7-ufunru. VoL 26. pp. 233-235 0039-9140/79/0301-0233102.

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8 Pergamon Press Ltd 1979. Printed in Great Britain

N-SUBSTITUTED PHENOTHIAZINES AS REDOX

INDICATORS IN BROMATOMETRY

H. SANKE GOWDA and S. AKHEEL AHMED

Department of Post-graduate Studies and Research in Chemistry, University of Mysore,
Manasa Gangotri, Mysore, India

(Received 13 December 1977. Revised 21 February 1978. Accepted 5 July 1978)

Summary-Diethazine hydrochloride, butaperazine dimaleate, trifluoperazine hydrochloride, prometha-

zine hydrochloride, prochlorperazine maleate and chlorpromazine hydrochloride have been studied
as indicators in bromate titration of quinol. metol and ascorbic acid. They give a very sharp reversible
colour change at the equivalence point. Their formal potentials have been determined. A simple but
accurate method for the estimation of quinol and metol is reported.

About ten reversible organic redox indicators have
been proposed for bromate titrations, although
numerous organic dyestuffs have been used as
irreversible bromometric indicators. Most of the
proposed reversible indicators are unsatisfactory for
one reason or another. c+Naphthoflavone’ forms a
brownish precipitate with free bromine liberated at
the end-point. p-Ethoxychrysoidine’ gives a variable
blank and its reversal cannot be repeated more than
twice. Quinoline Yellow3 gives a very faint colour
change and the blank is rather high. Ferroin,4 which
requires high temperature (4&50”) and catalysts
(osmic acid or sodium vanadate), gives sluggish end-
points. Fuchsine5 acts reversibly only at boiling
temperature. The colour of 2,6-dichlorophenolindo-
phenol6 at the end-point is immediately destroyed by
the addition of a drop of bromate. We have now
found the optimum conditions for the direct titration
of quinol, metol and ascorbic acid with potassium
bromate, using diethazine hydrochloride (DH), buta-
perazine dimaleate (BPDM), trifluoperazine hydro-
chloride (TFP), promethazine hydrochloride (PH),
prochlorperazine maleate (PCPM) and chlorproma-
zine hydrochloride (CPH) as reversible redox indi-
cators.
Determination of formal potentials
Ten-ml portions of the potentiopoised vanadate-vanadyl
solutions were mixed with 0.5 ml of indicator solution,
and the average of the potentials of the two solutions
bracketing the colour change was taken as the formal
redox potential. Schilt’s method” was also used. The
results are presented in Table 1.
Titration procedures
Quinol and metol. Take 20ml of 0.05401 M quinol,
lOm1 of %eo/, potassium bromide solution and enough
hydrochloric or sulphuric acid to give a concentration of
0.6 M (0.3 M sulphuric acid for CPH) at the end-point,
and dilute to 40 ml. Titrate with 0.025-0.005 M potassium
bromate to an orange-red, using 1 ml of 0.2% DH, BPDM,
TFP, PH. PCPM or CPH added near the end-point (after
95% titration). For titration of 0.005-0.0025 M quinol,
dilute 1Oml of sample, the acid and 3 ml of 10% potassium
bromide solution to 25 ml and titrate with 0.0025-
0.00125M potassium bromate, adding 0.5 ml of the indi-
cator towards the end-point. In the titration of metal, use
1M sulphuric or 0.5M hydrochloric acid medium and
1 ml of 0.2% DH, BPDM, TFP or PH near the end-point.
Ascorbic &id. Tai% ?i, til of 0.054025 M ascorb;ic acid,
10 ml of 10% potassium bromide solution and enough acid
to give a concentration of 1.5 M hydrochloric acid(0.8 M
for PCPM and CPH) or 1 M sulnhuric acid at the end-
point, and titrate as,ihe mixture fbr quinol.

