PROOF OF HIGH REACTIVITY OF REACTIVE DYE WITH

CELLULOSE

CELLULOSE CONTAINS BOTH PRIMARY AND SECONDARY OH GROUPS

NECESSARY TO ESTABLISH WHICH OH GROUPS TAKE PART INTO REACTION

EXPERIMENT

DETERMINATION OF RATE OF REACTION OF REACTIVE DYE WITH

N-PROPANOL (PRIMARY OH GROUP) CH3CH2CH2

OH
ISO PROPANAOL CH3CH2CH

OH
THE RELATIVE REACTION RATE CONSTANTS
N- PROPANOL 4.8
ISO PROPANOL 0.7 ie WITH PRIMARY OH RATE CONSTANT IS 7 TIMES THE
SECONDARY OH GROUP
 RATE CONSTANTS WITH OTHER COMPOUNDS
CONTAINING OH GROUPS

Compound Relative rate of

reaction
RATE OF REACTION WITH
Water 1.0 WATER IS LOWEST AMONG
THE COMPOUNDS
Methyl alcohol 12.3 CONTAINING PRIMARY OH
GROUPS
Ethyl alcohol 7.4
THIS PROVES THAT THE RATE
OF REACTION OF REACTIVE
n-propanol 4.8 DYE WITH CELLULOSE IS
MUCH HIGHER THAN WATER
iso-propanol 0.7

Glucose 5.5
(Representative
of cellulose)
 RATE OF REACTION WITH CELLULOSE AND WATER

DYE REACTIVITY TO OH GROUPS OF WATER AND CELLULOSE

PRELIMINARY THINKING IF DYE REACTS WITH WATER, NO OR LITTLE REACTION WITH

CELLULOSE

SINCE REACTIVE DYES ARE COMMERCIALLY SUCCESSFUL, IT SHOULD REACT WITH

CELLULOSE TO A GREATER EXTENT COMPARED TO WATER.

CLOSER EXAMINATION INDICATES THAT THE RATE OF REACTION OF REACTIVE DYE

WITH OH GR. OF CELLULOSE IS HIGHER THAT OH GR. OF WATER

REACTION OF DYE WITH WATER WHICH MAY BE WRITTEN AS

DCl + OH- D-OH + Cl-

The rate of reaction Rw is given by
 
Rw = Kw (DCl )s ( OH )s
 
Where, Kw = rate constant of the reaction.
(DCl)s = conc. Of dye in solution.
(OH )s = conc. Of OH ions in solution.
 
Similarly for the reaction with cellulose ions.
 
DCI + Cell-o- cell-o.D + Cl-
 
The rate of reaction Rc is
Rc = Kc (DCl )f ( cell-o - )
Kc = rate constant
(DCl )f = dye conc. in fibre.
(Cell-o-) = conc. Of cellulose ions.
The relative rate of reaction with cellulose to that with water is
 
Rc/Rw =  Kc\Kw .  (DCl )f / ( DCl)s .  (Cell-o-) / (OH)s
THE RELATIVE RATE THUS DEPENDS ON THREE FACTORS THE FIRST IS

1.RATIO OF THE TWO REACTION CONSTANT.

THE DETERMINATION OF THERE CONSTANTS IS DIFFICULT. BUT IT MIGHT BE

ANTICIPATED ON THEORETICAL GROUNDS THAT THERE IS WOULD BE LITTLE
DIFFERENCE BETWEEN THE REACTIVITY OF OH- IONS AND AN APPROX. THAT KC/KW =
1

A SECOND FACTOR IN THE EQUATION IS THE RELATIVE CONC. OF IONIZED GROUPS

INSIDE THE FIBRE AND IN SOLUTION.

SUMNER HAS CALCULATED THE CONC. OF IONIZED GROUPS IN CELLULOSE AT VARIOUS

EXTERNAL PH VALUES AND HAS SHOWN THAT THE RATIO CELLO- / OH- IS ALMOST
CONSTANT OVER THE PH RANGE 7 TO 11 WITH A VALUE OF APPROX. 3.0 DECREASING
SOMEWHAT AT HIGHER PH VALUES.
THE LAST FACTOR THE RELATIVE CONC. OF DYE INSIDE AND OUTSIDE
THE FIBRE IS EVEN MORE IMPORTANT.

ALTHOUGH SOME REACTIVE DYES HAVE LOW AFFINITY FOR CELLULOSE, THE CONC.
INSIDE THE FIBRE IS USUALLY VERY MUCH GREATER THAN IN SOLUTION .

A SIMPLE EXAMPLE WILL ILLUSTRATE THIS POINT.

SUPPOSE A PARTICULAR DYE HAS AN EXHAUSTION OF ONLY 30% UNDER CERTAIN

CONDITIONS WHEN 1 KG OF FIBRE IS DYED IN 30 LTS. OF WATER (M:L :: 1:30 )
CONTAINING 10 gm DYE (1% DYE CONC.)

30% DYE EXHAUSTION MEANS AT THE END OF DYEING 3 gms OF DYE ON FIBRE AND 7
gms DYE IN SOLUTION OF 30 liter

VOLUME OF CELLULOSE (WATER CLOSELY ASSOCIATED WITH FIBRE) IS 0.22 liter/kg OF

FIBRE

THIS MEANS THAT 3 gm DYE PRESENT IN 0.22 liter

AMOUNT OF DYE ON FIBRE HAVING 1 liter WATER WILL BE 3/0.33 = 13.6 gms
SIMILARLY AMOUNT OF DYE PRESENT IN 30 liter WATER IS 7 gms
IN 1 liter WATER IT WILL BE 7/30 = 0.23 gm

HENCE (DCL)F / (DCL )S = 13.6/0.23 = 59.

THE DYE WOULD REACT NEARLY 60 TIMES FASTER WITH COTTON THAN WITH THE
DYE BATH OWING TO THIS FACTOR ALONE AND

OBVIOUSLY THIS RELATIVE RATE WILL INCREASE GREATLY WITH INCREASING

EXHAUSTION OF THE DYE BATH.