BAHIR DAR UNIVERSITY

Ethiopian Institute of Textile and

Fashion Technology (EiTEX)
Post Graduate Program

Program: 1st year MSc. in Textile Technology

Course Name: Theory of Coloration (Ttec6052)

Review Title: Significance of Affinity in Dyeing, Substantivity and

Heat of Dyeing

Paper Reviewed By:

Name Id.No

Tewodros Birhan BDU1501720

Email address: teddybmail.1986@gmail.com

Submitted to: Dr K Murugesh Babu (Prof.)

Due Date: 15 May, 2023

Bahir Dar, Ethiopia

Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

Table of Contents
List of Figures .......................................................................................................................... iii

List of Tables ........................................................................................................................... iii

Abstract .................................................................................................................................... iii

1. Introduction ............................................................................................................................ 1

2. Dye–Fibre Systems ................................................................................................................ 3

2.1 Factors That Affect Dye Binding ..................................................................................... 4

3. Dye–Fibre Substantivity ........................................................................................................ 4

4. Dyeing Theory ....................................................................................................................... 5

5. Standard Affinity, Standard Heat and Standard Entropy of Dyeing ...................................... 6

5.1 Standard Affinity of Dyeing, Δμɵ..................................................................................... 7

5.1.1 Gibbs Energy, G ........................................................................................................ 7

5.1.2 Activity Coefficients.................................................................................................. 8

5.1.3 Chemical Potential ..................................................................................................... 8

5.2 Standard Heat of Dyeing, ΔHɵ ......................................................................................... 8

6. Kinetics of Dyeing ................................................................................................................. 9

7. Summary .............................................................................................................................. 11

ii
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

List of Tables
Table 1: Classification of dye–fibre systems based on application class .................................. 3
Table 2: Dye–fibre classification based on application character ........................................... 4

List of Figures
Figure 1: Schematic representation of the relationship between kinetics of dyeing and
thermodynamics of dyeing ......................................................................................................... 6
Figure 2: Simplified scheme of the equipment used for the dyeing process. ........................... 10

iii
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

Abstract
Dyeing is the process of colouring a textile substrate with suitable dyes or pigments. A
fundamental grasp of textile dyeing process and related terminologies are extremely
important to comprehend dyeing theory. Dyeing can be done at any stage of textile
production, including fibre, yarn, fabric, and completed textile products such as garments and
apparel. Textile dyeing techniques can be batch, continuous, or semi-continuous. The
procedure employed is determined by a number of factors, including the kind of material
(fibre, yarn, fabric, fabric construction, and garment), the generic type of fibre, the amount of
dye lots, and the quality standards in the dyed fabric. Under normal operating settings, the
dye is introduced to the mixing bath at the start of a dyeing cycle, and the process is operated
in batch mode, that is, without changing the amount of dye in the system. High recirculation
flow levels and low dispersion resistances benefit dye distribution factor (DDF) and dye
uptake (CDEP) in general. This paper reviewed the current state of the art in the Significance
of Affinity in Dyeing, Substantivity and Heat of Dyeing.

Keywords: Affinity, substantivity, heat of dyeing, dye/fiber system, dyeing rate, levelness,
Thermodynamic parameters

iii
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

1. Introduction
Knowledge of the forces which bind dyes to fibres is of obvious importance in the
development of a theory of dyeing. A dyeing process is the interaction of a dye with a fibre,
as well as the migration of dye into the fibre’s interior structure. In general, dyeing processes
involve adsorption (the transfer of colours from an aqueous solution to the fibre surface) and
diffusion (the diffusion of dyes into the fibre). The adsorption process implies. The selective
adsorption of one compound from the external phase in the adsorbent. Thus, when an
adsorbent is immersed in a solution, the adsorption takes place when the solute molecules are
transferred from the solution into the adsorbent, yielding a variation of concentration in
solution. As consequence the condition for a spontaneous transfer is the low energy state or a
high stability which has to be attended by the system. The released energy can be seen as a
free energy which supplies the driving force of adsorption. The opposite process of
desorption requires the energy to be brought back into the system (Shang 2013).

