NALCO SECTION ONE QUALITY ASSURANCE TEST PROCEDURE

Revision Date: 02/26/92

Classification: Approval Required

Test No. N1825

Revision No. 01
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COLORIMETRIC DETERMINATION OF HYDRAZINE

A. SCOPE
This method is used to determine hydrazine in water and other matricies which have been shown not
to interfere with test results. Prior to use, the applicability of the method in the matrix must be
established.
B. THEORY
Hydrazine is reacted with p-dimethylaminobenzaldehyde, (p-DAB), to form the intensely yellow
colored hydrazone. The absorbance of the colored solution is measured at 456 nanometers. A
solution of p-DAB in water is used as a blank. Hydrazine levels are determined by comparison with a
standard calibration curve.
C. EQUIPMENT
1. Bausch and Lomb Spectronic 21 or equivalent.
2. Spectrophotometer cells, 1 cm.
3. Volumetric flasks, assorted sizes.
4. Volumetric pipets, assorted sizes.
5. Beakers, assorted sizes.
6. Analytical balance capable of reading to nearest 0.1 mg.
D. REAGENTS
1. Sulfuric Acid, concentrated, Reagent Grade. CAUTION: CORROSIVE. Handle under the hood.
2. Distilled water and/or D.I. water.
3. p-Dimethylaminobenzaldehyde (p-DAB), Fisher Scientific, CAT. NO. D71-25, or Kodak Laboratory
Chemicals, CAT. NO. 101 7755, or equivalent.
4. p-DAB reagent: Under a hood, carefully add 200 mls of concentrated sulfuric acid to 700 mls of
distilled water. Stir and cool to room temperature. Add 40.0 g p-DAB, mix until dissolved. Dilute
to one liter with distilled water and mix well. Store this solution in amber glass or plastic bottles.
Use polyseal caps. Under ideal storage conditions, this reagent has a shelf life of approximately
one year.
Alternatively, the p-DAB reagent may be purchased from Applied Services: HZ-1, Solution 0718.
5. Hydrazine Sulfate, ACS reagent grade, Aldrich Chemical #21,604-6, or equivalent.

NALCO SECTION ONE QUALITY ASSURANCE TEST PROCEDURE

Revision Date: 02/26/92

Test No. N1825

Revision No. 01
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Classification: Approval Required

Note: Hydrazine is a carcinogen and mutagen. Work only under hood with gloves and use
extreme caution when working with hydrazine sulfate. Report any spills to your supervisor
immediately.
E. PREPARATION OF STANDARD CALIBRATION CURVE
1. Turn on the Spectrophotometer and set the wavelength to 456 nm. Allow the instrument to warm
up at least 15 minutes.
2. 1000 ppm hydrazine stock solution. Weigh to the nearest 0.1 mg, 0.81 grams of hydrazine
sulfate into a 200 ml volumetric flask. Fill approximately 2/3 with D.I. water and mix until
dissolved. Dilute to volume and mix well. Determine the exact concentration of hydrazine as
follows:
ppm hydrazine =

(W)(MW1) x (1000 mg/g)

(MW2)(0.2 L)

where:
W
= grams of hydrazine sulfate
MW1 = molecular weight of hydrazine = 32.05
MW2 = molecular weight of hydrazine sulfate = 130.12.
When not in use, store this solution in a sealed bottle in a refrigerator. Under these conditions,
the solution has a shelf life of approximately 3 months.
3. Pipet 10 mL of the 1000 ppm hydrazine stock solution into a 1000 mL volumetric flask and dilute
to volume, and mix well. This solution contains 10 ppm hydrazine.
NOTE:
DO NOT pipet directly from the 1000 ppm flask between uses. Pour the amount needed
into a beaker and discard the excess amount.
4. Pipet 5 mL of the 10 ppm standard to 100 mL volumetric flask and dilute to volume. This solution
contains 0.5 ppm hydrazine.
5. To four separate 25 mL volumetric flasks, pipet 0, 1, 3 and 5 mLs of the 0.5 ppm solution. Pipet
10 mls of the p-DAB solution to each flask and dilute to volume with D.I. water. Mix and allow the
color to develop for 10 minutes. Measure the absorbance of each solution at 456 nm within 5
minutes of the color development. The solution which has 0 mls of hydrazine is the blank and
should be used to zero the spectrophotometer. The other solutions contain approximately 0.020,
0.060 and 0.100 ppm hydrazine, respectively. Determine the exact concentrations based on the
weight of hydrazine sulfate used.
Note: The color development time needs to be kept constant, otherwise spurious results
will be obtained.
Note: The calibration range is linear up to approximately 0.5 ppm. The calibration curve can be
modified as necessary.
6. Plot the results with the concentration on the x-axis and the absorbance on the y-axis in order to
obtain the calibration curve (see attachment). Use RS1 or a calculator capable of doing linear
regression to determine the slope factor.

