Indian Journal of Chemistry
Vol. 46A, October 2007, pp. 1621-1624
Spectrophotometric determination of
hydrazine using bromine and methyl red
Mary Georgea, K S, Nagaraja a,* & N Balasubramanianb
a
Department of Chemistry, Loyola Institute of Frontier Energy
Loyola College, Chennai 600 034, India
b
Department of Chemistry, Indian Institute of Technology,
Madras, Chennai 600 036, India
Email: ksnagi@vsnl.net/ ksnraja@loyolacollege.edu
Received 13 November 2006; revised 17 August 2007
Hydrazine has been determined by its oxidation to nitrogen
with a known excess of bromine. Bromine in acidic medium
bleaches the dye methyl red. A known excess of bromine when
treated with hydrazine is reduced to bromide and the unreacted
bromine is determined using methyl red. The molar absorptivity is
calculated to be 9.95 x104 L mol-1cm-1. The method obeys Beer’s
law in the range 0-6 µg of hydrazine in an overall aqueous volume
of 25 mL with a correlation coefficient of 0.999.The detection
limit is 0.25µg of sample. The relative standard deviation is 2.7%
(n=10) at 3 µg of hydrazine. Interferences due to various foreign
ions have been studied. The proposed method has been
successfully applied for the estimation of hydrazine in boiler feed
water samples. The results obtained in the developed method
compare well with the p-dimethylaminobenzaldehyde (p-DAB)
method and by the recovery studies of added hydrazine.
IPC Code: Int. Cl.8 G01N21/25
Hydrazine is an important industrial chemical with
many applications in pharmaceutical, polymer,
photography and dye industries. It is used as a high-
energy rocket propellant. Hydrazine is widely used to
remove dissolved oxygen in boiler feed water and as
corrosion inhibitor. Besides being reactive and
explosive, hydrazine is highly toxic. It may cause skin
irritation and systemic poisoning. It is also a
suspected human carcinogen and the threshold limit
value for workroom air is 0.1 ppm in the USA. High
toxicity of hydrazine and its potential occurrence in
the workplace environment makes the development of
reliable and sensitive monitoring methods very
important.
Several methods have been suggested for the
determination of hydrazine all of which depend on
its basic character or reducing property1,2.
Spectrophotometric methods are more useful for the
determination of hydrazine at low concentration
levels3-5. Kinetic spectrophotometric methods for
determination of hydrazine has been reported6,7. A
sensitive spectrophotometric method has been
reported based on the reduction of hydrazine to
ammonium sulphate with Zn/H2SO4 reductor column
followed by the determination based on indophenol
dye formation8.
Bromine and its higher oxidation state compounds
are widely used in analytical determinations9. The
present note deals with the oxidation of hydrazine to
nitrogen with a known excess of bromine under acidic
condition. The unreacted bromine is determined based
on its ability to bleach the dye methyl red. Azo dye
methyl red has been selected for the evaluation based
on its reactivity towards bromine and colour stability
on standing. The developed method is more sensitive
(ε= 9.95 x 104 L mol-1cm-1) compared to the methods
based on the formation of indophenol dye8 (ε= 1.8
x104 L mol-1cm-1) and the reaction with p-dimethyl-
aminobenzaldehyde (ε= 3.6x104 L mol-1 cm-1)
Response of the proposed method in the presence of
potential interferents has been evaluated. The method
has been successfully applied to feed waters for high-
pressure steam generating boilers. The results were
validated with p-DAB method and by recovery
studies of added hydrazine.
Experimental
All absorbance measurements were made using
Elico SL 177 scanning spectrophotometer with 1 cm
matched glass cells. All chemicals used were
analytical grade reagents. Oxygen-free water was
used for the preparation of solutions. This was
prepared according to ASTM specification by boiling
distilled water and then cooling it under nitrogen
atmosphere to keep it free of dissolved oxygen.
For the stock solution, 0.1017 g of hydrazinium
sulphate was dissolved in 250 mL of water to give a
stock solution equivalent to 100 mg/L of hydrazine.
Bromate- bromide mixture for bromine generation
was prepared by dissolving 0.05g of potassium
bromate and 0.5 g of potassium bromide and diluting
to 500 mL with water. To generate 28 ppm of
bromine stock solution, 20 mL of bromate-bromide
mixture was diluted to 100 mL. An aliquot of this
stock solution (50 mL) was transferred into a 100 mL
calibrated flask containing 40 ml of 4.25 M sulphuric
1622 INDIAN J CHEM, SEC A, OCTOBER 2007
acid and diluted to 100 mL with water to get 14 ppm
of bromine solution. This bromine solution is stable
for only one day and was prepared on the day of use.
A solution of methyl red (0.01%) was prepared by
dissolving 0.1g of methyl red with 1 mL of 4.5M
sodium hydroxide and diluting to 100 mL; 10 mL of
this solution was diluted to 100 mL, after acidifying it
by adding 1 mL of 4.25 M sulphuric acid. Sulphuric
acid (4.25M) was prepared by adding 59 mL of conc.
sulphuric acid (sp. gravity 1.84) to 150 mL of water,
cooled and then diluting to 250 ml in a calibrated
flask. Sulphamic acid (0.5%) was prepared by
dissolving 0.5 g of sulphamic acid in 100 mL of
distilled water.
Procedure
To a 10 mL aliquot of sample containing 0-6 µg of
hydrazine, 5 mL of 14 µg mL-1 bromine solution was
added. The solutions were mixed well followed by the
addition of 1 mL of 0.01% of methyl red before
diluting to 25 mL with distilled water. The absorbance
of the solution was measured at 515 nm against
reagent blank using 1 cm glass cells.
A sample volume of boiler feed water (10 mL)
containing not more than 6µg of hydrazine was
subjected to analysis by following the described
procedure.
Results and discussion
Quantitative bleaching of azo dyes by halogens like
chlorine and bromine are widely used for their
spectrophotometric determinations9,10. In the present
Fig. 1 Absorption spectra of reagent blank of methyl red treated
with bromine water, (A) and that in the presence of - 1 µg
NH2NH2; (B) 2 µg NH2NH2; (C) - 3 µg NH2NH2; (D) - 4 µg
NH2NH2; (E) - 5 µg NH2NH2; (F) - 6µg NH2NH2; (All
measurements are taken against reagent blank).
investigation, reaction between bromine and methyl
red (4-dimethylaminoazobenzene-2-carboxylic acid)
is made use for the spectrophotometric determination
of hydrazine. Methyl red, an azo dye, shows two
absorption bands at 515 nm and 315 nm .The intensity
of the band at 315 nm is very weak as compared with
the band at 515 nm.
In the absence of hydrazine a known excess of
bromine bleaches the dye and the absorbance is very
low at 515 nm. In the presence of hydrazine, bromine
is reduced to bromide and the unreacted bromine
decolorizes the dye. A calibration graph was obtained
with a positive slope and the equation being
y = 0.12 x where y is the absorbance and x is the
concentration of hydrazine in µg. Thus, with the
increasing concentration of hydrazine, more of
bromine is reduced and this is observed by a linear
increase in the absorbance due to the unbleached
methyl red at 515 nm under acidic condition. It was
observed that with increasing bromine concentration,
absorption decreased for the band at 515 nm whereas
it increased for the band at 315 nm (Fig. 1).
This observation suggests ring substitution of
bromine in the dye molecule causing steric inhibition
of resonance as observed in the case of bromination of
similar dyes with azo functional groups10. This is
responsible for the decrease in absorbance at 515 nm
(Scheme 1).
 NOTES 1623

