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The Starch-Iodine Reaction
The Starch-Iodine Reaction
-
BY N. R. DHAR
Two distinct views have been put forward in order to explain the mecha-
nism of the starch iodine reaction. Several authors, notably Rouvierl, Euler
and Myrback2 and others have formulated the view that on the addition of
iodine t o starch paste, definite chemical compounde are formed. The number
of formulae denoting the compound starch-iodine has come up to thirteen, the
iodine content varying from .3 to more than 20 per cent.
In opposition to the above view, Kuster3 has shown that the blue colour
of starch iodide can be easily explained by the phenomenon of the adsorption
of iodine by starch. Padoa and Savare4, Katayama5, Berczeller6, Bancroft’
and Lottermosers are supporters of the adsorption view.
It is well known that starch forms a colloid when mixed with warm water
and on the addition of iodine to this colloidal starch the well known blue sub-
stance which is certainly colloidal in nature is obtained. It appears that
colloidal starch is negatively charged and on the addition of iodine the amount
of charge on each particle is increased. Like most colloidal substance starch
has a good adsorptive power, as has been shown by Robieong, LloydlO,
Rakovski” and others. Evidently there is hardly any doubt that adsorption
plays a very important part in the formation of the blue substance.
It is apparent that the blue substance, starch iodide, is colloidal in its
nature. I n order to throw light on the nature and on the constitution of the
blue substance, electric conductivity measurements were carried on. Several
years ago Duc1aux12,found positively charged ferric hydroxide sol is fairly con-
ducting. I n a recent paper Wintgrenla has determined the conductivity of
stannic acid peptised by alkali. Very recently Sen, Ganguly and Dhar have
found that ‘negatively charged ferric hydroxide sol is also fairly conducting.
Fifteen grams of Lintners’ soluble starch (British Drug Houses Ltd: Lon-
don) were made up to 1000cc. using warm water a t the beginning. The con-
ductivity of this colloidal solution was determined. When N/IO alcoholic
solution of iodine, the conductivity of which was determined before, was
added to the starch solution, it was found that the conductivity of the blue
Compt. rend. 117,461.
2Ann. 428, I (1922);Arkiv. Kem. Min. Geol. 8, No. 9, I (1922).
Ann. 283 364 (1891).
Atti, R.Accad. Lincei, 14, I, 467 (1905).
Z.anorg. Chem. 56,209 (1907).
Biochem. Z.84,106(1917).
“Applied Colloid Chemistry”, 104 (1921).
* Z. angew. Chem. 34,427 (1921).
Proc. Camb. Phil. SOC.15, 548 (1910).
lo J. Am. Chem. SOC. 33, 1213(1911).
I1 J. Russ. Phys. Chem. SOC.45, 7, 13 (1913);46,24 (1914).
l2Cornpt. rend. 140, 1468 (1905);Kolloid-Z. 3, 126 (1908).
lS Z.Phys. Chem. 103, 238 (1922).
126 N. R. DHAR
substance thus obtained is greater than the sum of the conductivities of the
two substances. The conductivity measurements were carried out a t 25’ and
the following results were obkained:-
TABLE I
Substance Conductivity
Absolute alcohol 4 . 8 6 X IO-^
N/ IO alcoholic iodine I .36X10-~
:.N/Io iodine (in alcohol) 8 . 7 6 X IO-^
Aqueous iodine (about N / ~ o o o ) 4.32 x IO-‘
Water 3 .37xIO-6
.*.Iodine (in water) 0 .g g x 10-6
Starch (colloidal) I 5 grams per litre 2.7 XIO-~
Starch (alone) 2.36X IO-^
20cc. starch+. I cc N / I O alcoholic iodine 2 . ~ ~ X I O - ~
11 11
+
. 2 cc l 1
11
” 2.63 X IO-^
l1 l’ +
.3 cc l 1 11 11
2 . 7 4 x IO+
l‘ +
.4cc1’ 11 ” 3.01x10-5
l1 l1 +
.5 cc l 1
+ .6 cc l 1
7)
l1 3.85xIo-5
l1 l1 11
3 .93 x
” ” +
. 8 cc ” 17
”
” 4 . 8 5 X IO-^
l1 l1 +
. g cc l 1 11
5.96X10-~ ))
T.4BLE 11
Substance Conductivity
2 0 cc. starch sol
11 l1 l1
+
+ cccc N/IO alcoholic iodine 7 . 7 4xx IO-^
I
2 ’l 11
IO-^
” I O . 01
11 l1
+ 3 cc 11 11
9.52 x
11
11
11
l1 lJ
++ 45 cccc 11
11
11
8.86 X IO-^
8 .28 X IO-^
”
++ 67 cccc
l1 ’l
11 11
l1 l1 ” 7.63X10-~
11 11 11
” 7 . I 5x
+ 8 cc
l1 l1
11
l1 l1 l1 11 ’) 6.77 X IO-^
TABLE I11
2 01 1cc starch sol
’) l1 ++
+
I
2
cc alcohol
cc
3 cc :;
l1
2.28X10-~’
I.99x10-5
I . 83 X IO-^
+
11 l1 l1
11 l1 l1 4 cc I .66X10-~
11
11
l1 ++ 5 cc
6 cc
l1
I . 5 I X I O -5
I . 3 9 x IO+
11
l1
)l
l1
l1 + 7 cc
l1
l’ 1.28X10-~
From the foregoing experimental results it is quite clear that on addition
of alcoholic iodine to a sol of starch, the conductivity is greatly increased. It
will be seen from Tables I and I1 that, as the amount of iodine goes on increas-
ing the conductivity of the mixture also goes on increasing to a maximum and
then it falls off on further addition of iodine. This decrease in the conductivity
is certainly due to the falling off of the conductivity of starch on the addition
of absolute alcohol. The experimental results in Tables I and I11 conclusively
prove that on addition of absolute alcohol to starch, the conductivity gradual-
ly falls off as we go on adding more of alcohol to a definite volume of the starclt
sol.
T H E STARCH-IODINE REACTION 127
See Zsigmondy: “Chemistry of Colloids”, I66 (1917); Pauli and Matula: Kolloid-Z.
21,49 (1917).
2 Wintgren: loc. cit.
Compare Dhar: Z. anorg. Chem. 1913, SO, 43 (1913).
I 28 N. R. DHAR
Summary
(I) When alcoholic iodine is added to starch sol, the conductivity of thc
substance formed is much greater than the sum of the conductivities of the
individual substances.
(2) The subEtance obtained by the adsorption of iodine by starch is
appreciably conducting and behaves something like an unstable iodide. It
seems probable that micellar ion? are given out in sol.
( 3 ) It eeems probable that the presence of outside iodide ions is not
necessary for the formation of the blue substance. The hydrolysis of iodine
is a slow process.
(4) Electrolytes have the general effect of intensifying the blue colour
by the coalescence of the smaller particles into bigger ions caused by thier
coagulating effects.
Chemical Laboratories,
Sllahabad University,
India.