Application Bulletin 125/3 e

Simultaneous determination of calcium, magnesium, and

alkalinity by complexometric titration with potentiometric or
photometric indication in water and beverage samples

Branch
Potentiometric determination
General analytical laboratories; water analysis; beverages
Instruments
 Titrator with DET mode
Keywords
 Burette, cylinder volume 20 mL
Titration; potentiometric titration; photometric titration;
 Stirrer
complexometric titration; water; beverages; water hardness;
calcium; calcium hardness; magnesium; magnesium
hardness; alkalinity; total hardness; EDTA; branch 1; branch Electrodes
2; branch 7; 6.0510.100; 6.0750.100; 6.1115.000
Combined Ca2+ selective 6.0510.100
electrode
Summary iEcotrode Plus with 6.0280.300
This bulletin describes the determination of calcium, 845 iConnect or 2.854.0010
magnesium, and alkalinity in water by complexometric Ecotrode gel with NTC 6.0221.600
titration with EDTA as titrant. It is grouped into two parts, the
potentiometric determination and the photometric
determination. Reagents

There are multiple definitions of the different types of water  Hydrochloric acid, c(HCl) = 0.1 mol/L and 5 mol/L
hardness. In this Application Bulletin, the following volumetric solutions.
definitions are used: alkalinity, calcium hardness,  Disodium ethylendiaminetetraacetate dihydrate,
magnesium hardness, total hardness, and permanent c(EDTA) = 0.05 mol/L volumetric solution
hardness. The explanation of these definitions and further  Acetylacetone, purum
expressions are mentioned in the appendix.
 Calcium carbonate, CaCO3, p.a.
In the potentiometric part, the determination of the alkalinity
 Tris(hydroxymethyl)aminomethane, TRIS, p.a.
is done in a separate acid-base titration before the
 Ammonium chloride, NH4Cl, purum
complexometric titration of calcium and magnesium in
water. From these values, the permanent hardness can be  Ammonia, w(NH3) = 25%, purum
calculated. Furthermore, the determination of calcium and
magnesium in beverages (fruit and vegetable juices, wine)
Solutions
is described.
Titrant 1 HCl, c(HCl) = 0.1 mol/L; titrant for
The photometric part includes the determinations of the total
the alkalinity.
and calcium hardness and thereby indirectly the magnesium
hardness using Eriochrome Black T and calconcarboxylic Titrant 2 EDTA, c(EDTA) = 0.05 mol/L;
acid as indicators (according to DIN 38406-3). titrant for the determination of
Ca2+ and Mg2+
Auxiliary solution Acetylactone and TRIS in dist.
water;
c(acetylacetone) = 0.1 mol/L and
c(TRIS) = 0.2 mol/L
For this solution TRIS has not to

Page 1 of 8
 Application Bulletin 125/3 e
Simultaneous determination of calcium, magnesium and
alkalinity by complexometric titration with potentiometric or
photometric indication in water samples and beverages

