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;trike an
mt hs art
~mi t t i ng
L- A- . - : -
? JJrP[m.rt
any sal
- 4 I - - L
I occur.
fied to give an equivalent depth of shade to h a t of a standard, e.g.
20% (w.cs.g.) of Cd ~ d o n Jade Green XNS, 4% Cibanone Ited 4B,
ctc.
The str-ke-levelling tests are designed to determine both the
I ~d the ability of partly dyed material to level. Two dye-
L .d according to the preferred dyeing method hut
t t and using only about 25% of the dye used lor
h e uyeing cesL.
A I ~ a t ~ k (5 g) is entered into one dyehath and turned continu-
ously for 2 min. A second hank is entered and both are turned for
a further 3 mLn after which they are removed and trcat~cl in the
same manner as in the dyeing test. The difference in depth of
shade between the t wo dyei ng is a measure of the initial strike of
the dye and is assessed in terms of the Grey Scale No. 2; the lower
the numerical value, the greater is the strike. The levelling test is
started in the same way as the strike kst, hut after turning the
second hank for 3 min, both hanks are left in the bath for a
further 35 min, for one minute in every five. This allows
some levelling t o Both hanks are removed, after-treated nq
before, and asses .he Grey Scale. As a check for this te.st, a
standard dyeing snoulu be carried out using 5% Caledon Jade
Green XNS Paste Fine applied by Method 1. This should have a
strike made of 2-3 and a levelling grade of 3-4.
The migration test is designed t o determine the ease with which
dye can be transferred horn dy d to undyed material. As l>efore. it
consists of treating dyed and undyed hanks together in a blank
dyebath. Two hanks are dyed using the amount of dye taken for
the stri kp-levelling test and after-treated wit11 the exce f
soapi in^". One of these hanks and rn undyed hank are p 1
bath containing the same amounts of sodium hydroxide 1
hydrosulphite, and water as for a 10 g hank ~ccording to the pre-
ferred method for 40 min, being turned for the first five mi nut es
and subsequently for one minute in every five. They are then
after-treated as before, the second dyed hank being includect at the
soaping s t ag. The t wo hanks treat& in the Mank bath are then
assessed for difference in depth of shade by Grey Scale No. 2. The
migration test is carried out at two temperatures A and B, accord-
ing to Table 3,
The object of dyeing two hanks initially is to compare the
migration at the lower and higher temperatures and to note any
change in hue which takes place. Again, a 5% dyeing of Caledon
Jade Green XNS Paste Fine by Method I may be used t o standard-
pt i on o
lut into i
, sodiur
TABLE 3
TempcraLurrs of migration t est
.
Dyeing m~t l i nd
-
I I 1 I t 1 1V V VF
A 50 5 0 20 50 50 50
I3 80 9 0 50 80 80 50
ise the test. At 50C, this sl ~oul d be Grade 1 and nt 80C Grade
3-4.
These properties assist in making a choice or dyes. Obviously to
mix dyes w it11 largely different strike properties is undesirable and
the levelling test will give an idea of the degree of levelling which
might he expected.
Disperse Dyes [ 4 ]
For secondary ce1l;ulose acetate, four kst s have been specified:
migration, temperature range, rate of dyeing, and build-up. In the
first of these, equal weights of dyed and undyed material (bright
satin, pmviously scoured) are heated for one hour at 80C in
distilled water containing a dispersing agent (2 mlll Dispersal VL)
at a liquor-to-goods mtio of 50:l. Three control standards are
supplied and the differences between the clyed and undyed rnateri-
d s arc mkd on the Grey Scale.
The temperature-range test is designed to determine to what
extent the uptake of dye i s govenled Ily temperature. This factor
is paetic~rlaly important, when clyeing in an open jig since the
edges of the roll of cloth are usually cansiderahly cooler than the
middle of the roll and, if a dye possessing poor temperature mnge
properties i s used, the selvedges will dye to a paler depth.