Affinity refers to the attraction of two substances; in dyeing, affinity essentially means the
dye's preferential attraction to the fibre rather than the dye bath solution. It is quantitative
expressing of Substantivity while Substantivity is defined as the ability of a dye to migrate
from a solution to fibres in the dye solution. It is a dye quality. Without Substantivity, most of
dyes would simply remain in solution or dispersion in the bath (Vigo 2013).

The heat of dyeing is a measurement of the strength of the bonds that hold the dye to the
fibre. Because the transfer of dye from the solution to the fibre includes a drop in the system's
free energy, heat is released, and the heat of dyeing is thus a negative number. The inverse is
also true, namely that dye migration from the fibre to the liquid phase is followed by heat
absorption. As a result, increasing the temperature promotes desorption and, as a result,
decreases the concentration of dye molecules in the fibre at equilibrium (Perkins 1991).

All dyes and the dyeing process rely heavily on dye affinity. The dye affinity and reactivity
determine the majority of a dye's qualities. A variety of factors influence this process,
including dyeing liquor ratio, dye physical and chemical properties (organic or inorganic),
dye bath additions (such as dye acid, organic or inorganic salts, and dyeing auxiliaries),
dyeing time (time from start to end of dyeing), dyeing temperature (temperature varies

1
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

depending on dyes and dyeing properties), and the degree of purity (Fleischmann,
Lievenbrück et al. 2015).

For dye affinity- controlled dyeing processes, a temperature is selected at which diffusion
proceeds at a relatively fast rate inside the dye bath. If it is assumed, as a model, that a dye
bath exhaustion equilibrium is established momentarily at any one time, then the kinetics of
exhaustion are given by the change in chemical equilibrium. For synthetic polyamide fibres
and natural wool fibre, the chemical equilibrium between the dye in the textile fibre
(concentration CF) and the dye in the liquor (CL) can be approached by a superimposed
Langmuir and Nernst distribution with the pH-dependent distribution coefficients kL and KN,
and the saturation value SL. The pH dependencies are both dye and fibre-specific (Gulzar,
Ozturk, E et al. 2015).

The absorbing capacity/attraction of dyes and fibres is described by dye affinity. This is why
water, energy, and chemical consumption are so crucial in cotton dyeing; both the surface of
cotton fibres and the dye chemicals are negatively charged and hence do not readily react
with each other. Cotton may only absorb about 75% of the dye even with the help of salts and
alkali. Cotton, in other terms, has a low dye affinity (i.e. dye absorption ability). The
environmental issue here is that significant amounts of chemicals and dyes used during the
dyeing process are often not fully absorbed and are discharged into rivers (Kumar and Kumar
2020).

2
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

2. Dye–Fibre Systems
Because fibres differ not only in terms of chemical and physical composition, but dyes also
differ in terms of chemical and physical composition, a variety of different application
methods have been developed for the various dye-fibre systems that differ in terms of the
application conditions used (e.g. pH, electrolyte, and temperature). Because of the diverse
physical and chemical properties of textile fibres, as well as the different chemical
composition of the dyes, this diversity in application methods is both historical and required.
Different conditions are frequently employed to apply dyes to the various physical forms in
which textile fibres are processed (for example, yarns, open width, rope, and so on). There is
no universal dye or universal fibre, just as there is no single dyeing method that is applicable
to all dyes and all fibres; instead, a variety of dye-fibre systems have been developed, and as
a result, there is no universal theory of dyeing, but rather several theories or models that
attempt to describe the practical dyeing behaviour of the various dye-fibre systems (Lewis
1996).

Table 1: Classification of dye–fibre systems based on application class

3
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

Table 2: Dye–fibre classification based on application character

2.1 Factors That Affect Dye Binding

The affinity of the dye component of the stain solution determines stain uptake. The tendency
of a dye to transfer from a staining solution onto a substrate is referred to as affinity. Factors
that affect affinity and ultimately staining include the following:

Dye Concentration - The higher the dye concentration, the more the dye is linked to the
substrate.

Temperature - As the temperature rises, the dye diffuses more quickly throughout the
substrate. It can also change the substrate components to make them more permeable to dye.

PH of the staining solution - The pH of the staining solution can have a direct effect on a
dye's capacity to bond with its intended tissue element.

Fixation - Fixation changes and reorganises certain molecular structures within the sample,
increasing permeability to staining.

