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Determination of Organoisothiocyanates Alone and in

Mixtures with Organoisocyanates or Thioureas
Published on 01 January 1973. Downloaded by University of California - Santa Cruz on 22/10/2014 16:26:06.

Bv B.1LBI R CHAND 3*ER6IA AND SWATANTAR KU6fA R

(Department of Chemistsy, Pu n jabi U›iiuemity, T'atiala, India)

An ioc1atortie†ric method for the determination of organoisotliiocyanates

is described. 4’he isothiocyanates are quantitatively cr›nverted with n-butyl-
amine in diinetliylfortnamide rnetlitim into the corresponding symmetrical IN-
H isuLstituted thioureas, which are titrated visually or potentiometrically in
acidic medium with potassium iodate solution. Methods liar e also been rlevelopcct
for the analj•sis r›f isothiocyanatc - isr›cyanate and isothio-
cyanate - thiourea mixtures on the some sample solution. A known excess
of the standard n-butylarninc solution added to the mixture in diinethyl-
formainitle converts the isothiocyanatc and isoc› anate into the corresponding
disitbstituted thiourea and urea, respectively. Acidimetric titration of the
excess of amine, and iodatometric titration of the thiourea present and
forrncd, enable the particular mixture to be analysed for both constituents.
The end-points can be detected both visually and potentiometrically. J’lie
methods described are simple, accurate, reliable and widely applicable.

ilosr titrimetric methods that are used for the determination of organoisothiocyanates are
based on the quantitative conversion of these compounds into tlic corresponding tliioureas.
rhis conversion was accomplished by some workers by heating the isothiocyanate with
ammonia in aqueous or alcoholic solutions, but because of the significant reaction of isothio-
cyanates with water or alcohol, ammonia was subsequently replaced with amines and the
reaction carried out in non-aqueous media. The unreacted amount of amine, after completion
of the reaction, w as determined by acidimetric titration with hydrochloric or sulphuric acid
in aqueous medium.
The earliest and most commonly adopted method is that developed by Siggia and
Hanna,' who determined organoisothiocyanates by treating the sample at room temperature
with a knovm excess of standard n-butylamine in dioxan :
RNCS -}- C H NHS —+- RNHCSNHC H
'the alkyl isotliiocyanates required 45 minutes for the reaction to occur. The aryl
isotliiocyanates, however, reacted immediately. Tfie excess of amine was titrated with a
standard solution of sulphuric acid, with methyl red as indicator. A blank was also run
as the presence of acidic or basic impurities in the sample Vould give rise to erroneous results.
Karten and dia* adapted this procedure to the micro-determination of isothiocyanates.
Vinson° succeeded in decreasing the reaction time between alkyl isothiocyanates and ri-butyl-
amine in Siggia and Hanna’s method to only 5 to 10 minutes by replacing the dioxan with
climethylforniamide. Methods involving the reaction of isothiocyanates with n-butylamine
in chlorobenzenc,' and with pipcridine in dioxan,° were also developed.
The determination of isothiocyanates, based on their reactions with amines in not-
aqueous media, can be achieved either by titration of the excess of amine or by titration of
the substituted thiourea formed. The methods de›•eloped for the determination of isotliio-
cyanates involve the titration of the excess of amine acidimetrically. Some significant
improvements in the determination of isothiocyanates can be effected if the substituted
thioureas formed (rather th an the excess :›f amine) can be determined oxidimetrically.
The determination of thiourea, p i ticularly by redox methods, has attracted much
attention and titrimctric r roccdures witl almost all the known oxidants have been developed.
The oxidimetric methods for the determ ination of thiourea are based mostly on its oxidation
under various conditions to urea and sulphate, to sulphate, carbonate and nitrogen or to
formamidinc clisulphide. Reynolds an‹1 \Verner° developed a method for the determination
o1 thiourea based on its oxidation t‹a forNiamidine disulphide with iodine in aqueous solution.
fl ilfillan7 however, reported that this method gave accurate results only with very dilute
@ SAC and the authors.
 501
8
thiourea solutions. Sliramovsky found that the reaction of thiourea with on alkaline solution
of iodine was slow and developed an indirect method for the determination of thiourea with
oxidant, and Gupta• determined thiourea by titrating it with iodine solution in the presence
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of sodium hydrogen carbonate. The slow rate of reaction of thiourea with an alkaline solution
of potassium hexacyanoferrate(III) enabled only an indirect determination of thiourea with
the oxidant to be made (Joshi'"). Berka and Zyka" titrated thiourea with N-bromosuccin
imide in a sodium hydrogen carbonate medium and Suchomelova and Zyka'" reported that the
oxidation o1 thiourea with lea‹l tetraacetate occurred in 50 per cent. acetic acid and als‹ in
the presence of sulphuric or hydrochloric acid.
During detailed studies'3 on the oxidimetric determination of thioureas, we found that
potassium iodate is one of the oxidants that oxidise thiourea and its mono-'• and symmetricallv
disubstituted (B. C. Verma, unpublished work) derivatives smoothly, rapidly and quanti- tatively
to corresponding disulphides at room temperature without the use t›f a catalyst :
RHN RHN
C— SH

