ANALYTICA CHIMICA ACTA 541

HYDRAZINE AS A TITRIMETRIC REAGENT IN IODOMETRY

PART I
I<. S. PANWAR, N. K. MATHUR AND S. I?. RAO
Deparfmcnt of Chemistry. Jaswarrt Cotiege, Jodlrprrv (India)
(Received October Igth, 1#o)

Direct and indirect iodometric procedures are very widely used both in inorganic and
organic analysis’ but the traditional methods possess certain disaclvantages. Standard
iodine solution can be prepared by direct weighin@ but this is somewhat inconvenient
and therefore standarclisation of an approximate solution is usually preferred. Arsenic
trioxide is a well-established iodimetric primary standard but its use is generally
limited to the standardisation of iodine solution and the preparation of stanclarcl
arsenite solution is laborious. Sodium thiosulphate solution3 is commonly used for
the determination of free iodine ; however, unless cart is taken during its preparation,
standarclisation and storage, the reagent is not satisfactory. Moreover, there is a
possibility of side-reactions owing to atmospheric oxidation and acid decomposition
of the titrant. A general study of the disadvantages of thiosulphatc, and to some
estent sodium arsenite, has been made by BANK+.
A survey of methods showed that previous work has aimed either at determining
hydrazineb itself or at its use as a clirect reductant 6. Uecause of the limitations of
arsenite and thiosulphate solutions an attempt has been made to study the general
behaviour of hydrazinc as a reagent in iodometric titrations. This is not a new appli-
cation’ and no originality is claimed in this respect; however, we have studied the
general use of the reagent in iodometry. as well as the optimum conditions for the
iodometric determination of various substances. The direct and indirect detcrmina-
tions of a large number of substances are described below.

EXPERIMENTAL

l+ej5avalion, standardisatiow and stability of hydrazinc solution

Fret hydrazine base itself is unstable8 but its hydrochloride and sulphate salts are
quite stable. Analytically pure” salts can be easily prepared by recrystallisation of
the C.P. product from water.
A 0.1 N solution of hydrazine was prepared by dissolving 2.6237 g of pure hydrazine
hydrochloride (B.D.H.) in r 1 of glass-distilled water. The solution was stored in glass-
stoppered bottles. Its concentration was checked by titrating against an iodine
solution which had been standardiscd against sodium arsenite and bromate solution.
The solution. was highly acidic (PH 1.4 to 2) and was quite stable. The change in
titre of the solution corresponded to only 0.05 ml of 0.1 IV iodine solution when roe ml
were titrated after standing for a week.

~nai. CJcim. Acta, 24 (1961) 541-545

542 K. S. PANWAR, N. K. MATHUR, S. I’. RAO

GemvrcL method for titrating excess or liberated iodine with hydrazine solution
The reaction between hydrazinc and iodine is slow in acid medium9 but rapid in
presence of bicarbonate’0 (PH 7 to 7.4) ; excess of bicarbonate should be avoided
because high results are obtained at high pH values owing to decomposition of
hydrazinc. A suitable amount of bicarbonate is 0.5-I g per 25 ml of 0.1 i‘V hydrazinc
solution. After iodine has been liberated from an aliquot of the test solution by adding
potassium iodide in acid or neutral medium, the solution is ncutralised with sodium
bicarbonate. l’he titration is then carried out in presence of a slight excess of bi-
carbonate, the end-point being dctcctcd by the usual starch or starch glycollate incli-
cator. Near the cncl-point the reaction is rather slow and the titrant must bc added
slowly with stirring. If the colour of the starch-iodide complex is obscured by the
prescncc of other colourccl substances, the cncl-point can lx detected by the potentio-
metric “dead-stop” technique1 1. Sargent’s 15lcctrornetric ‘I’itration Apparatus ‘Arnpot’
with two similar platinum elcctrocles at an applied polarising potential of 20-30 mV
was usccl in the present work. Tn presence of ioclinc the electrodes remain clepolarised
as indicated by a current of IS-zo mA flowing through the cell. In presence of c.sccss
of llyclraxine the clectrocles are polarised and the current reduces nearly to zero. 130th
the visual indicator method and the “cleacl-stop” technique gave identical and re-
producible, results but the latter method is to lx preferred because of certain dis-
advantages of the starch indicator.

