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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)
• 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.
Standard affinity of dyeing, Δμɵ, the standard heat of dyeing, ΔHɵ, and
the standard entropy of dyeing, ΔSɵ, are related as
∆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.
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).
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
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,… )
• 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
• 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