Hardness, Total, Sequential 8329

Hardness, Total, Sequential DOC316.53.01230

Titration Method using EDTA Method 8329

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

Test preparation

Before starting the test:

The first titration gives calcium hardness and the second titration gives total hardness. The difference between the values is
magnesium hardness. All of these concentrations are in mg/L as CaCO3. See Hardness conversions for conversions to
other units.

Four drops of Hardness 2 Indicator Solution or a 0.1-g scoop of ManVer 2 Hardness Indicator Powder can be added in place
of the ManVer 2 Hardness Indicator Powder Pillow.

A 0.1-g scoop of CalVer® 2 Calcium Indicator Powder can be used in place of the CalVer 2 Calcium Indicator Powder Pillow.

For added convenience when stirring, use the TitraStir® stirring apparatus1.
1 See Optional reagents and apparatus.

Collect the following items:

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 (see Range-specific information—mg/L (mg/L) or Range-specific 1 cartridge

information—G.d.h. (German degrees of hardness))

Digital titrator 1

Delivery tube for digital titrator 1

Erlenmeyer flask, 250 mL 1

Graduated cylinder 1

See Consumables and replacement items for reorder information.

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Hardness, Total, Sequential
Hardness, total, sequential
See
Table 1
or
Table 2
1. Select a sample
volume and titration
cartridge from Range-
specific information—mg/L
or Range-specific
information—G.d.h..
5. If the sample volume
is 100 mL, add 2 mL of
8 N Potassium Hydroxide
Standard Solution. If the
sample volume is 50 mL or
less, add 1 mL of
8 N Potassium Hydroxide
Standard Solution. Swirl to
mix.
Hardness, Total, Sequential
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2. Insert a clean delivery 3. Hold the Digital
tube into the titration Titrator with the cartridge
cartridge. Attach the tip pointing up. Turn the
cartridge to the titrator. delivery knob to eject a
few drops of titrant. Reset
the counter to zero and
wipe the tip.
6. Add the contents of 7. Place the delivery tube
one CalVer 2 Calcium into the solution and swirl
Indicator Powder Pillow. the flask. Turn the knob on
Swirl to mix. the titrator to add titrant to
the solution. Continue to
swirl the flask and add
titrant until the color
changes from red to pure
blue.
Write down the number of
digits on the counter.
4. Use a graduated
cylinder or pipet to
measure the sample
volume from Range-
specific information—mg/L
or Range-specific
information—G.d.h..
Transfer the sample into a
clean, 250-mL Erlenmeyer
flask. If the sample volume
is less than 100 mL, dilute
to approximately 100 mL
with deionized water.
8. Use the multiplier in
Range-specific
information—mg/L (or
Range-specific
information—G.d.h.) to
calculate the
concentration:
Total digits from step 7 and
step 12 x multiplier =
mg/L (or G.d.h.) Calcium
as CaCO3
 Hardness, Total, Sequential

Hardness, total, sequential (continued)

9. Add 1 mL of 5.25 N
Sulfuric Acid Standard
Solution. Continue to add
the acid by drops while
swirling until the solution
changes from pure blue to
purple and finally to red.
Swirl the flask to make
sure that all the
precipitated magnesium
hydroxide has dissolved.
10. Add 2 mL of 11. Add the contents of 12. Place the delivery tube
Hardness 1 Buffer one ManVer 2 Hardness into the solution and swirl
Solution. Swirl to mix. Indicator Powder Pillow. the flask. Turn the knob on
Swirl to mix. the titrator to add titrant to
the solution. Continue to
swirl the flask and add
titrant until the color
changes from red to pure
blue.
Write down the number of
digits on the counter.

13. Use the multiplier in

Range-specific
information—mg/L (or
Range-specific
information—G.d.h.) to
calculate the
concentration:
digits x multiplier =
mg/L (or G.d.h.) total
hardness as CaCO3

Hardness, Total, Sequential

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Hardness, Total, Sequential

Table 1 Range-specific information—mg/L

Range (mg/L as CaCO3) Sample volume (mL) Titration cartridge (M EDTA) 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 Range-specific information—G.d.h.

Range (G.d.h as CaCO3) Sample volume (mL) Titration cartridge (M EDTA) 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

Table 3 Hardness conversions

To convert from To Multiply by
mg/L as CaCO3 mg/L as Ca 0.400
mg/L as Mg 0.243
grains per gallon (gpg) 0.0584
German degrees hardness (Gdh) 0.0559

Hardness relationships
mg/L Mg Hardness as CaCO3

= mg/L Total Hardness as CaCO 3 – mg/L Ca Hardness as CaCO 3

mg/L MgCO 3 = mg/L Mg Hardness as CaCO 3 × 0.842

mg/L Mg = mg/L MgCO 3 × 0.29

Interferences
WARNING:
Do not use potassium cyanide to eliminate interferences because it will generate deadly
hydrogen cyanide gas when the sulfuric acid solution is added.
• Although less common than calcium and magnesium, other polyvalent metal ions cause the
same hardness effects and will be included in the results.
• Some transition and heavy metals complex the indicator and prevent the color change at the
end point.