The effect of variation in acidity for an effective ions studied in hydrazine determination are
reaction between bromine and methyl red was summarized in Table 1.
established and this was found to be 0.3 – 1 M with Hydroxylamine is a potential interferent in most
respect to sulphuric acid. A reaction acidity of 0.34 M of the methods for hydrazine determination.
was maintained by taking 5 mL of bromine solution Hydroxylamine when present along with hydrazine
with an overall acidity of 1.7 M. also undergoes oxidation and causes positive
The proposed method was useful for the interference. In the proposed method, formaldehyde
determination of hydrazine in the concentration range solution is added to eliminate hydroxylamine
of 0-6 µg in a sample volume of 10 mL with a interference. Reaction between formaldehyde and
detection of 0.25 µg. The molar absorptivity of the hydroxylamine to form the oxime is very fast as
colored system was found to be 9.95 x 104 L mol-1 compared to the reaction between hydrazine and
cm-1 and the dye color remained stable upto 17 days. formaldehyde. In the present method, hydroxylamine
The correlation coefficient was 0.999 and the relative is tolerated up to a concentration of 500 µg in the
standard deviation was 2.7% (n=10) for 3µg of presence of 1 mL of 6000 ppm formaldehyde solution
hydrazine. when present along with 3 µg of hydrazine.
Nitrate and nitrite, greater than 10 µg, cause
Interferences interference in the estimation of hydrazine. Nitrite
The interfering effects of common anions and interference upto 100 µg was overcome by the
cations, which may coexist with hydrazine, were addition of 1 mL of 0.5% sulphamic acid. Nitrate is
evaluated. Any deviation in the absorbance value of first reduced to nitrite with HCHO in sulphuric acid
3% to that obtained in the absence of other interfering medium in the presence of sulphamic acid. The
ions in hydrazine determination was taken as sign of formed nitrite is decomposed by sulphamic acid. For
interference. Varying concentrations of interfering nitrate interference, 10 mL sample containing 7.5µg
species were added to 3 µg of hydrazine and the of hydrazine and nitrate (100µg) was treated with
absorbance values were compared to that in the 1 mL of 1000ppm HCHO solution followed by 5 mL
absence of interference. Tolerance limits of various of 8M sulphuric acid and 1 mL of 0.5% of sulphamic
acid. The solution was diluted to 25 mL in a
Table 1 Effect of some interfering species in the hydrazine
determination (NH2NH2 = 3 µg) 25 ml-calibrated flask and 10 mL was used for
analysis.
Ion Amt tolerated (µg)
Phosphate, Oxalate, Citrate, Tartrate, 1000 Application to real samples
Borate, Chloride, Carbonate Hydrazine is normally added in small amounts
HCHO 6000
(0.2%) to boiler feed water. Hydrazine is oxidized by
Hydroxylamine 0.1
Hydroxylamine a 500 dissolved oxygen to nitrogen and prevents the
Ba(II), Pb(II), Mg(II), Co(II), Cd(II), 1000 corrosion of boilers.
Bi(III), Ni(II), Li(I), Mn(II), Sr(II), The application of the proposed method has been
Cr(III), NH4+ b evaluated with feed water samples taken from high-
Cu(II), Hg(II) 50
Fe(II) 1.5 pressure steam generating boilers to determine the
NO2- 10 hydrazine concentration. Boiler feed water samples
NO2- c 100 were collected on different days and analyzed. One ml
NO3- 10 of sample was diluted to 100 mL. An aliquot of 1 mL
NO3- d 100
of diluted sample was further diluted to 10 mL and
a
Treated with HCHO solution before the addition of bromine subjected to analysis. The results obtained using the
solution. proposed method was validated by comparison with
b
If it is in the form of NH3 (NH4OH) treat the sample with 1 mL
of 0.1 M H2SO4 before treating with bromine solution
the p-dimethylaminobenzaldehyde (p-DAB) method
c
Treated with 1 mL of 0.5% sulphamic acid before treating with used by Deepa et al8. Calibration graph for p-DAB
bromine solution. method was prepared using 0-10 µg of hydrazine in
d
Treated with 1 mL of 1000 ppm HCHO solution followed by 5 10 mL of sample volume. Boiler feed water sample
mL of 8 M sulphuric acid and 1 mL of 0.5% of sulphamic acid
and diluted to 25 mL prior to analysis. 10 mL of sample was (10 mL) containing not more than 10 µg of hydrazine
used for analysis. was taken in a 25 mL-calibrated flask. To this, 10 mL
1624 INDIAN J CHEM, SEC A, OCTOBER 2007

