Journal of Analytical Sciences, Methods and Instrumentation, 2012, 2, 98-102
http://dx.doi.org/10.4236/jasmi.2012.22018 Published Online June 2012 (http://www.SciRP.org/journal/jasmi)
Developed New Procedure for Low Concentrations of
Hydrazine Determination by Spectrophotometry:
Hydrazine-Potassium Permanganate System
S. Ganesh1, Fahmida Khan2, M. K. Ahmed1, P. Velavendan1, N. K. Pandey1, U. Kamachi Mudali1
1Reprocessing Group, Indira Gandhi Centre for Atomic Research, Kalpakkam, India; 2Department of Chemistry, National Institute of
Technology, Raipur, India.
Received October 12th, 2011; revised November 23rd, 2011; accepted January 9th, 2012
ABSTRACT
An indirect, sensitive and accurate method for the determination of trace amounts of hydrazine is described. In this
proposed the spectrophotometric method is based on its reduction properties of hydrazine with a known concentration
of potassium permanganate to reduce the colour. The absorbance of unreduced permanganate is measured the colour
difference at different wavelengths 546 and 526 nm which show an absorption spectrum with hydrazine. Hydrazine can
be determined in the range of 100 - 700 µg/ml with correlation coefficient of 0.999 and relative standard deviation 1%.
The method is successfully applied for the determination of hydrazine in water streams in nuclear reactors/purex proc-
ess/boiler water and polluted water samples.
Keywords: Hydrazine/Potassium Permanganate; UV-Vis Spectrophotometry; Reducing Property; Water Streams;
Nuclear Reactors
1. Introduction
Hydrazine and its analogues have found various applica-
tions in many industrial, agriculture and other fields, in-
cluding the manufacture of metal films, photographic
chemicals, antioxidants, insecticides and blowing agents
for plastics. In addition, hydrazines and their derivatives
are suspected to be carcinogens. Hydrazine is widely
used as a scavenger to remove traces of oxygen in boiler
feed water system [1]. Several methods have been de-
scribed for the determination of trace amounts of hydra-
zine, including spectrophotometry, gas chromatography
[2] and ion chromatography [3]. Most of these are based
on the reaction of hydrazine with aromatic aldehydes such
as benzaldehyde [4], salicylaldehyde [5], p-dimethyl-
aminobenzaldehyde [6], pentafluorobenzaldehyde [7] and
5-nitro-2-hydroxybenzaldehyde [8] to form aldazines.
Accordingly, their determination at the micro level is of
great importance. Despite the accuracy of most of the
redox methods [9,10] used for the determination of hy-
drazines, only few are suitable for extremely dilute solu-
tions, and some require carefully controlled conditions.
Most of the spectrophotometric procedures available so
far in the literatures [11-22] are tedious and involve the
use of rare and expensive colour reagents. The present
work describes a very simple, sensitive and accurate
spectrophotometric procedure for the determination of
ppm concentrations of hydrazine salts based on reaction
with potassium permanganate and measurement of the
decolourisation of permanganate.
2. Experimental
2.1. Instrumentation
Fiber optic aided spectrophotometery with 1 cm path
length probe is used for measuring absorbance.
Metrohm make modular Ion-chromatograph equipped
with 820 IC separation center, lambda 1010 IC detector
(UV-VIS), 818 IC pump (Isocratic), 833 IC liquid han-
dling unit and 830 IC interface and a Metrohm Post
column derivatization kit were used. Sample was injected
through a 20 µL PEEK loop fitted with injector. IC-net
2.3 metrohm software was used for instrument control
and data acquisition.
Ion Chromatographic Conditions
Ion chromatograph: Metrohm modular Ion chromatog-
raphy system
Eluent concentration: 5 mM Hydrochloric acid
Eluent flow rate: 0.4 ml/min
Pressure: 13.5 MPa
Detector: Lambda 1010 UV-VIS detector.

Developed New Procedure for Low Concentrations of Hydrazine Determination by Spectrophotometry:
Hydrazine-Potassium Permanganate System
99
Analytical mode: Isocratic
Injection loop: 20 µL
Temperature: Ambient (25˚C)
Run time: 10 min
2.2. Reagents
All the reagents used were of analytical grade and double
distilled water was always used. A stock solution of hy-
drazine nitrate (obtained from Orion Chem.Pvt.Ltd.,
Mumbai) was prepared freshly by dilution to the appro-
priate volume with water. Fresh work solutions are pre-
pared daily by dilution to the appropriate volume of 3.3 ×
10–3 M aqueous solutions. The hydrazine nitrate solutions
were standardized by titration with standard potassium
iodate solutions [23,24]. The standard potassium per-
manganate solutions (Prolabo, purity = 98%) were pre-
pared and analyzed by titration with oxalic acid [25].
