Ana&ca Chuntca Acta, 269 (1992) 269-272 269

Elsevler Science Pubhshers B V , Amsterdam

Stability of dithizone in chloroform-acetic acid

solvent system
N ThlagaraJan and M Subbalyan
Department of Analytuzal Chemrstry, Unrversap of Madras, Gumdy Campus, Madras Mx) 025 (Indra)
(Recewed 11th July 1991, revised manuscnpt received 7th June 1992)

Abstract

Dlthlzone IS very unstable m solution when exposed to direct sunlight and more so when kept at high room
temperature An efflclent method for prepanng the reagent solution and using it under the above-mentloned
condltrons was developed The simple protocol involves equlhbratmg the reagent solution m chloroform with 6 M
acetic acid This mixture can be stored for a reasonable length of time (2 3 weeks) urlthout any detenoratlon and
consequent decrease m actlvlty
Keywords UV-Vlslble spectrophotometry, Dlthlzone, Stablhzatlon

The deterioration of stock solutions of dlthl-
zone m orgamc solvents when exposed to sunhght
and at high room temperatures IS well estab-
lrshed Other promment factors contnbutmg to
its mstablhty include the presence of traces of
heavy metals and oxidants [1,2] Its unstable na-
ture therefore makes it more difficult to use as
careful measures have to be undertaken durmg
its preparation and storage
Irving and co-workers mvestlgated dlthlzone
extensively and reported the causes of its deteno-
ration m chloroform under light and temperature
conditions [3], and also ldentlfled the oxldatlon
products m the presence of different oxldlzmg
agents and m different media [4-61
In this laboratory it was found that when the
ambient temperature reached 35C and above m
summer and m bright light (under laboratory
condltlons) a 0 001% dlthlzone solution diluted
Correspondence to N Thlagarajan, Department of AnalytIcal
Chemistry, Umverslty of Madras, Gumdy Campus, Madras
600 025 (India)
mediately from a freshly prepared stock solu-
tion of 0 01% m chloroform deteriorated rapidly
Attempts to preserve this solution unmedlately
after preparation by refrigerating it at 10C under
diffuse light condltlons also faded This may pos-
sibly be because the time lag of 5-10 mm that 1s
required for the preparation of the reagent solu-
tion under the above-mentloned condltlons can
have an adverse effect on Its stablhty and once
the deterioration has commenced it presumably
cannot be controlled or reversed merely by refrlg-
eratlon The stock solution was also found to be
slmllarly affected, although to a lesser extent, and
was not fit for contmuous use
To obtain a stable dlthlzone solution, many
workers have suggested the use of the pure
reagent [71 and/or the solvent 181 Some have
attempted to give a standardlzatlon procedure for
the reagent [9] prior to use The use of sul-
phurous acrd or other holding reductants such as
hydroxylamme or sodium thlosulphate for this
purpose proved to be less effective All these
approaches, although aldmg the potential use of
the reagent, are laborious

