Method 8196

VOLATILE ACIDS (0 to 2800 as mg/L HOAc) For digestor sludges

Esterification Method*

1. Enter the stored 2. Press: 96 ENTER 3. Pipet 0.5 mL of 4. Filter or centrifuge

program number for The display will show deionized water into a 25 mL of the sample.
Volatile Acids as acetic mg/L, HOAc and the dry 25-mL sample cell Note: Centrifugation is
acid (HOAc). ZERO icon. (the blank). faster than filtration.
Press: PRGM Note: If high levels of Note: Use a Class A or
dissolved solids or mineral TenSette Pipet.
The display will show:
acids are present, distill as Note: Adjust the pH of
PRGM ? described in the Hach stored samples before
Note: For most accurate Distillation Apparatus analysis.
results, perform a Reagent manual.
Blank Correction using
deionized water (see
Section 1).

5. Pipet 0.5 mL of the 6. Pipet 1.5 mL of 7. Pipet 0.2 mL of 8. Place both cells into
filtrate or supernatant ethylene glycol into each 19.2 N Sulfuric Acid a boiling water bath.
into another dry 25-mL sample cell. Swirl Standard Solution into Note: Samples may be
sample cell (the to mix. each cell. Swirl to mix. boiled in a 600-mL beaker.
prepared sample).
Note: Use a Class A or
TenSette Pipet.

* Adapted from The Analyst, 87, 949 (1962)

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VOLATILE ACIDS, continued

9. Press: TIMER 10. When the timer 11. Pipet 0.5 mL of 12. Pipet 2.0 mL of
ENTER beeps, cool solutions to Hydroxylamine 4.5 N Sodium
A 3-minute reaction 25 °C (until cells feel Hydrochloride Solution Hydroxide Standard
period will begin. cool) with running tap into each cell. Swirl Solution into each cell.
water. Then dry the cells to mix. Cap and invert to mix.
with a soft cloth.

13. Add 10 mL of Ferric 14. Add 10 mL of 15. The display will 16. When the timer
Chloride Sulfuric Acid deionized water to each show: 3:00 TIMER 2 beeps, immediately
Solution to each cell. cell. Cap and invert Press: ENTER place the blank into the
Cap and invert to mix. cell holder. Tightly
A 3-minute reaction
to mix. cover the sample cell
period will begin.
with the instrument cap.
Note: After this three-
minute reaction period,
proceed immediately
through steps 16-19.

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VOLATILE ACIDS, continued

17. Press: ZERO 18. Place the prepared 19. Press: READ
The cursor will move to sample into the cell The cursor will move to
the right, then the holder. Tightly cover the the right, then the result
display will show: sample cell with the in mg/L Volatile Acids
instrument cap. as acetic acid will
0 mg/L HOAc
be displayed.
Note: If Reagent Blank
Correction is on, the
display may flash “limit”.
See Section 1.

Sampling and Storage

Collect samples in plastic or glass bottles. Analyze samples as
soon as possible after collection. Samples can be stored up to 24
hours by cooling to 4 °C (39 °F) or below. Warm to room
temperature before testing.

Accuracy Check
Standard Additions Method
a) Snap the neck off a Volatile Acids PourRite Ampule
Standard Solution, 62,500 mg/L as acetic acid.

b) Use the TenSette Pipet to add 0.1, 0.2, and 0.3 mL of

standard, respectively, to three 25-mL graduated mixing
cylinders, each containing 25 mL of filtered sample.
Stopper. Shake well to mix.
c) Remove a 0.5 mL aliquot of sample from each cylinder;
add to three dry sample cells. Analyze all three samples
along with the original test sample beginning with Step 5
of the procedure. The volatile acid concentration should
increase 250 mg/L volatile acids as acetic acid for each 0.1
mL of standard added.

d) If these increases do not occur, see Standard Additions in

Section 1.

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VOLATILE ACIDS, continued
Standard Solution Method
Prepare a 500 mg/L volatile acid standard by using the TenSette
Pipet to add 0.8 mL of a Volatile Acids PourRite Ampule
Standard Solution (62,500 mg/L as acetic acid) to a 100-mL
volumetric flask. Dilute to volume with deionized water. Stopper
and invert to mix.

Method Performance
Precision
In a single laboratory, using a standard solution of 500 mg/L
volatile acids as acetic acid and two representative lots of reagent
with the instrument, a single operator obtained a standard
deviation of ±8 mg/L.

