Method:

ACRN-5

Revision:
6 Final
Revision Date: 08/15/07
Last Review: 08/15/07
Next Review: 08/15/11

Acrylonitrile
Specification Tests
Aldehydes

Page 1 of 6
Reviewed by: Karen Runge

METHOD SUMMARY
The aldehydes in the sample are reacted with 3-methyl-2-benzothiazolinone
hydrazone hydrochloride (MBTH) and then with an oxidizer to form a blue color
whose intensity is proportional to the concentration of aldehydes present. The
intensity of the blue color is measured spectrophotometrically at about 620 nm and
is converted to ppm aldehydes as acetaldehyde by means of a calibration curve
prepared from standards of known concentrations of acetaldehyde. Detection
range is 2-20 ppm. Repeatability for an individual analyst should be better than 2.5
ppm.
SAFETY
Acrylonitrile is hazardous to the health and dangerous to handle. Use acrylonitrile
in a well-ventilated hood. Review the MSDS for detailed information concerning
toxicity, first aid procedures and safety precautions.
Refer to the appropriate safety section or site manual for the necessary protective
equipment to use when handling any reagents or samples.
REFERENCES
STM C17-76 (SOHIO Test Method) "Aldehyde in Acrylonitrile"
INTERFERENCES
The inhibitor, MEHQ, usually present in acrylonitrile, will react with the oxidizing
reagent to produce a color that interferes with this procedure. The inhibitor is
Technical information contained herein is furnished without charge or obligation, and is given and accepted at recipients sole risk.
Because conditions of use may vary and are beyond our control, INEOS USA LLC makes no representation about, and is not responsible
or liable for the accuracy or reliability of data, nor for toxicological effects or Industrial Hygiene requirements associated with particular
uses of any product described herein. Nothing contained in this document shall be considered a recommendation for any use that may
infringe patent rights, or an endorsement of any particular material, equipment, service, or other item not supplied by INEOS USA LLC.
The Properties and Applications listed in this document are not specifications. They are provided as information only and in no way
modify, amend, enlarge, or create any specification or warranty, and ALL WARRANTIES, EXPRESS OR IMPLIED, INCLUDING
WITHOUT LIMITATION THE WARRANTIES OF MERCHANTABILITY AND FITNESS FOR A PARTICULAR PURPOSE, ARE
EXCLUDED.
October 2006

2006 INEOS USA LLC

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Method:

ACRN-5

Revision:
6 Final
Revision Date: 08/15/07

Acrylonitrile
Specification Tests

Last Review: 08/15/07

Aldehydes

Next Review: 08/15/11

Page 2 of 6
Reviewed by: Karen Runge

removed by washing the sample with dilute caustic or by distillation. About 65% of
the acrolein present will also react.

APPARATUS AND REAGENTS

1.

MBTH Color Reagent, (0.08 g/L)

The solution may be prepared in the following manner: Dissolve 0.08 gm of
3-methyl-2 benzothiazolinone hydrazone hydrochloride in water and dilute
to 1000 mL. Store in a brown bottle.
Note: Fresh color reagent should be used with each new calibration curve
and replaced monthly. Using color agent longer will result in bias high
results.

2.

Oxidizer Reagent
The solution may be prepared in the following manner: Add 8.33 gm ferric
chloride (FeCl3 . 6H2O) and 8.0 gm sulfamic acid to a 1000 mL volumetric
flask. Dissolve in water and dilute to volume. Store in a brown bottle.

3.

Spectrophotometer - Hitachi U2000 or equivalent (CAL-1).

4.

Quartz Cells. 1 cm pathlength

5.

Acetaldehyde - Eastman #468 or equivalent. This should be re-distilled

prior to use as a standard at least every month. This may be done using
helium as a carrier gas and an ice water solution as the coolant for the
condenser.

6.

ASTM Type II water , or equivalent. Minimum electrical resistivity 1.0

M cm at 298 K; maximum total organic carbon 50 g/L; maximum sodium
5 g/L; maximum chlorides 5 g/L; maximum total silica 3 g/L. Detailed
specifications can be obtained from ASTM: www.astm.org.

7.

Syringes, 50 L, 10 L.

8.

Balance, analytical, readability to 0.1 mg.

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Method:

ACRN-5

Revision:
6 Final
Revision Date: 08/15/07

Acrylonitrile
Specification Tests

Last Review: 08/15/07

Aldehydes

Next Review: 08/15/11

Page 3 of 6
Reviewed by: Karen Runge

9.

MEHQ, (4-methoxyphenol), CP grade.

10.

3-Methyl-2-benzothiazolinone hydrazone hydrochloride [CAS 4338-981] Fisher EK119-8688 or equivalent.

11.

Ferric chloride hexahydrate, [CAS 10025-77-1] ACS reagent grade,

Aldrich 23,648-9 or equivalent.

12.

Sulfamic Acid, [CAS 5329-14-6] 99%, Aldrich 24,277-2 or equivalent.

