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Chlorine, Hypochlorite DOC316.53.

01219

Iodometric Method1 Method 10100


50–150 g/L or 5–15% as Cl2 (HR) Digital Titrator
Scope and application: For concentrated liquid bleach (sodium hypochlorite, soda bleach) used as a disinfectant
in drinking water or wastewater treatment
1 Adapted from ASTM method D2022.

Test preparation

Before starting
The optional TitraStir Titration Stand can hold the Digital Titrator and stir the sample.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.
Dispose of reacted solutions according to local, state and federal regulations. Refer to the Safety Data Sheets for disposal
information for unused reagents. Refer to the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.

Items to collect
Description Quantity

HR Hypochlorite (Bleach) Reagent Set, 5–15% as Cl2 1


®
Pipet, TenSette , 0.1–1.0 mL 1
®
Pipet tips, for TenSette Pipet, 0.1–1.0 mL 1
Digital Titrator 1
Delivery tube for Digital Titrator 1
Erlenmeyer flask, 125 mL 1
Water, deionized varies

Refer to Consumables and replacement items on page 4 for order information.

Sample collection
• Collect samples in clean glass bottles.
• Analyze the samples as soon as possible for best results.
• Prevent exposure of the sample to heat or light.
• If prompt analysis is not possible, keep the samples in a cool and dark location.

1
Test procedure

1. Insert a clean delivery 2. Hold the Digital Titrator 3. Fill a clean 125‑mL 4. Add the contents of one
tube into the 2.26 N Sodium with the cartridge tip up. Erlenmeyer flask to Potassium Iodide Powder
Thiosulfate Titrant Solution Turn the delivery knob to approximately the 75‑mL Pillow.
cartridge. Attach the eject air and a few drops of mark with deionized water
cartridge to the Digital titrant. Reset the counter to or tap water.
Titrator. zero and clean the tip. Note: The level of residual
chlorine in tap water will not
cause interference with the
test.

5. Swirl to mix. 6. Add the contents of one 7. Swirl to mix. 8. Use a TenSette pipet
Acid Reagent Powder with a new tip to add 0.2 mL
Pillow. of bleach sample to the
flask. Make sure to add the
sample below the solution
level.

9. Swirl to mix. 10. Put the end of the 11. Add one dropperful of 12. Swirl to mix.
The color of the solution delivery tube fully into the Starch Indicator Solution. The color of the solution
changes to dark brown. solution. Swirl the flask. changes to dark blue or
Turn the knob on the Digital green.
Titrator to add titrant to the
solution. Continue to swirl
the flask. Add titrant until the
color changes to pale
yellow.

2 Chlorine, Hypochlorite, Iodometric Titration—Digital Titrator (150 g/L)


13. Put the end of the 14. Calculate the
delivery tube fully into the concentration.
solution. Swirl the flask. Digits used × 0.5 = g/L
Turn the knob on the Digital chlorine.
Titrator to add titrant to the
g/L chlorine × 0.10 = %
solution. Continue to swirl
chlorine by volume ("trade
the flask. Add titrant until the
percent").
color changes from dark
blue to colorless. Record the
number of digits on the
counter.

Interferences
The test determines the hypochlorite ion (ClO–) and also the chlorite ion (ClO2 –).
However, the chlorite level in commercial bleach is not important (typically less than
0.2%). Other interferences are unlikely.
Interfering Interference level
substance
Caustic agent A high level of caustic can cause low results. To remove the interferences:

1. After the Acid Reagent Powder Pillow is added, examine the pH of the solution with pH Paper. The
pH must be less than 3.
2. If the pH is not less than 3, add more Acid Reagent, one pillow at a time, until the pH of the
solution is below 3.

Temperature For most accurate results, the temperature of the dilution water must be less than 20 °C (68 °F).

Accuracy check
Standard solution method
Use the standard solution method to validate the test procedure, reagents, apparatus and
technique.
Note: The strength of the Sodium Thiosulfate Standard Solution is validated with Potassium Iodide-
Iodate Standard Solution. It is recommended to validate the reagent accuracy with each new lot of
reagents.
Items to collect:
• Potassium Iodide-Iodate Standard Solution, 0.0125 N
• Potassium Iodide Powder Pillows
• Acid Reagent Powder Pillows
• 125-mL Erlenmeyer flask
• 50-mL volumetric pipet, Class A and pipet filler safety bulb

1. Use a Class A pipet to add 50.00 mL of the standard solution to a 125-mL


Erlenmeyer flask.
2. Add the contents of one Potassium Iodide Powder Pillow to the flask. Swirl to mix.
3. Add the contents of three Acid Reagent Powder Pillows to the flask. Swirl until all of
the powder is dissolved.

Chlorine, Hypochlorite, Iodometric Titration—Digital Titrator (150 g/L) 3


4. Titrate the prepared standard solution to the endpoint color. The correct number of
digits for this titration is 217–250 digits.
5. Compare the actual number of digits that were used in the titration to the correct
number of digits. If much more or less titrant was used, there can be a problem with
user technique, reagents or apparatus.

Precision
When a commercial bleach sample of 91.2 g/L (9.12 %) Cl2 is tested, one analyst caused
a standard deviation of ±1.5 g/L (±1.5 %) Cl2.
Summary of method
In acidic conditions, hypochlorite reacts with iodide to form an equivalent quantity of
triiodide (I3–). The released I3– is titrated with sodium thiosulfate to a colorless end point.
The quantity of sodium thiosulfate required is directly related to the hypochlorite
concentration in the sample.
Consumables and replacement items
Required reagents

Description Quantity/Test Unit Item no.

HR Hypochlorite (Bleach) Reagent Set, 5–15% as Cl2 — each 2687000


Acid Reagent Powder Pillows 1 pillow 100/pkg 104299
Potassium Iodide Powder Pillows 1 pillow 50/pkg 2059996
Sodium Thiosulfate Titration Cartridge, 2.26 N varies each 2686901
Starch Indicator Solution 1 mL 100 mL MDB 34932

Required apparatus

Description Quantity/test Unit Item no.

Clippers for plastic pillows 1 each 96800


Digital Titrator 1 each 1690001
Delivery tube for Digital Titrator, J-hook tip 1 5/pkg 1720500
Flask, Erlenmeyer, 125 mL 1 each 50543
®
Pipet, TenSette , 0.1–1.0 mL 1 each 1970001
®
Pipet tips, for TenSette Pipet, 0.1–1.0 mL 1 50/pkg 2185696

Recommended standards

Description Unit Item no.

Potassium Iodide-Iodate Standard Solution, 0.0125 N 1L 1400153

Optional reagents and apparatus

Description Unit Item no.

Paper, pH, 0–14 pH range 100/pkg 2601300


Bottle, sample, glass, 4 oz, with cap 3/pkg 2161303
Pipet, volumetric, Class A, 50 mL each 1451541
Pipet filler, safety bulb each 1465100
Stir bar, octagonal each 2095352
TitraStir® Titration Stand, 115 VAC each 1940000

4 Chlorine, Hypochlorite, Iodometric Titration—Digital Titrator (150 g/L)


Optional reagents and apparatus (continued)
Description Unit Item no.

TitraStir® Titration Stand, 230 VAC each 1940010


Delivery tube for Digital Titrator, 90-degree bend for use with TitraStir Titration Stand 5/pkg 4157800

Chlorine, Hypochlorite, Iodometric Titration—Digital Titrator (150 g/L) 5


FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: HACH COMPANY
In the U.S.A. – Call toll-free 800-227-4224 WORLD HEADQUARTERS
Outside the U.S.A. – Contact the HACH office or distributor serving you. Telephone: (970) 669-3050
On the Worldwide Web – www.hach.com; E-mail – techhelp@hach.com FAX: (970) 669-2932

© Hach Company/Hach Lange GmbH, 2007–2015. All rights reserved. 04/2015, Edition 8
Hardness, Calcium DOC316.53.01175

Titration Method with EDTA Method 8204


10–4000 mg/L as CaCO3 Digital Titrator
Scope and application: For water, wastewater and seawater.

Test preparation

Before starting
Magnesium is not included in the results but must be in the sample for a sharp endpoint. If the sample does not contain
magnesium, add 1 to 2 drops of Magnesium Standard Solution, 10-g/L as CaCO3, to the sample before the test is started.
As an alternative to the CalVer 2 Calcium Indicator Powder Pillow, use a 0.1-g scoop of CalVer 2 Calcium Indicator Powder.
The optional TitraStir Titration Stand can hold the Digital Titrator and stir the sample.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.
Dispose of reacted solutions according to local, state and federal regulations. Refer to the Safety Data Sheets for disposal
information for unused reagents. Refer to the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.

Items to collect
Description Quantity

CalVer 2 Calcium Indicator Powder Pillow 1 pillow


Potassium Hydroxide Standard Solution, 8 N 1 or 2 mL
EDTA Titration Cartridge (refer to Sample volumes and digit multipliers on page 3) 1
Digital Titrator 1
Delivery tube for Digital Titrator 1
Graduated cylinder (use a size that is applicable to the selected sample volume) 1
Erlenmeyer flask, 250 mL 1
Water, deionized varies

Refer to Consumables and replacement items on page 5 for order information.

Sample collection
• Collect samples in clean glass or plastic bottles that have been cleaned with a
detergent and rinsed with 1:1 nitric acid and deionized water.
• To preserve samples for later analysis, adjust the sample pH to 2 or less with
concentrated nitric acid (about 2 mL per liter). No acid addition is necessary if the
sample is tested immediately.
• Keep the preserved samples at room temperature for a maximum of 6 months.
• Before analysis, adjust the pH to 7 with Potassium Hydroxide Standard Solution.
• Correct the test result for the dilution caused by the volume additions.