(R and H’ — hydrogen atoms or alkyl or aryl groups)

No indicator is required, the end-point being signalled by the appearance of iodine with the
first excess drop of iodate solution, which imparts a distinct yellow colour to the solution.
The end-point can, however, be made more perceptible by using amylose as an indicator.
The titrations can also be carried out potentiometrically by using platinum-wire and saturated
calomel electrodes. The potential attains a steady value immediately with each addition
of oxidant, a sharp jump in potential bcing observed at the equivalence point.
The simplicity and reliability of the iodatometric method for the determination of
thioureas prompted us to apply this method to the determination o1 isotliiocyanates alter
their quantitative conversion into substituted thioureas in the manner described. The
oxidimetric (i‹idatometric) method possesses some distinct advantages over the acidimetric
method for the determination of isothiocyanates: (i) as in the oxidimetric method, the amine
is ret{uired solely to convert isotliiocyanates into the corresponding substituted thioureas and
the excess of amine need not be measured, and an amine solution of approximate concentration
(unstandardised) can therefore be used for the conversion. In addition, the excess of amine
‹foes not interfere in the iodatometric determination of thioureas ; (ii) potassium iodate is a
reliable and w'idely used primary standard and hence by using the oxidimetric method, tlic
necessity of standardising the acid (hydrochloric or sulphuric acid) used in the acidimetric
method can lie eliminated ; (iii) any acidic or laasic im F• rities in the isothiocyanate samples
would not aftcct the results owing to the oxidimetric character of the method ; (ir) the iodato-
metric titrations can be performed without the use of an additional indicator ; and (r) isothio-
cyanates can be determined in the presence of isocyanates by the iodatometric method, as the
substituted ureas formed by the reaction o1 isocyanate with amine do not cause interference in
the titration of thioureas.

Jb ALYSIS OF ISOTHI OCYANATE - ISOCYANATn riixTUnEs—

Organoisothiocyanates and isocyanates are structurally similar c‹aiupounds and arc
significantly similar in their reactions, espec1ally with ammonia and amines to form sub-
stituted thioureas and ureas, respectively. They also find extensive use as intermediates
in the synthesis of polymers, hence their determination in the presence of each other is of
great interest.
A simple and accurate method for their determination in a single aliquot of sample
solution consists in treating the solution of the mixture in dimethylformamide with a known
excess or a standard solution of n-butylamine in dimethylformamide. The isothiocyanates
and isocyanates are converted into the correspon‹1ing symmetrical NN-disubstituted thioureas
and ureas, respectively. The excess of amine on titration with standard acid solution gives
the total amount of isothiocyanate and isocyanate in the mixture. Titration with standard
Potassium iodate solution of the disubstituted thiourea formed gives the isothiocyanate content
o1 the mixture and the amount of isocyanate present can be calculated by difference. Both
the visual and potentiometric methods of detection of the end-points are reliable.
 902 VE RâIA A N D KU LIAR : DETERM I NATI ON OF ORGANOI SOTH IOCYANATES Analyst, \’o1. 98