When dyeinp are carried out for one hour at different tempera-
tures, the amount of dye taken up in general reaches a maximum
and then decreases [cf. Fig. 3). The prescribed t e s t consisb of
dyeing samples at 50, 60, 70,80, and 90C with a quantity of dye
necessary to give a standard depth of shade at 80C. If the maxi-
mum is not reached when the temperature has reached 90-100" C,
the dye must be slow dyeing.
For dyes that show increasing depth with increase in tempera-
ture, the sample dyed at 90C is cornpared with those at other
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1
! PHYSICAL METI-IODS
Dye Estimation ancl Purification
Tlic d~veloprnenk of the quantitative aspects of dye sorption has
relied in a large measure on the facility of e:tq and rapid ~stirna-
tion. Earlier workers wPre forced t o k~se chemi ral estimations of
dye conc~ntration at to rely on visual comparisons between the
udnur of the unknown nnd a standard (51. Chemical estirnalions
rely on t hc prcsence of a particular group in the dye molecule.
Such r n~t hods arc limited in applicability but do h a w t he advan-
:
tage in bcing nl>soliilP.
Colorimetric rntlthods, on the other hand, are applicahle for
-timatSon of the concentration of dye in solution but suffer from
the disaclvanLi,l~e o l htting c:ompnrative; the logarithm of the
amount of liglat absorbed by the solution is proportional to the
conccn tration of dye, the proportionality constant being obtained
Ijy cdibration wi t l ~ a standard dyc solution. Originally, colorimct-
ric methods were rather tedious but lor t he last thirty or more
i
years, visrial pstimations have been replaced by spsctrophotornetric
measurcment.q. Spectrophotometry haq now reached a h ~ g h pltch
of sophistication and i s almost universally employed far t he esti-
mation of the concentrntion of dye in solution.
Dye conwnlrations may be determined in terms of the standard
strength of dye as supplied by the dyestuff manufacturers. Com-
rnerc~al dyes may be used, e.g. to oht ai n Ihe data idiscussed in
Chapkr 3, but for much work, pure dyes are required. A very
hr i ~f disrussion of these factors i s givm in this chapter, together
with t he kind of techniques used t o measure rates of dyelng and
equilibrium vdues.
Optical Estimatiom
When a beam of white IighS, passes through a colour~d solution,
the various regions of the spcctrum are absorbed to lesser or great-
cr extents. I n Fig. 1 is shown the way in which the transmission
varies for t wo selected dyes over the range of visible wavplengths.
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NON-IONIC DYES. EQUILIBRIUM S'L'UDIES
Classification of dyeing systems
The various synthetic fibres ilvaiEabl~ are dyed with cliflescnt
classes of dyes but, compared with haturd fibres, the choice is
somewhat restricted. For exampke, cotton and wool can he dyed
wit11 several types of dye (direct, acid, etc.), whereas polyethylene
krephthdate and celIulose triacetate are dyed only with disperse
and to a lesser extent xzoic dyes, and acrylics with I.)asic or dis-
perse dyes. Of the synthetic fibres, nylon perhaps hns the widest
choice being dyed with acid, chrome, reactive, and disperse dyes.
Since it is necessary tu produce a uniform result, further restric-
tions are sometimes imposed by the level dyeing or levelling prop-
erties of the dyes on a fibre, e.g. basic dyes are difficult to dye in
pale shad= on acrylics because of their high "strike" and by short-
comings in the yarns themselves. Until recently, nylon continuous-
filament fabrics were dyed with disperse dyes since wakr-soluhle
dyes tend to emphasise irregularities in the ynm and Iead to
striped or ban6 fabrics.
Examination of the kinds of dyes used and the ways in which
the different variables modify dye uptake enables a simplified clas-
sification of dyeing systems to be drawn up. This is
(1) Non-ionic. The more hydrophobic fibres such as polyesters,
polyamides, etc. ate wadily dyed with non-ionic dyes of low
aqueous solnhility.