be dried. Titer EDTA

24.2 g TRIS are weighed into a 50 – 90 mg CaCO3 are weighed out into a titration beaker
1000 mL volumetric flask and with an accuracy of 0.1 mg and suspended in 20 mL dist.
dissolved in approx. 500 mL dist. H2O. Under stirring, c(HCl) = 5.0 mol/L is added dropwise
H2O. 12 mL acetylacetone are until the CaCO3 has dissolved completely. After the addition
added and the solution is made up of 30 mL dist. H2O and 5 mL buffer pH 10, the solution is
to the mark with dist. H2O. titrated with c(EDTA) = 0.05 mol/L to the first endpoint.
This solution has to be used within
Water sample
a few days.
The auxiliary solution enhances 100 mL sample are placed in the titration vessel and titrated
the separation Ca2+ and Mg2+ and in a first titration with c(HCl) = 0.1 mol/L to the first or
masks Fe3+ and Al3+. second equivalence point, using the combined pH electrode
in order to determine the alkalinity.
Buffer pH 10 54 g NH4Cl and 350 mL
w(NH3) = 25% are dissolved in Afterwards, 15 mL auxiliary solution are added and after a
dist. H2O and made up to 1 liter short waiting time the calcium and magnesium ions are
with dist. H2O. titrated in a second titration using c(EDTA) = 0.05 mol/L.
The first equivalence point corresponds to the Ca2+ content,
the difference between the second and first equivalence
Standards point to the Mg2+ content.
TRIS TRIS is dried over night in a drying Beverages
oven at 105 °C and allowed to
To the prepared sample solution 20 mL auxiliary solution
cool down in a desiccator for at
and 10 mL buffer pH 10 are added. The titration is
least 1 h.
performed using c(EDTA) = 0.05 mol/L.
CaCO3 CaCO3 is dried over night in a
drying oven at 140 °C and allowed
to cool down in a desiccator for at Parameters
least 2 h.
Water samples
Parameters for the determination of the alkalinity
Sample preparation Mode DET pH
Water samples Drift 20 mV/min
No sample preparation required. Max. waiting time 38 s
Meas. point density 4
Beverages (fruit and vegetable juices, wine)
Min. increment 10 µL
25.0 mL sample are pipetted into an evaporating dish and
evaporated in a drying cabinet at 140 °C. The residue is EP criterion 5
grinded as fine as possible and then heated to a red glow in EP regonition all
a muffle furnace at 600 °C, until a white ash remains. After
cooling down, 2 mL c(HCl) = 5 mol/L, are added. The Parameters for the determination of Ca2+ and Mg2+
mixture is heated to dissolve the ash and the resulting Mode DET U
solution rinsed into a titration vessel with dist. H2O.
Pause 30 s
Drift 50 mV/min
Analysis Max. waiting time 26
Titer HCl Meas. point density 4

80 – 150 mg TRIS are weighed out into the titration beaker Min. increment 10 µL
with an accuracy of 0.1 mg, dissolved in 50 mL dist. H2O EP criterion 5
and immediately titrated with c(HCl) = 0.1 mol/L to the first EP regonition all
endpoint.

Page 2 of 8
 Application Bulletin 125/3 e
Simultaneous determination of calcium, magnesium and
alkalinity by complexometric titration with potentiometric or
photometric indication in water samples and beverages

Beverages
Ca hardness: Amount of calcium in the sample in
Mode DET U
mmol/L
Drift 10 mV/min Mg hardness: Amount of magnesium in the sample in
Max. waiting time 52 s mmol/L
Total hardness: Total hardness of the sample in mmol/L
Meas. point density 1
VEP1: Titrant consumption until the first
Min. increment 10 µL equivalence point in mL
EP criterion 5 VEP2: Titrant consumption until the second
EP recognition all equivalence point in mL
c(EDTA): Concentration of titrant in mol/L; here
c(EDTA) = 0.05 mol/L
Calculation f: Correction factor («titer») without unit
1000: Conversion factor to obtain result in
Titer
mmol/L
ms
Titer = Vs: Sample size in mL
VEP1 × c(Titrant) × MA

Titer: Titer of the selected titrant The permanent hardness can be calculated by subtracting
the alkalinity from the total hardness.
m s: Mass of standard in mg
VEP1: Titrant consumption until the first If a higher value is obtained for the alkalinity than for the
equivalence point in mL total hardness, the alkalinity is given as being the total
c(Titrant): Concentration of the selected titrant in hardness.
mol/L; here either c(HCl) = 0.1 mol/L or
c(EDTA) = 0.05 mol/L Beverages
MA : Molecular weight of the analyte; here VEP1 × c(EDTA) × f × MA × 1000
Ca content =
either 100.09 g/mol (CaCO3) or Vs
121.14 g/mol (TRIS). (VEP2 - VEP1 ) × c(EDTA) × f × MA × 1000
Mg content =
Vs
1 mL c(HCl) = 0.1 mol/L corresponds to 12.114 mg TRIS.
1 mL c(EDTA) = 0.05 mol/L corresponds to 5.005 mg Ca content: Amount of calcium in the sample in mg/L
CaCO3.
Mg content: Amount of magnesium in the sample in
Water sample mg/L
VEP1 × c(HCl) × f × 1000 VEP1: Titrant consumption until the first
Alkalinity = equivalence point in mL
VS
VEP2: Titrant consumption until the second
equivalence point in mL
Alkalinity: Alkalinity in mmol/L
c(EDTA): Concentration of titrant in mol/L; here
VEP1: Titrant consumption until the first c(EDTA) = 0.05 mol/L
equivalence point in mL
f: Correction factor («titer») without unit
c(HCl): Concentration of titrant in mol/L; here
c(HCl) = 0.1 mol/L MA : Molar mass of analyst; here 24.31 g/mol
(Mg2+) respectively 40.08 g/mol (Ca2+).
f: Correction factor («titer») without unit
1000: Conversion factor to obtain result in mg/L
1000: Conversion factor to obtain result in
mmol/L Vs: Sample size in mL
VS : Sample size in mL
1 mL c(EDTA) = 0.05 mol/L corresponds to 2.004 mg Ca2+
VEP1 × c(EDTA) × f × 1000 or 1.216 mg Mg2+
Ca hardness =
Vs