1
Test procedure

1. Select a sample volume 2. Insert a clean delivery 3. Hold the Digital Titrator 4. Use a graduated cylinder
and titration cartridge from tube into the digital titration with the cartridge tip up. or a pipet1 to measure the
Table 1 on page 3. cartridge. Attach the Turn the delivery knob to sample volume from Table 1
cartridge to the Digital eject air and a few drops of on page 3.
Titrator. titrant. Reset the counter to
zero and clean the tip.

5. Pour the sample into a 6. If the sample volume is 7. Swirl to mix. 8. If the sample volume is
clean, 250-mL Erlenmeyer 100 mL, add 2 mL of 8 N less than 100 mL, dilute to
flask. Potassium Hydroxide approximately 100 mL with
Standard Solution. If the deionized water.
sample volume is 50 mL or
less, add 1 mL of 8 N
Potassium Hydroxide
Standard Solution.

1 Titration accuracy has a direct relation to the accuracy of the sample volume measurement. For smaller
volumes, it is recommended to use a pipet to increase accuracy.

2 Hardness, Calcium, Titration with EDTA—Digital Titrator (4000 mg/L)


9. Add the contents of one 10. Swirl to mix. 11. Put the end of the 12. Use the multiplier in
CalVer 2 Calcium Indicator delivery tube fully into the Table 1 on page 3 to
Powder Pillow. solution. Swirl the flask. calculate the concentration.
Turn the knob on the Digital Digits used × digit multiplier
Titrator to add titrant to the = mg/L (or Gdh) Ca as
solution. Continue to swirl CaCO3.
the flask. Add titrant until the
color changes from red to
pure blue. Record the
number of digits on the
counter.

Sample volumes and digit multipliers


Select a range in Table 1 or Table 2 as applicable, then read across the table row to find
the applicable information for this test. Use the digit multiplier to calculate the
concentration in the test procedure.
Example: A 50-mL sample was titrated with 0.800 M EDTA titration cartridge and the
counter showed 250 digits at the endpoint. The concentration is 250 digits × 2.0 =
500 mg/L as CaCO3 (or with the 0.714 M EDTA titration cartridge, 250 x 0.1 = 25 mg/L
Gdh).
Table 1 Sample volumes and digit multipliers—mg/L
Range (mg/L as CaCO3) Sample volume (mL) Titration cartridge Digit multiplier
10–40 100 0.0800 0.1
40–160 25 0.0800 0.4
100–400 100 0.800 1.0
200–800 50 0.800 2.0
500–2000 20 0.800 5.0
1000–4000 10 0.800 10.0

Table 2 Sample volumes and digit multipliers—Gdh


Range (Gdh as CaCO3) Sample volume (mL) Titration cartridge Digit multiplier
1–4 100 0.1428 0.01
4–16 25 0.1428 0.04
10–40 50 0.714 0.1
25–100 20 0.714 0.25
> 100 10 0.714 0.5

Hardness, Calcium, Titration with EDTA—Digital Titrator (4000 mg/L) 3


Conversions units
To change the units or chemical form of the test result, multiply the test result by the
factor in Table 3.
Table 3 Conversions
mg/L Ca as CaCO3 to... multiply by... Example
mg/L as Ca 0.40 1000 mg/L as CaCO3 x 0.40 = 400 mg/L Ca
German degrees hardness (Gdh) 0.056 1000 mg/L as CaCO3 × 0.056 = 56 Gdh
Grains per gallon (gpg) 0.058 1000 mg/L as CaCO3 x 0.058 = 58 gpg

Interferences

WARNING
Chemical hazard. Potassium cyanide is toxic. Make sure to add potassium cyanide to the
sample after the Potassium Hydroxide has been added. Keep cyanide solutions at more
than pH 11 to prevent exposure to hydrogen cyanide gas. Dispose of reacted solutions
according to local, state and federal regulations.

An interfering substance can prevent the color change at the titration endpoint. A smaller
sample volume can often dilute the interfering substance to a level at which the
substance does not interfere. Table 4 shows the substances that can interfere with this
test.
Table 4 Interferences
Interfering substance Interference level
Acidity 10,000 mg/L acidity as CaCO3 does not interfere.
Alkalinity 10,000 mg/L alkalinity as CaCO3 does not interfere.
Aluminum Causes a slow endpoint. The sample can contain a maximum of 200 mg/L aluminum if sufficient
time is given for the color change.
Barium Barium is titrated at the same time with calcium and interferes with this test, but it is unusual to find
high levels of Barium in natural waters.
Chloride The chloride level in seawater does not interfere. Solutions that are saturated with chloride do not
show a sharp endpoint.
Cobalt Interferes directly and is included in the test result. Add 0.5 grams of potassium cyanide after the
Potassium Hydroxide during the test procedure to remove the interference from a maximum of
20 mg/L cobalt.
Copper Interferes at 0.1 mg/L copper. Add 0.5 grams of potassium cyanide after the Potassium Hydroxide
during the test procedure to remove the interference from a maximum of 100 mg/L copper.
Iron More than 8 mg/L iron causes an orange-red to green endpoint. Results are accurate to 20 mg/L
iron with this endpoint.
Magnesium The formation of magnesium hydroxide at the high test pH prevents interference from 200 mg/L
magnesium. Samples with more than 200 mg/L magnesium do not give a distinct endpoint.
Manganese Interferes at more than 5 mg/L manganese.
Nickel Interferes at 0.5 mg/L nickel. Add 0.5 grams of potassium cyanide after the Potassium Hydroxide
during the test procedure to remove the interference from a maximum of 200 mg/L nickel.
Orthophosphate Forms calcium phosphate and causes a slow endpoint. If sufficient time is given to let the calcium
phosphate dissolve during the titration, the orthophosphate will not interfere with the test.
Polyphosphates Interfere directly and are included in the test result.
Strontium Strontium is titrated at the same time with calcium and interferes with this test, but it is unusual to
find high levels of Strontium in natural waters.

4 Hardness, Calcium, Titration with EDTA—Digital Titrator (4000 mg/L)


Table 4 Interferences (continued)
Interfering substance Interference level
Temperature Samples at 20 °C (68 °F) or colder should be titrated slowly near the endpoint to give sufficient
time for the color change.
Zinc Interferes at 5 mg/L zinc. Add 0.5 grams of potassium cyanide after the Potassium Hydroxide
during the test procedure to remove the interference from a maximum of 100 mg/L zinc.
Highly buffered samples Can prevent the correct pH adjustment (of the sample) by the reagents. Sample pretreatment may
or extreme sample pH be necessary.

Accuracy check
Standard additions method (sample spike)
Use the standard additions method to validate the test procedure, reagents, apparatus,
technique and to find if there is an interference in the sample.
Items to collect:
• Hardness Voluette Ampule Standard Solution, 10,000 mg/L as CaCO3
• Ampule Breaker
• Pipet, TenSette, 0.1–1.0 mL and pipet tips

1. Use the test procedure to measure the concentration of the sample.


2. Use a TenSette pipet to add 0.1 mL of the standard solution to the titrated sample.
3. Titrate the spiked sample to the endpoint. Record the number of digits on the counter.
4. Add one more 0.1-mL addition of the standard solution to the titrated sample.
5. Titrate the spiked sample to the endpoint. Record the number of digits on the counter.
6. Add one more 0.1-mL addition of the standard solution to the titrated sample.
7. Titrate the spiked sample to the endpoint. Record the number of digits on the counter.
8. Compare the actual result to the correct result. The correct result for this titration is 10
digits of 0.800 M titration cartridge or 100 digits of 0.0800 titration cartridge (11 digits
of 0.714 M or 56 digits of 0.1428 M titrant) for each 0.1-mL addition of the standard
solution. If much more or less titrant was used, there can be a problem with user
technique, reagents, apparatus or an interference.

Summary of method
Potassium hydroxide is added to the sample to adjust the pH to 12 to 13, which causes a
magnesium hydroxide precipitate to form. CalVer 2 Calcium Indicator is then added,
which reacts with calcium to give a red color. The EDTA titrant is added, which reacts
with all the free calcium. After the EDTA has reacted with all of the free calcium ions, the
EDTA removes the calcium from the indicator. The indicator color then changes from red
to blue.
Consumables and replacement items
Required reagents

Description Quantity/Test Unit Item no.

Reagent set, 10–160 mg/L range (approximately 100 tests): — each 2447200
CalVer 2 Calcium Indicator Powder Pillows 1 pillow 100/pkg 85299
Potassium Hydroxide Standard Solution, 8 N 1–2 mL 100 mL MDB 28232H
EDTA Titration Cartridge, 0.0800 M varies each 1436401
Reagent set, 100–4000 mg/L range (approximately 100 tests): — each 2447500
CalVer 2 Calcium Indicator Powder Pillows 1 pillow 100/pkg 85299
Potassium Hydroxide Standard Solution, 8 N 1–2 mL 100 mL MDB 28232H

Hardness, Calcium, Titration with EDTA—Digital Titrator (4000 mg/L) 5


Consumables and replacement items (continued)
Description Quantity/Test Unit Item no.

EDTA Titration Cartridge, 0.800 M varies each 1439901


Reagent set, 1–16 G.d.h. range (approximately 100 tests): — each 2447300
CalVer 2 Calcium Indicator Powder Pillows 1 pillow 100/pkg 85299
Potassium Hydroxide Standard Solution, 8 N 1–2 mL 100 mL MDB 28232H
EDTA Titration Cartridge, 0.1428 M varies each 1496001
Reagent set, 10–100 G.d.h. range (approximately 100 tests): — each 2447400
CalVer 2 Calcium Indicator Powder Pillows 1 pillow 100/pkg 85299
Potassium Hydroxide Standard Solution, 8 N 1–2 mL 100 mL MDB 28232H
EDTA Titration Cartridge, 0.714 M varies each 1495901

Required apparatus

Description Quantity/test Unit Item no.