(2) Ionic. These systems may b~ sub-divided into two classes
according to whttth~r or not the fibre contains groups of opposite
charge to those carried by the dye molecule, (a) Fibres which
possess charged groups. There are sev~ral which fall into this cate-
gory. Acrylic fibres which contain negatively charged sulphonic or
catboxylic acid noups cnn he dyed with basic dyes whereas wool,
silk, anc? nylon which possess charged ammonium groups (-NH:)
can be dyed with dyes containing sulphonic acid groups. ( b) Fibres
which contain no charged groups. Cellulose is dyed with direct and
vat dyes both of which carry negative charges. The dye is adsorbed
by virtue of it< attraction to the fibre and in so doing is accom-
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NON-IONIC DYES. EQUILIBRIUM S'L'UDIES
Classification of dyeing systems
The various synthetic fibres ilvaiEabl~ are dyed with cliflescnt
classes of dyes but, compared with haturd fibres, the choice is
somewhat restricted. For exampke, cotton and wool can he dyed
wit11 several types of dye (direct, acid, etc.), whereas polyethylene
krephthdate and celIulose triacetate are dyed only with disperse
and to a lesser extent xzoic dyes, and acrylics with I.)asic or dis-
perse dyes. Of the synthetic fibres, nylon perhaps hns the widest
choice being dyed with acid, chrome, reactive, and disperse dyes.
Since it is necessary tu produce a uniform result, further restric-
tions are sometimes imposed by the level dyeing or levelling prop-
erties of the dyes on a fibre, e.g. basic dyes are difficult to dye in
pale shad= on acrylics because of their high "strike" and by short-
comings in the yarns themselves. Until recently, nylon continuous-
filament fabrics were dyed with disperse dyes since wakr-soluhle
dyes tend to emphasise irregularities in the ynm and Iead to
striped or ban6 fabrics.
Examination of the kinds of dyes used and the ways in which
the different variables modify dye uptake enables a simplified clas-
sification of dyeing systems to be drawn up. This is
(1) Non-ionic. The more hydrophobic fibres such as polyesters,
polyamides, etc. ate wadily dyed with non-ionic dyes of low
aqueous solnhility.
(2) Ionic. These systems may b~ sub-divided into two classes
according to whttth~r or not the fibre contains groups of opposite
charge to those carried by the dye molecule, (a) Fibres which
possess charged groups. There are sev~ral which fall into this cate-
gory. Acrylic fibres which contain negatively charged sulphonic or
catboxylic acid noups cnn he dyed with basic dyes whereas wool,
silk, anc? nylon which possess charged ammonium groups (-NH:)
can be dyed with dyes containing sulphonic acid groups. ( b) Fibres
which contain no charged groups. Cellulose is dyed with direct and
vat dyes both of which carry negative charges. The dye is adsorbed
by virtue of it< attraction to the fibre and in so doing is accom-
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ni ffusion processes
F~E. 2. n ~ p c n d ~ n c c of Lhe rate of dyeiup: on t h ~ rate of diffusion and solrlbi-
l i l y or lhc clyr (24 1. m. W ~ P S on ihceI:rlr:' '. t l y ~ s i > t l nylr~n.
( I) the conv~cti vc transfer of dye from the ZluIk of the liquor to
the fibre surface,
(2) the adsorption or dye at the fibre surfacr,
( 3) diffusion from thc surface into the polymer itself.
'I'he first of these is concerned with the procrss by which dye is
transported to the fibre surface through I l ~e liquor. Since the dye
is vrry rapidlv adsorbed o t ~ the fibre surface, the xdjncenl liqdor
hecomes deficient in dye; the d~ficiency is made good hy diffusion
Ihrough the liquor flowing pnsl the surface. The ease with whiclz
the dye reaches the surface deprncls on the velocity of liquor flow,
b ~ i n g increased as this variable increases. Ultimately, the spccd of
dyeing reacl~cs a limit at which wsistance t o transfer in thr liquid
has become minimal. For the presrnt purpose, it is nssurnecl t hat
this aspect may Ije ignored provided that dyeing is carried out
under c~ncl i l i ons of adequate agitation.
