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 Conversion 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 (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 (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 M EDTA 0.1
40–160 25 0.0800 M EDTA 0.4
100–400 100 0.800 M EDTA 1.0
200–800 50 0.800 M EDTA 2.0
500–2000 20 0.800 M EDTA 5.0
1000–4000 10 0.800 M EDTA 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 M EDTA 0.01
4–16 25 0.1428 M EDTA 0.04
10–40 50 0.714 M EDTA 0.1
25–100 20 0.714 M EDTA 0.25
> 100 10 0.714 M EDTA 0.5

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

4 Hardness, Total, Sequential (4000 mg/L)

Conversion 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 CDTA 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 CDTA 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.

Hardness, Total, Sequential (4000 mg/L) 5

 Table 4 Interferences (continued)
Interfering substance Interference level
Nickel Interferes at all levels. Add a CDTA powder pillow to remove the interference. Refer to Use CDTA to
remove metal interferences on page 6.
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 CDTA 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 (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
Sulfuric Acid Standard Solution, 5.25 N varies 100 mL MDB 244932
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

Hardness, Total, Sequential (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
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
Sampling bottle, 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

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© Hach Company/Hach Lange GmbH, 2007–2015, 2019. All rights reserved. 11/2019, Edition 9