Graduated cylinders—Select one or more for the sample volume:


Cylinder, graduated, 5 mL 1 each 50837
Cylinder, graduated, 10 mL 1 each 50838
Cylinder, graduated, 25 mL 1 each 50840
Cylinder, graduated, 50 mL 1 each 50841
Cylinder, graduated, 100 mL 1 each 50842
Digital Titrator 1 each 1690001
Delivery tube for Digital Titrator, J-hook tip 1 5/pkg 1720500
Flask, Erlenmeyer, 250 mL 1 each 50546
®
Pipet, TenSette , 0.1–1.0 mL 1 each 1970001
®
Pipet tips, for TenSette Pipet, 0.1–1.0 mL 1 50/pkg 2185696

Recommended standards

Description Unit Item no.

Calcium Hardness Standard Solution, 10,000-mg/L as CaCO3, 10-mL Voluette ampule 16/pkg 218710
Hardness Quality Control Standard, high range 500 mL 2833349
Hardness Quality Control Standard, low range 500 mL 2833449

Optional reagents and apparatus

Description Unit Item no.


®
Ampule Breaker, 10-mL Voluette Ampules each 2196800
CalVer® 2 Calcium Indicator Powder 113 g 28114H
CDTA Magnesium Salt Powder Pillow 100/pkg 1408099
Delivery tube for Digital Titrator, 90-degree bend for use with TitraStir Titration Stand 5/pkg 4157800
Magnesium Standard Solution, 10 g/L as CaCO3 29 mL 102233
Nitric Acid, concentrated 500 mL 15249
Nitric Acid Solution, 1:1 500 mL 254049

6 Hardness, Calcium, Titration with EDTA—Digital Titrator (4000 mg/L)


Optional reagents and apparatus (continued)
Description Unit Item no.

Pipet filler, safety bulb each 1465100


Pipet, volumetric, Class A, 10 mL each 1451538
Pipet, volumetric Class A, 20 mL each 1451520
Pipet, volumetric, Class A, 25 mL each 1451540
Potassium Cyanide, ACS 100 g 76714
Potassium Hydroxide, 8 N 500 mL 28249
Sampling bottle with cap, low density polyethylene, 500-mL 12/pkg 2087079
Bottle, sampling, with cap, low density polyethylene, 250 mL 12/pkg 2087076
Spoon, measuring, 0.1 g each 51100
Stir bar, octagonal each 2095352
TitraStir® Titration Stand, 115 VAC each 1940000
TitraStir® Titration Stand, 230 VAC each 1940010

Hardness, Calcium, Titration with EDTA—Digital Titrator (4000 mg/L) 7


FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: HACH COMPANY
In the U.S.A. – Call toll-free 800-227-4224 WORLD HEADQUARTERS
Outside the U.S.A. – Contact the HACH office or distributor serving you. Telephone: (970) 669-3050
On the Worldwide Web – www.hach.com; E-mail – techhelp@hach.com FAX: (970) 669-2932

© Hach Company/Hach Lange GmbH, 2007–2015. All rights reserved. 04/2015, Edition 8
Hardness, Total DOC316.53.01176

Titration Method with EDTA Method 8213


10–4000 mg/L as CaCO3 Digital Titrator
Scope and application: For water, wastewater and seawater.

Test preparation

Before starting
As an alternative to the ManVer 2 Hardness Indicator Powder Pillow, use 4 drops of Hardness 2 Indicator Solution or a 0.1-g
scoop of ManVer 2 Hardness Indicator Powder.
The optional TitraStir Titration Stand can hold the Digital Titrator and stir the sample.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.
Dispose of reacted solutions according to local, state and federal regulations. Refer to the Safety Data Sheets for disposal
information for unused reagents. Refer to the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.

Items to collect
Description Quantity

ManVer 2 Hardness Indicator Powder Pillow 1


Hardness 1 Buffer Solution 2 mL
EDTA Titration Cartridge (refer to Sample volumes and digit multipliers on page 3) 1
Digital Titrator 1
Delivery tube for Digital Titrator 1
Graduated cylinder (use a size that is applicable to the selected sample volume) 1
Erlenmeyer flask, 250 mL 1
Water, deionized varies

Refer to Consumables and replacement items on page 6 for order information.

Sample collection and storage


• Collect samples in clean glass or plastic bottles that have been cleaned with a
detergent and rinsed with 1:1 nitric acid and deionized water.
• To preserve samples for later analysis, adjust the sample pH to 2 or less with
concentrated nitric acid (about 2 mL per liter). No acid addition is necessary if the
sample is tested immediately.
• Keep the preserved samples at or below 6 °C (43 °F) for a maximum of 7 days.
• Before analysis, adjust the pH to 7 with sodium hydroxide solution.
• Correct the test result for the dilution caused by the volume additions.

1
Test procedure

1. Select a sample volume 2. Insert a clean delivery 3. Hold the Digital Titrator 4. Use a graduated cylinder
and titration cartridge from tube into the digital titration with the cartridge tip up. or a pipet1 to measure the
Table 1 on page 3. cartridge. Attach the Turn the delivery knob to sample volume from Table 1
cartridge to the Digital eject air and a few drops of on page 3.
Titrator. titrant. Reset the counter to
zero and clean the tip.

5. Pour the sample into a 6. If the sample volume is 7. Add 2 mL of Hardness 1 8. Swirl to mix.
clean, 250-mL Erlenmeyer less than 100 mL, dilute to Buffer Solution.
flask. approximately 100 mL with
deionized water.

9. Add the contents of one 10. Swirl to mix. 11. Put the end of the 12. Use the multiplier in
ManVer 2 Hardness delivery tube fully into the Table 1 on page 3 to
Indicator Powder Pillow. solution. Swirl the flask. calculate the concentration.
Turn the knob on the Digital Digits used × digit multiplier
Titrator to add titrant to the = mg/L (or Gdh) total
solution. Continue to swirl hardness as CaCO3.
the flask. Add titrant until the
color changes from red to
pure blue. Record the
number of digits on the
counter.

1 Titration accuracy has a direct relation to the accuracy of the sample volume measurement. For smaller
volumes, it is recommended to use a pipet to increase accuracy.

2 Hardness, Total, Titration with EDTA—Digital Titrator (4000 mg/L)


Sample volumes and digit multipliers
Select a range in Table 1 or Table 2 as applicable, then read across the table row to find
the applicable information for this test. Use the digit multiplier to calculate the
concentration in the test procedure.
Example: A 50-mL sample was titrated with 0.800 M EDTA titration cartridge and the
counter showed 250 digits at the endpoint. The concentration is 250 digits × 2.0 =
500 mg/L as CaCO3 (or with the 0.714 M EDTA titration cartridge, 250 x 0.1 = 25 mg/L
Gdh).
Table 1 Sample volumes and digit multipliers—mg/L
Range (mg/L as CaCO3) Sample volume (mL) Titration cartridge Digit multiplier
10–40 100 0.0800 0.1
40–160 25 0.0800 0.4
100–400 100 0.800 1.0
200–800 50 0.800 2.0
500–2000 20 0.800 5.0
1000–4000 10 0.800 10.0

Table 2 Sample volumes and digit multipliers—Gdh


Range (Gdh as CaCO3) Sample volume (mL) Titration cartridge Digit multiplier
1–4 100 0.1428 0.01
4–16 25 0.1428 0.04
10–40 50 0.714 0.1
25–100 20 0.714 0.25
> 100 10 0.714 0.5

Conversions units
To change the units or chemical form of the test result, multiply the test result by the
factor in Table 3.
Table 3 Conversions
mg/L Total Hardness as CaCO3 to... multiply by... Example
mg/L Total Hardness as Ca 0.40 1000 mg/L as CaCO3 x 0.40 = 400 mg/L Ca
German degrees hardness (Gdh) 0.056 1000 mg/L as CaCO3 × 0.056 = 56 Gdh
Grains per gallon (gpg) 0.058 1000 mg/L as CaCO3 x 0.058 = 58 gpg
mg/L Total Hardness as Mg 0.243 1000 mg/L as CaCO3 x 0.243 = 243 mg/L Mg

Hardness relationships
• mg/L Mg Hardness as CaCO3 = mg/L Total Hardness as CaCO3 – mg/L Ca
Hardness as CaCO3
• mg/L MgCO3= mg/L Mg Hardness as CaCO3 × 0.842
• mg/L Mg = mg/L MgCO3 × 0.29

Hardness, Total, Titration with EDTA—Digital Titrator (4000 mg/L) 3


Interferences

WARNING
Chemical hazard. Potassium cyanide is toxic. Make sure to add potassium cyanide to the
sample after the Hardness 1 Buffer Solution has been added. Keep cyanide solutions at
more than pH 11 to prevent exposure to hydrogen cyanide gas. Dispose of reacted
solutions according to local, state and federal regulations.