The second process i s generally considered to occur instantnn-
~ o u s l y so that the d y ~ in the liquid adjacent to the surface is in
rquilil,rium with Illat adsorbed on the f i h r ~ surface itself. The
t hi rd aspect. namely rliffusian i nl o the fibre, is v ~ l y rnricl~ dower
than that through the liquid ~ n d may be taken t o be the rate-
d~t cr mi ni ng step in dyeing with the proviso, t hat the dyebath is
well stirsccl so that the dyr can diffuse to the surface at a rate
greater Ihan that with which it difhzses into the polymer. In such
circumstancrs, a state will be rapidly establisl~ed belween thc fillre
surfncc and Ihe solution which may Ile rcgarrled as approximating
( 0 . n o u t i l i l ~ v i ~ ~ n ~ q i f l ~ ~ ~ t i o ~ .
Wllcrl a 61,rc. (ur EL ~ ) c ) t y ~ nt ~ TiEm) is immt.rstd in an : ~r l l ~c ~~us
bath, waler is taken up nnd the riljrc (or film) swells to an t*stt.tlt
dcpcnclil~g on its chc~rlical chnrnctcr. Uecaust! uC tfiuir snl:~ll rncl!r.-
cultlt size, watcr molecules penetr;~tt! the fillre very mpjrlly, lo S)e
followed l ~ y the more slorvly ditrusing dye molecule: ho~vcvcr, khr
number of dyc n~olecules is normally small and 1hcy ,are not rx-
pected to caust* any further changes in tllp polymer dimensions or
structure. No allowance need tl~erefore t)e made for changes in
film or fibrtx rlirncnsic:ns when dyeing d:l;lil are andyser! n>aLhr:-
matically.
In t he more fundamentnl studies of dyeing, films have the ad-
vantage of simplicity; 1ht.s~ may be made cornmerci;dly or prc-
pnrecl in the laboratory Isy melt or solvent casling for esarnple. In
thcst Inst two cases, it i s necessmy to pretreat Llle samples in l~lan k
dycl~nths prior to study. in orctcr t o shbiljse thc polyrnrr stmc-
t u r ~ . Surnt. examples of l l ~e ohanpys in rdle of uplnkc l ) e f o r ~ :tnd
after ~~rsllreatrnent are shown in Fig. 3(a) and ( b) 111. 'She prv-
Ireatmianl of films is of greater import:~nce than wit11 fil~rt-s since
the latter, Iiaving: heen drawn, may be cxpec ted to possess a mrwr
stable structur~. For the films, introduction into an aqueous cln-
vironmenll is ccrts~in to cause some readjustment of the structusc.
At the I~egi nni ng of the dyeing process, the dye is distributtbd
non-uniform! y through the substrate with a high concentration at
the surface and a zero concentration inside. A concentration @a-
client is tl~erefore set up which causes the dye to transfer itself
from the higher to I hc Power regions of concentration. This behav-
iour is described in terms of Fick's Law which states that the flus
of clyc ( g or g-rnoles/unit mxl uni t time) is proportional to the
gsadic~nt of concentration. If the dye is cliffusing In one dimension
3s in n film, l l ~i s equation may l)c written as
where dQJdl i s Ihe qunntily of material crossing vnil area in kinit
timc and is equal to tllc flux J. D is the rliffiision coefficient anrl C
is the concentration at any point distance x from the surface.