Mordants: are substances that may be required to enhance the affinity of the dyes. They can
also be employed to enhance the staining effects.

3. Dye–Fibre Substantivity
When a fibre is immersed in an aqueous dye bath, dye molecules travel from the aqueous dye
solution to the fibre, with the resulting loss of dye from the solution indicating the dye's
substantivity towards the substrate. Substantivity is described as the attraction of a dye to a
fibre, resulting in the dye being adsorbed on the fibre (Raja et al. 2019). The mechanical and
physicochemical causes of dye-fibre substantivity are discussed. In essence, dye molecules

4
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

dissolved in water can be imagined as travelling through myriad water-filled pores, channels,
and capillaries found in water-swollen, non-crystalline regions of a fibre and becoming
adsorbed onto the internal channel walls as a result of various physical forces of interaction
(ion-ion, ion-dipole, H-bonding, and so on) operating between the dye molecules and the
fibre macromolecules (Burkinshaw 2016).

Because dye-fibre substantivity involves both mechanical and physicochemical

characteristics, it follows that the substantivity of a given dye towards a specific fibre can be
influenced by manipulating both the level of fibre-dye bath interchange and the nature and
extent of the various dye-fibre forces of interaction, for example, through the use of adequate
rates of dye bath/fibre agitation, pH adjustment, control of dyeing temperature, liquor ratio,
and so on. The substantivity of different colours towards a certain fibre varies significantly;
also, a given dye will have varied substantivity towards different fibres (Tayebi,
Yazdanshenas et al. 2015).

The two most prevalent dye classes, reactive dyes and disperse dyes, and the most popular
fibre blend, PES/cotton, present a simple illustration. Disperse dyes have a high substantivity
towards PES but very little substantivity towards cotton, whereas reactive dyes have the
reverse tendency. Dye-fibre substantivity distinguishes dyeing from simple imbibition: during
dyeing, the fibre becomes coloured and the amount of dye in the dye solution decreases;
during imbibition, the fibre is simply stained with coloured liquid, but the amount of dye in
the dye solution remains essentially unchanged (Chinta et al.2013).

4. Dyeing Theory
In essence, dyeing theory is concerned with how a given dye is taken up by a particular
textile fibre.

Two approaches are used to study the mechanism of dyeing insofar as the dyeing system is
studied:

(1) At equilibrium (thermodynamics of dyeing);

(2) Before equilibrium is attained (kinetics of dyeing)

5
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

Figure 1: Schematic representation of the relationship between kinetics of dyeing and

thermodynamics of dyeing
The aqueous dyeing process is heterogeneous in the sense that it involves two phases: a fibre
phase, which initially consists of the textile substrate, and an aqueous phase, which contains a
dye solution in which the initially undyed fibre is immersed.

Dye molecules travel or diffuse through the aqueous phase (the dye bath) to the fibre phase,
where they diffuse and collect within the water-filled, swollen substrate during dyeing. The
kinetics of dyeing, which is often represented by a rate of dyeing curve (left-hand plot in
Figure 1), considers the rate at which dyeing proceeds and hence concerns the rate at which
the dye diffuses in both the aqueous phase and the fibre phase. A rate of dyeing plot depicts
the amount of dye adsorbed by the fibre, DF, as a function of dyeing time, t (Lara et al. 2022).

5. Standard Affinity, Standard Heat and Standard Entropy of Dyeing

For any dye–fibre system, the amount of dye adsorbed by the fibre at equilibrium enables
three important thermodynamic parameters to be determined, namely the standard affinity of
dyeing, Δμɵ, the standard heat of dyeing, ΔHɵ, and the standard entropy of dyeing, ΔSɵ.

Δμɵ = ΔHɵ −TΔSɵ

6
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

5.1 Standard Affinity of Dyeing, Δμɵ

The standard affinity (units: J mol−1; kcal mol−1), which is commonly abbreviated to 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. (the symbol ɵ represents the particular chosen standard state).

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 dye bath. Although the terms substantivity and affinity are often used
synonymously, this is not correct, as the two parameters differ, insofar as affinity can be
regarded as that part of dye–fibre substantivity that is affected by temperature.

Where 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.

Clearly, the parameters μ (chemical potential) and activity (af and as) require consideration; for this,
recourse must first be made to Gibbs energy.