An interfering substance can prevent the color change at the titration endpoint. A smaller
sample volume can often dilute the interfering substance to a level at which the
substance does not interfere. Table 4 shows the substances that can interfere with this
test.
Table 4 Interferences
Interfering substance Interference level
Acidity 10,000 mg/L acidity as CaCO3 does not interfere.
Alkalinity 10,000 mg/L alkalinity as CaCO3 does not interfere.
Aluminum Interferes when the sample contains more than 0.20 mg/L aluminum. Add 0.5 grams of potassium
cyanide after the Hardness 1 Buffer Solution during the test procedure to remove the interference
from a maximum of 1 mg/L aluminum.
As an alternative, add a CDTA powder pillow to remove the interference. Refer to Use CDTA to
remove metal interferences on page 5.
Barium Barium is titrated at the same time with calcium and interferes with this test, but it is unusual to find
high levels of Barium in natural waters.
Chloride The chloride level in seawater does not interfere. Solutions that are saturated with chloride do not
show a sharp endpoint.
Cobalt Interferes directly and is included in the test result. Add 0.5 grams of potassium cyanide after the
Hardness 1 Buffer Solution during the test procedure to remove the interference from a maximum of
20 mg/L cobalt.
As an alternative, add a CDTA powder pillow to remove the interference. Refer to Use CDTA to
remove metal interferences on page 5.
Copper Interferes when the sample contains 0.1 mg/L copper. Add 0.5 grams of potassium cyanide after the
Hardness 1 Buffer Solution during the test procedure to remove the interference from a maximum of
100 mg/L copper.
As an alternative, add a CDTA powder pillow to remove the interference. Refer to Use CDTA to
remove metal interferences on page 5.
Iron More than 8 mg/L iron causes an orange-red to green endpoint. Results are accurate to 20 mg/L
iron with this endpoint.
Manganese Interferes when the sample contains more than 5 mg/L manganese.
Nickel Interferes when the sample contains 0.5 mg/L nickel. Add 0.5 grams of potassium cyanide after the
Hardness 1 Buffer Solution during the test procedure to remove the interference from a maximum of
200 mg/L nickel.
As an alternative, add a CDTA powder pillow to remove the interference. Refer to Use CDTA to
remove metal interferences on page 5.
Orthophosphate Forms calcium phosphate and causes a slow endpoint. If sufficient time is given to let the calcium
phosphate dissolve during the titration, the orthophosphate will not interfere with the test.
Polyphosphates Interferes at all levels.
Polyvalent metal ions Although less common than calcium and magnesium, other polyvalent metal ions are titrated with
the calcium and magnesium and are included in the results.
Strontium Strontium is titrated at the same time with calcium and interferes with this test, but it is unusual to
find high levels of Strontium in natural waters.

4 Hardness, Total, Titration with EDTA—Digital Titrator (4000 mg/L)


Table 4 Interferences (continued)
Interfering substance Interference level
Zinc Interferes at 5 mg/L zinc. Add 0.5 grams of potassium cyanide after the Hardness 1 Buffer Solution
during the test procedure to remove the interference from a maximum of 100 mg/L zinc.
As an alternative, add a CDTA powder pillow to remove the interference. Refer to Use CDTA to
remove metal interferences on page 5.
Highly buffered Can prevent the correct pH adjustment (of the sample) by the reagents. Sample pretreatment may
samples or extreme be necessary. Before analysis, adjust the pH to 7.
sample pH

Use CDTA to remove metal interferences


Add one CDTA Magnesium Salt Powder Pillow to remove the interference from metals at
or below the levels shown in Table 5. If more than one metal is in the sample at or more
than the concentration in Table 5, add an additional CDTA Magnesium Salt Powder
Pillow.
The results given with CDTA Magnesium Salt include the hardness from these metals. If
the concentration of each metal is known, a correction can be made to get the hardness
from calcium and magnesium only. The hardness value from different metal ions is shown
in Table 6.
Metal hardness = (mg/L of metal in the sample) x (hardness equivalence factor)
Calcium and magnesium hardness = (total hardness) – (metal hardness)
Table 5 Interference level with one CDTA pillow
Interfering substance Interference level
Aluminum 50 mg/L
Cobalt 200 mg/L
Copper 100 mg/L
Iron 100 mg/L
Manganese 200 mg/L
Nickel 400 mg/L
Zinc 300 mg/L

Table 6 Hardness equivalence factors (mg/L as CaCO3)


Interfering substance Hardness equivalence factor
Aluminum 3.710
Barium 0.729
Cobalt 1.698
Copper 1.575
Iron 1.792
Manganese 1.822
Nickel 1.705
Strontium 1.142
Zinc 1.531

Accuracy check
Standard additions method (sample spike)
Use the standard additions method to validate the test procedure, reagents, apparatus,
technique and to find if there is an interference in the sample.

Hardness, Total, Titration with EDTA—Digital Titrator (4000 mg/L) 5


Items to collect:
• Hardness Voluette Ampule Standard Solution, 10,000 mg/L as CaCO3
• Ampule Breaker
• Pipet, TenSette, 0.1–1.0 mL and pipet tips

1. Use the test procedure to measure the concentration of the sample.


2. Use a TenSette pipet to add 0.1 mL of the standard solution to the titrated sample.
3. Titrate the spiked sample to the endpoint. Record the number of digits on the counter.
4. Add one more 0.1-mL addition of the standard solution to the titrated sample.
5. Titrate the spiked sample to the endpoint. Record the number of digits on the counter.
6. Add one more 0.1-mL addition of the standard solution to the titrated sample.
7. Titrate the spiked sample to the endpoint. Record the number of digits on the counter.
8. Compare the actual result to the correct result. The correct result for this titration is 10
digits of 0.800 M titration cartridge or 100 digits of 0.0800 titration cartridge (11 digits
of 0.714 M or 56 digits of 0.1428 M titrant) for each 0.1-mL addition of the standard
solution. If much more or less titrant was used, there can be a problem with user
technique, reagents, apparatus or an interference.

Standard solution method


Use the standard solution method to validate the test procedure, reagents, apparatus and
technique.
• Calcium Chloride Standard Solution, 1000-mg/L as CaCO3
• Hardness 1 Buffer Solution
• ManVer 2 Hardness Indicator Powder Pillow
• 20-mL volumetric pipet, Class A and pipet filler safety bulb
• 250-mL Erlenmeyer flask
• Deionized water

1. Use a pipet to add 20.0 mL of the calcium chloride standard solution to a 250-mL
Erlenmeyer flask.
2. Dilute the standard solution to approximately 100 mL with deionized water.
3. Add one Hardness 1 Buffer Solution and one ManVer 2 Hardness Indicator Powder
Pillow. Swirl to mix.
4. Titrate the prepared standard solution to the endpoint. Calculate the concentration of
the standard solution. The correct result is 1000 mg/L or 55.9 Gdh as CaCO3.
5. Compare the actual result to the correct result. If much more or less titrant was used,
there can be a problem with user technique, reagents or apparatus.

Summary of method
A buffer solution (an organic amine and one of its salts) is added to the sample to adjust
the pH to 10.1. An organic dye, calmagite, is then added as the indicator for the test. The
organic dye reacts with calcium and magnesium ions to give a red-colored complex. The
EDTA (ethylenediaminetetraacetic acid) titrant is added, which reacts with all of the free
calcium and magnesium ions in the sample. After the EDTA has reacted with all of the
free magnesium ions, the EDTA removes the magnesium ions from the indicator. The
indicator color then changes from red to blue.
Consumables and replacement items
Required reagents

Description Quantity/Test Unit Item no.

Reagent set, 10–160 mg/L range (approximately 100 tests): — each 2448000
ManVer 2 Hardness Indicator Powder Pillows 1 pillow 100/pkg 85199

6 Hardness, Total, Titration with EDTA—Digital Titrator (4000 mg/L)


Consumables and replacement items (continued)
Description Quantity/Test Unit Item no.

Buffer Solution, Hardness 1 1 mL 100 mL MDB 42432


EDTA Titration Cartridge, 0.0800 M varies each 1436401
Reagent set, 100–4000 mg/L range (approximately 100 tests): — each 2448100
ManVer 2 Hardness Indicator Powder Pillows 1 pillow 100/pkg 85199
Buffer Solution, Hardness 1 1 mL 100 mL MDB 42432
EDTA Titration Cartridge, 0.800 M varies each 1439901
Reagent set, 1–16 G.d.h. range (approximately 100 tests): — each 2447800
ManVer 2 Hardness Indicator Powder Pillows 1 pillow 100/pkg 85199
Buffer Solution, Hardness 1 1 mL 100 mL MDB 42432
EDTA Titration Cartridge, 0.1428 M varies each 1496001
Reagent set, 10–100+ G.d.h. range (approximately 100 tests): — each 2447900
ManVer 2 Hardness Indicator Powder Pillows 1 pillow 100/pkg 85199
Buffer Solution, Hardness 1 1 mL 100 mL MDB 42432
EDTA Titration Cartridge, 0.714 M varies each 1495901

Required apparatus

Description Quantity/test Unit Item no.

Graduated cylinders—Select one or more for the sample volume:


Cylinder, graduated, 5 mL 1 each 50837
Cylinder, graduated, 10 mL 1 each 50838
Cylinder, graduated, 25 mL 1 each 50840
Cylinder, graduated, 50 mL 1 each 50841
Cylinder, graduated, 100 mL 1 each 50842
Digital Titrator 1 each 1690001
Delivery tube for Digital Titrator, J-hook tip 1 5/pkg 1720500
Flask, Erlenmeyer, 250 mL 1 each 50546
®
Pipet, TenSette , 0.1–1.0 mL 1 each 1970001
®
Pipet tips, for TenSette Pipet, 0.1–1.0 mL 1 50/pkg 2185696

Recommended standards

Description Unit Item no.

Calcium Chloride Standard Solution, 1000-mg/L as CaCO3 1L 12153


Hardness Standard Solution, 10,000-mg/L as CaCO3, 10-mL Voluette ampule 16/pkg 218710
Hardness Quality Control Standard, high range 500 mL 2833349
Hardness Quality Control Standard, low range 500 mL 2833449

Hardness, Total, Titration with EDTA—Digital Titrator (4000 mg/L) 7


Optional reagents and apparatus

Description Unit Item no.


