218 Short communications

REFERENCES
1 T. Momose and A. Inaba, Chem. Pharm. Bull. (Tokyo), 1959,7,541.
BT. Momose, A. Inaba, Y. Mukai, and M. Watanabe, Talanta, 1960, 4, 33.
a T. Momose, A. Inaba, Y. Mukai and T. Shinkai, Chem. Pharm. Bull. (Tokyo), 1960, 8, 514.

Note on the titration of iodide by the Andrews method

(Received 28 June 1960)

INTRODUCTION
ANDREWS’method’ for the determination of iodides involves two major stages:

IO,- + 51- + 6H+ --f 31, + 3H,O (1)

IO,- + 212 + 5Cl- + 6Hf --, 5ICl+ 3H,O (2)
The second of these is usually said to require the presence of relatively concentrated hydrochloric
acid (at least 3N). Most standard text-books of titrimetric analysis, however, do not make it clear
whether hydrochloric acid is specific, nor why it must be so concentrated.
Andrews realised that it was necessary to prevent the hydrolysis of iodine monochloride and the
subsequent disproportionation of the hypoiodous so formed. He represented the hydrolysis in terms
of a molecular equation:
ICI + H,O --f HOI + HCl (3)
It is now clear, however,2 that the iodine monochloride is converted to the ion ICI,-. In the original
form of the titration, it was necessary for this ion to be formed and retained in the aqueous layer so
that the presence of iodine in the organic layer (chloroform or carbon tetrachloride) should not be
masked by molecular iodine monochloride.
The position of the equilibrium:
ICI + Cl- 2 ICI,- (4)
is, however, reported8 to be substantially independent of the concentration of hydrochloric acid
between 0.2N and 10N. Moreover, we have calculated from Faull’s data4 that in a titration of O.lN
iodate against O.lN iodide, a final chloride ion concentration of only O.lN would reduce the con-
centration of free iodine monochloride below the level at which it could interfere with the end-point
of the titration.
Once this minimum concentration of chloride ion has been reached, it is not clear why a much
higher concentration of hydrochloric acid should be needed to achieve a satisfactory titration.
Swift6 has suggested that a high concentration of hydrogen ions is needed, not to suppress hydrolysis
of iodine monochloride, but to increase the rate of reaction (2). The following results provide some
experimental support for this suggestion, though the precise function of the hydrogen ion in this
reaction is not yet clear.
EXPERIMENTAL
Titrations were carried out in which (a) the concentration of hydrochloric acid was varied, (b)
the hydrochloric acid was replaced by combinations of other acids with potassium chloride to give
varying concentrations of hydrogen and chloride ion. The results are shown in Table I.
The specific effects of hydrogen and chloride ion on reaction (2) were also investigated (Table II).
The concentrations used were too low for satisfactory titration and the extent of oxidation of iodine
was measured as a function of time. The effect of indifferent salts was also examined.
Reagents: The reagents used were of AnalaR grade, except for sulphuric acid and carbon
tetrachloride. A sample of hydrochloric acid of “analytical reagent quality” liberated a small but
significant quantity of iodine from potassium iodide. It probably contained free chlorine and was
rejected as unsuitable for this work.
 Short communications 219

TABLE I. OXIDATIONOF I- TO ICla-

Series I Concentration* Nature of

of HCI, M Reaction?

4.68 A
2.81 B
0.93 C
0.46 D

Series II Concentration Concentration of

of KCI, M HJ’O,, M

0.13 5.0 D
0.63 5.0 D
1.13 5.0 C
3.00 5.0 A

Series III Concentration Concentration of

of KCI, M HCI, M

3.0 0.0 no reaction

3.0 0.2 D
3.0 0.5 C
3.0 1.0 B
3.0 2.0 A-B

Series IV Concentration Concentration of

of KCI, M HzS04, M

0.2 2.5 D
0.5 2.5 D-C
1.0 2.5 C
0.2 1.5 D
0.5 1.5 D-C
1.0 1.5 C
0.2 0.5 D
0.5 0.5 D
1.0 0.5 D-C

* The concentrations are those obtaining at the end of each titration.

t A: the reaction proceeds at the optimum rate for titration,
B: the reaction is slower than in A, but fast enough for use in titrations,
C: the reaction is too slow for use in titration,
D: the reaction is slower than in C, taking up to 30 min for completion.

Procedure: The titrations (Table I) were carried out with standard solutions of approximately
O.lN potassium iodate (@025M) and potassium iodide (0.05M). A standard volume, 5 ml, of carbon
tetrachloride was used to indicate when the iodine liberated in the first stage had been completely
removed. The volumes of solution used were arranged to give the quoted concentrations at the end
of the titrations.
In the subsequent experiments (Table II), a standard solution of iodine in carbon tetrachloride
was shaken with aqueous solutions of the remaining substances. For each point the carbon tetra-
chloride layer was separated from the aqueous layer at the stated time, washed quickly with a large
volume of distilled water and separated again. The remaining iodine was then determined by titration
with aqueous sodium thiosulphate.
The experiments were carried out at room temperature.
10
280 Short communications