.13 i s essentially the sped with which the dye molecules move
under the action ol unit force and has the dimensions
( I ~ n d h ) ' /time. Most experimental studies have heen directed to-
Fif. 3. Ral e of dyeing measurements with Duranol Rcd 2E [ 1 1. Effect or
different prrtrratments. ( a) Film< dyed in an aqueous dispersion containing
1 c/ I LiswpoI LS. Preir~atrnent: +.distilled water; *, none (eir-dsy film^ werr
used); r,, Lissapol LS. Curvc 1, triacetate film aL 55.5'~ ( f ar clarity the points
are displaced upwards by I .O optical density units); curve 2, secondary act..
tate film a t 97.2"~; curve 3, nylon 66 film at 55.5'~; curve 9, secondary
acetate film at 5 5 , ~ r ~ ~ . ( b) Pretreated films dyed in an aqueous dispersion
containing I g/l Liswpal LS at 87.5"~. Curve 1, air-dry secondary acetate;
curve 2, secondary acetate pretreated in water or blank dye bath; curve 3,
air-dry triacetate; curvp 4 , tri ac~tate pretreated in water or blank dye bath:
curve 5, ai r- dq polyethylene ter~phthal nte; curve 6, polyethylene tesephtha.
late pretreated in water o r blank dye bath.
wards detrrminntion of diffusion coefficients, rirst to attempt to
corrclnte tltis factor with Clie structure of the tlyc ul ~dl or o f Lhe
f i l m, and seconcfly wilh the aim of calculating mtrs of rlycing or
rates of desorption which may assess the practical si tunticln. 'l'hr!
cliffusion cotafficient is of more fundamenhl significance com-
pared with ~rnpi ri cd parnmetcrs such as time of half-dyring or
velocity constants nnc1 snme experimental evidence is availal~le to
s l ~ow that sotutions of Lhe cliffusion equations give! bcttcr descrip-
tions of rate-of-dyeing curves than the hyperbola described in
Chapter 3 [31].
In eqn. (11, the force responsjble for the flux, namely concen-
tration gradient, has been hken ,as "ideal"; a more correct ,assign-
ment is given by the gradient ai chemical potential, i.e.
I
wher~ 13" is the relevant diffusion cocfricitlnt. Substituting for p
(i.e. p = p0 + RT In a ) gives
t
I f bn a is urritkn as Cy where y is the activity corllicicnt, eqn. ( 3)
becomes
The effect of introducing the non-ideal behaviour into eqn. (21 is
to ernphasise the Snct t hat t he measured diffusion coefficient rlc-
pends on t he thermodynamic properties. With the disperse dyes, :ts
judged by the equililxium data which indicate apparent "ideal"
behaviour, it is to he expected t hat y may be equated to unity and
hence diffusion follows essentially eqn. (1) with D replaced by
RT Do .
Determination of D
Diffusion coefficients may be determined from the diffusion of
dye in "non-steady" or "steadyw-state conditions. In the former,
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Fig. 7. Rate of dyeing of celluloa~ acebtc yarn wiLh Duranol X3B 300 rrom a
dyebath o h constant composition ( 5 g/l). The continuous cum- were cnl-
culrited Iron1 eqn. ( 21) [ 2 1 .
For many fibres, notably lhose which are melt spun and hence
have circular cross-sections, eqn. (21) is appropriate. An example
of the awgreement between eqn. (21) and experjmer,tal data is
shown in Fig. 7- With other fibres. e.g. many wet spun. dry spun
and natural fibres with non-circular crass-sections, the application
of the equation must be treated with somc reserve if values o l D
ate required. For comparison .of dyes, npplication of the equation
will yield values of a parameter close to the values of D/ aZ : these
may be adequate for many purposes.