®
Ampule Breaker, 10-mL Voluette Ampules each 2196800
CDTA Magnesium Salt Powder Pillow 100/pkg 1408099
Delivery tube for Digital Titrator, 90-degree bend for use with TitraStir Titration Stand 5/pkg 4157800
ManVer Hardness Indicator Solution 100 mL 42532
ManVer 2 Hardness Indicator Powder 113 g 28014
Nitric Acid, concentrated 500 mL 15249
Nitric Acid Solution, 1:1 500 mL 254049
Pipet filler, safety bulb each 1465100
Pipet, volumetric, Class A, 10 mL each 1451538
Pipet, volumetric Class A, 20 mL each 1451520
Pipet, volumetric, Class A, 25 mL each 1451540
Potassium Cyanide, ACS 100 g 76714
Bottle, sampling, with cap, low density polyethylene, 250 mL 12/pkg 2087076
Spoon, measuring, 0.1 g each 51100
Sodium Hydroxide Solution, 5 N 50 mL 245026
Spoon, measuring, 0.1 g each 51100
Spoon, measuring, 0.5 g each 90700
Stir bar, octagonal each 2095352
TitraStir® Titration Stand, 115 VAC each 1940000
TitraStir® Titration Stand, 230 VAC each 1940010

FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: HACH COMPANY


In the U.S.A. – Call toll-free 800-227-4224 WORLD HEADQUARTERS
Outside the U.S.A. – Contact the HACH office or distributor serving you. Telephone: (970) 669-3050
On the Worldwide Web – www.hach.com; E-mail – techhelp@hach.com FAX: (970) 669-2932

© Hach Company/Hach Lange GmbH, 2007–2015. All rights reserved. 04/2015, Edition 8
Hardness, Total, Sequential DOC316.53.01230

Titration Method with EDTA Method 8329


10–4000 mg/L as CaCO3 Digital Titrator
Scope and application: For water, wastewater and seawater.

Test preparation

Before starting
The first titration gives the results for calcium hardness and the second titration gives total hardness. The difference between
the values is the magnesium hardness level. All the concentration results are in mg/L as CaCO3. Refer to Conversions units
on page 5 for conversions to other units.
As an alternative to the CalVer 2 Calcium Indicator Powder Pillow, use a 0.1-g scoop of CalVer 2 Calcium Indicator Powder.
As an alternative to the ManVer 2 Hardness Indicator Powder Pillow, use 4 drops of Hardness 2 Indicator Solution or a 0.1-g
scoop of ManVer 2 Hardness Indicator Powder.
The optional TitraStir Titration Stand can hold the Digital Titrator and stir the sample.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.
Dispose of reacted solutions according to local, state and federal regulations. Refer to the Safety Data Sheets for disposal
information for unused reagents. Refer to the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.

Items to collect
Description Quantity

CalVer 2 Calcium Indicator Powder Pillow 1


Potassium Hydroxide Standard Solution, 8 N 1 mL
Hardness 1 Buffer Solution 1 mL
ManVer 2 Hardness Indicator Powder Pillow 1
Sulfuric Acid Standard Solution, 5.25 N 1 mL
EDTA Titration Cartridge (refer to Sample volumes and digit multipliers on page 4) 1
Digital Titrator 1
Delivery tube for Digital Titrator 1
Graduated cylinder or pipet (use a size that is applicable to the selected sample volume) 1
Erlenmeyer flask, 250-mL 1
Water, deionized varies

Refer to Consumables and replacement items on page 7 for order information.

Sample collection and storage


• Collect samples in clean glass or plastic bottles that have been cleaned with a
detergent and rinsed with 1:1 nitric acid and deionized water.
• To preserve samples for later analysis, adjust the sample pH to 2 or less with
concentrated nitric acid (about 2 mL per liter). No acid addition is necessary if the
sample is tested immediately.
• Keep the preserved samples at or below 6 °C (43 °F) for a maximum of 6 months.

1
• Before analysis, adjust the pH to 7 with Potassium Hydroxide Standard Solution.
• Correct the test result for the dilution caused by the volume additions.

Test procedure

1. Select a sample volume 2. Insert a clean delivery 3. Hold the Digital Titrator 4. Use a graduated cylinder
and titration cartridge from tube into the digital titration with the cartridge tip up. or a pipet1 to measure the
Table 1 on page 4. cartridge. Attach the Turn the delivery knob to sample volume from Table 1
cartridge to the Digital eject air and a few drops of on page 4.
Titrator. titrant. Reset the counter to
zero and clean the tip.

5. Pour the sample into a 6. If the sample volume is 7. Swirl to mix. 8. If the sample volume is
clean, 250-mL Erlenmeyer 100 mL, add 2 mL of 8 N less than 100 mL, dilute to
flask. Potassium Hydroxide approximately 100 mL with
Standard Solution. If the deionized water.
sample volume is 50 mL or
less, add 1 mL of 8 N
Potassium Hydroxide
Standard Solution.

1 Titration accuracy has a direct relation to the accuracy of the sample volume measurement. For smaller
volumes, it is recommended to use a pipet to increase accuracy.

2 Hardness, Total, Sequential, Titration with EDTA—Digital Titrator (4000 mg/L)


9. Add the contents of one 10. Swirl to mix. 11. Put the end of the 12. Use the multiplier in
CalVer 2 Calcium Indicator delivery tube fully into the Table 1 on page 4 to
Powder Pillow. solution. Swirl the flask. calculate the concentration.
Turn the knob on the Digital Digits used × digit multiplier
Titrator to add titrant to the = mg/L (or Gdh) Calcium as
solution. Continue to swirl CaCO3.
the flask. Add titrant until the
color changes from red to
pure blue. Record the
number of digits on the
counter.

13. Add 1 mL of 5.25 14. Add more acid, 1 drop 15. Add 2 mL of Hardness 16. Swirl to mix.
Sulfuric Acid Standard at a time until the color 1 Buffer Solution.
Solution. changes from pure blue to
purple, and then to red.
Swirl the flask to make sure
that all the precipitated
magnesium hydroxide has
dissolved.

Hardness, Total, Sequential, Titration with EDTA—Digital Titrator (4000 mg/L) 3


17. Add the contents of one 18. Swirl to mix. 19. Put the end of the 20. Use the multiplier in
ManVer 2 Hardness delivery tube fully into the Table 1 on page 4 to
Indicator Powder Pillow. solution. Swirl the flask. calculate the concentration.
Turn the knob on the Digital Digits used × digit multiplier
Titrator to add titrant to the = mg/L (or Gdh) total
solution. Continue to swirl hardness2 as CaCO3.
the flask. Add titrant until the
color changes from red to
pure blue. Record the
number of digits on the
counter.

Sample volumes and digit multipliers


Select a range in Table 1 or Table 2 as applicable, then read across the table row to find
the applicable information for this test. Use the digit multiplier to calculate the
concentration in the test procedure.
Example: A 50-mL sample was titrated with 0.800 M EDTA titration cartridge and the
counter showed 250 digits at the endpoint. The concentration is 250 digits × 2.0 =
500 mg/L as CaCO3 (or with the 0.714 M EDTA titration cartridge, 250 x 0.1 = 25 mg/L
Gdh).
Table 1 Sample volumes and digit multipliers—mg/L
Range (mg/L as CaCO3) Sample volume (mL) Titration cartridge Digit multiplier
10–40 100 0.0800 0.1
40–160 25 0.0800 0.4
100–400 100 0.800 1.0
200–800 50 0.800 2.0
500–2000 20 0.800 5.0
1000–4000 10 0.800 10.0

Table 2 Sample volumes and digit multipliers—Gdh


Range (Gdh as CaCO3) Sample volume (mL) Titration cartridge Digit multiplier
1–4 100 0.1428 0.01
4–16 25 0.1428 0.04
10–40 50 0.714 0.1
25–100 20 0.714 0.25
> 100 10 0.714 0.5

2 Total digits = digits from step 11 + digits from step 19.

4 Hardness, Total, Sequential, Titration with EDTA—Digital Titrator (4000 mg/L)


Conversions units
To change the units or chemical form of the test result, multiply the test result by the
factor in Table 3.
Table 3 Conversions
mg/L Total Hardness as CaCO3 to... multiply by... Example
mg/L Total Hardness as Ca 0.40 1000 mg/L as CaCO3 x 0.40 = 400 mg/L Ca
German degrees hardness (Gdh) 0.056 1000 mg/L as CaCO3 × 0.056 = 56 Gdh
Grains per gallon (gpg) 0.058 1000 mg/L as CaCO3 x 0.058 = 58 gpg
mg/L Total Hardness as Mg 0.243 1000 mg/L as CaCO3 x 0.243 = 243 mg/L Mg

Hardness relationships
• mg/L Mg Hardness as CaCO3 = mg/L Total Hardness as CaCO3 – mg/L Ca
Hardness as CaCO3
• mg/L MgCO3= mg/L Mg Hardness as CaCO3 × 0.842
• mg/L Mg = mg/L MgCO3 × 0.29

Interferences

WARNING
Chemical hazard. Do not use potassium cyanide to remove interferences because it will
form deadly hydrogen cyanide gas when the sulfuric acid solution is added.