NALCO SECTION ONE QUALITY ASSURANCE TEST PROCEDURE

Revision Date: 02/26/92

Test No. N1825

Revision No. 01
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Classification: Approval Required

Alternatively, the slope factor can be calculated manually by determining the slope factor for
each pair of X,Y values. The slope factor is calculated as:
m=Y/X
Where
Y = absorbance
X = concentration
m = slope factor
The average of the slope factors is the slope factor to be used in subsequent calculations.
NOTE: Once a calibration curve has been developed for a particular spectrophotometer, a
one point calibration check can be employed. To do this, determine the absorbance of the
mid range standard, (zero the instrument with the 0 ppm standard as described above). If the
absorbance is within 10% of the existing value for that standard, the existing calibration curve
may be used. However, if the absorbance is outside this limit, a fresh 1000 ppm hydrazine
stock solution must be made and a new calibration curve must be constructed from the fresh
hydrazine solution. Also, if a different spectrophotometer is used or if conditions of the
existing spectrophotometer change, (ie. a new lamp), a new calibration curve must be
constructed.
F. PROCEDURE
1. Weigh to the nearest 0.1 mg the amount of sample stated in the addendum or section III an
appropriately sized volumetric flask. Dilute to volume with D.I. water and mix well.
2. Pipet 10 ml of the above solution into a 25 ml volumetric flask. Add via pipet 10 ml of p-DAB
reagent, dilute to volume and mix well. Allow the color to develop for exactly 10 minutes.
3. Zero the instrument with a blank solution as described in the standardization section. Measure
the absorbance of the sample at 456 nm within 5 minutes of complete color development.
G. CALCULATION & DATA REPORTING
ppm hydrazine = (A)(D)
(S)(W)
Where:
A = absorbance
S = slope factor
D = volume dilution factor
W = sample weight in grams
H. PERFORMANCE DATA
1. Calibration Range: 0 - 0.100 ppm hydrazine.
2. Precision: The standard deviation (s) is 0.37 ppm hydrazine as determined by one operator on
one sample of Eliminox, (average hydrazine concentration of 11.8 ppm), with a total of nine
replicates and a total of eight degrees of freedom. The precision of the test method is three times

NALCO SECTION ONE QUALITY ASSURANCE TEST PROCEDURE

Revision Date: 02/26/92
Classification: Approval Required

Test No. N1825

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the standard deviation and therefore estimated to be plus or minus 1.11. The method has a
percent relative standard deviation (%RSD) of 3.2%.
3. Elapsed Time: 30 minutes.
4. Operator Time: 15 minutes.
Note: An additional 90 minutes is necessary to prepare the calibration curve.
5. Issue Date: 2/14/92
I.

REFERENCES
1. ASTM method D 1385 - 86.
2. Corporate Quality Assistance, Naperville, W. J. Swanson.
3. Reviewers: D. R. Maynard, S. M. Stole.

NOTE: This methodology was developed by Nalco Chemical Company and is to be considered its
property. It is, to the best of our knowledge, valid. However, Nalco makes no claim that it is
applicable under all conditions of use. Nalco assumes no liability connected with the use or misuse of
this methodology. Release of this methodology to parties outside Nalco Chemical Company does not
give them permission to subsequently release this information to others.

NALCO SECTION ONE QUALITY ASSURANCE TEST PROCEDURE

Revision Date: 02/26/92
Classification: Approval Required

Test No. N1825

Revision No. 01
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NALCO SECTION ONE QUALITY ASSURANCE TEST PROCEDURE

Revision Date: 02/26/92
Classification: Approval Required

****INTERNAL USE ONLY****

Restricted Appendix of Nalco Quality Assurance Test Methods
1. Author: W. J. Swanson
2. Test Method Reviewer: D. R. Maynard
3. Research Laboratory Notebook: 3140
4. Performance Data Specific to a Particular Product:
5. Details Restricted From Customers and Suppliers:
6. Product or Raw material Validated in Method:

Test No. N1825

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