Analysis of Ions in an Aqueous System

Using Conductometric Titration of Calcium Nitrate with Sodium

Phosphate to asses Stoichiometric Proportions
Analysis of Ions in an Aqueous System Using Conductometric
Titration of Calcium Nitrate with Sodium Phosphate to asses
Stoichiometric Proportions

A conductometric titration was conducted in order to examine and confirm stoichiometric

proportions. 50mL of a 0.100 M Sodium phosphate solution was titrated with 60.0mL of a 0.100 M
calcium nitrate solution. It was expected, due to the stoichiometric proportions, that 40mL of the
0.100 M Sodium phosphate solution would react completely with 60mL of the 0.100 M calcium
nitrate solution which would in turn produce a minimum conductivity value. A suspension of 0.002
moles of Calcium phosphate was expected to form in the resulting 100mL 0.120 M sodium nitrate
solution. In calibration of the conductor probe a preparation of 0.120 M sodium nitrate solution was
used and recorded at a conductance value of 11600 µS cm-1. The mean volumetric addition at the
equivalence point was 40.3mL (table 1) and the mean conductivity value at equivalence point was
found to be 12205 µS cm-1 which was noticeably higher than predicted although consistent with the
hypothesis and stoichiometric relationship it indicated potentially higher quantities of ions remained
in solution than expected.
Introduction:

Ions are atoms or molecules which contain an unequal number of protons and electrons. This
inequality leads to a positively or negatively charged particle. Ionic compounds, consisting of a
positively charged cation and a negatively charged anion, which dissociate and ionize in water are said
to be electrolytes.

Moeller and O’Connor (1972) stated that the original theory of electrolytic dissociation, as
propounded by Svante Arrhenius in 1887, assumed that when a solute is placed in contact with water,
equilibrium is established between solute molecules and ions in solution. The conductivity of a
solution is directly dependent on the concentrations and the relative charges of the ions also on the
size and velocities of the particles. When an electric field is applied across a solution, a force is
exerted on the ions that will cause them to move as illustrated by Kealey, Haines (2002).

The reaction of sodium phosphate and calcium nitrate is given by the ionic equation:

[3Ca2+(aq) + 6NO3+(aq) + 6Na+(aq) + 2PO43– (aq) = Ca3(PO4)2(s) + 6Na+(aq) + 6NO3– (aq)]

In which three molecules of calcium nitrate react with two molecules of sodium phosphate to form a
precipitate of calcium phosphate this quantitative relationship is analyzed through Stoichiometry. The
calcium 2+ cation, the sodium cation and the nitrate anion are all soluble in aqueous solution. The
phosphate 3- anion is insoluble as per IUPAC guidelines. In titrating Ca(NO3)2 with Na3PO4 the dilution
and reduction in the concentrations of all ions as well as the precipitation of Ca 3(PO4)2 reduce
conductivity approaching the equivalence point and subsequently conductivity should increase as the
remaining sodium phosphate solution is added providing greater quantities of ions in solution.
Materials and Methods:

In preparation of 250mL of a 0.100 M solution of sodium phosphate 9.503g of (Na 3PO4-12H2O) was
dissolved with dH2O in a volumetric flask. The 0.100 M Sodium phosphate was placed in a 50mL
burette used in the titration 60.0mL of 0.100 M calcium nitrate was measured using a graduated
cylinder and placed under the burette in a 250mL beaker and stirred with a magnetic stir bar.

Data was collected using the Logger Pro software program where 25 successive 2mL additions of the
sodium phosphate titrant were added to the aqueous calcium nitrate solution. Conductivity was
measured using a sensor to calibrate conductivity at two points, a value of zero while held in air and a
value of 11600 µS cm-1 submerged in 0.120 M sodium nitrate solution. Two subsequent titrations
were completed measuring the volume and conductance at the equivalence point.

Results:

Test 1 produced a minimum conductivity value of 12287 µS cm-1; test 2 produced a minimum
conductivity value of 12131 µS cm-1. In test 1 the volume of added titrant at lowest conductivity value
was 40.5mL; test 2 the volume of added titrant at lowest conductivity value was 39.7mL, mean values
presented in table 1.

Table 1: Volumetric Addition and Conductivity at Equivalence Point.

Volumetric addition at the Conductivity value at the

equivalence point equivalence point
Test 1 40.5mL 12,278 µS cm-1
Test 2 39.7mL 12,131 µS cm-1
Mean Value 40.3mL 12,205 µS cm-1

Initial conductivity in test 1 was 16024 µS cm-1 upon complete addition of sodium phosphate
conductivity was recorded at 13092 µS cm-1 (fig 1). Initial conductivity in test 2 was recorded at
15590µS cm-1 upon complete addition of sodium phosphate conductivity was recorded at 13038µS
cm-1 (fig 2).
Discussion:

The data obtained for volumetric addition were consistent with predictions based on the reaction
equation and stoichiometric proportions. A discrepancy was found in conductivity values, 12,278 µS
cm-1 in test 1 and 12,131 µS cm-1 in test 2, both values higher than expected equating to an
experimental error of 5.2 %( appendix 1). This value is most likely attributable to errors in calibration
and measurement of sodium phosphate solution also in the transfer from volumetric flask to beaker.
The higher than expected conductance values indicate slightly higher concentrations of ions at the
equivalence point due to discrepancies in molarity values. The removal of ions from solution in
forming the calcium phosphate precipitate contributed to reduced conductivity also the
concentration of aqueous ions was reduced due to dilution by addition of aqueous sodium and
phosphate ions during the titration. The remaining 10mL of sodium phosphate added after the
equivalence point had been reached contributed a further 10mL 0.00 M of aqueous sodium+ cation
which remained in solution together with the nitrate anions to the 110ml 0.120 M sodium

References:

 Moeller, T., & O’Connor, R. (1972). Ions in Aqueous Systems.USA: McGraw-Hill, Inc.
 Kealey, D. & Haines, P.J. (2002). Analytical Chemistry. Oxford, UK: Bios Scientific Publishers Ltd.