An interfering substance can prevent the color change at the titration endpoint. A smaller
sample volume can often dilute the interfering substance to a level at which the
substance does not interfere. Table 4 shows the substances that can interfere with this
test.
Table 4 Interferences
Interfering substance Interference level
Acidity 10,000 mg/L acidity as CaCO3 does not interfere.
Alkalinity 10,000 mg/L alkalinity as CaCO3 does not interfere.
Aluminum Interferes at all levels. Add a DTA powder pillow to remove the interference. Refer to Use CDTA to
remove metal interferences on page 6.
Barium Barium is titrated at the same time with calcium and interferes with this test, but it is unusual to find
high levels of Barium in natural waters.
Chloride The chloride level in seawater does not interfere. Solutions that are saturated with chloride do not
show a sharp endpoint.
Cobalt Interferes at all levels. Add a DTA powder pillow to remove the interference. Refer to Use CDTA to
remove metal interferences on page 6.
Copper Interferes when the sample contains 0.10 and 0.20 mg/L copper.
Heavy metals Some transition and heavy metals have an effect in the indicator and prevent the color change at the
end point.
Iron Iron does not interfere until 15 mg/L. More than this level will cause a red-orange to green endpoint,
which is sharp and usable with a maximum of 30 mg/L iron. Change a 0.0800 M CDTA or 0.800 M
CDTA titration cartridge for the 0.0800 M EDTA or 0.800 M EDTA titration cartridges, respectively, if
iron interference is possible. For results in Gdh, divide the mg/L result by 17.9.
Manganese Interferes when the sample contains more than 20 mg/L manganese. Add a 0.1-gram scoop of
hydroxylamine hydrochloride to increase this level to 200 mg/L manganese.
Nickel Interferes at all levels. Add a DTA powder pillow to remove the interference. Refer to Use CDTA to
remove metal interferences on page 6.

Hardness, Total, Sequential, Titration with EDTA—Digital Titrator (4000 mg/L) 5


Table 4 Interferences (continued)
Interfering substance Interference level
Orthophosphate Forms calcium phosphate and causes a slow endpoint. If sufficient time is given to let the calcium
phosphate dissolve during the titration, the orthophosphate will not interfere with the test.
Polyphosphates Interferes at all levels.
Polyvalent metal ions Although less common than calcium and magnesium, other polyvalent metal ions are titrated with
the calcium and magnesium and are included in the results.
Strontium Strontium is titrated at the same time with calcium and interferes with this test, but it is unusual to
find high levels of Strontium in natural waters.
Zinc Interferes at all levels. Add a DTA powder pillow to remove the interference. Refer to Use CDTA to
remove metal interferences on page 6.

Use CDTA to remove metal interferences


Add one CDTA Magnesium Salt Powder Pillow to remove the interference from metals at
or below the levels shown in Table 5. If more than one metal is in the sample at or more
than the concentration in Table 5, add an additional CDTA Magnesium Salt Powder
Pillow.
The results given with CDTA Magnesium Salt include the hardness from these metals. If
the concentration of each metal is known, a correction can be made to get the hardness
from calcium and magnesium only. The hardness value from different metal ions is shown
in Table 6.
Metal hardness = (mg/L of metal in the sample) x (hardness equivalence factor)
Calcium and magnesium hardness = (total hardness) – (metal hardness)
Table 5 Interference level with one CDTA pillow
Interfering substance Interference level
Aluminum 50 mg/L
Cobalt 200 mg/L
Copper 100 mg/L
Iron 100 mg/L
Manganese 200 mg/L
Nickel 400 mg/L
Zinc 300 mg/L

Table 6 Hardness equivalence factors (mg/L as CaCO3)


Interfering substance Hardness equivalence factor
Aluminum 3.710
Barium 0.729
Cobalt 1.698
Copper 1.575
Iron 1.792
Manganese 1.822
Nickel 1.705
Strontium 1.142
Zinc 1.531

6 Hardness, Total, Sequential, Titration with EDTA—Digital Titrator (4000 mg/L)


Summary of method
This test procedure is a combination of the calcium and total hardness procedures. Refer
to each method for more information.
Consumables and replacement items
Required reagents

Description Quantity/Test Unit Item no.

Calcium and Total Hardness Reagent Set (approximately 100 tests): — each 2272100
Buffer Solution, Hardness 1 1 mL 100 mL MDB 42432
CalVer 2 Calcium Indicator Powder Pillows 1 100/pkg 94799
ManVer 2 Hardness Indicator Powder Pillows 1 100/pkg 85199
(x2) Potassium Hydroxide Standard Solution, 8 N 1 mL 100 mL MDB 28232H
EDTA Titration Cartridge, 0.0800 M varies each 1436401
EDTA Titration Cartridge, 0.800 M varies each 1439901
EDTA Titration Cartridge, 0.1428 M varies each 1496001
EDTA Titration Cartridge, 0.714 M varies each 1495901

Required apparatus

Description Quantity/test Unit Item no.

Graduated cylinders—Select one or more for the sample volume:


Cylinder, graduated, 5 mL 1 each 50837
Cylinder, graduated, 10 mL 1 each 50838
Cylinder, graduated, 25 mL 1 each 50840
Cylinder, graduated, 50 mL 1 each 50841
Cylinder, graduated, 100 mL 1 each 50842
Digital Titrator 1 each 1690001
Delivery tube for Digital Titrator, J-hook tip 1 5/pkg 1720500
Flask, Erlenmeyer, 250 mL 1 each 50546
®
Pipet, TenSette , 0.1–1.0 mL 1 each 1970001
®
Pipet tips, for TenSette Pipet, 0.1–1.0 mL 1 50/pkg 2185696

Recommended standards

Description Unit Item no.

Calcium Chloride Standard Solution, 1000-mg/L as CaCO3 1L 12153


Hardness Standard Solution, 10,000-mg/L as CaCO3, 10-mL Voluette ampule 16/pkg 218710
Hardness Quality Control Standard, high range 500 mL 2833349
Hardness Quality Control Standard, low range 500 mL 2833449

Optional reagents and apparatus- DT hardness total sequential

Description Unit Item no.


®
Ampule Breaker, 10-mL Voluette Ampules each 2196800
CDTA Magnesium Salt Powder Pillow 100/pkg 1408099

Hardness, Total, Sequential, Titration with EDTA—Digital Titrator (4000 mg/L) 7


Optional reagents and apparatus- DT hardness total sequential (continued)
Description Unit Item no.

CDTA cartridge for Digital Titrator, 0.08 M each 1440201


CDTA cartridge for Digital Titrator, 0.80 M each 1440301
Delivery tube for Digital Titrator, 90-degree bend for use with TitraStir Titration Stand 5/pkg 4157800
Hydroxylamine Hydrochloride 113 g 24614
ManVer Hardness Indicator Solution 100 mL 42532
ManVer 2 Hardness Indicator Powder 113 g 28014
Nitric Acid, concentrated 500 mL 15249
Nitric Acid Solution, 1:1 500 mL 254049
Pipet filler, safety bulb each 1465100
Pipet, volumetric, Class A, 10 mL each 1451538
Pipet, volumetric Class A, 20 mL each 1451520
Pipet, volumetric, Class A, 25 mL each 1451540
Bottle, sampling, with cap, low density polyethylene, 250 mL 12/pkg 2087076
Spoon, measuring, 0.1 g each 51100
Sodium Hydroxide Solution, 5 N 50 mL 245026
Spoon, measuring, 0.1 g each 51100
Spoon, measuring, 0.5 g each 90700
Stir bar, octagonal each 2095352
TitraStir® Titration Stand, 115 VAC each 1940000
TitraStir® Titration Stand, 230 VAC each 1940010

FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: HACH COMPANY


In the U.S.A. – Call toll-free 800-227-4224 WORLD HEADQUARTERS
Outside the U.S.A. – Contact the HACH office or distributor serving you. Telephone: (970) 669-3050
On the Worldwide Web – www.hach.com; E-mail – techhelp@hach.com FAX: (970) 669-2932

© Hach Company/Hach Lange GmbH, 2007–2015. All rights reserved. 04/2015, Edition 8
Iron DOC316.53.01177

TitraVer Titration Method Method 8214


10–1000 mg/L as Fe Digital Titrator
Scope and application: For water, wastewater and seawater.

Test preparation

Before starting
The optional TitraStir Titration Stand can hold the Digital Titrator and stir the sample.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.
Dispose of reacted solutions according to local, state and federal regulations. Refer to the Safety Data Sheets for disposal
information for unused reagents. Refer to the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.

Items to collect
Description Quantity

Citrate Buffer Powder Pillow 1


Sodium Periodate Powder Pillow 1
Sulfosalicylic Acid Powder Pillow 1
TitraVer Standard Solution Titration Cartridge (refer to Sample volumes and digit multipliers
1
on page 3)
Digital Titrator 1
Delivery tube for Digital Titrator 1
Graduated cylinder (use a size that is applicable to the selected sample volume) 1
Erlenmeyer flask, 125 mL 1
Water, deionized varies

Refer to Consumables and replacement items on page 4 for order information.

Sample collection
• Collect samples in clean glass or plastic bottles.

1
Test procedure

1. Select a sample volume 2. Insert a clean delivery 3. Hold the Digital Titrator 4. Use a graduated cylinder
and titration cartridge from tube into the digital titration with the cartridge tip up. or a pipet1 to measure the
Table 1 on page 3. cartridge. Attach the Turn the delivery knob to sample volume from Table 1
cartridge to the Digital eject air and a few drops of on page 3.
Titrator. titrant. Reset the counter to
zero and clean the tip.

5. Pour the sample into a 6. If the sample volume is 7. Add the contents of one 8. Swirl to mix.
clean, 125-mL Erlenmeyer less than 50 mL, dilute to Citrate Buffer Powder
flask. approximately 50 mL with Pillow.
deionized water.

9. Add the contents of one 10. Swirl to mix. 11. Add the contents of one 12. Swirl to mix.
Sodium Periodate Powder The color of the solution Sulfosalicylic Acid Powder The color of the solution
Pillow. changes to yellow if iron is Pillow. changes to red if iron is in
in the sample. the sample.

1 Titration accuracy has a direct relation to the accuracy of the sample volume measurement. For smaller
volumes, it is recommended to use a pipet to increase accuracy.