Estimated Detection Limit

The estimated detection limit for program 96 is 17 mg/L HOAc.
For more information on the estimated detection limit, see
Section 1.

Summary of Method
The volatile acids test is designed specifically for the
determination of volatile acids in digestor sludges. The method is
based on esterification of the carboxylic acids present and
determination of the esters by the ferric hydroxamate reaction.
All volatile organic acids present are reported as their equivalent
mg/L acetic acid.

REQUIRED REAGENTS
Cat. No.
Volatile Acids Reagent Set (90 tests)............................................................................ 22447-00
Includes: (1) 2039-53, (2) 2042-53, (1) 818-42, (1) 2040-53, (1) 2038-32
Quantity Required
Description Per Test Units Cat. No.
Ethylene Glycol ......................................................... 3 mL.................1000 mL............ 2039-53
Ferric Chloride-Sulfuric Acid Solution .................... 20 mL................1000 mL............ 2042-53
Hydroxylamine Hydrochloride Solution, 100 g/L..... 1 mL...................100 mL............ 818-42
Sodium Hydroxide Standard Solution, 4.5 N ........... 4 mL.................1000 mL............ 2040-53
Sulfuric Acid Standard Solution, 19.2 N ................. 0.4 mL .................100 mL............ 2038-32
Water, deionized...................................................... 20.5 mL .......................4 L............ 272-56

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VOLATILE ACIDS, continued
REQUIRED APPARATUS
Quantity Required
Description Per Test Units Cat. No.
Cots, finger ....................................................................2 .........................2/pkg ..........14647-02
Cylinder, graduated, 10 mL...........................................1 ...........................each .......... 508-38
Filter Paper, folded, 12.5 cm .........................................1 .....................100/pkg .......... 1894-57
Flask, erlenmeyer, 50 mL..............................................1 ...........................each .......... 505-41
Funnel, poly, 65 mm......................................................1 ...........................each .......... 1083-67
Hot Plate, circular, 3.5-inch diameter............................1 ...........................each ..........12067-01
Pipet Filler, safety bulb .................................................1 ...........................each ..........14651-00
Pipet, serological, 2 mL.................................................2 ...........................each .......... 532-36
Pipet, volumetric, Class A, 0.5 mL ...............................3 ...........................each ..........14515-34
Pipet, volumetric, Class A, 10.00 mL ...........................3 ...........................each ..........14515-38
Sample Cell, 10-20-25 mL, w/cap ................................2 .........................6/pkg ..........24019-06
Water Bath and Rack.....................................................1 ...........................each .......... 1955-55

OPTIONAL REAGENTS
Volatile Acids Standard Solution, PourRite ampule,
62,500 mg/L as acetic acid, 10 mL ....................................................16/pkg ..........14270-10

OPTIONAL APPARATUS
Ampule Breaker, PourRite ..........................................................................each ..........24846-00
Beaker, 600 mL ...........................................................................................each ..............500-52
Bottle, wash, 500 mL ..................................................................................each ..............620-11
Centrifuge, laboratory, 115 Vac...................................................................each ..........26765-00
Centrifuge, laboratory, 230 Vac...................................................................each ..........26765-02
Centrifuge Tubes, 15 mL.........................................................................10/pkg ..........22787-39
Centrifuge Tube Caps..............................................................................20/pkg ..........25852-20
Cylinder, graduated, mixing, 25 mL ...........................................................each .......... 1896-40
Cylinder, graduated, plastic, 250 mL ..........................................................each .......... 1081-46
Distillation Apparatus .................................................................................each ..........22653-00
Distillation Heater and Support Apparatus .................................................each ..........22744-00
Flask, volumetric, Class A, 100 mL............................................................each ..........14574-42
Pipet, TenSette, 0.1 to 1.0 mL .....................................................................each ..........19700-01
Pipet Tips, for 19700-01 TenSette Pipet .................................................50/pkg ..........21856-96
Pipet Tips, for 19700-01 TenSette Pipet .............................................1000/pkg ..........21856-28
Pipet, TenSette, 1.0 to 10.0 mL ...................................................................each ..........19700-10
Pipet Tips, for 19700-10..........................................................................50/pkg ..........21997-96

For Technical Assistance, Price and Ordering

In the U.S.A.—Call 800-227-4224
Outside the U.S.A.—Contact the Hach office or distributor serving you.

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