Developed New Procedure for Low Concentrations of Hydrazine Determination by Spectrophotometry: Hydrazine-Potassium Permanganate System

doi:10.4236/jasmi.2012.22018

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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.

Email: [email protected]

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

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.

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