3. Procedure
Suitable aliquot of hydrazine and permanganate were
added into a series of 10 ml volumetric flasks and made
up to mark with distilled water. The absorbance changes
of the solution were measured from 700 to 400 nm using
fiber optic aided spectrophotometry. Blank also was run
in the same manner.
Ion-Chromatography
In order to compare the results obtained by spectropho-
tometric analysis with those of Ion chromatographic
technique, experiment were conducted for the determina-
tion of hydrazine present in aqueous phase by formation
of yellow coloured azine complex by post column deri-
vatization of hydrazine with (pDMAB) para-dimethyl-
aminobenzaldehyde and then analyzing by Ion chroma-
tographic technique using UV-Vis detector. Various hy-
drazine standards of known concentrations (1 - 10 µg/ml)
were prepared by dissolving hydrazine nitrate in Milli-
pore water. 20 µL of these solutions directly injected into
In this method determination of hydrazine, the reduction
of potassium permanganate with hydrazine has been
thoroughly studied and hence, no significant changes
were done to adapt the experimental conditions for the
determination of hydrazine. The absorption spectrum of
potassium permanganate in water shows two absorption
maxima at 546 and 526 nm (Figure 1) for which the molar
absorptivities are 2192.18 and 2279.27 L·Mol–1·cm–1
respectively. The experimental conditions for the quanti-
tative reduction of potassium permanganate with hydra-
zine are well established. Similar results were obtained
for hydrazine determination with permanganate. The
most commonly used p-dimethylaminobenzaldehyde
procedures are tedious and suffer from interferences par-
ticularly by amines, urea and semicarbazides. High purity
and fresh preparation of the colour reagent are essential.
Therefore, it was of interest to investigate the possibility
of developing a procedure for the determination of hy-
drazine covering a reasonably wide concentration range
and keeping in mind sensitivity, availability and stability
of the colour reagent as well as reducing the number of
interfering species encountered in the p. dimethylamino-
benzaldehyde methods. Standard absorption spectrum
and calibration graph for potassium permanganate are
shown in Figures 1 and 2. Beer’s law was obeyed within
the ion-chromatography column connected with UV-Vis
detector. Hydrochloric acid (5 mM) with a flow rate of
0.4 ml/min was used as mobile phase. A mixture of p-
dimethylaminobenzaldehyde (42 mM), hydrochloric acid
(0.6 M) and methanol (1%) with a flow rate of 0.6 ml/min
was used as derivatization reagent. A calibration graph
was made for the concentration range of hydrazine from
0.05 to 10 µg/ml with RSD 0.807% and correlation coef-
ficient of 0.9999. Synthetic aqueous solution containing
known concentration of hydrazine was prepared in water,
injected 20 µL aqueous sample in to Ion chromatography.
4. Result and Discussion
Figure 1. Typical absorption spectrum of KMnO4. Figure 2. Calibration graph for KMnO4 at 526 & 546 nm.

Developed New Procedure for Low Concentrations of Hydrazine Determination by Spectrophotometry:
Hydrazine-Potassium Permanganate System
100
the concentration range investigated. The calculated mo-
lar absorptivity of potassium permanganate at 546 and
526 are 2192.18 and 2279.27 L·Mol–1·cm–1 respectively.
Figure 3 shows that typical absorption spectrum of dif-
ferent concentration of hydrazine with permanganate.
Figure 4 shows that calibration graph was made for hy-
drazine concentration rang of 15 - 125 µg/ml with corre-
lation coefficient of 0.99549 and RSD 1% at different
wavelengths with potassium permanganate. The accuracy
of the present method was checked by determining hy-
drazine in various samples by both the present method
and by an independent technique, namely, Ion chroma-
tography (IC). A typical chromatogram and a calibration
curve are shown in Figures 5-6. The results obtained for
hydrazine by the proposed and by the ion IC method
agreed well within the limits of experimental error and
represented in Table 1. Typical results obtained by using
this methodology and instrumentation for the determina-
tion of hydrazine in water samples are reported in Table 2.