TABLEII. OX~AT~ONOF 1%TO ICI%-

A. Effect of [Cl-]

/ Time,min / o&gd

(i) 02MKCI 1 22
0.5M HaSOl 1 2 32
5 44
10 50

(ii) 05M KC1 1 61

05M H$Od I 2 71
5 81
10 89

(iii) Oe2M KC1 1 20

0.3M KNO, 2 28
@5M HBS04 I 5 46
10 52

B. Effect of [H+]

(i) @5M H&SO4 1 28

0.2M NaCl 2 32
5 44
10 52

(ii) le5M H&O&

@2M NaCI : ! ::
5 77
10 86

(iii) 0*5M HpSOI 1 10

1.OM Na,SO, 2 21
0~2M NaCI 1 5 24
10 31

DISCUSSION
(a) Concentration of hydrochloric acid
From Table I it is clear that, for a satisfactory titration, the solution titrated should be no Iess
than 3N in h~r~hIoric acid at the end of the reaction. Chloride ions must be present in a con-
centration greater than that required for substantially complete conversion of ICI to ICI,-.
Whereas some deficiency in hydrogen ions can be made up by excess of chloride ions (Series III),
the reverse is not obviously the case (Series II*). Even in the former case, it appears that the ionic
product, [H+][Cl-1, must correspond to that in 3M hydrochloric acid.

(6) Elfecf of i~di~rent ions

From Table II it is clear that indifferent ions either do not seriously affect the rate of reaction (21,
or reduce it, depending on the ionic strength of the solution.
This investigation clarifies the conditions needed for satisfactory titration of iodide by the Andrews

* For this purpose, phosphoric acid is regarded as being, to a first approximation, a monobasic acid.
 Short communications 281

method. It is not yet clear, however, whether the dependence of the rate of the slow reaction on the
concentrations of hydrogen ion and chloride ion is due to their presence as reactants or as catalysts.

Summary-For a satisfactory determination of iodide by Andrews’ method, the concentration of

hydrochloric acid in the solution should not fall below 3N. A high concentration of each ion is
required; that of chloride ion is much greater than is needed for conversion of ICI to ICll-. The
effects of varying the concentrations of H +, Cl- and indifferent ions on the rate of the slow stage
(oxidation of Ie to ICI) are demonstrated.

Zusannnenfassung-Fur eine zuverllssige Bestimmung von Jodid nach der Andrews Methode sol1 die
Salzslurekonzentration in der Losung nicht unter 3 n absinken. Eine hobe Konzentration fiir jedes
Ion ist notig, Die Chloridkonzentration ist vie1 griisser als an sich fur die Uberfiihrung von JCI in JCl-
st~hiometr~sc~ not@. Der Einfluss wechselnder Ko~2entrationen von II*, Ci- und indiffe~n~n
ionen auf die G~h~n~gkeit des langsamen Reakt~on~hrittes (Uxydation van Jp zu JCl) wird
demonstriert.

RBsum~Pour une estimation satisfaisante de l’iodure par la methode d’Andrews, la concentration

de l’acide chlorhydrique dans la solution ne devrait pas btre inferieure ii 3 N. Une forte concentration
de chaque ion est necessaire; celle de l’ion chlorure est beaucoup plus grande que cela n’est necessaire
pour la transfo~at~on de ICi en ICl,. Les influences des variations des concentrations de II+, Cl-
et des indifferents sur la vitesse du stade lent (oxydation de IS enIC1) sent demon&&s.

REFERENCES
1 L. W. Andrews, J. Amer. Chem. Sot., 1903, 25, 756.
2 N. V. Sidgwick, The Chemical Elements and their Compounds, Clarendon Press, Oxford, 1950.
3 A. C. Gillam and R. A. Morton, Proc. Roy. Sot., 1931, A132,152.
I 3. H. Fat%, J. Amer. Ckm. Sot., 1934,55, 522.
5 E. Ii. Swift, i&d., 1930, 52, 834.

Contribution to the basic problems of complexometry-III

Some adwaz&agesof mrcet~tebuffer

IT is well known, that some bivalent metals can be readily determined by EDTA titrations in a weak
acid medium (pH S-6). In addition, other indicators, Xylenol Orange” and Methyl Thymol Bluee,
have been recommended for these titrations because of their brilliant colour changes. Solutions are
usually buffered with urotropine. Some cations having incomplete inner orbits, sucir as copper*
nickel, cobalt etc. form substitution-stabs complexes with these indicators, thus making direct
complexometric titration impossible. It is not possible, for exampb, to titrate copper using Xylenol
Orange or Methyl Thymol Blue, even at higher temperatures, but only copper solutions buffered with
urotropine. We have found that by the use of acetate buffer it is possible to titrate copper directly at
a temperature of about 70”, using either indicator, with the accuracy of the usual complexometric
methods. Recent& PiibiP discovered that in the direct titration of copper in the cold, after the
addition of a small amount of ~p~nan~~o~~e, the colour change of Xylenol Grange was
substantialfy improved. This phenomenon he expiained on the basis of the formation of a
substifution-labile copper complex with o-phenanthroline, which reacts with EDTA easily at the
end-point.
In a detailed study it was found, that cr:a’-bipyridyl*, cupferron, ethylendiamine, dicuprale,
* cr:a-Bipyridyl at about pH 5.5 may be used like o-phenanthroline for masking most of bivdent metals.