EXPERIMENT 12: DETERMINATION OF

SO42- AS BaSO4 USING GRAVIMETRY

AND BY “SCATTERING”.

OBJECTIVE: To determine the sulfate content of sea

water brine (used in salt manufacturing) using gravimetry
and turbidimetry, and to compare the methods.

EQUATIONS & PRINCIPLES:

The Beer Lambert law
 Is the linear relationship between Absorbance and
concentration of an absorbing species.
A=E.b.C which becomes S=k.b.c
S-scattering read as absorbance.
B-remains as path length
C-is the analyte concentration prior to precipitation.

MATERIALS/EQUIPMENTS AND SAFETY PRECAUTIONS:

equipments reagent Reagent description

Weighing bottle Unknown so42- sample

Water bottle Barium chloride (Bacl2)

Beakers (100cm3 and Hydrochloric acid (HCL)

250cm3)

Glass rod Potassium sulfate (k2so4)

Dropper Water (H2O)

Pipette (5,10 and 25cm3)

Crucible

Heat source(Bunsen
burner)
Dessicator
Analytical balance
Ashles filter paper
Filter funnel
Flask
Volumetric flask
Magnetic stirrer
Spectrophotometer

SAFETY PRECAUTIOS
  Lab clothing (lab coats and closed must be worn)
 No eating or drinking in the lab
 Ground sulfur is essentially non-toxic through skin contact,
ingestion and inhalation. However, it can irritate the skin
and eyes as well as the respiratory system.
 Barium chloride is poisonous. It is harmful if inhaled and in
contact with the skin, and may be fatal if swallowed, wear safety
glasses and work in fume wood cupboard.
 Potassium sulfate is harmful if swallowed and may be harmful if
inhaled or absorbed through the skin.

PRECALCULATIONS:
Part 1
Mass of o, 2M Bacl2
250 ml
0, 2mol × 1000 ml
=0, 05 mol
Mass = mols×Mm
=0, 05mol×204,2g/mol
=10,41g

10% weighing range:

 10
10, 41 g × 100 = 1.041 g

(10, 41 ± 1,041) g = 9,369 g ↔ 11,45 g

Part 2
Mass of 0,2M k2so4
100 ml
0,2mols × 100 ml

=0, 02 mol
Mass = mol × Mm
=0,02mol × 174, 2 g/mol
=3, 4842 g
10% weighing range:
10
3, 4842 g× 100 =0, 3485 g

(3, 4842 g ± 0, 3485 g) =3, 1355 g ↔ 3, 832 g

EXPERIMENTAL PROCEDURE:
Note: Refer to experiment 12, from page 1to 2.

Results
Table 1: Mass of BaSO4 weighed
Crucible Mass (g) Crucible + product Mass (g) Product Mass (g)
6.6082 6.9017 0.2935

Table 2: Absorbance measurement and concentration of standards

for calibration
Standard Volume Absorbance Concentration Absorbance/volume ratio
(cm³)
5 0.179 2 x 10⁻⁵ 0.0358
10 0.265 4 x 10⁻⁵ 0.0265
15 0.330 6 x 10⁻⁵ 0.0220
20 0.406 8 x 10⁻⁵ 0.0203
25 0.483 10 x 10⁻⁵ 0.0193
Average ratio 0.0248
[Link] 0.00675
95%CL 0.0248±0.00591
Q-Test 95%CL 0.564
Cut off Q value @ 95 CL 0.710

Table 3: Sample absorbance reading

Sample runs Absorbance
A 0.281
B 0.255
C 0.230
Average 0.255
Std. dev. 0.0255
95% CL 0.255±0.0153

Table 3: Absorbance reading delay in time

Time (min) Absorbance
4 0.920
6 0.920
11 0.918
16 0.910
21 0.897
Figure 1: Absorbance versus concentration of sulfate
ion
0.93

0.92

0.92

0.91

0.91

0.9

0.9

0.89

0.89
4 6 11 16 21

Figure 2: Scattering versus Time

Table 4: data for Std. deviation model calculation
N X x x−x ( xᵢ−x ) ² ∑( xᵢ−x ) ²
1 0.281 0.255 0.026 0.000676 0.001301
2 0.255 _ 0 0 _
3 0.230 _ 0.025 0.000625 _