NALYSIS OF ISOTHIOCYANATE - THI OUREA MIXTURES—

One or the simple and general methods for the preparation of substituted thioureas
involves the reaction of isothiocyanates with ammonia or amines. As a large number of
Published on 01 January 1973. Downloaded by University of California - Santa Cruz on 22/10/2014 16:26:06.

substituted thioureas have been prepared by such reactions, mixtures o1 isothiocyanate and
thiourea may be encountered.
A simple and accurate method has been dev-eloped so as to enable the same aliquot
of sample solution to be used for the determination of both components of such mixtures.
The solution of the mixture in dimethylformamide is allowed to react with a known excess
of the standard n-butylamine solution. The excess of amine is titrated with standard acid
followed by titration of total thiourea (already present in the sample solution as well as
disubstituted thiourea obtained from isothiocyanate by the reaction with n-butylamine) with
standard iodate solution. From the acidimetric titration the amount of isothiocyanate in
the mixture can be calculated and from the iodatometric titration the total amount of
isothiocyanate and thiourea in the mixture. The thiourea content of the mixture can be
found by difference.
ExPERIMENTAL
A wArcs—
Redox potentiometric titrations were performed with an Osaw Crompton (India) potentio-
meter, and an Osaw spot-reflecting galvanometer, a bright platinum-wire indicator electrode
and a saturated calomel reference electrode.
Acid - base potentiometric titrations were performed with a Philips pH meter (electronic
millivoltmeter) and glass and saturated calomel electrodes.
Microbiiretle—Ol 10-ml capacity, graduated in 0-02-ml divisions.
REAGENTS—
Ditns/ñJ//ortnatnids—Commercial grade material was purified by storing it over
analytical- reagent grade anhydrous sodium carbonate for 2 days. The solvent was decanted
off, distilled and the fraction distilling at l48'5 to 149-5 °C was collected in a coloured bottle.
Potassium iodate solution, 0-05 N—This solution was prepared by dissolving 1-7834 g of the
dried analytical-reagent grade compound in water and making the volume up to 1 litre.
Sulphuric acid, ñ-1 N—This solution was standardised with potassium hydrogen
phthalate, with phenolphthalein as indicator.
n-Butylamine solution, 0-2 N—This solution was prepared by dissolving slightly more
than the calculated amount of amine (purified by distillation over barium oxide) in dimethyl-
formamide. The solution was standardised by titration with standard sulphuric acid, with
methyl red as indicator.
A1ky1 isothiocyanates and alkylthioureas were prepared by well known methods.' Phenyl
isothiocyanate (commercial grade) was distilled before use; plienyltliiourea (commercial
grade) was recrystallised before use; phenyl isocyanate was prepared by the method of Allen
and Bel11"; butyl isocyanate (commercial grade) was distilled before use; and o-methoxy-
phenyl isothiocyanate was prepared by the method of Dains, Brewster and Olander."
PROCEDURE—
Determination of organoisothiocyanates—to an aliquot of the solution in dimethylform-
amide or cacti isothiocyanate contained in a glass-stoppered titration flask 5 ml of approxi-
mately 0-2 N n-buty1amine in dimethy1(ormamide were added. The volume of the solution
was made up to 10 ml with the solvent. The flask was stoppered, swirled in order to mix
the reactants and set aside for 10 minutes so as to ensure completion of the reaction. Sufficient
water and sulphuric acid to maintain the normality of the solution at 2 0 to 2-5 N and its
volume at 100 ml were added. The solution was cooled to room temperature (26 °C) in each
instance and titrated with 0-05 N potassium iodate solution to the appearance of a distinct
and permanent yellow colour. lf desired, amylose (0'2 ml of a 1 per cent. aqueous solution)
can be used as an indicator, the solution acquiring a blue colour at the end-point.
In potcntiometric titrations, the solution was stirred magnetically during the titration.
A sharp jump in potential was observed at the equivalence point.
From the volume or standard 0-05 N {)Otassium iodate used corresponding to the end-
point in visual and potentiometric titrations, the amount of disubstituted thiourea formed
 December, 1973] ALONE AND WITH ORGANCIISOCYANATES Olt THIOUREAS 903