VEP2 - VEP1 × c(EDTA) × f × 1000

Mg hardness=
Vs

VEP2 × c(EDTA) × f × 1000

total hardness =
Vs

Page 3 of 8
 Application Bulletin 125/3 e
Simultaneous determination of calcium, magnesium and
alkalinity by complexometric titration with potentiometric or
photometric indication in water samples and beverages

Example determination  For fully automated determinations of further

parameters of water samples see Metrohm Application
Bulletin No. 178.
 Ca2+ selective electrodes should be stored dry.
 To prolong the lifetime of the titrant KOH can be added.
The concentration of KOH should be
c(KOH) = 0.1 mol/L

Fig. 1: Determination of Ca2+ (109.8 mg/L) and Mg2+

(21.89 mg/L) in tap water from Herisau using a combined
Ca ISE.

Comments
 Before starting the titration of the alkalinity, the pH
value of the water sample is measured. This value can
be printed out as pH(init).
 The added volume of the auxiliary solution can be
optimized according to the magnesium content. As a
rule of thumb, the molar ratio Mg/acetylacetone should
be approximately 0.05.
 Ca2+ electrodes, that have been stored dry, are
conditioned in c(CaCl2) = 0.01 mol/L for approx. 10 min
prior to the titration. Alternatively, the first three
determinations are discarded.
 The alkalinity is defined by the m value (pH 4.3) and p
value (pH 8.2). Not for every water sample a p value
can be determined, therefore one does not necessarily
get two equivalence points in the alkalinity titration.
These values can be determined using a fixed
endpoint; for more information concerning their
determination see Metrohm Application Bulletin No.
AB-178.
 Samples containing only small amounts of magnesium
besides high calcium concentrations yield only one
single potential jump for the sum of both ions. In such
cases, an auxiliary solution has to be used, to which a
defined quantity of Mg2+ standard has been added. This
addition of Mg2+ ions must, of course, be taken into
account in the calculations.
 In beverages, analyzed calcium and magnesium are
only partially present as free ions. The rest is bound in
complexes with organic components. In order to
determine the total metal contents, it is therefore
necessary to ash the samples.

Page 4 of 8
 Application Bulletin 125/3 e
Simultaneous determination of calcium, magnesium and
alkalinity by complexometric titration with potentiometric or
photometric indication in water samples and beverages

night in a drying oven at 140 °C

Photometric determination and allowed to cool down in a
Instruments desiccator for at least 2 h.

 Titrator with MET mode

 20 mL burette Sample preparation

 Stirrer No sample preparation required.