0003-2670/92/$05 00 8 1992 - Elsevler Science Pubhshers B V All nghts reserved

270 N Thuzgara)anand M Subbatyan /Anal
From previous work [lo] it 1s evident that the
photochromic deterloratlon of metal dlthlzonates
1s not favoured m polar media, and thrs 1s espe-
cially so m acetic acid Also, It has been empha-
sized that photochromism 1s probably an inherent
property of the hgand and it 1s the central metal
atom that determines the photochemlcal stability
and the rate of the return reaction Hence it can
be deduced that if the hgand solution m chloro-
form 1s kept m the same polar medium (acetic
acid), the hgand and the metal complex should be
stabilized against photochemlcal conversion
Based on these facts, m this mvestlgatlon chlo-
roform-dlthlzone solution mixed with acetic acid
by suitable means was tested for its stability un-
der various condltlons The effect of acetic acid
assoclatlon on the solublhty of the hgand m the
aqueous phase and thereby its influence on the
complexatlon and extractability of the metal com-
plex were also established and are discussed The
results are compared with those obtained for a
simple dlthlzone-chloroform solution
EXPERIMENTAL
Dlthlzone was obtained from E Merck (India)
and assayed for a mmnnum of 99% punty by
chelatometry [ll] Chloroform, acetic acid and
mercury(I1) chloride were of AnalaR grade
(BDH) Doubly distilled water was used for clean-
mg the glassware and preparing the required
solutions
Glassware was washed with chromic-sulphunc
acid cleaning solution, followed by hot (1 + 1)
nitric acid, and copiously rinsed with water
Procedure
Imtlally, 25 ml of 6 M acetic acid m a separat-
mg funnel were equilibrated with 5 ml of chloro-
form by vigorous mwng and the organic phase
was discarded Then 100 ml of 0 01% dlthlzone
solution m chloroform were transferred unmedl-
ately mto the above acetic acid solution, shaken
well for 3-4 mm to ensure complete equlhbra-
tlon, removed from the aqueous phase and stored
A lo-ml volume of the above stock solution
was diluted to 100 ml with chloroform to give a
Chrm Acta 269 (1992) 269-272
solution of concentration 0 001% and when fur-
ther ddutlon was required the 100 ml of this
murture was again equilibrated with 25 ml of 6 M
acetic acid that had been thoroughly mixed with 5
ml of chloroform beforehand as mentioned ear-
her, removed from the aqueous phase and stored
The entire procedure was carried out at room
temperature (a 35C) and m daylight The
reagents were protected from direct exposure to
sunlight only on storage One-day-old reagent
solution stored at 10C and under diffuse light
condltlons was used for the analysis
The simple dlthuone-chloroform solution was
prepared at 20C and m diffuse light
The amount of acetic acid transferred mto the
organic phase was determined tltrlmetncally [12]
using sodium hydroxide and phenolphthalem as
indicator, m the aqueous phase before and after
equlhbratlon of the dlthlzone solution with the
above aqueous acetic acid solution
Beers law
From a stock solution of mercury@) chloride
m 0 5 M sulphurlc acid with a metal ion concen-
tration of 5 pg ml-, aliquots contammg 5-25 pg
of metal ion were placed m a separating funnel m
a total volume of 20 ml To this, 7 ml of 0 001%
reagent solution were added and shaken well for
l-2 mm and the absorbance was read at 495 mn,
at which the complex exhibits the absorption
maxima Beers law was found to be obeyed up to
22 5 pg for the acetic acid-dlthlzone-chloroform
system and for the sunple dlthlzone-chloroform
solution The amount of acetic acid (sp gr 105)
transferred was found to be 3 9 g
RESULTS AND DISCUSSION
The absorption spectrum of the reagent exhlb-
lted two mmma, one corresponding to 600 mn
and the other to 450 nm, as reported earlier [l]
The freshly prepared acetic acid-dlthlzone-
chloroform solution was found to have a greater
absorbance (absorbance at 600 nm = 2 32 and at
450 nm = 140) than the simple dlthlzone-chloro-
form solution (absorbance at 600 nm = 155 and
at 450 nm = 0 58) with the same dlthlzone con-
N Thurgaralan and A4 Subbaryan /Anal Chm Acta 269 (1992) 269-272
0 IO 20 30
METAL ION CONCENTRATION ( pg 1
Fig 1 Adherence to Beers law o = Dlthlzone-chloroform
solutlon, q = fresh acetlc acid-dlthlzone-chloroform solu-
tlon, A = l-day-old acetlc aad-dlthlzone-chloroform solu-
tlon kept at 10C and m diffuse hght
centration (3 9 X 10m5 M) Further, Beers law
was obeyed up to 22 5 pg of the metal ion m 7 ml
of extract, m both instances However, slightly
higher absorbance values were obtamed for the
metal dlthlzonate complex at higher metal ion
concentrations m the workmg range (Fig 1) with
the former system
For the reagent solution after storage for 1 day
at 10C m diffuse light, the absorbance values
were comparable to that of the dlthtzone-chloro-
form reagent (absorbance at 600 nm = 167 and
at 450 nm = 0 65) and, as possible stablhzatlon of
the medium was attained, it remained almost
unaltered for the mmlmum period of 3 weeks
tested However, for this l-day-old solution the
Beers law upper limit was found to decrease
from 22 5 to 17 5 pg and the absorbance values
for the metal dlthlzonate complex remamed al-
most constant thereafter However, below 17 5
pg of the metal ion, the absorbance values are
comparable with that of the fresh solution (Fig 1)
and also no further change m this trend was
observed for the same mmlmum pergod men-
tioned with this solution This discrepancy was
also observed to the same extent when 5 ml of
271
the reagent solution were employed and the
Beers law upper hmlt was found to be 12 5 pg