and consequently the amount of isothiocyanate present was calculated. The results are
recorded in Table I.
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TABLE I
IODATOMETRIC DETERMINATION OF ORGANOISOTHIOCYANATES
Values are means of six determinations with standard deviations
Amount found*/mg Amount found}Jmg
\''isua1 Potentiometric Visual Potentiometric
Compound method method method method
CH NCS S-05 —[- 0 020 'i &9 —|- 0-017 30- 14 -|- 0-032 30-06 —[- 0-019
CHtCHtNCS 8 04 —|- 0-028 8-00 —|- 0 011 29'93 0 032 29•94 —[- 0'031
CH CHtCHthCS 7-98 0-020 7 98 —|- 0-015 30 14 -}- 0-031 30-05 —{- 0-01I
(CH )tCHNCS 8-04 0-031 8 01 —|- 0-025 30- 17 —|- 0-027 30-00 —|- 0-025
CHtCH CHtCH NCP 8-05 -I- 0-024 8-03 -I- 0'0l5 30-14 —|- 0-032 29-82 0-01.5
(CH ) CHCHtNCS 7 87 0-031 7 88 -t- 0-015 30-23 —t- 0-037 30'13 0-031
C HtNCS 8-05 0'034 5-00 0-028 29-96 0-038 30'00 0 031
o-(OCHt)CtH MCS 8-03 -J- 0-030 7 99 0-028 29'(10 0 042 29-80 0-028
* Amount taken S mg.
t Arrrount taken 30 mg.

Determination of organoisothiocyanales and isocyanates iii ltte presence of each other—

Aliquots of the solution in dimethylformamide of synthetic mixtures with various proportions
of isothiocyanate and isocyanate were placed in glass-stoppered titration flasks containing a
known excess (7 ml) of standard (0-2 N) solution o1 n-butylamine in dimethylformamide. ’the
volume of each solution was made up to l5 ml with the solvent. The flask was stoppered,
swirled in order to mix the reactants and set aside for 10 minutes so as to ensure completion
of the reaction. The solution was diluted with 30 to 40 ml of distilled water, cooled to room
temperature and titrated with standard 0-1 N sulphuric acid, with methyl red as indicator. To
the same solution sufficient water and sulphuric acid to maintain the normality of the solution at
2-0 to 2-.5 N and its volume at 125 ml were added. The solution was cooled to room
temperature (26 °C) and titrated with standard 0-05 N Otassium iodate solution, with amylose as
indicator. The colour changed sharply from rcd to blue at the end-point.
Both the acidimetric and iodatometric titrations were also performerl potentiometrically.
The solution was stirred magnetically in these titrations.
The volume of standard acid used in thc acidimetric titration corresponds to the total
amount of isothiocyanate and isocyanate present in the sample, and that of iodate solution
used in the iodatometric titration corresponds to the amount of disubstituted thiourea torment
and consequently the amount of isothiocyanate present. The iosocyanate content of the
sample can therefore be determined by difference. The results of the analysis of phenyl iso-
thiocyanate and phenyl isocyanate mixtures by both visual and potentiometric titrations are
recorded in Table II.
TABLE II
DETERâIINATION OF PHENYL ISOTHIOCYANATE AND PHENYL ISOGYANATE
IN ADMIXTURE
Values are means of six determinations with standard deviations
Amount Amount
of Amount found/mg of Amount (oundJng
C H NCS CtHtNCO
in the Potentio- in the Potentio- Rato of
mixtures Visual metric mixtures Visual metric CtH,NCS to
mg method method mg method method CH,NCO
10-00 10'03 0-055 S 97 0-039 10-00 TO 04 0-076 9'98 0'058 I:I
10-00 10'05 0 004 10 02 0-015 20-00 19-96 —|- 0'093 20'00 U_ 0 084 1:3
T0-00 1 0 06 0 024 10 0S -{- 0 028 30-00 28-83 0-124 29-90 0'084 1:3
10 00 9-94 0-028 9 97 0-015 40-00 39-85 0'124 38-89 0'03l I:4
20-00 20-12 0-078 20-08 —|- 0-056 I0 00 10'04 0-065 9-96 0-040 3:I
30-00 S0-23 —|- 0-0'77 30-10 —[- 0-057 10-00 9-96 —[- 0-085 5-98 0-022 3:I
40 00 40-29 -{- 0-080 40- 18 0-052 10'00 10-03 0 083 0 9B j- 0-040 4:l
 fi04 VERâL1 AR D KUMAR : DkTERMI NATI ON OF ORGANOI SOTHI OCYANATES {A n alyst, ¥’ol. 98
Determination of organoisolhi‘ocyanates and thioureas in the presence of each other The
procedure adopted was similar in detail to that used for mixtures of organoisothiocyanates and
isocyanates, except that an excess of 5 ml of 0-2 N solution of n-butylamine in dimethyl-
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formamide was used. The value for total thioureas included that originally present in the
mixture.
Both the acidimetric and oxidimetric titrations were also carried out potentiometrically.
From the volume of staridard acid used in the acidimetric titration, the amount of
isothiocyanate in the mixture was calculated. The total amount of isothiocyanate and thio-
urea in the mixture was calculated from the volume of standard potassium iodate used in the
oxidimetric titration. The thiourea content of the mixture was calculated by difference.
The results of the analysis of a mixture of ethyl isothiocyanate and ethylthiourea by both
visual and potentiometric methods are given in Table III.