Electrodes Analysis

Optrode 6.1115.000 Titer of EDTA

10 mL CaCl2 standard are pipetted into a titration vessel or
80 – 150 mg of dried standard are weighed into a titration
Reagents
vessel. 90 mL dist. H2O, 1.5 mL calconcarboxylic acid
 Disodium ethylendiaminetetraacetate dihydrate, indicator as well as 4 mL c(NaOH) = 2 mol/L are added. The
c(EDTA) = 0.1 mol/L volumetric solution solution is then titrated immediately with c(EDTA) = 0.1
 Magnesium disodium ethylendiaminetetraacetate mol/L until after the first equivalence point.
monohydrate, Mg complexonate, MgEDTA, puriss
Total hardness
 Sodium hydroxide, c(NaOH) = 0.1 mol/L volumetric
To 100 mL sample, about 0.1 g MgEDTA and 10 mL buffer
solution and = 2 mol/L volumetric solution
pH 10 are added. After the addition of 0.25 mL Eriochrome
 Ammonium chloride, NH4Cl, purum Black T indicator the solution is titrated using c(EDTA) = 0.1
 Ammonia, w(NH3) = 25%, purum mol/L, to the first equivalence point.
 Eriochrome Black T, Reag. Ph. Eur. Calcium hardness
 Ascorbic acid, purum To 100 mL sample, 1.5 mL calconcarboxylic acid indicator
 Calconcarboxylic acid, analytical grade and 4 mL c(NaOH) = 2 mol/L are added. The solution is
 CaCl2 anhydrous, p.a. or certified CaCl2 standard (e.g. titrated using c(EDTA) = 0.1 mol/L, to the first equivalence
Metrohm ion standard 6.2301.070) point.

Solutions Parameters

Eriochrome Black T 100 mg Eriochrome Black T are Titer

indicator dissolved in 100 mL dist. H2O and Mode MET U
100 mg ascorbic acid are added to
λ 610 nm
stabilize the solution.
Start volume 9.5 mL
Calconcarboxylic 50 mg calconcarboxylic acid are
acid indicator dissolved in 100 mL of Drift 50 mV/min
c(NaOH) = 0.1 mol/L. Max. waiting time 26 s
Buffer pH 10 54 g NH4Cl and 350 mL Volume increment 0.1 mL
w(NH3) = 25% are dissolved in EP criterion 30 mV
dist. H2O and made up to 1 liter EP recognition all
with dist. H2O.
Total hardness
Mode MET U
Standards
λ 610 nm
CaCl2 It is recommended to use a
Pause 30 s
calibrated standard solution (e.g.
Metrohm ion standard Drift 50 mV/min
6.2301.070). Max. waiting time 26
Otherwise CaCl2 is dried over Volume increment 0.1 mL

Page 5 of 8
 Application Bulletin 125/3 e
Simultaneous determination of calcium, magnesium and
alkalinity by complexometric titration with potentiometric or
photometric indication in water samples and beverages

EP criterion 30 mV Calcium hardness

EP regonition greatest VEP1 × c(EDTA) × f × 1000
Ca hardness =
Vs
Calcium hardness
Mode MET U Mg hardness = Total hardness - Ca hardness
λ 610 nm
Ca hardness: Amount of calcium in the sample in
Pause 10 s
mmol/L
Drift 50 mV/min Mg hardness: Amount of magnesium in the sample in
Max. waiting time 26 mmol/L
Volume increment 0.1 mL VEP1: Titrant consumption until the first
equivalence point in mL
EP criterion 30 mV c(EDTA): Concentration of titrant in mol/L; here
EP regonition all c(EDTA) = 0.1 mol/L
f: Correction factor («titer») without unit
1000: Conversion factor to obtain result in mg/L
Calculation
Vs: Sample size in mL
Titer
Vs × c(CaCl2 )
Titer = The total hardness can be saved as a common variable and
VEP1 × c(EDTA)
used for the Mg hardness later on.

or
Example determination

ms
Titer =
VEP1 × c(EDTA) × MA

Titer: Titer of the titrant

Vs: Added volume standard solution in mL
ms: Mass of standard in mg
c(CaCl2): Exact concentration of standard solution in
mol/L
VEP1: Titrant consumption until the first
equivalence point in mL
c(Titrant): Concentration of the selected titrant in
mol/L; here c(EDTA) = 0.1 mol/L
MA : Molecular weight of the analyte; here
110.98 g/mol (CaCl2) Fig. 2: Determination of the total hardness.