EXPERIMENTAL
Reagents
Indicator solutions. All reaRents were analytical-trade
chemicals. Aqueous solutions 10.2%w/v) of CH, BFDM,
TFP, PH. PCPM and CPH were DreDared and stored in
amber bottles. BPDM and PCPM’ were dissolved in hot
water (60”).
Potentiopoised solutions. Equimolar vanadate-vanadyl
potentiopoised solutions in 0.0062540 M sulphuric acid
were prepared.‘.’
Reductants. Approximately 0.05 M solutions of quinol,
metol and ascorbic acid were prepared by dissolving the
requisite quantity of material in 0.04 M and 1 M sulphuric
acid and 0.01% EDTA solution respectively. The quinol
and met01 solutions were standardized with ceric sulphateg
and the ascorbic acid with potassium iodate.” The solu-
tions were stored in amber bottles and diluted as required.
RESULTS AND DISCUSSION
DH, TFP, PH, PCPM and CPH are highly soluble
in water, giving colourless solutions. BPDM gives a
light yellow solution in water. The aqueous solutions
are stable for about 3 days at room temperature (27”)
and for about 2 months in an amber bottle at low
temperature (8”); they slowly undergo photochemical
oxidation to give a pale pink colour, but this does
not interfere in their indicator action. They undergo
one-electron reversible oxidation to a red inter-
mediate which is believed to be a radical cation.12
_me radical cation is further oxidized irreversibly by
excess of oxidant to a colourless sulphoxide, with the.
loss of one electron.13*14 The mechanism of oxidation

T&I..
26/3--o 233
234 H. SANRE GOWDA and S. AKHEEL AHMED

of DH can be represented as follows:

The mechanism of oxidation of BPDM. TFP, PH.

PCPM and CPH is similar. The formal potential of the indicator correction is almost negligible. All
PCPM has already been reported to be 0.795 V,r5 five indicators give very sharp pink end-points which
that of CPH 0.799 V,16 of PH 0.883 V,” and of DH are stable for about 8 min in the titration of
0.856 v.s 0.0025XUlO5M quinol. The results compare favour-
ably with those obtained potentiometrically with
Titrations cerium(IV) sulphate.
Quinol. Kolthoff’s reported that the end-point of The minimum potassium bromide concentration
the potentiometric titration of quinol with potassium required in the titration of 0.025-0.05M quinol is
bromate is not sharp because of formation of the w 1.5%, and 1% for titration of 0.0025-0.005M quinol.
addition compound of quinone with the bromine Higher concentrations (up to 16%) do not affect the
liberated at the equivalence point. Francis and HillI results.
proposed adding excess of bromate-bromide and At least 1.0 ml of 0.2% indicator solution is necess-
determining the unreacted bromate iodometrically. ary in the titration of 0.02~0.05M quinol but
No attempts have previously been made to use indi- >2.5 ml gives premature end-points. In the titration
cators for titrating quinol directly with bromate. We of 0.0025-0.005M quinol 0.5 ml of 0.2% indicator
have found that DH, BPDM. TFP. PH PCPM and solution is required; > 1.5 ml gives higher titration
CPH can be used for this purpose. All six give no values.
colour change if the hydrochloric acid concentration The sharpness of the end-points is in the order
is below OSM; the useful acidity ranges are 0.5- BPDM > TFP > DH > PH > CPH > PCPM.
1.5M for BPDM and TFP, OS-l.OM for PH and Merol. Metol has not previously been estimated
DH and 0.5-0.8 M for PCPM and CPH. At higher with bromate. Its accurate estimation is of importance
acidities the results are too high. The colour change because of its application in photography. The
is from light yellow to orange-red in the titration of methods using iodine,” iodine monochloride,”
0.025-0.05M quinol. The end-point colour is stable cerium(IV) sulphate’ and sodium vanadate” are not
for about 90 sec. The end-points are brighter and quite satisfactory. The estimation with bromate, using
sharper in the titration of 0.0025-0.005N quinol. The DH. BPDM, TFP and PH as reversible redox indi-
end-point colour (pink) is stable for about 10min. cators, is simple but accurate.
At higher acidities under-titration occurs. Metol is quantitatively oxidized by bromate to
BPDM, TFP, PH and DH do not function at N-methyl-p-quinonimine in a two-electron change in
sulphuric acid concentrations less than 0.5M. CPH hydrochloric or sulphuric acid medium containing
does not give a colour change at acidities below bromide. Stoichiometric results are obtained in sul-
0.25M sulphuric acid. BPDM and TFP give sharp phuric acid medium ranging from 0.75 to 1.5M, with
end-points in 0.551.75M, PH in 0.5-0.75M, DH in sharp end-point changes from light yellow to an
OS-l.OM and CPH in 0.2550.4M sulphuric acid. orange-red which is stable for about 70 set in the
Results are too high at higher acidities. The colour titration of 0.02550.05M metol. Low results are
change for 0.025-0.05M quinol is from light yellow obtained at higher acidity and the indicators do not
to orange-red which is stable for about 70 set and function at lower acidities.
All four indicators give no colour change at acidi-
Table I. Determination of formal potentials (rnY) of
ties less than 0.4M hydrochloric acid. BPDM and
BPDM, TFP, PH. DH. PCPM and CPH
TFP give sharp colour change from light yellow to
Potentiopoised orange-red in 0.4-0.8M hydrochloric acid and PH
method Schilt’s method and DH in 0.40.6M hydrochloric acid. The end-
point colour is stable for about 90 sec. At higher
CWO,lM
acidities premature end-points are obtained.
Indicator 0.075 0.20 0.25 0.5 0.75 1.0 1.25 1.50
All four indicators give very sharp colour change
\
BPDM 900 - 881 865 838 828 812 793 from very light yellow to pink in the titration of
TFP - 921 893 881 870 863 854 836 0.0025-0.005M metol. The end-point colour is stable
PH 900 - 883 877 870 862 852 842 for 2-3 min in hydrochloric or sulphuric acid
DH 900 - 856 845 834 825 810 797 medium. The indicator correction is almost negligible
PCPM - 807 799’ 785 771 758 748
- 799 788 760 753 732 721
in the titration of 0.025005 M metol. The results
CPH
compare favourably with potentiometric values
 Phenothiazines as redox indicators 235