Table 2 Determination of residual hydrazine in boiler feed water

a
Sample Added NH2NH2 Amount of NH2NH2(µg) in diluted Recovery of added Amount of NH2NH2(µg) in diluted
(µg) samples by proposed method (ppm)b hydrazine (%) samples by p-DAB method (ppm)b
Sample 1 - 2.98 - 2.95
2 4.96 99.0 -
- 2.95 - 2.90
2 4.95 100.0 -
- 2.99 - 2.90
2 5.00 100.5 -
2.97c(297) b 2.92c (292) b
Sample 2 - 1.98 - 1.95
2 3.99 100.5 -
- 2.01 - 1.93
2 4.01 100.0 -
- 1.95 - 2.00
2 3.95 100.0 -
1.98c (198) b 1.96c (196) b
Sample 3 - 1.98 - 1.95
2 3.97 99.5 -
- 2.05 - 2.00
2 4.05 100 -
- 1.96 - 1.93
2 3.95 99.5 -
2.00c (200) b 1.96c (196) b
a
Water samples were withdrawn at the entry point of the boiler on different days.
b
1 mL of the sample was diluted to 100 mL before analysis and one mL of the diluted sample was used for hydrazine determination.
c
Average of three determinations

of p-dimethylaminobenzaldehyde solution was added References

and made upto the mark with 1 M hydrochloric acid.
The absorbance was measured at 458nm against the
reagent blank. Recovery of added hydrazine was also
evaluated for the developed method (Table 2). The
results of the proposed method compared well with
those obtained by p-DAB method.
The proposed method for the determination of
hydrazine is simple, sensitive and reliable. The
method is useful for the determination of hydrazine in
the concentration range 0-6 µg.The molar absorptivity
is found to be 9.95 x 104 Lmol-1 cm-1. Interfering
species such as hydroxylamine, nitrate and nitrite
have a higher tolerance limit in the proposed method.
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