In acidic medium dichromate, pcrmanganate and cerium(IV) are reduced to definite

lower valency states (Cr = 3, Mn = z and Ce =1: 3) by hydrioclic acid, liberating _
equivalent amounts of iodine. After the free acid has been neutraliscd with bicarbonate,
the libcratecl iodine can be titrated with stanclard hyclraeine solution as described
above. Sufficient sample should be taken to consume 5-25 ml of 0.x N hyclrazine.
when the results arc precise to & 0.3 to & 0.6%.

Iodine is liberatccl from solutions containing no free mineral acid by adding I g of

potassium iodide per 0.6 g of copper sulphate present. ‘The reaction tnixturc is then
ncutraliscd and titratccl as nbovc. The results are precise to & 0.5%.

To IO ml of chlorate solution (cu. 0.2 N) are added T g of potassium bromide and

20 ml of concentrated hydrochloric acid (the final acid concentration should be 8 N).
The flask is stoppercd and allowccl to stand for 5 min ; TO ml of ~o’l/o potassium iodide
solution arc then adclcd and the titration is complctecl as before.

13vontate avul iodate

Iocline is liberated from an aliquot of the test solution containing 0.5~2.5 mequiv.
of bromate or iodate by adding I g of potassium iodide and sufficient hydrochloric
acid, and the ioclinc is titrated as described earlier. In the case of lx-ornate the reaction
is slow and the reaction mixture should be allowed to stand for z min before the
libcratccl ioclinc is titrated. The results arc precise to _I: 0.3 to & 0.50/.
 HYDRAZINE AS REAGENT IN IODOMETRY 543

Periodnte
To a solution of periodate containing 0.5 mmoles of the salt, 20 ml of saturated
borax solution containing 0.5 g of boric acid are added followed by z. g of potassium
iodide; the liberated iodine is titrated as described above.

Hypocltiorite und blenching +owder

z g of potassium iodide and IO ml of glacial acetic acid are added to the test solution
and the liberated iodine is titrated as before.

Setknitc
To 20 ml of approsimatcly 0.05 N selenitc solution are added 150 ml of water,
15 ml of starch solution, TO ml of N potassium iodide and IO ml of 5 N hydrochloric
acid. The reaction mixture is allowed to stand for 15 min to complete the reduction
of selenite to selenium and then titrated after neutralisation.

Hydrogen +zroxide
To a 25-ml portion of cu. 0.1 N peroxide are added IO ml of 4 N sulphuric acid and
G ml of N potassium iodide followed by 3 drops of ammonium molybdate solution,
and the liberated iodine is titrated as before. If ammonium molybdate is not added
as catalyst, the reaction mixture should be allowed to stand for 15 min in a closed
vessel before titration. The method can also be applied to metallic peroxides.

I;evvicyanide and zi?rc

To 25 ml of a solution containing ctr. 0.1 g of ferricyanide are added 20 ml of 10%
potassium iodide, 2 ml of 2 N hydrochloric or sulphuric acid and 15 ml of a solution
containing z g zinc sulphate. Liberated iodine is then titrated after neutralisation.
Zinc sulphatclz is added to prevent the back-reaction involving the conversion of
ferrocyanide to ferricyanide.
By suitable modification, i.e. by employing an excess of ferricyanidc and a definite
amount of zinc solution, the method can also bc employed for the determination of
zinc.

Mautgnnese dioxide
To a suspension of x50 mg of the powdered dioxide and 20 ml of 4 N phosphoric
acid in a glass-stoppered flask is added sufficient bicarbonate to remove air followed
by 1.5 g of potassium iodide. The flask is allowed to stand till all the dioxide has
dissolved. The liberated iodine is then titrated as usual after neutralisation with
sodium bicarbonate.

Sulphide, sulphite, phosphite and nitrite are oxidised in acidic medium by standard
iodine solution to sulphur, sulphatc, phosphate and nitrate respectively but iodate-
iodide mixture is preferable as a source of iodine. The solution containing 2.5 mmoles
of the salt is mixed with the iodate-iodide mixture and then acidified. The excess io-
dine is then titrated as usual after standing for some time.