5.1.1 Gibbs Energy, G

In thermodynamics, the maximum amount of energy that can be extracted from a closed
system12 to do work other than that of expansion at constant pressure, is the Gibbs energy or
free energy, G (aka Gibbs free energy, Gibbs function; units: J mol−1 ) (Hossain et al.2021).
In the case of a reaction, Gibbs energy is a measure of the tendency for reaction to occur (i.e.
is a criterion of spontaneous change); free energy is a function of enthalpy, H, and entropy, S.

ΔG = ΔH – TΔS

For a constant pressure process, free energy describes the spontaneity of reaction (and
position of equilibrium) in so far as when:

ΔG = negative: the process is spontaneous (i.e. moves towards equilibrium);

7
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

ΔG = 0: the system is at equilibrium;

ΔG = positive: the process is not spontaneous (i.e. moves away from equilibrium)

5.1.2 Activity Coefficients

Activity coefficients are thermodynamic parameters that are used to account for deviations
from ideal behaviour displayed by interacting molecules in solution. 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 solution because, in the case of more concentrated
solutions, owing to interactions between the molecules and their surroundings, deviations
from ideality occur and recourse must be made to the use of the activity, a, of the species
rather than its concentration.

The relationship between activity and concentration is given by the following, where a is the
activity, c concentration and f the activity coefficient, the latter parameter describing the
extent to which a particular system deviates from ideal behaviour.

a = cf

5.1.3 Chemical Potential

The chemical potential (aka 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.

5.2 Standard Heat of Dyeing, ΔHɵ

As mentioned, the standard affinity of dyeing, Δμɵ, the standard heat of dyeing, ΔHø, and the
standard entropy of dyeing, ΔSɵ, are related by:

Δμɵ = ΔHɵ −TΔSɵ

The heat of dyeing is a measure of the change in enthalpy of the dyeing process when dye
adsorption occurs. 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. The value of ΔH determines the way in
which the affinity changes with temperature. From a practical viewpoint, the heat of dyeing is
of significance as it describes the effect that a change of dyeing temperature has on the

8
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

position of dye bath–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 ensuing molar heat of dyeing, ΔHɵ, is given as follows:

For most dyeing systems, ΔHɵ is negative, indicating that dye adsorption is an exothermic
process and, therefore, an increase in dyeing temperature reduces the extent of dye adsorption
at equilibrium (i.e. the standard affinity is reduced).

6. Kinetics of Dyeing
The basic goals of commercial dyeing procedures are to provide consistent dyeing’s with the
necessary level of fastness in the shortest amount of time achievable. As a result, much
emphasis is paid to the creation of dyeing recipes and process parameters that allow for the
reliable and reproducible uniform distribution of dye throughout a given textile material
(Chairat et.al 2005). Because commercial dyeing is rarely done to equilibrium, much
attention has been paid to understanding the kinetic aspects of dyeing processes, with special
emphasis on the rate at which dyes diffuse within the textile fibre, which is most commonly
expressed in terms of the measured diffusion coefficient of the dye molecule within the fibre
(Ujhelyiova, Bolhova et al. 2007).

In essence, dye sorption onto textile fibres can be divided into at least four sequential 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.

9
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

Figure 2: Simplified scheme of the equipment used for the dyeing process.

The bobbins are loaded first, and then the water and auxiliary goods are introduced to the
system at room temperature (20°C). When the basic dye is introduced to the dye bath, it is
promptly heated to 70°C. Starting with the addition of the dye, the bath is heated (at a rate of
around 0.3°C per minute) until it reaches 102°C. This temperature is maintained throughout
the dyeing process. The pump (Figure 1a) permits the dye bath liquid to be recirculated to the
perforated support, where it is collected and re-injected into the external bath (Kozłowski,
Wang et al. 2020).