Figure 3. Typical absorption spectrum of hydrazine with
KMnO4.
Figure 4. Calibration graph for Hydrazine with potassium
permanganate at different wavelengths.
Figure 5. Calibration graph of hydrazine.
Figure 6. Ion Chromatogram of hydrazine standard.

Developed New Procedure for Low Concentrations of Hydrazine Determination by Spectrophotometry:
Hydrazine-Potassium Permanganate System
101
Table 1. Comparsion of two different analytical technique.
Concentration of hydrazine (µg/ml)
S.No.
Spectrophotometry Ion-chromatographic
Technique
1 6.24 6.303
2 10.80 10.01
3 25.30 24.80
4 12.28 12.10
Table 2. Typical results of hydrazine in water samples (Water
samples were collected from various located in Chhatisgarh
state, India).
S.No Absorbance Conc. of Hydrazine (μg/ml)
S1 0.814 534.054
S2 0.660 828.375
S3 0.528 1035.469
S4 0.878 406.524
S5 1.542 67.714
S6 0.971 107.534
S7 0.918 113.743
5. Conclusion
A simple, rapid and sensitive spectrophotometric proce-
dure is described for ppm determination of hydrazine
salts. It is based on reduction of potassium permanganate
and measurement of the absorbance at 546 and 526 nm.
When compared with other procedures, this method was
proved to be of comparable sensitivity and has less inter-
ference.
6. Acknowledgements
Authors are highly indebted to Shri. S.C.Chetal, Director,
IGCAR, Kalpakkam. Authors are grateful to Shri. R.
Natarajan, Director, RpG for his valuable suggestions
and encouragement during the course of this work.
REFERENCES
[1] L. F. Audrieth and B. A. Ogg, “The Chemistry of Hy-
drazines,” John Wiley & Sons, Inc., New York, 1951, p.
225.
[2] V. Vatsala, V. Bansal, D. K. Tuili, M. M. Rai, M. M. Jain,
S. P. Srivastava and A. K. Bhatnagar, “Gaschroma-
tographic Determination of Residual Hydrazine and
Morpholine in Boiler Feed Water and Steam Conden-
sates,” Chromatographia, Vol. 38, No. 7-8, 1994, p. 456.
doi:10.1007/BF02269836
[3] S. L. Larson and A. B. Strong, Technical Report, IRRP-
96-3, 1996.
[4] F. Matsui, D. L. Robertson and E. G. Lovering, “De-
termination of Hydrazine in Pharmaceuticals III: Hydra-
lazine and Isoniazid Using GLC,” Journal of Pharmaceu-
tical Sciences, Vol. 72, No. 8, 1983, pp. 948-951.
doi:10.1002/jps.2600720829
[5] P. E. Kester and N. D. Danielson, “Determination of Hy-
drazine and 1,1-Dimethylhydrazine as Salicyldehyde
Derivates by Liquid Chromatography with Electrochemi-
cal Detection,” Chromatographia, Vol. 18, No. 3, 1984,
pp. 125-128. doi:10.1007/BF02258767
[6] G. W. Watt and J. D. Chrisp, “Spectrophotometric
Method for Determination of Hydrazine,” Analytical Che-
mistry, Vol. 24, No. 12, 1952, pp. 2006-2008.
doi:10.1021/ac60072a044
[7] Y. Y. Liu, J. Schemeltz and D. Hoffman, “Chemical
Studies on Tobacco Smoke. Quantitative Analysis of Hy-
drazine in Tobacco and Cigarette Smoke,” Analytical
Chemistry, Vol. 46, No. 7, 1974, pp. 885-889.
doi:10.1021/ac60343a046
[8] G. Neurath and W. J. Luttich, “Gas Chromatographic
Separation of 5-Nitro-2-hydroxybenzal Derivatives of
Unsymmetric Hydrazines,” Journal of Chormatography
A, Vol. 34, 1968, pp. 257-258.
doi:10.1016/0021-9673(68)80047-0
[9] S. Ganesh, F. Khan, M. K. Ahmed and S. K. Pandey,
“Sequential Determination of Free Acidity and Hydrazine
in Presence of Hydrolysable Ions,” Radiochimica Acta,
Vol. 99, No. 9, 2011, pp. 587-591.
doi:10.1524/ract.2011.1836
[10] S. Ganesh, F. Khan, M. K. Ahmed and S. K. Pandey,
“Potentiometric Determination of Free Acidity in Pres-
ence of Hydrolysable Ions and Sequential Determination
of Hydrazine,” Talanta, Vo. 85, No. 2, 2011, pp. 958-963.
