January 2008

1.00961.0001
8. Procedure
Total Hardness 8.1 Determination of total hardness

Cell Test Pretreated sample

(20 - 30 °C)
1.0 ml Pipette into a reaction cell, close the cell, and mix.

Reagent H-1K 1.0 ml Add with pipette, close the cell, and mix.

Leave to stand for 3 min (reaction time), then measure the sample in the photometer:
total hardness
1. Definition
The hardness (total hardness) of a given water is due to its content of salts of the al-
kaline earth metals calcium, magnesium, strontium, and barium (“hardening constit- 8.2 Differentiation between Ca and Mg (possible only with measurement in mmol/l)
uents”). Since strontium and barium are generally present in waters only in traces,
the hardness is defined as the content in a water of calcium ions, Ca2+, and magne- Determine the total hardness in mmol/l (result A) - procedure see section 8.1
sium ions, Mg2+ (“hardness ions”). The conventional procedure is to relate the state-
ment of the water hardness only to calcium, in other words to express also the con- Reagent H-2K 3 drops 1) Add to the sample already analyzed for total hard-
tent of magnesium ions as calcium content. ness, close the cell, and mix.

The units for the water hardness relate to calcium or its compounds CaO (1 °d = Measure anew: Mg content in mmol/l (result B)
= 10 mg/l CaO) or CaCO3 (1 °e = 14.25 mg/l CaCO3; 1 °f = 10 mg/l CaCO3), with
1) Hold the bottle vertically while adding the reagent!
the magnesium content being expressed as calcium content and included in the cal-
culation accordingly.
Calculation of the Ca content:
2. Method mmol/l Ca = result A - result B
In neutral solution calcium and magnesium ions react with phthalein purple to form a
violet dye that is determined photometrically. Notes on the measurement:
The use of a selective masking agent permits a differentiation between calcium
and magnesium. • For photometric measurement the cells must be clean.
Wipe, if necessary, with a clean dry cloth.
3. Measuring range and number of determinations • Measurement of turbid solutions yields false-high readings.
• The pH of the measurement solution must be approx. 7.5.

Measuring range 1)
Number of
determinations
• The colour of the measurement solution remains stable for at least 60 min after
the end of the reaction time stated above or, respectively, after the addition of
reagent H-2K.
5 - 215 mg/l Ca
0.9 - 37.6 °e 25 9. Conversions
12 - 537 mg/l CaCO3
required mmol/l mg/l German English French mg/l
1) for conversion factors see section 9 Ca (ppm) degree degree degree (ppm)
given (CaCO3) Ca °d °e °f CaCO3
For programming data for selected photometers / spectrophotometers see the website.
1 mmol/l
Ca (CaCO3) 1 40.08 5.61 7.02 10.01 100.1
4. Applications
1 mg/l (ppm)
Sample material: Ca 0.025 1 0.140 0.175 0.250 2.50
Groundwater and surface water
Drinking water and mineral water 1 German
Boiler water degree °d 0.178 7.15 1 1.25 1.78 17.85
This test is not suited for seawater. 1 English
degree °e 0.142 5.71 0.799 1 1.43 14.25
5. Influence of foreign substances 1 French
degree °f 0.100 4.00 0.560 0.702 1 10.00
This was checked in solutions containing 125 mg/l Ca (21.9 °e). The concentrations
of foreign substances given in the table lie below the limit at which the determination 1 mg/l (ppm)
is interfered with. CaCO3 0.010 0.400 0.056 0.070 0.100 1

Concentrations of foreign substances in mg/l or %

10. Analytical quality assurance
Al3+ 10 Fe3+ 50 NO2- 1000 EDTA 25 The measurement results can be officially recognized under the precondition that
BO33- 1000 K+ 1000 PO43- 500 Na-acetate 1%
analytical quality-assurance measures are taken (DWA A 704).
Cr3+ 25 Mn2+ 50 Zn2+ 100 NaCl 2%
Cr2O72- 50 Mo6+ 25 NaNO3 2% To check the photometric measurement system (test reagents, measurement device,
Cu2+ 25 NH4+ 1000 Na2SO4 1% handling) and the mode of working, a dilute calcium standard solution containing
F- 500 Ni2+ 2.5 100 mg/l Ca (17.5 °e) can be used. For this purpose, add 4 ml of sodium hydroxide
solution 1 mol/l to 10.0 ml of calcium standard solution, Cat. No. 119778, make up to
100 ml with distilled water, and mix. The pH must be in the range 3 - 9. Check with
6. Reagents and auxiliaries universal indicator strips.
Sample-dependent interferences (matrix effects) can be determined by means of
Please note the warnings on the packaging materials! standard addition.
The test reagents are stable up to the date stated on the pack when stored closed Characteristic quality data:
at +15 to +25 °C. In the production control, the following data were determined in accordance with ISO
8466-1 and DIN 38402 A51:
Package contents:
1 bottle of reagent H-1K Standard deviation of the method + 1.8 (+ 0.3 °e)
1 bottle of reagent H-2K (mg/l Ca)
25 reaction cells Coefficient of variation of the method + 1.6
1 cell with blank (white screw cap); required only when using the SQ 118 (%)
photometer
Confidence interval + 4 (+ 0.7 °e)
1 sheet of round stickers for numbering the cells
(mg/l Ca)
Other reagents and accessories: Number of lots 13
Universal indicator strips pH 0 - 14, Cat. No. 1.09535.0001
Sodium hydroxide solution 1 mol/l, Cat. No. 109137 Characteristic data of the procedure:
Hydrochloric acid 1 mol/l, Cat. No. 109057
Merckoquant® Total Hardness Test, Cat. No. 1.10025.0001, Sensitivity: 2 (0.4 °e)
measuring range <4 - >26 °e or Absorbance 0.010 A
Merckoquant® Total Hardness Test, Cat. No. 1.10046.0001, corresponds to (mg/l Ca)
measuring range >6 - >31 °e
Accuracy of a measurement value max. + 5 (+ 0.9 °e)
Calcium standard solution CertiPUR®, 1000 mg/l Ca (175 °e), (mg/l Ca)
Cat. No. 119778
Pipette for a pipetting volume of 1.0 ml For quality and batch certificates for Spectroquant® test kits see the website.

7. Preparation 11. Notes

• Analyze immediately after sampling. • Reclose the reagent bottles immediately after use.
• The pH must be within the range 3 - 9.
Adjust, if necessary, with sodium hydroxide solution or hydrochloric acid.
• For information on disposal/return for disposal please contact your local
Merck organization or Merck dealer.
• Check ®
the total hardness with the Merckoquant Total Hardness Test.
Samples containing more than 37.6 °e (215 mg/l Ca) must be diluted with
distilled water.
• Filter turbid samples.
Merck KGaA, 64271 Darmstadt, Germany, Tel. +49(0)6151 72-2440, Fax +49(0)6151 72-7780
environmental.analysis@merck.de http://photometry.merck.de