EXPERIMENT 8 Dissolved oxygen by redox titration (The winkler method) Muhammad Nazar

Introduction The solubility of oxygen in the water depends on the partial pressure of oxygen in atmospheric air, water temperature and mineral consisting in water. The Dissolved oxygen which is usually abbreviated as DO is determined as the quantity of free oxygen present in water. The DO is important for aquatic organisms such as aerobic bacteria and fish to survive. In this experiment, DO was quantified using Winkler method. In this method, the titration is
employed to determine dissolved oxygen in the water sample. A sample bottle is filled completely with water (avoid any air left inside the bottle). The dissolved oxygen in the sample is fixed by adding a series of reagents producing an acid compound and then titrated with thiosulfate solution which changes the colour. From the end point of titration where the iodine colour start to disappear producing a clear solution, the amount of oxygen then can be calculated considering the following reaction: 4H+ + O2 + 4S2O32_ 2S4O62- + 2H2O Experimental The standardization of thiosulfate solution was carried out by dissolving 2 g of KI in 100 mL distilled water followed by addition of 2M sulfuric acid and standard potassium dichromate. The mixture was titrated using thiosulfate solution until the iodine colour was pale yellow. The indicator of starch was added and titration continued until the colour disappears. The following reactions are involved: 6KI + 7H2SO4 + K2Cr2O7 Cr2(SO4)3 + 3I2 + 7H2O + 4K2SO4 (reaction 1) 2Na2S2O3 + I2 Na2S4O6 + 2NaI (Reaction 2) Part B and Part C works referred to CHEM 250 Analytical Chemistry Manual Book

Results and calculations Standardisation of thiosulfate Run 1 24.8 V of thiosulfate (mL) Run 2 24.8 Average 24.6

Mass of KI= 2 g, MW = 166, mole= 2/166 = 0.012 moles Moles of K2Cr2O7 = 0.025 mL x 0.00416 M = 1.04x10-4 moles, since moles of K2Cr2O7 is much smaller than KI So, using reaction 1 Concentration of I2 = 3/1 x 1.04x10-4 moles = 3.12x10-4 moles In reaction 2, moles of thiosulfate is 2x3.12x10-4 = 6.24x10-4 moles Concentration of thiosulfate = 6.24x10-4/0.0246 = 0.0253 M Volume of titrant at various temperatures

Volume of thiosulfate (mL) 17.7 14.1 9.3 12.4* * Tap water

Temperature (oC) 4 16 27 12.5*

For temperature of 4 and 16 BOD flask 1 was used and for temperature 0f 27 and tap water BOD flask 2 was used. Volume of BOD flask 1= 334.27/0.9995 = 334.437 mL Volume of BOD flask 2 = 292.05g/0.9995 = 292.196 mL Moles of O2 at 4oC = (0.0253 mol/L x 17.7/1000 L = 1.1195x10-4 moles {1.1195x10-4 moles x (334.437-4)(334.437)/334.4372} x 334.437-25/334.437 = 1.008x10-4 moles [O2] = 1.008x10-4/0.334 = 3.01x10-4 mol/L In ppm = 3.01x10-4 mol/L x 32 g/mole x 1000 ml/L = 9.65 ppm

For temperature of 16 (0.0253 x 14.1/1000 = 8.92x10-5 {8.92x10-5 x (334.437-4)(334.437)/334.4372} x 334.437-25/334.437 =8.086x10-5 moles [O2] = 8.086x10-5 moles/0.334 = 2.42x10-4 mol/L 2.42x10-4 mol/L x 32 g/mole x 1000 ml/L = 7.747 ppm At temperature of 27 (0.0253 x 9.3/1000) = 5.88x10-5 {5.88x10-5 x(292.2-4)(292.2-2)/292.22} x 292.2-25/292.2 = 5.26x10-5 moles [O2] = 5.26x10-5 moles/0.292 = 1.8x10-4 mole/L In ppm 1.8x10-4 mole/L x 32 x 1000 = 5.76 ppm Tap water (0.0253 x 12.4/1000) = 7.84x10-5 =7.84x10-5 (292.2-4)(292.2-2)/292.22} x 292.2-25/292.2 =7.01x10-5 moles [O2] = 7.01x10-5 moles/0.292 = 2.4x10-4 = 7.68 ppm [O2] (ppm) 9.65 7.74 5.76 Temperature (K) 277 289 300

Graph. 1 Plot of log [O2] vs 1/T

log O vs 1/T
1.2 1 y = 804.58x - 1.9123 R = 0.9828

log [O2]

0.8 0.6 0.4 0.2 0 0.0033 0.0034 0.0035 1/T 0.0036 0.0037 log O Linear (log O)

The linearity of this graph depends on the temperature. The higher the temperature, the lesser oxygen will be detected in the water. The solubility of oxygen in water is strongly temperature dependent. When temperature increase the soluble oxygen is very likely to be evaporated to the air rather than remain in the water. The solubility of oxygen in the tap water sample can be obtained by using the plotted graph above. Since the temperature of tap water was 12.5 oC or 285.5 K so 1/K = 3.5x10-3. As line drawn on the graph shows that the value of log [O2] = 0.9, hence [O2] = 7.94 ppm. The percentage saturation is: Mole O2= [0.0253 x 12.4/1000] = 7.84x10-5 Saturated O2 in tap water = 7.84x10-5 / 0.292 = 2.68x10-4 M = 8.59 ppm [O2] (ppm) 14.19 11.27 9.07 Temperature (K) 274 283 293 [O2]corr 12.46 9.89 7.96

The values of [O2]corr were obtained from calculation by using the following formula:

Graph 2. Plot of log [O2]corr vs 1/T

log [O2] vs 1/T

1.2 1 y = 822.01x - 1.9062 R = 0.9992

log [O2]

0.8 0.6 0.4 0.2 0 0.0034 0.0035 1/T 0.0036 0.0037 log [O] Linear (log [O])

This plot of log [O2] vs 1/T is slightly better than the first plot using the experimental data. This plot has R2 value of 0.999 closer to 1 and the plot using experimental data has the R2 value of 0.9828. Both slope and intercept of the two graphs are also slightly different. As can be seen from the plotting graph and the results of this experiment, the solubility of oxygen in water is a temperature dependent. The solubility decreases when the temperature increases.

References Skoog, D.A, West, D.M and Holler F. J (1988). Fundamentals of Analytical Chemistry. 5 th ed. Saunders College Publishing: New York. Christian, G. D, (1986). Analytical Chemistry, 4th ed. John Wiley & Sons: New York.