Table 5: Confidence limit for different number of

values
Numbe  3 4 5 6 7 8 9 10
r of
values:
Q90%: 0.941 0.765 0.642 0.560 0.507 0.468 0.437 0.412
Q95%: 0.970 0.829 0.710 0.625 0.568 0.526 0.493 0.466
Q99%: 0.994 0.926 0.821 0.740 0.680 0.634 0.598 0.568

Calculations
Gravimetric calculation of sulfate concentration in sea water.

Mol BaSO4in 25 cm3

mass
mol BaSO ₄=
Molar mass

0 .2935
¿
233 .39

¿ 1 .258 ×10 ˉ ³ mol

Mol SO4 in 25 cm3

¿ Mol BaSO ₄ ( 1 :1 )

¿ 1.258 ×10 ˉ ³ mol

Mol SO4 in 1000 cm3

1000 cm ³
1.258 ×10 ˉ ³ mol ×
250 cm ³

¿ 5.032× 10 ˉ ³ M
Graphical determination of Sulfate concentration

¿ the graph we get : 4.28 x 10 ˉ ⁵ M

Dilution factor :×100
Therefore SO 4=4.28 x 10 ˉ 3 M

Standerd deviation model calculation

s=
√ ∑ ( x ᵢ−x )2
i=1
N −1
0.001301
¿
√ 2
0.0255

Model calculation for 95% Confidence limet (95CL)

zs
95 %CL=x ±
√N
1.96 ×0.0255
¿ 0.255 ±
√3
¿ 0.255 ± 0.0153

Q-test calculation using abundance /volume ratio in table 2

Gap
Q=
Range
0.0358−0.0265
¿
0.358−0.0193
¿ 0.564

Discussion

From part 1 and part 2 we get similar values for sulphate concentrations. In part 1 we get a
slightly higher concentration than part 2, this increase in concentration could be as a results of
interference by the contamination of the apparatus. This contamintion could have resulted to a
mass increase in the Barium sufate weighed. Another factor that could have resulted in the
increase in the barium sulfate is the effect of the humidity in the lab, which could have
moistened the the product.
The curve in figure 1 was well callibrated with the first reading being considerd as an outlier as
proven by the Q-test fro the calculations, since the ratio of the absobance to volume of the first
reading gave the Q-value that is less than that of 95 CL for five velues (0.564 <0.710). The cut of
value for the confidence limit for 0.564 must be below 90% CL. Hence the value is considered
an outlier.

From figure 2 we can see the effect that the time has on the measure of the scattering of the
particles. As the time increase the scattering decreases gradually. This decrease may be due to
the colloidal particles settling down the bottom of the beaker resulting in decreased scattering
of the solution. This effect of decreasing scattering can be clearly seen form table 3 absorbance
measure; here the absorbance decreases from sample A to C. Another effect could be the effect
of drying to constant mass that is the maximum drying temperature.

From figure 1 we can see a linear relationship between SO₄²ˉconcentration and absorbance.
The ratio of absorbance to volume is almost constant for the last four values (around 0.02). This
shows the precision of the calibration. The precision can also be supported by the standard
deviation in table 2, which shows very little deviation between different points.

Conclusion

From both part one and part two, we can determine the concentration of the sulfate content in
the sea water and they both produce similar results. The gravimetric determination of sulfate
being the most time consuming method of determining the concentration of sulfate seawater.
Scattering is a much more time efficient method of analysis than the gravimetric method of
analysis. The rate of the scattering can be used as the background correction method to
determine the exact scattering or absorbance of the solution.

……………Completed on 23 March 2011……..

Questions

1. Our results were both in the same order of magnitude (4-5 x 10ˉ³M)
5.032× 10ˉ ³−4.028× 10ˉ ³
% Gravimetry= ×100
5.032× 10ˉ ³
2. The colloidal precipitate of the solution creates the absorbance
3. To eliminate the possibility of interfering ions
4.