Ab-125 3 en
Ab-125 3 en
Ab-125 3 en
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
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
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
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
Electrodes Analysis
Solutions Parameters
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
or
Example determination
ms
Titer =
VEP1 × c(EDTA) × MA
Total hardness
VEP1 × c(EDTA) × f × 1000
Total hardness =
VS
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
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
Page 8 of 8