10
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

7. Summary
Dyeing is a process that is used to transform raw textile resources into finished items and
considerably improve the appearance of textile products. Dyeing textiles involves a variety of
colours, techniques, and machinery. Almost every textile material can be coloured at any step
of production. Each textile is coloured with specific colourants using its unique procedure.
Synthetic dyestuffs have introduced a wide range of colourfastness and bright hues to the
market. The majority of the equilibrium features of a dyeing system are determined by three
quantities: affinity, dyeing heat, and entropy change. The amount of dye absorbed by a textile
fibre at equilibrium when temperature varies permits thermodynamic and kinetic sorption
parameters such as standard affinity, dyeing heat, dyeing entropy, and diffusion activation
energy to be considered. The standard affinity, Δμ° is the transfer of one mole of dye from its
standard state in solution to its standard state in the fibre. The heat content change during the
dyeing process is the ΔH°, whereas the degree of disorder of the dye molecules during the
dyeing process corresponds to the entropy change, ΔSº.

11
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

References

[1] Burkinshaw, S. M. (2016). Physico-chemical aspects of textile coloration, John Wiley &
Sons.

[2] Chairat, M., Rattanaphani, S., Bremner, J.B. and Rattanaphani, V., 2005. An adsorption
and kinetic study of lac dyeing on silk. Dyes and Pigments, 64(3), pp.231-241.

[3] Chinta, S.K. and VijayKumar, S., 2013. Technical facts & figures of reactive dyes used in
textiles. Int J Eng Manag Sci, 4(3), pp.308-12.

[4] Fleischmann, C., et al. (2015). "Polymers and dyes: developments and applications."
Polymers 7(4): 717-746.

[5] Gulzar, Briggs, T.R., 2002. The physical chemistry of dyeing: substantive dyes. The
Journal of Physical Chemistry, 28(4), pp.368-386.

[6] Khatri, A., Peerzada, M.H., Mohsin, M. and White, M., 2015. A review on developments
in dyeing cotton fabrics with reactive dyes for reducing effluent pollution. Journal of Cleaner
Production, 87, pp.50-57.

[7] Kozłowski, Lenher, S. and Smith, J.E., 2002. A Diffusion Study of Dyes. The Journal of
Physical Chemistry, 40(8), pp.1005-1020.

[8] Kumar, P. and A. Kumar (2020). "In silico enhancement of azo dye adsorption affinity
for cellulose fibre through mechanistic interpretation under guidance of QSPR models using
Monte Carlo method with index of ideality correlation." SAR and QSAR in Environmental
Research 31(9): 697-715.

[9] Lara, L., Cabral, I. and Cunha, J., 2022. Ecological approaches to textile dyeing: a
review. Sustainability, 14(14), p.8353.

[9] Lewis, El Harfi, S. and El Harfi, A., 2017. Classifications, properties and applications of
textile dyes: A review. Applied Journal of Environmental Engineering Science, 3(3),
pp.00000-3.

12
Significance of Affinity in Dyeing, Substantivity and
Heat of Dyeing BDU, EiTEX

[10] Ozturk, E., Karaboyacı, M., Yetis, U., Yigit, N.O. and Kitis, M., 2015. Evaluation of
integrated pollution prevention control in a textile fiber production and dyeing mill. Journal
of cleaner production, 88, pp.116-124.

[11] Perkins, W. S. (1991). "A Review of Textile Dyeing Processes." Textile Chemist &
Colorist 23(8).

[12] Raja, Elshemy, N.S., 2011. Unconventional natural dyeing using microwave heating
with cochineal as natural dyes. Research Journal of Textile and Apparel.

[13] Shang, Ketema, A. and Worku, A., 2020. Review on intermolecular forces between
dyes used for polyester dyeing and polyester fiber. Journal of Chemistry, 2020, pp.1-7.

[14] Tayebi, H.-A., et al. (2015). "The isotherms, kinetics, and thermodynamics of acid dye
on nylon6 with different amounts of titania and fiber cross sectional shape." Journal of
Engineered Fibers and Fabrics 10(1): 155892501501000110.

[15] Ujhelyiova, A., et al. (2007). "Kinetics of dyeing process of blend

polypropylene/polyester fibres with disperse dye." Dyes and Pigments 72(2): 212-216.

[16] Vigo, Choudhury, A.K.R., 2018. Eco-friendly dyes and dyeing. Advanced Materials and
Technologies for Environmental, 2, pp.145-76.

[17] Wang, L., Fu, X., He, J., Shi, X., Chen, T., Chen, P., Wang, B. and Peng, H., 2020.
Application challenges in fiber and textile electronics. Advanced Materials, 32(5),
p.1901971.

13