11ucd. Ctrirn. Ada, 24 (Igbr) 541-545

544 K. S. PANWAR, N. K. MATHUR, S. I’. RAO

To about 240 mg of mercurous chloride 25 ml of 0.1 N iodine and I g of potassium

iodide are added and the mixture is shaken till the precipitate dissolves completely.
It is then titrated as usual after neutralisation.
i;errotrs iron
To the ferrous solution arc added 5 ml of 4 N sulphuric acid and sufficient sodium
bicarbonate to remove air from the flask; 5 g of powdered sodium pyrophosphateis
arc then added and the mixture is stirred till all the salt has dissolved. Iodine is then
added and back-titrated after standing for a few seconds in the usual way.

To about 2.5 ml of a solution containing 5-25 mmolcs of ferrocyanide in an Erlen-

meycr flask, are added 25 ml of TOO/~disodium monohydrogen phosphate solution,
25 ml of 20”/0 acetic acid and 25 ml of 0.1 N iodine solution. The reaction mixture is
then left in the dark for about 15-20 min and excess of iodine is titrated as usual.

To 200 mg of mercuric chloride, x-2 g of potassium iodide are added and shaken till
the precipitate dissolves; TO ml of 4 iV soclium hydroxide solution and 3 ml of 35o/o
formalclcbydc are then added with continuous shaking, followed by ro ml of water.
After 2 min 10 ml of acetic acid and 25 ml of 0.1 N iodine solution are added. The
reaction mixture is shaken till all the mercury dissolves and then excess of iodine is
titratccl after ncutralisation.
DISCUSSION

Tile quantitative reaction of hydrazine and iodine is well established and in presence
of a slight excess of sodium bicarbonate (PH - 7.4) the reaction proceeds rapidly
and smoothly. The present study has shown that hydrazine can also be used for the
titration of ioclinc liberated from iodide by certain oxidants such as pcrmanganate,
dichromatc and ccrium(IV), as well as for the determination of excess of iodine left
after the oxidation of certain reductants.
It has been establisbcd that the reduction products of certain oxidants, i.e. Mn+Q,
Cr+a, Cc+a, Zn+z, Se, CusIs, Cl-, 13r-, I-, ancl oxidation products of certain rcductants,
i.e. Fe+“, S, Sod-“, NOa-, POa- J etc. do not interfere in the hydrazinc-iodine reaction.
Hydrazinc can therefore be recommended as a suitable reagent in the iodometric
determination of these compounds. Interfcrcnce was observed in two cases, i.e. when
ferric or ferrocyanide ions are present but this can be eliminated by complexing with
phosphate or zinc ions respectively. Additional advantages of hydrazinc salts are their
availability in an analytically pure form which can bc used as a primary standard,
the stability of their solutions and the uniform conditions of the reaction with iodine.
The clisaclvantage is that the cost of the reagent is higher than that of sodium thio-
sulphate. Iodometric dctcrminations of other compounds, including organic sub-
stances, is under investigation and the results will be communicated shortly.

ACKNOWLEDGEMENT

The authors express their sincere thanks to Prof. I<. P. HALUAR for his keen interest
in the work.

rlttal. Cltitn. Aclo, 24 (Igbr) 541-545

 HYDRAZINE AS REAGENT IN IODOMETRY 545

SUMMARY
The preparation, standardisation and stability of hydrazinc solution is dcscribcd. The optimum
conditions for the titration with hydrazinc solution of put-c iodine solution of iodine libcratcd from
oxidants and of excess of iodine left after oxidation of certain reductants have been cletermincd.
The advantages of hydrazinc over other iodometric reagents arc discussccl.

L’hydrazinc pcut Otrc utilisec comma rcactif pour Ic titragc iodomctriquc tic nombrcuscs substan-
ccs. Dans cette prcmicrc partic, Its auteurs ont cxaminc la prbparation, l’cltalonnagc et la stnbilitd
dcs solutions d’hydrazinc.

ZUSARIMENPASSUNG
Beschrcibung dcr Hcrstcllung. Standardisicrung und Stabilitiit van Hydrazinl0sungcn. clcrcn
Titration mif Jodlbsung und Anwcndung bei der Bcstimmung x-011 Oxydations- und Rcduktions-
mittel.

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- . . I_
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Arwl. C/rim. rich, 24 (190x) 54 r--545