Rate-of-dyeing experiments have shown that t he mte curves are
iidependen t of dye concentration provided no interference occurs
from changes in concentration of the surfachnt (Table I) . The
independenc~ of D on concrntmtion has I~een confirmed by Pnt-
kr son and Sheldon who dyed three dyes at different concentra-
tions on polyethylene terephthnlak fillre (Terytene) I S] . Plotting
the mo unt of dye on the fibre divided by that in the tsath yields,
with due allowance for experimental scatter, the same line
(Fig. 8) . In addition, when diffusion coefficients are calculated
from eqn. (21) for different times of dyeing of polyethylene
tereph thalak (Dacron) from infinite dyebaths. reasunably con-
stant values are obtained over a range of Pl,JhI, values (Table 5)
Fig. 8. ETTPcZ or dyrbath cencentrmlion on rate ofdyoi ng with p-nitro-n-anisi-
dine 4 di(P-hydroxy~thyl3aniline [ g ] . Dye concentration: a, 360 m ~ l k ~ : X .
235 rnplkfi; 0, 1 15 mg/kp.
181. Diffusion coefficjents of some eleven commercial dyes on
nylon fibre have dse been detennined in this way using an infinite
dyebath condition; the data are shown in Table 6.
'Aqueous solutions have been employed by Majury who men-
sured Lhe diffusion of l i ve model compounds at 60 and 8 6 C on
Diffusion of dyes into polyeth ylent! lerepllthalste (Dacron) at 100DC 18 ]
Dyc
Diffusion coelficient
(crn21sec x )
hydroxyelkyE)aminoazuhenzene 0.06
2-Cl1loro-4-nitro-G-bromo-3'-chlor0-4'-diethy!-
aminoazat~enzenc 0.26
4-Nitro-2'-chloro-4'-di(P-liydrox y ethyl)+amino-
azollcnzene 0.04
hminonaphfhalcn~ azobcna~ne -+ phenol 0.1 3
H ~ ~ r r ~ r l r p s p p . 18. 4- - I N9
TABLE 6
I
Difrusion ~ocl f i ci cnL~ OF disperse dyes in nylon s t 80C (21
Motecu tar Ditrurion
Dye weight co~f f i ci ent
(crn2/aec x 10' I
An thmquinone dcriualiver
Duranol Red 6300
Durano! Violet 2R300
Duranol Brilliant Blue G300
Duranol Red X3B300
Duranol Blue G300
Duranol Blue 2G300
Arninoozo derivatives
Dispersol Fast Orange GI60
nispersol Fmt Yellow A150
Dispersol Fast Crimson 81 50
Dispetsol Fast Orange A150
Dixpersol Fast Orange B150
~econdary cellulose acetate and triacetxte films [ 131 (Table 7).
The results show that diffusion in the more crystalline celluIose
triacehte is slower and more sensitive to temperature.
I t may also be not& that in the measurements of diffusion
coefficients, care must be taken to ensure that the dissoIution of
dye i s not a slow step in the process. I t is essential, therefore, if a
dispersion is used, that it should be sufficiently fine to maintain
the solution concentration to ensure that diffusion is the control-
ling step [I21 .
(c) Cal cf~l at i ons us in^ fin it^ dyehaths
The infinite dyebath condition has often been employed be-
cause the solutions of the diffusion equations are relatively simpIe.
1
However, in practical dyeing, the bath exhausts M, that aa dill*-
[
sion proceeds, the concentration in the external liquor is continu-
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I
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of constant surface concentration must be replaced by the condi-
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a constant. If, in addition, the partition of dye between the liquor
and the fibre surface is assumed t o be a constant, eqns. (7) and
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CHAP'I'ER 7
The usc of high temperatures to obtain npi d fixation has becn
exploited i n t he process first introduced t ~nder tlre name
"Thermosol" [ I ] . Essentially, the cloth is padded, dried and
pawed into a hot chamber, usually a stentor or a flue baker; a l the
hjgh ternpcrntures employed, t he rate of dyeing is sufficiently
rapicl t o achieve full fibre penetrntion, the fixation being l)etwec!n
75 and 90% /2,3,5] : indeed, calculations of the expecterl speed of
diffusion suggest that the dye can re F the fillre in a
few scconrls 141 . 111 practic:~, a dyeir ; several hours
at 100C can be acllieved in less t 130C and i n
20- 60 s w at 200" C. l f t he temperature IS too low or the lime too
short, ring dyeings me obtained with a concomitant loss of coIour
stwngtl~ 1221. To obtain maximum yielil, n minimum kmper at ur c
and time must he decidrrl, a short fixation time being largely
cuutilerl~alnt~uud l ~ y a hi gh temperature and v ~ c e versa. 'l'he yield
thus varies with the fixing temperature nncl time fur any one dye.