Total hardness
VEP1 × c(EDTA) × f × 1000
Total hardness =
VS

Total hardness: Total hardness in mmol/L

VEP1: Titrant consumption until the first
equivalence point in mL
c(EDTA): Concentration of titrant in mol/L; here
c(EDTA) = 0.1 mol/L
f: Correction factor («titer») without unit
1000: Conversion factor to obtain result in
mmol/L
VS: Sample size in mL
Fig. 3: Determination of the Ca hardness

Page 6 of 8
 Application Bulletin 125/3 e
Simultaneous determination of calcium, magnesium and
alkalinity by complexometric titration with potentiometric or
photometric indication in water samples and beverages

Comments  SCA, blue book 43

 The light intensity must have stabilized sufficiently Total hardness, calcium hardness, and magnesium
before use. Each time the optical electrode is switched hardness in raw and potable waters by EDTA titrimetry
on or the wavelength changed one should wait at least  SCA, blue book 44
for five minutes before starting the first determination. The determination of alkalinity and acidity in water
 It is not recommended to use CaCO3 for titer  Metrohm Application Bulletin AB-206
determination, as the titration needs to be carried out at Titer determination in potentiometry
pH 12 to 13 and thereby CaCO3 precipitates.  Metrohm Application Bulletin AB-221
 If the expected amount of Ca2+ ions is too high Standard methods in water analysis
(> 100 mg/L, 2.5 mmol/L respectively) CaCO3 can
precipitate. It is therefore recommended to dilute such
samples. Author

 A concentration of more than 1 mg/L orthophosphate Competence Center Titration

ions lead to a precipitation of calcium at the pH used for Metrohm International Headquarters
the titration.
 When working with a sample changer, the buffer pH 10
would release NH3, what can cause alteration of the pH
value of the following samples. In this case it is
advisable to use alkaline borate buffer or to cover the
samples.
 When performing photometric titrations, attention has to
be paid to the fact that no air bubbles are incorporated
through stirring.
 According to the norm DIN 38406-3 the photometric
method is not suitable for sea water and waters with a
similar salinity as well as waste water.

References
 DIN 38406-3
German standard methods for the examination of
water, waste water and sludge – Cations (group E) –
Part 3; Determination of calcium and magnesium,
complexometric method (E 3)
 EN ISO 9963-1
Water quality – Determination of alkalinity – Part 1:
Determination of total and composite alkalinity
 EPA 130.2
Hardness, Total (mg/L as CaCO3) (Titrimetric, EDTA)
 EPA 310.1
Alkalinity (Titrimetric, pH 4.5)
 ASTM D1126
Standard Test Method for Hardness in Water
 Christiansen, T.F.; Busch, J. E.; S. C. Krogh
Successive determination of calcium and magnesium in
drinking water by complexometric, potentiometric digital
titration to two equivalence points, Anal. Chem. 70
(1976) 1051–1056.

Page 7 of 8
 Application Bulletin 125/3 e
Simultaneous determination of calcium, magnesium and
alkalinity by complexometric titration with potentiometric or
photometric indication in water samples and beverages

Appendix
Table of the definitions for water hardness used in this Application Bulletin as well as further expressions.
Alkalinity The alkalinity is defined as the acid neutralizing capacity, the result is given in mmol/L
Calcium hardness The calcium hardness gives the amount of Calcium in mmol/L
Magnesium hardness The magnesium hardness gives the amount of Magnesium in mmol/L
Total hardness The total hardness is the sum of the calcium and magnesium hardness in mmol/L
Permanent hardness The permanent hardness can be calculated from the total hardness and the alkalinity (see
calculations in potentiometric part)
Carbonate hardness The carbonate hardness is another expression for the alkalinity
Temporary hardness The temporary hardness is another expression for the alkalinity
Remaining hardness The remaining hardness is another expression for the permanent hardness

Table for the conversion of the different hardness units

mmol/L mg/L CaCO3 °dH °fH °e
1 mmol/L = 1 100.0 5.6 10.00 7.02
1 mg/L CaCO3 = 0.01 1 0.056 0.1 0.07
1 °dH = 0.1783 17.8 1 1.78 1.253
1 °fH = 0.1 10 0.560 1 0.702
1 °e = 0.142 14.3 0.798 1.43 1
mg/L CaCO3 corresponds to the American degree.
°dH German degrees
°fH French degrees
°e English degrees

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