
μ = μɵ + RTlna
• Since dyeing process comprises two components (solution phase and
the fibre phase), the above equation for the system becomes
μ = μɵ + 𝑅𝑇𝑙𝑛𝑎
𝑓 𝑓 𝑓 (for fibre)
μ𝑠 = μɵ
𝑠 + 𝑅𝑇𝑙𝑛𝑎𝑠 (for solution)

At equilibrium, μf = μs, then

μɵ𝑓 + 𝑅𝑇𝑙𝑎𝑓 = μɵ + 𝑅𝑇𝑙𝑛𝑎
𝑠 𝑠
ɵ ɵ ɵ 𝑎𝑓
−∆μ𝑓 = − μ𝑓 − μ𝑠 = 𝑅𝑇𝑙n
𝑎𝑠
Standard affinity of the dye
• −Δμɵ is the standard affinity of the dye and is the difference in
chemical potential, Δμɵ, of the dye within the solution and fibre
phases, determined under prescribed standard conditions.
• −Δμɵ is a measure of the tendency of the dye to move from its
standard state in solution (i.e. the dyebath) to the fibre.
• In terms of the thermodynamics of dyeing, the driving force for
dyeing can be expressed in terms of −Δμɵ.
• Affinity is the quantitative expression of substantivity.
• Negative values of chemical potential change (i.e. −Δμɵ) are obtained
for dyeing systems, denoting that the transfer of dye is a spontaneous
process, thermodynamically.
Standard Heat of Dyeing, ΔHɵ
• The standard affinity of dyeing,, the standard heat of dyeing and the
standard entropy of dyeing are related by
Δμɵ =ΔHɵ – TΔSɵ
• The heat of dyeing is defined as the increase in enthalpy (heat content) of a
dye–fibre system when dye is sorbed by the fibre.
• It describes the effect of dyeing temperature on the position of dyebath–
fibre equilibrium.
• It can be considered as the heat absorbed, δH, when a small amount of dye
(δn moles) is transferred from a large volume of solution, in which the dye
is in its standard state, to a large mass of dyed fibre in which the dye is also
in its standard state.
• The molar heat of dyeing, ΔHɵ, is given as follows
ΔHɵ =δH/δn
• For most dyeing systems, ΔHɵ is negative, indicating that dye
adsorption is an exothermic process.
• Hence an increase in dyeing temperature reduces the extent of dye
adsorption at equilibrium
• In other words, the standard affinity is reduced.
• It can be determined from the slope of a plot of Δμɵ/T as a function of
1/T (at a selected value of T) .
Relationship between affinity and temperature for a C.I. Disperse red 19 on CA
Standard Entropy of Dyeing, ΔSɵ

• The standard affinity of dyeing,, the standard heat of dyeing and the
standard entropy of dyeing are related by
Δμɵ =ΔHɵ – TΔSɵ
• There is no direct experimental method for determining the entropy
change that occurs during dye adsorption.
• The values are calculated from measurements of the standard affinity
of dyeing and the standard heat of dyeing (above equation)
• Or from the slope of a plot of Δμɵ as a function of T (assuming ΔHɵ is
constant).
Kinetics of Dyeing

• Commercial dyeing processes –

• To achieve uniform dyeings

• Accepted level of fastness in as short a processing time as possible
• Commercial dyeing is rarely carried out to equilibrium
• Hence, understanding the kinetic aspects of dyeing processes with
focus on rate of dye diffusion within the textile fibre is key
• Dye diffusion is commonly expressed in terms of the measured
diffusion coefficient of the dye molecule within the fibre.
Sorption of dyes onto textile fibres
• Consists of at least four stages–
(i) diffusion of the dye molecules through the external medium (usually water) to the
fibre surface
(ii) diffusion of the dye molecules through the diffusional boundary layer present at
the fibre surface
(iii) adsorption of the dye molecules onto the surface of the substrate
(iv) diffusion of the dye molecules within the fibre interior

• The first two stages are influenced by the dye –fibre interchange and hence
by dye liquor circulation, fabric construction etc.
• Adsorption of the dye molecules onto the surface of the substrate is
considered spontaneous
• The fourth stage is the rate-determining step
Diffusion
• Diffusion involves the random molecular motion of individual molecules
• The driving force for this is concentration difference
• The movement of dye molecules from the dyebath phase to the fibre phase
is driven by the concentration gradient between the two phases
• Concentration gradient → the rate of change of (dye) concentration, C, as a
function of distance, x, i.e., dC/dx
• Such diffusional transfer eventually results in equalisation of concentration
and, therefore, of chemical potential throughout the system
• The chemical potential of the diffusant (i.e. the dye molecule) will be
constant throughout the system only when dynamic equilibrium has been
achieved, even though the concentration of the dye within each phase may
differ markedly.
Representation of concentration gradient
• The diffusion or the movement of the molecules is referred to as
diffusivity and is expressed in terms of the diffusion constant, D.
• The diffusion constant reflects the mobility of the diffusing molecule
within a particular environment.
• In a gas, diffusion processes are far more rapid (D ~ 0.1 cm2 s−1) than
in either liquids (~10−5 to 10−6 cm2 s−1) or solids (~10−10 to 10−7 cm2 s−1)
• Diffusion in polymers lies between that in liquids and solids
• The diffusion coefficient of disperse dyes in PES at 130oC is ~10−10 cm2
s−1
• The estimation of diffusion is more difficult using theoretical models
(due to issues related to swelling, plasticisation, segmental chain
mobility, crystallinity, porosity, etc.)
• In the context of dyes and textile fibres, the rate of dyeing depends on:
• Polymer properties like diffusion constant
• Various fibre characteristics such as fibre linear density, fibre cross-
sectional shape, fabric construction
• Dye characteristics (e.g. solubility and affinity)
• Physico-chemical parameters, like temperature, pH, liquor ratio,
electrolyte concentration, rate of fibre/dye solution interchange, etc.
• As so many factors influence dyeing rate, dyeing systems are studied on
the basis of much simpler idealised situations carried out under precise
experimental conditions (referred to as boundary conditions) demanded
by the theoretical models employed
• Unfortunately, such conditions generally do not represent the practical,
industrial dyeing processes
Steady-State and Non-Steady-State Diffusion
• There are two types of diffusional process: steady state and non-steady
state
• Steady-state diffusional system-
• The rate of flow of matter per unit area or flux occurs at a constant rate
(dC/dx = constant)
• There is no accumulation of matter at any point in the system (dC/dt =
0).
• Non-steady-state system-
• The rate of diffusion is a function of time (dC/dt ≠ 0) and therefore,
dC/dx ≠ 0,
• The two diffusional processes are described by Fick’s laws of diffusion
• It is assumed that the overall rate of dyeing is determined by the rate of
dye diffusion within the fibre
Fick’s Law of Diffusion
• Proposed by Fick In 1855
• It governs mass transfer in an homogeneous, isotropic medium
• Assumption - the rate of transfer of a diffusant through a unit area of
material is proportional to the concentration gradient measured
normal to the material
𝜕𝐶
𝐽 = −𝐷
𝜕𝑋
• where J is the diffusional flux (diffusive mass flux) (gm−2 s−1), dC/dx (g
m−4) the concentration gradient of the diffusive component in the
mass transfer direction (i.e. positive x direction) and D (m2 s−1) the
diffusion coefficient