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 Hardness, Total, Sequential

• Iron does not interfere up to 15 mg/L. Above this level it causes a red-orange to green end
point which is sharp and usable up to 30 mg/L iron. Substitute 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 probable. For results in G.d.h., divide the mg/L result by
17.9.
• Manganese titrates directly up to 20 mg/L but masks the end point above this level. Adding a
0.1-gram scoop of hydroxylamine hydrochloride raises this level to 200 mg/L manganese.
• Copper interferes at levels of 0.10 and 0.20 mg/L. Cobalt and nickel interfere at all levels and
must be absent or masked.
• Orthophosphate causes a slow end point and polyphosphate must be absent for accurate
results.
• Acidity and alkalinity at 10,000 mg/L (as CaCO3) do not interfere.
• Saturated sodium chloride solutions do not give a distinct end point, but the titration can be run
directly on sea water.
• Adding the contents of one CDTA Magnesium Salt Powder Pillow removes metal interferences
at or below the levels shown in Metal interferences.
• If more than one metal is present at or above the concentrations shown in Metal interferences,
an additional CDTA Magnesium Salt Powder Pillow may be required.
• Results obtained by this procedure include the hardness contributed by polyvalent metal ions.
If the concentration of each metal is known, a correction can be applied to obtain the calcium
and magnesium hardness concentration. The hardness (in mg/L as CaCO3) contributed by
each mg/L of metal is listed in Hardness contributed by each mg/L of metal. Hardness
contributed by metals can be subtracted from the total hardness value obtained to determine
the calcium and magnesium hardness concentration.
• Barium, strontium and zinc titrate directly.

Table 4 Metal interferences

CDTA Removes Interference Below this
Metal
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

Hardness, Total, Sequential

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Hardness, Total, Sequential

Table 5 Hardness contributed by each mg/L of metal

Hardness as CaCO3 Contributed
Metal
by Each mg/L of Metal
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

Sample collection, preservation and storage

• Collect samples in plastic or glass bottles that have been washed with a detergent and rinsed
with tap water. Then rinse the bottles in 1:1 nitric acid solution and deionized water.
• The following storage instructions are necessary only when immediate analysis is not
possible. To preserve the sample, add 1.5 mL of nitric acid per liter (or quart) of sample. Mix.
• Measure the sample pH to make sure that the pH is 2 or less. Add more nitric acid in 0.5-mL
increments if necessary.
• Mix thoroughly and check the pH after each addition until the pH is 2 or less.
• Store samples at 4 °C (39 °F) or below. Preserved samples can be stored for at least six
months.
• Before starting the test, warm the sample to room temperature and adjust the pH to
approximately pH 7 with potassium hydroxide solution. Mix thoroughly.
• If a significant amount of nitric acid was added, make a volume correction for the extra acid
and hydroxide.
• Divide the total volume (sample + acid + hydroxide) by the volume of the sample and multiply
the result from the test by this value.

Summary of method
This test procedure is a combination of the calcium and total hardness procedures. Refer to each
method for a detailed description of the methods.

Hardness, Total, Sequential

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 Hardness, Total, Sequential

Consumables and replacement items

Required reagents
Description Quantity/Test Unit Catalog number
Calcium and Total Hardness Reagent Set (approximately 100 tests) 2272100
(1) Buffer Solution, Hardness 1 1 mL 100 mL MDB 42432
(1) CalVer 2 Calcium Indicator Powder Pillows 1 100/pkg 94799
(1) ManVer 2 Hardness Indicator Powder Pillows 1 100/pkg 85199
(2) Potassium Hydroxide Standard Solution, 8 N 1 mL 100 mL MDB 28232H
(1) EDTA Titration Cartridge, 0.0800 M varies each 1436401
(1) EDTA Titration Cartridge, 0.800 M varies each 1439901
Sulfuric Acid Standard Solution, 5.25 N varies 100 mL MDB 244932

Required apparatus
Description Quantity/Test Unit Catalog number
Digital Titrator 1 each 1690001
Flask, Erlenmeyer, graduated, 250-mL 1 each 50546
Graduated cylinder—select one or more based on range:
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
Delivery tube for Digital Titrator, 180° hook 1 5/pkg 1720500
Delivery tube for Digital Titrator, 90° hook 1 5/pkg 4157800

Recommended standards
Description Unit Catalog number
Calcium Chloride Standard Solution, 1000-mg/L as CaCO3 1L 12153
Hardness Standard Solution, Voluette ampule, 10,000-mg/L as CaCO3, 10-mL 16/pkg 218710
Voluette Ampule breaker 10 mL each 2196800

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Hardness, Total, Sequential

Optional reagents and apparatus

Description Unit Catalog number

CalVer® 2 Calcium Indicator Powder 113 g 28114H

ManVer 2 Hardness Indicator Powder 113 g 28014
Nitric Acid Solution, ACS 500 mL 15249
Stir bar, octagonal 28.6 mm x 7.9 mm each 2095352
TenSette Pipet, 0.1 to 1.0 mL each 1970001
TitraStir Stir Plate, 115 VAC each 1940000
TitraStir Stir Plate, 230 VAC each 1940010
Water, deionized 500 mL 27249
pH paper, 0–14 100/pkg 2601300
Pipet Tips, for TenSette Pipet 1970001 50/pkg 2185696
Pipet Tips, for TenSette Pipet 1970001 1000/pkg 2185628
Weighing papers 500/pkg 1473800
Spoon, measuring, 0.1 g capacity each 51100
Spoon, measuring, 0.5 g capacity each 90700
Hydroxylamine Hydrochloride 113 g 24614
Magnesium CDTA powder pillows 100/pkg 1408099
CDTA cartridge for digital titrator, 0.08 M each 1440201
CDTA cartridge for digital titrator, 0.80 M each 1440301

FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: HACH COMPANY

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© Hach Company, 2007. All rights reserved. Printed in the U.S.A. Updated February 2008, Edition 5