For tlifferent dyes, more dye is fixed the more resistant it is to
sublimalion. After tlicrniofjxation, n scouring treatment is
necessary tu remove :my tin lixed dye or, if the shade is a deep one,
a reduction clear may be nec:cssqr.
~ C I I Ule I
~g which
han an
centre a1
I require!
hour at
This s h g ~ musl I E carri~rl out with sorncl carp since tho lack of
al~sorl)ency of the synlhclic fibres results in low pick-up and
prol~lrms in drying. In the earlier stages of drying, the liquid
rnimatcs to t l ~e drylng surk~re and if not controll~d, will lcad to a
mal-dislril~ution of Ihe pigment particles yielding a two-sicled
effect. The liquid in the Inljric after padding may be regarded as
residirrg in clrannels in thc interstices between fibres and yams;
onw the continuity of these channels has Iwen broken, t he
migration ueaqes. Migration may he controlled hy passage of t he
1
cloth tl~rough infrared dricrs so t hnt the fabric is evenly dried in
I
the initial stnee or. what is more common. by the addition of a
I
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Fi p. 17. 'l'cst of ~crns. ( 3 4 ) and (38). ( aH has been put equal l o OD) [ 2 1 .
Uyc: Metanil Ycllow YK.
This is identical with t hal derived for t he adsorption of hydro-
chloric acid (eqn. (18)) and offers an agreement with theory which
is t he same order of accuracy. In Fig. 17, the results for t he sorp-
tion of the Free acid of Metanil Yellow YK have been plotted
according to eqns. (34) and (38).
Finally, if the quant i t y of amino groups is not considered to be
equal to t hat 01 the carboxyl groups, the Iatter being in excess by
an amount no, eqn. (36) may be written as
t H*l "ao [Dill-
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S-lH*I S-[D,I
For electrical neutrality, [HA ] = [DA ] ; eqn. (39) may be re-
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Fig. 18. Pfot o l litration data or A, Naphtl ~al cne Red J free acid and m, Orange
I1 rree acid Tor dyeings at 90" C for 6 h [64 1.
have br
3m whic
;, a valt
I n a series of cxl~erirncnts 1641, t he data for t wo monosulpho-
nated dyes :en plotted and shown to give a straight line
(Fig. 18) fn 11 KH K, and hence ICD and S may he found.
I n the plot le of a, of 0.05 mollkg was used based on
experiments using hydrochloric acid [ 42] . S ~t t o he larger
than 0.9 rnoleslkg (Table 14) presumably d~ mited amount
of hydrolysis. Equation (40) is probably a 1 ay of plotting
t he data to obtain t he constants as compareu with reciprocal
plots: t he incorporation of a, is not of major importance although
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centrations.
The values of I<, are surprisingly consistent bearing in mind
that a certain amount of hydrolysis of the fibre had occurred.
' turns 01
ie to a lil
letter w:
. - .. - -1 ..
Isothernts wizcre the dye concentration remains conslan t
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adjusted by additions of sodium hydroxide 1641. Over most of t he
ranRe studied, t he amount of sodium ion on t he fibre was small
compared with the quantity of dye (Fig. 19) so that t he dye was
adsorbed ef f ect i v~l y as the free acid. I n addition, though small in
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