doi:10.1016/j.talanta.2011.05.001
[11] C. Gojon and B. Dureault, “Spectrophotometric Study of
the Reaction between Hydrazine and p-Dimethylamino-
benzaldehyde,” Journal of Nuclear Science and Technol-
ogy, Vol. 33, No. 9, 1966, pp. 731-735.
doi:10.3327/jnst.33.731
[12] R. Kaveeshwar and V. K. Gupta, “A New Spectropho-
tometric Method for the Determination of Hydrazine in
Environmental Samples,” Fresenius’ Journal of Analyti-
cal Chemistry, Vol. 344, No. 3, 1992, pp. 114-117.
doi:10.1007/BF00325125
[13] S. Amlathe and V. K. Gupta, “Spectrophotometric De-
termination of Trace Amounts of Hydrazine in Polluted
Water,” Analyst, Vol. 13, No. 9, 1988, pp. 1481-1483.
doi:10.1039/an9881301481
[14] J. Manes, P. Campillos, G. Front, H. Martre and P.
Prognon, “Extraction-Spectrophotometric Determination
of Hydrazine with 2-Hydroxy-1-naphthaldehyde,” Ana-
lyst, Vol. 112, No. 8, 1987, pp. 1183-1184.
doi:10.1039/an9871201183
[15] A. Besada, ”Analytical Use of Copper(II)-Neocuproine in
the Spectrophotometric Determination of Hydrazines,”
Analytical Letters, Vol. 21, 10, 1988, pp. 1917-1925.
doi:10.1080/00032718808066357
[16] O. S. Sire and J. Burno, Talanta, Vol. 47, 1979, p. 26.
[17] M. Roth and J. Rieder, “Spektrofluorometrische Bestim-

Developed New Procedure for Low Concentrations of Hydrazine Determination by Spectrophotometry:
Hydrazine-Potassium Permanganate System
102
mung von Hydrazinen und Deren Anwendungzur Quanti-
tativen Bestimmung von Benzylhydrazin in Biologischen
Proben,” Analytica Chimica Acta, Vol. 27, 1962, pp. 20-
26. doi:10.1016/S0003-2670(00)88442-1
[18] T. Pal, D. S. Maity and A. Ganguly, “Use of a Silver-
Gelatin Complex for the Determination of Micro-
Amounts of Hydrazine in Water,” Analyst, Vol. 111, No.
12, 1986, pp. 1413-1415. doi:10.1039/an9861101413
[19] A. Besada, “A Simple Spectrophotometric Method for the
Determination of Hydrazine Salts by Reaction with Phos-
phomolybdic Acid,” Mikrochimica Acta, Vol. 111, No.
5-6, 1985, pp. 343-346. doi:10.1007/BF01196832
[20] R. P. V. Krishna, R. R. Samba Siva and C. Rambabu,
Acta Ciencia Indica, Vol. 4, 1978, p. 13.
[21] M. George, K. S. Nagaraj and N. Balasubramanian,
“Spectrophotometric Determination of Hydrazine,” Ta-
lanta, Vol. 75, No. 1, 2008, pp. 27-31.
doi:10.1016/j.talanta.2007.09.002
[22] A. M. Haji Shabani, S. Dadfarnia and K. Dehghan, “Indi-
rect Spectrophotometric Determination of Trace Quanti-
ties of Hydrazine,” Bulletin of the Korean Chemical Soci-
ety, Vol. 25, No. 2, 2004, pp. 213-215.
doi:10.5012/bkcs.2004.25.2.213
[23] J. Mendham, R. C. Denney, J. D. Barnes and M. Thomas,
“Vogel’s Text Book of Quantitative Chemical Analysis,”
6th Edition, 2002, p. 441.
[24] S. Ganesh, F. Khan, M. K. Ahmed and S. K. Pandey,
“Sequential Determination of Uranium(IV), Free Acidity
and Hydrazine in a Single Aliquot,” Journal of Radio-
analytical and Nuclear Chemistry, Vol. 286, No. 1, 2010,
pp. 33-37. doi:10.1007/s10967-010-0663-9
[25] J. Mendham, R. C. Denney, J. D. Barnes and M. Thomas,
“Vogel’s Text book of Quantitative Chemical Analysis,”
6th Edition, 2002, p. 350.