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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- mediately from a freshly prepared stock solu-
zone m orgamc solvents when exposed to sunhght tion of 0 01% m chloroform deteriorated rapidly
and at high room temperatures IS well estab- Attempts to preserve this solution unmedlately
lrshed Other promment factors contnbutmg to after preparation by refrigerating it at 10C under
its mstablhty include the presence of traces of diffuse light condltlons also faded This may pos-
heavy metals and oxidants [1,2] Its unstable na- sibly be because the time lag of 5-10 mm that 1s
ture therefore makes it more difficult to use as required for the preparation of the reagent solu-
careful measures have to be undertaken durmg tion under the above-mentloned condltlons can
its preparation and storage have an adverse effect on Its stablhty and once
Irving and co-workers mvestlgated dlthlzone the deterioration has commenced it presumably
extensively and reported the causes of its deteno- cannot be controlled or reversed merely by refrlg-
ration m chloroform under light and temperature eratlon The stock solution was also found to be
conditions [3], and also ldentlfled the oxldatlon slmllarly affected, although to a lesser extent, and
products m the presence of different oxldlzmg was not fit for contmuous use
agents and m different media [4-61 To obtain a stable dlthlzone solution, many
In this laboratory it was found that when the workers have suggested the use of the pure
ambient temperature reached 35C and above m reagent [71 and/or the solvent 181 Some have
summer and m bright light (under laboratory attempted to give a standardlzatlon procedure for
condltlons) a 0 001% dlthlzone solution diluted the reagent [9] prior to use The use of sul-
phurous acrd or other holding reductants such as
hydroxylamme or sodium thlosulphate for this
Correspondence to N Thlagarajan, Department of AnalytIcal
purpose proved to be less effective All these
Chemistry, Umverslty of Madras, Gumdy Campus, Madras approaches, although aldmg the potential use of
600 025 (India) the reagent, are laborious
From previous work [lo] it 1s evident that the solution of concentration 0 001% and when fur-
photochromic deterloratlon of metal dlthlzonates ther ddutlon was required the 100 ml of this
1s not favoured m polar media, and thrs 1s espe- murture was again equilibrated with 25 ml of 6 M
cially so m acetic acid Also, It has been empha- acetic acid that had been thoroughly mixed with 5
sized that photochromism 1s probably an inherent ml of chloroform beforehand as mentioned ear-
property of the hgand and it 1s the central metal her, removed from the aqueous phase and stored
atom that determines the photochemlcal stability The entire procedure was carried out at room
and the rate of the return reaction Hence it can temperature (a 35C) and m daylight The
be deduced that if the hgand solution m chloro- reagents were protected from direct exposure to
form 1s kept m the same polar medium (acetic sunlight only on storage One-day-old reagent
acid), the hgand and the metal complex should be solution stored at 10C and under diffuse light
stabilized against photochemlcal conversion condltlons was used for the analysis
Based on these facts, m this mvestlgatlon chlo- The simple dlthuone-chloroform solution was
roform-dlthlzone solution mixed with acetic acid prepared at 20C and m diffuse light
by suitable means was tested for its stability un- The amount of acetic acid transferred mto the
der various condltlons The effect of acetic acid organic phase was determined tltrlmetncally [12]
assoclatlon on the solublhty of the hgand m the using sodium hydroxide and phenolphthalem as
aqueous phase and thereby its influence on the indicator, m the aqueous phase before and after
complexatlon and extractability of the metal com- equlhbratlon of the dlthlzone solution with the
plex were also established and are discussed The above aqueous acetic acid solution
results are compared with those obtained for a
simple dlthlzone-chloroform solution Beers law
From a stock solution of mercury@) chloride
m 0 5 M sulphurlc acid with a metal ion concen-
EXPERIMENTAL tration of 5 pg ml-, aliquots contammg 5-25 pg
of metal ion were placed m a separating funnel m
Dlthlzone was obtained from E Merck (India) a total volume of 20 ml To this, 7 ml of 0 001%
and assayed for a mmnnum of 99% punty by reagent solution were added and shaken well for
chelatometry [ll] Chloroform, acetic acid and l-2 mm and the absorbance was read at 495 mn,
mercury(I1) chloride were of AnalaR grade at which the complex exhibits the absorption
(BDH) Doubly distilled water was used for clean- maxima Beers law was found to be obeyed up to
mg the glassware and preparing the required 22 5 pg for the acetic acid-dlthlzone-chloroform
solutions system and for the sunple dlthlzone-chloroform
Glassware was washed with chromic-sulphunc solution The amount of acetic acid (sp gr 105)
acid cleaning solution, followed by hot (1 + 1) transferred was found to be 3 9 g
nitric acid, and copiously rinsed with water
room for the same mmlmum duration It could damage to the reagent and to be stored for a
also be stored at room temperature (ca 35C) m reasonable period of time
diffuse light for a mmlmum of 20 days tested
The development of a new absorption peak at Conchon
312 5 mn by suppressmg the characterlstlc peak Dlthlzone solution eqmhbrated with 6 M acetic
for dlthlzone was not observed wth these solu- acid 1s more smtable for routme determmatlon of
tions, 1 e one stored at 10C (tested for 3 weeks) metal Ions as no stringent care needs to be taken
and the other at room temperature (ca 35C, with respect to light and high temperature either
tested for 10 days) under diffuse light condltlons during preparation of the reagent or m Its use As
This IS m accordance with an earlier report [5] m the stock solutron 1s stable for a reasonable length
which the absorption peak (at 312 5 nm) started of time, the reagent 1s also fit for infrequent use
to appear notably after a perrod of 4 days due to This ehmmates the need for standardlzatlon of
the photochemlcal formatlon of thladlazohne the stock solution before each set of experiments
products However, this is for a simple dlthlzone and the purlfrcatlon of the reagent and/or the
solution contammg a higher concentration of solvent before use
acetic acid (ca lo-fold excess> m the absence of
One of the authors (N T 1 thanks UGC, India,
chloroform under unspecified storing condltlons
for financial assistance
Mode of stabdrtatton
The primary cause of the deterloratlon of REFERENCES
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2 G Iwantsheff, Das Dlthlzon und seme Anwendung m der
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4 H M N H Irving, AM Swan, D C Rupamwar and S S
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(1939) 395
equlhbratlon (phase-transfer) process, the possl-
8 DA Blddle, Ind Eng Chem , Anal Ed, 8 (1936) 99
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11 P Grey and G C B Cave, Can J Chem , 47 (1969) 4543
acetic acid associates and protects the reagent
12 A I Vogel, Text Book of Quantltatlve Inorgamc Analysis,
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