TABiE III
DETERMINATION OF ETHYL ISOTHIOGYANATE AND ETHYLTHIOUREA
IN ADMIXTURE
Values are means of six determinations with standard deviations
Amount Amount
of Amount lound/mg of ethyl- Amount found/mg
C H,NCS thiourea —,
in the rotentio- in the Potentio- Ratio of
mixtures Visual metric mixtures Visual metric C H NCS to
mg method method tag method method @HtNHCSNH
10-00 10 00 -I- 0-069 10 00 0-038 10 00 9 ss oboes 9 9g odors i: i
l0'00 10-04 —|- 0 043 9 96 0 027 20-00 1& 87 —{- 0'051 20-00 -|- 0-047 I:2
10-00 10 03 —I- 0-071 9 97 -I- 0-015 30 00 30 24 0'072 30-12 -I- 0-057 1:3
10-00 10-04 0 041 10 03 0 030 40-00 39-64 —|- 0'057 39'73 0-032 I:4
20 00 20 08 —|- 0 043 19 97 —|- 0-022 10-00 10-05 -|- 0'020 9 96 -}- 0 016 Z: 1
30-00 30-22I 0-068 30 121 0 022 10 00 10-04I 0-026 l0'031 0 011 3: 1
40-00 40 37 0-058 40-33 0-043 10 00 10-04 -j- 0 049 10-02 0-022 4:1