2 Iron, TitraVer Titration—Digital Titrator (1000 mg/L)


13. Put the end of the 14. Use the multiplier in
delivery tube fully into the Table 1 on page 3 to
solution. Swirl the flask. calculate the concentration.
Turn the knob on the Digital Digits used × digit multiplier
Titrator to add titrant to the = mg/L Fe.
solution. Continue to swirl
the flask. Add titrant until the
color changes from red to
yellow. Record the number
of digits on the counter.

Sample volumes and digit multipliers


Select a range in Table 1, then read across the table row to find the applicable
information for this test. Use the digit multiplier to calculate the concentration in the test
procedure.
Example: A 50-mL sample was titrated with 0.0716 M TitraVer Standard Solution
Titration Cartridge and the counter showed 250 digits at the endpoint. The concentration
is 250 digits x 0.1 = 25 mg/L Fe.
Table 1 Sample volumes and digit multipliers
Range (mg/L as Fe) Sample volume (mL) Titration cartridge Digit multiplier
10–40 50 0.0716 0.1
25–100 20 0.0716 0.25
100–400 50 0.716 1.0
250–1000 20 0.716 2.5

Accuracy check
Standard additions method (sample spike)
Use the standard additions method to validate the test procedure, reagents, apparatus,
technique and to find if there is an interference in the sample.
Items to collect:
• Iron Standard Solution, 1000 mg/L as Fe
• Pipet, TenSette, 0.1–1.0 mL and pipet tips

1. Use the test procedure to measure the concentration of the sample.


2. Use a TenSette pipet to add 0.5 mL of the standard solution to the titrated sample.
3. Titrate the spiked sample to the endpoint. Record the number of digits on the counter.
4. Add one more 0.5-mL addition of the standard solution to the titrated sample.
5. Titrate the spiked sample to the endpoint. Record the number of digits on the counter.
6. Add one more 0.5-mL addition of the standard solution to the titrated sample.
7. Titrate the spiked sample to the endpoint. Record the number of digits on the counter.
8. Compare the actual result to the correct result. The correct result for this titration is 10
digits of 0.0716 M TitraVer Standard Solution Titration Cartridge (100 digits of the

Iron, TitraVer Titration—Digital Titrator (1000 mg/L) 3


0.0716 M titration cartridge) for each 0.5-mL addition of the standard solution. If much
more or less titrant was used, there can be a problem with user technique, reagents,
apparatus or an interference.

Summary of method
Ferrous iron Fe2+ is oxidized by sodium periodate to ferric ion Fe3+. The ferric ion
develops a red complex with sulfosalicylic acid. The red complex is removed by titration
with EDTA. Citric acid is used to buffer the solution and to make the ferric ion stable in the
solution.
Consumables and replacement items
Required reagents

Description Quantity/Test Unit Item no.

Reagent set, 10–100 mg/L range (approximately 100 tests): — each 2449200
Citrate Buffer Powder Pillows 1 pillow 100/pkg 2081599
Sodium Periodate Powder Pillows 1 pillow 100/pkg 98499
Sulfosalicylic Acid Powder Pillows 1 pillow 100/pkg 2081669
TitraVer Standard Solution Titration Cartridge, 0.0716 M varies each 2081701
Reagent set, 100–1000 mg/L range (approximately 100 tests): — each 2449300
Citrate Buffer Powder Pillows 1 pillow 100/pkg 2081599
Sodium Periodate Powder Pillows 1 pillow 100/pkg 98499
Sulfosalicylic Acid Powder Pillows 1 pillow 100/pkg 2081669
TitraVer Standard Solution Titration Cartridge, 0.716 M varies each 2081801

Required apparatus

Description Quantity/test Unit Item no.

Graduated cylinders—Select one or more for the sample volume:


Cylinder, graduated, 25 mL 1 each 50840
Cylinder, graduated, 50 mL 1 each 50841
Digital Titrator 1 each 1690001
Delivery tube for Digital Titrator, J-hook tip 1 5/pkg 1720500
Pipet filler, safety bulb 1 each 1465100
Pipet, volumetric, Class A, 20 mL 1 each 1451520
Flask, Erlenmeyer, 125 mL 1 each 50543

Recommended standards

Description Unit Item no.

Iron Standard Solution, 1000 mg/L as Fe 100 mL 227142


Iron Standard Solution, 10 mg/L as Fe 500 mL 14049
Iron Standard Solution, 25 mg/L as Fe 10 mL/16 1425310
Iron Standard Solution, 50 mg/L as Fe 10 mL/16 1425410
Iron Standard Solution, 100 mg/L as Fe 100 mL 1417542

4 Iron, TitraVer Titration—Digital Titrator (1000 mg/L)


Optional apparatus

Description Unit Item no.


®
Ampule Breaker, 10-mL Voluette Ampules each 2196800
®
Pipet, TenSette , 1.0–10.0 mL each 1970010
®
Pipet tips for TenSette Pipet, 1.0–10.0 mL 50/pkg 2199796
Stir bar, octagonal each 2095352
TitraStir® Titration Stand, 115 VAC each 1940000
TitraStir® Titration Stand, 230 VAC each 1940010
Delivery tube for Digital Titrator, 90-degree bend for use with TitraStir Titration Stand 5/pkg 4157800

Iron, TitraVer Titration—Digital Titrator (1000 mg/L) 5


FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: HACH COMPANY
In the U.S.A. – Call toll-free 800-227-4224 WORLD HEADQUARTERS
Outside the U.S.A. – Contact the HACH office or distributor serving you. Telephone: (970) 669-3050
On the Worldwide Web – www.hach.com; E-mail – techhelp@hach.com FAX: (970) 669-2932

© Hach Company/Hach Lange GmbH, 2007–2015. All rights reserved. 04/2015, Edition 8
Nitrite DOC316.53.01178

Ceric Acid Titration Method Method 8351


100–2500 mg/L as NaNO2 Digital Titrator
Scope and application: For cooling tower waters.

Test preparation

Before starting
The optional TitraStir Titration Stand can hold the Digital Titrator and stir the sample.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.
Dispose of reacted solutions according to local, state and federal regulations. Refer to the Safety Data Sheets for disposal
information for unused reagents. Refer to the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.

Items to collect
Description Quantity

Ferroin Indicator Solution 1


Sulfuric Acid Standard Solution, 5.25 N 1
Ceric Standard Solution Titration Cartridge, 0.5 N 1
Digital Titrator 1
Delivery tube for Digital Titrator 1
Graduated cylinder (use a size that is applicable to the selected sample volume) 1
Erlenmeyer flask, 125 mL 1
Water, deionized varies

Refer to Consumables and replacement items on page 4 for order information.

Sample collection and storage


• Collect samples in clean glass or plastic bottles.
• Analyze the samples as soon as possible for best results.
• If immediate analysis is not possible, keep the samples at or below 6 °C (43 °F) for a
maximum of 24 hours.
• Let the sample temperature increase to room temperature before analysis.

1
Test procedure

1. Select a sample volume 2. Insert a clean delivery 3. Hold the Digital Titrator 4. Use a graduated cylinder
from Table 1 on page 3. tube into the digital titration with the cartridge tip up. or a pipet1 to measure the
cartridge. Attach the Turn the delivery knob to sample volume from Table 1
cartridge to the Digital eject air and a few drops of on page 3.
Titrator. titrant. Reset the counter to
zero and clean the tip.

5. Pour the sample into a 6. Dilute to approximately 7. Add 5 drops of 5.25 N 8. Swirl to mix.
clean, 125-mL Erlenmeyer 75 mL with deionized water. Sulfuric Acid Standard
flask. Solution.

9. Add one drop of Ferroin 10. Swirl to mix. 11. Put the end of the 12. Use the multiplier in
Indicator Solution. delivery tube fully into the Table 1 on page 3 to
solution. Swirl the flask. calculate the concentration.
Turn the knob on the Digital Digits used × digit multiplier
Titrator to add titrant to the = mg/L sodium nitrite as
solution. Continue to swirl NaNO2.
the flask. Add titrant until the
color changes from orange
to pale blue. Record the
number of digits on the
counter.

1 A pipet is recommended for sample volumes less than 10 mL.

2 Nitrite, Ceric Acid Titration—Digital Titrator (2500 mg/L)


Sample volumes and digit multipliers
Select a range in Table 1, then read across the table row to find the applicable
information for this test. Use the digit multiplier to calculate the concentration in the test
procedure.
Example: A 25-mL sample was titrated with 0.5 N Ceric Standard Solution Titration
Cartridge and the counter showed 250 digits at the endpoint. The concentration is
250 digits x 0.86 = 215 mg/L sodium nitrite as NaNO2.
Table 1 Sample volumes and digit multipliers
Range (mg/L as NaNO2) Sample volume (mL) Digit multiplier
100–400 25 0.86
400–800 10 2.15
800–1500 5 4.31
1500–2500 2 10.78

Accuracy check
Standard solution method
Use the standard solution method to validate the test procedure, reagents, apparatus and
technique.
Items to collect:
• Sodium Nitrite, ACS
• 1000-mL volumetric flask, Class A
• 5-mL volumetric pipet, Class A and pipet filler safety bulb
• Deionized water

1. Prepare a 1000-mg/L sodium nitrite standard solution as follows:


a. Add 1.000 gram of sodium nitrite to the volumetric flask.
b. Dilute to the mark with deionized water. Mix well.
2. Use the test procedure to measure the concentration of the prepared standard
solution. Use 5.0 mL of the prepared standard solution.
3. Compare the actual result to the correct result. The correct result for this titration is
approximately 1000 mg/L as NaNO2.