13.

Acrylonitrile, inhibitor free.

14.

Sodium Hydroxide, 5N. The solution may either be purchased (ACS

Certified) or be prepared in the following manner: Add 200 g of reagent
grade sodium hydroxide to ~ 600 mL of water. Dissolve and dilute to 1 liter.

15.

Volumetric flasks, 50 mL, Class A

16.

Pipettes, 1, 2, 25 mL, Class A

17.

Separatory funnel, 2L with stopper.

18.

EPA Vials: 40 mL plus teflon lined septum and screw cap.

CALIBRATION
Inhibitor Removal
Remove the inhibitor by one of the following procedures:
1.

Extraction - To a 2 liter separatory funnel, add 600 mL of acrylonitrile, 540

mL of water and 60 mL of 5N sodium hydroxide. Shake, allow solution to
separate into layers, and discard the bottom layer. Add 600 mL of water,
shake, allow solution to separate and discard the bottom layer. This
procedure may also remove some aldehydes.

2.

Distillation - Distill at least 95% of the acrylonitrile. The distilled material from
the distillation test may be used for MEHQ free acrylonitrile.
Both procedures to remove the inhibitor may also remove some aldehyde.

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Method:

ACRN-5

Acrylonitrile
Specification Tests

Revision:
6 Final
Revision Date: 08/15/07
Last Review: 08/15/07

Aldehydes

Next Review: 08/15/11

Page 4 of 6
Reviewed by: Karen Runge

Standard Preparation
Stock Solutions
1.

Weigh five 40 mL EPA vials with Teflon-lined septa and screw cap.

2.

In a hood, add 40 mL of scrubbed acrylonitrile at room temperature to each

vial.

3.

Weigh each stock solution just prior to and just after the acetaldehyde
addition. Using an ice cold 50 L syringe, add about 0, 10, 20, 30 and 40 L
of the distilled, chilled acetaldehyde below the acrylonitrile surface.

4.

From the weight added, calculate the ppm acetaldehyde added to each of the
vials (Stock Solutions):
Acetaldehyde, ppm = [W1 (W1 + W2)] x 106
Where:

W1 = weight acetaldehyde added, g.

W2 = weight acrylonitrile, g.

Standard Solutions
1.

Dilute each Stock Solution with acrylonitrile to give the desired acetaldehyde
standards by pipetting 1.0 mL of each above stock solution into another 50
mL volumetric flask containing about 40 mL scrubbed acrylonitrile, then dilute
to volume with the scrubbed acrylo, stopper tightly and mix thoroughly.

2.

Calculate ppm acetaldehyde added in each standard.

For Example: 250.3 ppm x 1 mL 50 mL = 5.01 ppm acetaldehyde added.

3.

Pipette 25 mL of MBTH solution and 1.0 mL of the standard into a 50 mL

volumetric flask. Let sit for 45 + 5 minutes.

4.

Pipette 2.0 mL of the oxidizer reagent into each flask. Dilute to volume with
water and mix thoroughly. Let sit for 20 + 1 minutes.

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Method:

ACRN-5

Revision:
6 Final
Revision Date: 08/15/07

Acrylonitrile
Specification Tests

Last Review: 08/15/07

Aldehydes

Next Review: 08/15/11

5.

Page 5 of 6
Reviewed by: Karen Runge

Scan the 4th standard from 700 to 600 nm and measure the absorbance
against the blank. Use the Trace option in the Hitachi to find the maximum
absorbance (~ 620 nm).

6.

Determine the absorbance of each standard against the 0 standard at the

maximum absorbance wavelength.

7.

After the determination of the last standard, a 1st order linear curve will be
generated by the program in the Hitachi. If the data points (+s) are in good
agreement with the instrument generated line, then store the curve. If one
or more points are in poor agreement, repeat those and replot.

8.

Enter the date, worksheet(s), initials of calibrator and any comments in the
appropriate log.

PROCEDURE
1.

Remove the inhibitor from the sample by extraction or distillation as outlined

in the calibration procedure.

2.

Pipette 1.0 mL of the sample into a 50 mL volumetric.

3.

Pipette 25 mL of MBTH solution into each flask and let sit for 455 min.

4.

Add 2 mL of the oxidizer reagent into each flask. Dilute to volume with water
and mix thoroughly.

5.

Let set for 201 min.

6.

Measure the absorbance at the maximum near 620 nm in the same manner
as the standards.

CALCULATIONS
The sample ppmw will be calculated using the stored value from the slope and
intercept in the Hitachi.
REPORT
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Method:

ACRN-5

Revision:
6 Final
Revision Date: 08/15/07
Last Review: 08/15/07

Acrylonitrile
Specification Tests
Aldehydes

Next Review: 08/15/11

Page 6 of 6
Reviewed by: Karen Runge

Report aldehyde as acetaldehyde to the nearest ppm:

aldehydes, ppmw = 4

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http://techservice.innovene.com and select Acrylonitrile in Browse by Product.