for the l-day-old solution compared with 17 5 pg
for the fresh acetlc acid-dlthlzone-chloroform
solution An experiment carried out at either 20
or ca 35C m diffuse light gave the same trend
This increased absorbance m acetic acid
medium 1s possibly due to its stronger association
with the hgand, thereby decreasing the solublhty
of the hgand m the aqueous phase and keepmg
the concentration of the hgand m the organic
phase high This m turn would aid extractablhty,
resulting m higher absorbance values The de-
creased Beers law limit for l-day old solution 1s
probably due to the more stronger association
which may lead to msufflclent hgand concentra-
tion m the aqueous phase resulting m earlier
saturation
The trend observed with the absorbance values
clearly indicates the contmued assoclatlon of
ace& acid with the hgand both durmg and after
extraction m the orgamc phase, although some
might have been back-extracted This 1s an added
advantage for the stablhzatlon of the metal dlthl-
zonate complex agamst light condltlons as re-
ported earlier [131, which mvolves the use of
acetic acid m the aqueous phase for this purpose
during extraction Supportmg this, the metal-
hgand complex was found to be stable for a
mmlmum of 2 days m dayhght and at high room
temperature (ca 35C) under laboratory condl-
tions
The reagent stored at room temperature (max-
imum 2 35C, mmlmum 26C) and m diffuse
light can be used effectively for 3 days without
any change m the Beers law hmlt or m the
absorbance values Subsequently a decreasing
trend was observed as mentioned earlier, which
starts slowly and saturates wlthm 3-4 days This
trend shows that a longer time 1s required for the
enhanced assoclatlon of acetlc acid with the h-
gand kept at higher room temperatures
The original stock solution (0 01%) stored at
10C m diffuse light gave identical 0 001% solu-
tions for at least 1 month It can also be stored
without any deterloratlon at 18-2oC, and ex-
posed to the maximum daylight possible under
laboratory condltlons m a mildly air-condltloned
272 N ThurgaraJanand A4 Subbaryan/Ad
room for the same mmlmum duration It could
also be stored at room temperature (ca 35C) m
diffuse light for a mmlmum of 20 days tested
The development of a new absorption peak at
312 5 mn by suppressmg the characterlstlc peak
for dlthlzone was not observed wth these solu-
tions, 1 e one stored at 10C (tested for 3 weeks)
and the other at room temperature (ca 35C,
tested for 10 days) under diffuse light condltlons
This IS m accordance with an earlier report [5] m
which the absorption peak (at 312 5 nm) started
to appear notably after a perrod of 4 days due to
the photochemlcal formatlon of thladlazohne
products However, this is for a simple dlthlzone
solution contammg a higher concentration of
acetic acid (ca lo-fold excess> m the absence of
chloroform under unspecified storing condltlons
Mode of stabdrtatton
The primary cause of the deterloratlon of
dlthlzone m chloroform medmm was reported to
be due to abstraction of hydrogen from dlthlzone
by phosgene [31 orlgmatmg from the photocheml-
cal degradation of chloroform The use of acetic
acid with this solution may hinder this process by
protecting the reagent through hydrogen bond-
mg In a snmlar way, condensation of the aldehy-
dlc and ketomc impurities with the hgand by
hydrogen abstractlon, thus leading to Its deteno-
ration [5], 1s possibly also prevented Moreover,
as the reagent 1s taken m chloroform medium
and acetic acid 1s not added directly but by an
equlhbratlon (phase-transfer) process, the possl-
blhty of mclplent rapld assoclatlon of these lmpu-
rltles with the reagent is mmlmlzed to a great
extent as their effective concentration 1s very low
under this condltlon whereas the well dlstrlbuted
acetic acid associates and protects the reagent
favourably through hydrogen bonding These fac-
tors permit the solution to be prepared m day-
light and at a high room temperature without any
Chm Acta 269 (1992) 269-272
damage to the reagent and to be stored for a
reasonable period of time
Conchon
Dlthlzone solution eqmhbrated with 6 M acetic
acid 1s more smtable for routme determmatlon of
metal Ions as no stringent care needs to be taken
with respect to light and high temperature either
during preparation of the reagent or m Its use As
the stock solutron 1s stable for a reasonable length
of time, the reagent 1s also fit for infrequent use
This ehmmates the need for standardlzatlon of
the stock solution before each set of experiments
and the purlfrcatlon of the reagent and/or the
solvent before use
One of the authors (N T 1 thanks UGC, India,
for financial assistance
REFERENCES
1 H M N H Irving, Dlthlzone (AnalytIcal Sciences Mono-
graph No 51, Chemical Society, London, 1977
2 G Iwantsheff, Das Dlthlzon und seme Anwendung m der
Mlkro- und Spurenanalyse, Verlag Chemle, Wemhenn,
19.58
3 H MN H Irvmg and D C Rupamwar, Anal Chum Acta,
48 (1969) 187
4 H M N H Irving, AM Swan, D C Rupamwar and S S
Shota, Anal Chum Acta, 56 (1971) 205
5 H M NH Irvmg and U S Mahnot, Talanta, 15 (1968) 811
6 H M NH Irvmg and U S Mahnot and D C Rupamwar,
Anal Chum Acta, 49 (1970) 261
7 I Natama and D Matukawa, J Blochem (Tokyo), 30
(1939) 395
8 DA Blddle, Ind Eng Chem , Anal Ed, 8 (1936) 99
9 S Alegret, M Blanco and J M Paul, Anal Chum Acta,
177 (1985) 285
10 L S Mertwether, E C Breltner and CL Sloan, J Am
Chem Sot , 87 (1965) 4441
11 P Grey and G C B Cave, Can J Chem , 47 (1969) 4543
12 A I Vogel, Text Book of Quantltatlve Inorgamc Analysis,
Longman, 4th edn , 1985, p 308
13 J F Perth and KW Gerntsma, Reel Trav Chum Pays-Bas,
64 (1945) 4