Table 2. Titration of quinol, metol and ascorbic acid in The indicator correction is almost negligible. The
presence of DH. BPDM. TFP, PH. PCPM and CPH effect of indicators and bromide concentration is simi-
indicators
lar to that for quinol. The sharpness of the end-points
Reductant Reductant Standard is in the order TFP > BPDM > DH > PH > CPH
taken, found.* deviation, > PCPM in hydrochloric acid medium and DH =
‘Y my mg BPDM > TFP > PH > CPH in sulphuric acid
medium.
Quinol
111.3 111.4 0.09 Oxalic, citric, tartaric, succinic, acetic and malic.
85.5 85.5 0.08 acids, glucose, fructose, sucrose, starch and acetone
55.4 55.4 0.07 do not interfere in the determination of a tenth of
10.43 10.45 0.07 their amount of ascorbic acid. The results compare
5.58 5.59 0.07
favourably with those obtained by Ballentine.”
2.23 2.24 0.07
Metol
Comparison with other indicators
157.2 157.3 0.05
120.2 120.2 0.08 All six indicators have advantages over p-ethoxy-
40.5 40.5 0.09 chrysoidine in that they.give sharper and brighter
15.12 15.14 0.09
12.04 0.05 end-points which can be reversed several times. They
12.02
4.42 4.43 0.01 are superior to 2,6-dichlorophenolindophenol because
Ascorbic acid (i) they give sharper and brighter end-points, (ii) the
166.3 166.5 0.05 end-point colour is more stable and (iii) a slight
122.4 122.5 0.01
excess of bromate after the equivalence point does
88.5 88.5 0.01
40.6 40.6 0.01 not destroy the colour.
In all the bromate titrations of quinol, metol and
* Average of five determinations. ascorbic acid the results are accurate to + 0.2%
(Table 2).
obtained with cerium(IV) sulphate. The influence of
REFERENCES
the bromide and indicator concentration is similar
to that for titration of quinol. 1. R. Uzel. Collecrion Czech. Chem. Commun., 1935, 7,
The sharpness of the end-points is in the order 380.
2. E. Schulek, J. Kovacs and P. Rozsa, Z. Anal. Chem.,
BPDM > PH > TFP > DH.
1941, 121, 17.
Ascorbic acid. pEthoxychrysoidine2 and 2,6-di- 3. R. Belcher, Anal. Chim. Acta, 1951, 5, 30.
chlorophenolindopheno16 are the only reversible 4. L. Szebelledy and W. Madis. Z. Anal. Chem., 1938-39,
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Khim., 1947. 2, 173.
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in this titration, giving a sharp reversible colour Bolyai, 1968, 13, 23.
change from colourless to pink (orange-red for TFP). 7. G. F. Smith and W. M. Banick, Jr., Talanta. 1959. 2,
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PCPM is stable for about 90 set in hydrochloric acid
22. G. G. Rao and T. P. Sastri, Z. Anal. Chem., 1956, 151,
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