RESULTS AND DISCUSSION

The results recorded in Table I show that methyl, ethyl, n-propyI, isopropyl, n-butyl,
isobutyl, phenyl or o-methoxypheny1 isothiocyanate can be determined visually and potentio-
metrically after conversion into symmetrical NO-disubstituted thioureas by reaction with n-
butylamine in dimethylformamide medium. The over-all standard deviation from the pooled results
o1 all the visual and potentiometric titrations performed with 8 mg of each isothio- cyanate have
been found to be —|-0-027 and -{-0-010, respectively, and for 30 mg of each com- pound -|-0-034
and -|-0-024, respectively. The method is free from interferences from organoisocyanates, thiocyanates
or ureas even when present in up to five-fold amounts. Thioacetainide, tliiosemicarbazide,
thioureas, dithiocarbamates and xanthates, however, interfere. •
Although efforts had been made to develop methods that are applicable to the analysis
of pure samples of organoisothiocyanates, organoisocyanates or thioureas, no attention
appears to have been directed towards determining these compounds in mixtures containing
them. The proposed methods for the analysis of isothiocyanate - isocyanate and isothio-
cyanate - thiourea mixtures, besides being simple, accurate and reliable, have the added
advantage that the analyses can be conducted on the same sample solution, thus resulting
in a saving of time and effort. The acidimetric titration of the excess of amine added to the
mixture, followed by iodatometric titration of thiourea present and formed, enables the
mixture to be analysed for both constituents. The red colour of the acidic form of methyl
red will persist throughout the iodatometric titration, which is carried out in sulphuric acid
medium immediately after the acidimetric titration. There is, however, a sharp colour
change from red to blue at the end-point. The analysis with both visual and potentiometric end-
point detection is reliable, but blanks are required to be run if the samples or the solvents used
are likely to be contaminated with acidic or basic impurities.
The synthetic mixtures of phenyl isothiocyanate and phenyl isocyanate with ratios in
the range 1 : 4 to 4: 1 can be analysed by both visual and potentiometric methods with an
 December, 19 i 3 ALONE AND WITH ORGANOISOC YAfiATES OR THIOUREAS 905
average standard deviation of 0-29 per cent. (for isothiocyanate) and 0'44 per cent. (for iso-
cyanate), respectively (Table II). The method has also been applied to the analysis of a
mixture of n-butyl isothiocyanate and n-butyl isocyanate, the results agreeing well with those
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obtained for the above mixture of aromatic compounds. The results recorded (Table III)
for the analysis of synthetic mixtures of ethyl isothiocyanate and ethylthiourea with ratios
also in the range 1 : 4 to 4: 1 show that they can be analysed by the visual and potentiometric
methods with an average standard deviation of 0-29 per cent. (for ethyl isothiocyanate) and 0-
23 per cent. (for etliylthiourea), respectively. The method has also been extended to other
mixtures such as methy], isothiocyanate - methylthiourea, n-propyl isothiocyanate - n-propyl-
thiourea, isopropyl isothiocyanate - isopropylthiourea, n-butyl isothiocyanate - n-butyl-
thiourea, isobutyl isothiocyanate - isobutylthiourea and phenyl isothiocyanate - phenyl-
thiourea, the components of which have been determined with the same degree of accuracy.
The authors thank the Council of Scientific and Industrial Research (India) for the
award of a research fellowship to one of them (S.K.).
REFERENCES
I. Siggia, S., and Hanna, J. G., A cal yl. Ghem., 1948, 20, 1084.
2. Karten, D. S., and Ma, T. S., Microchem. J., 1959, 3, 507.
Vinson, J. A., Anal yf. Che»i., i g . 41, lfi6l.
4. Roth, H., Mi Prochim. A cta, 1958 773.
Venkataraghavan, R., and Rao, C. N. R., MfissisI Anal yet, l9fl2. 51, 48.
Reynolds, J. E., and Werner, E. A., J. Chsm. Soc.. 1003, 83, I.
7. Gilfillan, F. •< . J A iner. Cic or. Soc., 1920, 42, 2072.
8. Skrauiovskv, S., Chem. ZentBl., 1941, 11, 379.
9. Gupta, P. C., J. Indian G hem. Soc., 1960, 37, 213.
10. Joshi, M. K., i4"aturwissenscha/len, 1957, 44, 537.
11. Berka, A., atld Zyka, J., C hemicée Listy, 1957, 51, 1823.
12. Suchomelova, L., and Zyka, J., /. fi/ectroana/yf. C6sw., 1963, 5, 57.
13. Singh, B. and Verma, B. C., J. Scient. lad. Res., l96ii, 24, 536.
14. , J. JnO(yA Chum., 1963, 194, 112.
1s. Drake, N. L., Org. S ynth., 1941, 21, 81 and 83.
18. Allen, C. F. H., and Bell, A., Ibid., 1955, Collect. Vol. 3, 84B.
17. Dains, F. B., Brewster, R. Q,., and Olander, C. P., /titd., 1955, Collect. Vol. 3, 447.
RcceivedMQy2lsl, l8G
Acceptcd Septc iber 3rd, 1973