Standardization of the ceric standard solution


The normality of the ceric standard solution can decrease over time. Before use, examine
the normality with the standardization procedure. It is recommended to do the
standardization procedure monthly.
Items to collect:
• Sodium Thiosulfate Titration Cartridge, 0.200 N
• 125-mL Erlenmeyer flask
• Deionized water

1. Use a graduated cylinder to measure 50 mL of deionized water into a 125-mL


Erlenmeyer flask.
2. Use a pipet to add 5 mL of 19.2 N Sulfuric Acid Standard Solution. Swirl to mix.
3. Insert a clean delivery tube into the Ceric Standard Titration Cartridge. Attach the
cartridge to the titrator.
4. Hold the Digital Titrator with the cartridge tip pointing up. Turn the delivery knob to
eject a few drops of titrant. Reset the counter to zero and wipe the tip.
5. Put the delivery tube into the solution and swirl the flask. Turn the knob on the titrator
to add 200 digits of titrant to the solution.

Nitrite, Ceric Acid Titration—Digital Titrator (2500 mg/L) 3


6. Insert a clean delivery tube into a 0.200 N Sodium Thiosulfate Titration Cartridge.
Attach the cartridge to the titrator.
7. Hold the Digital Titrator with the cartridge tip pointed up. Turn the delivery knob to
eject a few drops of titrant. Reset the counter to zero and clean the tip.
8. Titrate the solution until the color changes from intense yellow to faint yellow. Record
the number of digits on the counter. The correct number of digits for this step is
400–450 digits.
9. Add 1 drop of Ferroin Indicator Solution to the flask. Swirl to mix. The color of the
solution changes to faint blue.
10. Continue the titration with Sodium Thiosulfate until the color changes to orange.
Record the number of digits on the counter.
11. Divide the number of digits by 500 to calculate the correction factor.
12. Multiply the mg/L sodium nitrite from the titration procedure by the correction factor to
get the correct sodium nitrite concentration.

Summary of method
Ferroin indicator and acid is added to the sample. The sample is titrated with tetravalent
cerium ion, which is a strong oxidant. After the cerium oxidizes the nitrite, the indicator is
oxidized and causes a color change from orange to pale blue. The quantity of titrant used
changes in relation to the concentration of sodium nitrite in the sample.
Consumables and replacement items
Required reagents

Description Quantity/Test Unit Item no.

Ceric Standard Solution Titration Cartridge, 0.5 N 1 each 2270701


Ferroin Indicator Solution 1 29 mL DB 181233
Sulfuric Acid Standard Solution, 5.25 N 1 100 mL MDB 244932

Required apparatus

Description Quantity/test Unit Item no.

Cylinder, graduated, 100 mL 1 each 50842


Digital Titrator 1 each 1690001
Delivery tube for Digital Titrator, J-hook tip 1 5/pkg 1720500
Flask, Erlenmeyer, 125 mL 1 each 50543
Pipet filler, safety bulb 1 each 1465100
Pipet, volumetric, Class A, 2.00 mL 1 each 1451536
Pipet, volumetric, Class A, 5.00 mL 1 each 1451537
Pipet, volumetric, Class A, 10.0 mL 1 each 1451538
Pipet, volumetric, Class A, 20.0 mL 1 each 1451520

Recommended standards

Description Unit Item no.

Sodium Nitrite, ACS 454 g 245201


Sodium Thiosulfate Titration Cartridge, 0.200 N each 2267501
Sulfuric Acid Standard Solution, 19.2 N 100 mL 203832

4 Nitrite, Ceric Acid Titration—Digital Titrator (2500 mg/L)


Optional apparatus

Description Unit Item no.


®
Ampule Breaker, 10-mL Voluette Ampules each 2196800
®
Pipet, TenSette , 1.0–10.0 mL each 1970010
®
Pipet tips for TenSette Pipet, 1.0–10.0 mL 50/pkg 2199796
Stir bar, octagonal each 2095352
TitraStir® Titration Stand, 115 VAC each 1940000
TitraStir® Titration Stand, 230 VAC each 1940010
Delivery tube for Digital Titrator, 90-degree bend for use with TitraStir Titration Stand 5/pkg 4157800

Nitrite, Ceric Acid Titration—Digital Titrator (2500 mg/L) 5


FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: HACH COMPANY
In the U.S.A. – Call toll-free 800-227-4224 WORLD HEADQUARTERS
Outside the U.S.A. – Contact the HACH office or distributor serving you. Telephone: (970) 669-3050
On the Worldwide Web – www.hach.com; E-mail – techhelp@hach.com FAX: (970) 669-2932

© Hach Company/Hach Lange GmbH, 2007–2015. All rights reserved. 04/2015, Edition 8
Volatile Acids DOC316.53.01182

Sodium Hydroxide Method Method 8218


100–2400 mg/L CH3COOH Digital Titrator
Scope and application: For wastewater.

Test preparation

Before starting
Refer to the Volatile Acids Procedure, Sample Distillation in the distillation apparatus documentation to distill the sample. As
an alternative, refer to the distillation procedure in Standard Methods for the Examination of Water and Wastewater.
The final result is adjusted to give the correct answer based on a 70% correction factor. For higher recoveries, use the
esterification method.
The optional TitraStir Titration Stand can hold the Digital Titrator and stir the sample.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.
Dispose of reacted solutions according to local, state and federal regulations. Refer to the Safety Data Sheets for disposal
information for unused reagents. Refer to the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.

Items to collect
Description Quantity

Phenolphthalein Indicator Powder Pillows 1


Sodium Hydroxide Titration Cartridge, 0.9274 N 1
Digital Titrator 1
Delivery tube for Digital Titrator 1
Graduated cylinder (use a size that is applicable to the selected sample volume) 1
Erlenmeyer flask, 250-mL 1
Water, deionized varies

Refer to Consumables and replacement items on page 3 for order information.

Sample collection
• Collect samples in clean glass or plastic bottles.

1
Test procedure

1. Collect 125 mL of 2. Select a sample volume 3. Insert a clean delivery 4. Hold the Digital Titrator
distillate. and titration cartridge from tube into the digital titration with the cartridge tip up.
Table 1 on page 3. cartridge. Attach the Turn the delivery knob to
cartridge to the Digital eject air and a few drops of
Titrator. titrant. Reset the counter to
zero and clean the tip.

5. Use a graduated cylinder 6. Pour the sample into a 7. If the sample volume is 8. Add the contents of one
or a pipet to measure the clean, 250-mL Erlenmeyer less than 150 mL, dilute to Phenolphthalein Indicator
sample volume from Table 1 flask. approximately 150 mL with Powder Pillow.
on page 3. deionized water.

9. Swirl to mix. 10. Put the end of the 11. Use the multiplier in
delivery tube fully into the Table 1 on page 3 to
solution. Swirl the flask. calculate the concentration.
Turn the knob on the Digital Digits used × digit multiplier
Titrator to add titrant to the = mg/L Volatile Acids (as
solution. Continue to swirl acetic acid, CH3COOH).
the flask. Add titrant until the
color changes to light pink.
Record the number of digits
on the counter.

2 Volatile Acids, Sodium Hydroxide Titration—Digital Titrator (2400 mg/L)


Sample volumes and digit multipliers
Select a range in Table 1, then read across the table row to find the applicable
information for this test. Use the digit multiplier to calculate the concentration in the test
procedure.
Example: A 150-mL sample was titrated with 0.9274 N Sodium Hydroxide Titration
Cartridge and the counter showed 250 digits at the endpoint. The concentration is
250 digits x 1 = 250 mg/L Volatile Acids (as acetic acid, CH3COOH).
Table 1 Sample volumes and digit multipliers
Range (mg/L as CH3COOH) Sample volume (mL) Digit multiplier
100–400 150 1
200–800 75 2
600–2400 25 6

Summary of method
The sample is acidified with sulfuric acid and distilled with deionized water. The distillate
is titrated to the phenolphthalein endpoint with sodium hydroxide standard.
Consumables and replacement items
Required reagents

Description Quantity/Test Unit Item no.

Volatile Acid Reagent set (approximately 100 tests): — each 2460200


Phenolphthalein Indicator Powder Pillows 1 pillow 100/pkg 94299
Sodium Hydroxide Titration Cartridge, 0.9274 N varies each 1484201
Water, deionized varies 100 mL 27242

Required apparatus

Description Quantity/test Unit Item no.

Graduated cylinders—Select one or more for the sample volume:


Cylinder, graduated, 5 mL 1 each 50837
Cylinder, graduated, 10 mL 1 each 50838
Cylinder, graduated, 25 mL 1 each 50840
Cylinder, graduated, 50 mL 1 each 50841
Cylinder, graduated, 100 mL 1 each 50842
Digital Titrator 1 each 1690001
Delivery tube for Digital Titrator, J-hook tip 1 5/pkg 1720500
Flask, Erlenmeyer, 250 mL 1 each 50546

Recommended standards

Description Unit Item no.

Volatile Acids Standard Solution, 1000 mg/L as Acetic Acid 100 mL 1420542

Volatile Acids, Sodium Hydroxide Titration—Digital Titrator (2400 mg/L) 3


Optional apparatus

Description Unit Item no.


®
Ampule Breaker, 10-mL Voluette Ampules each 2196800
Stir bar, octagonal each 2095352
TitraStir® Titration Stand, 115 VAC each 1940000
TitraStir® Titration Stand, 230 VAC each 1940010
Delivery tube for Digital Titrator, 90-degree bend for use with TitraStir Titration Stand 5/pkg 4157800

FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: HACH COMPANY


In the U.S.A. – Call toll-free 800-227-4224 WORLD HEADQUARTERS
Outside the U.S.A. – Contact the HACH office or distributor serving you. Telephone: (970) 669-3050
On the Worldwide Web – www.hach.com; E-mail – techhelp@hach.com FAX: (970) 669-2932

© Hach Company/Hach Lange GmbH, 2007–2015. All rights reserved. 04/2015, Edition 8

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