Etiket Arşivleri: Dissolved Oxygen

Determination of Dissolved Oxygen By Winkler Titration

Lab 1:

DETERMINATION OF DISSOLVED OXYGEN BY WINKLER TITRATION

1. Background

Knowledge of the dissolved oxygen (O2) concentration in seawater is often necessary in environmental and marine science. It may be used by physical oceanographers to study water masses in the ocean. It provides the marine biologist with a means of measuring
primary production – particularly in laboratory cultures. For the marine chemist, it provides a measure of the redox potential of the water column. The concentration of dissolved oxygen can be readily, and accurately, measured by the method originally developed by Winkler in 1888 (Ber. Deutsch Chem. Gos., 21, 2843). Dissolved oxygen can also be determined with precision using oxygen sensitive electrodes; such electrodes require frequent standardization with waters containing known concentrations of oxygen. They are particularly useful in polluted waters where
oxygen concentrations may be quite high. In addition, their sensitivity can be exploited in environments with rapidly-changing oxygen concentrations. However, electrodes are less reliable when oxygen concentrations are very low. For these reasons, the Winkler titration is often employed for accurate determination of oxygen concentrations in aqueous samples.


Source: https://ocw.mit.edu/courses/earth-atmospheric-and-planetary-sciences/12-097-chemical-investigations-of-boston-harbor-january-iap-2006/labs/dissolved_oxygen.pdf

Determination of Dissolved Oxygen

The classical method for the determination of dissolved oxygen in aqueous solutions is known as the Winkler Method. In an alkaline solution, dissolved oxygen will oxidize manganese(II) to the trivalent state – 2+ 8 OH (aq) + 4 Mn (aq) + O (aq) + 2 H O (l) => 4 Mn(OH) (s) 2 2 3 Potassium iodide is also added to the solution which is oxidized by the manganic hydroxide when the solution is acidified. – + – 2+ 2 Mn(OH) (s) + 3 I (aq) + 6 H (aq) => I (aq) + 3 H O(l) + 2 Mn (aq) 3 3 2 The triiodide produced is then titrated with sodium thiosulfate, S O 2-. 2 3 2- – 2- – 2 S O (aq) + I (aq) => S O (aq) + 3 I (aq) 2 3 3 4 6 Therefore, for each mole of dissolved oxygen, four moles of thiosulfate are used in the titration. The convoluted set of steps is necessary to produce a fast, stoichiometric titration. Success of the method is critically dependent upon the manner in which the sample is manipulated; at all stages, every effort must be made to assure that oxygen is neither introduced to nor lost from the sample. Biological Oxygen Demand (BOD) bottles are designed to minimize the entrapment of air. The sample should be free of any solutes that will oxidize iodide or reduce iodine. Numerous modifications have been developed to permit use of the Winkler method in the presence of such species. In this experiment the thiosulfate solution will be standardized against triiodide generated from primary standard potassium iodate. – + – + KlO (aq) + 8 I (aq) + 6H (aq) => 3I (aq) + 3H O(l) + K (aq) 3 3 2 PROCEDURE Preparation of Approximately .050 M Sodium Thiosulfate Solution. Boil about 1 liter of deionized water for at least 5 minutes. Cool and add about 12 g of Na S O .5H O and 0.2 g of Na CO . Stir until the solution is complete, then transfer to a clean 2 2 3 2 2 3 stoppered bottle (glass or plastic). Store in the dark. (How long will this last? Find out!) Standardization of Thiosulfate Solution. Weigh by difference (to the nearest 0.1 mg) about 0.6 g samples of dried, primary standard KIO into a small beaker. Dissolve in 75 ml of water, and add about 6 g of iodate-free KI. 3 Transfer with several rinses to a 250 ml volumetric flask. Bring to the mark with deionized water and mix well. Use a 2.00 ml pipet to transfer an aliquot of this standard solution to conical flask. Add about 40 ml of deionized water and 10 ml of 1.0 M HCl, and titrate immediately with the thiosulfate solution until the color of the solution becomes pale yellow. Run triplicate determinations. Calculate the mean and standard deviation of your standard thiosulfate. Follow the titration using a redox electrode. (How does this electrode work? Find out!)

Dissolved Oxygen Samples. Transfer the sample to a 300 ml BOD bottle, taking care to minimize exposure to air. (Some filling methods will be demonstrated.) Fill the bottle to overflowing. Add 1 ml of MnSO4 solution; discharge the reagent well below the surface (some overflow will occur). Similarly, introduce 1 ml of the KI-NaOH solution. Place the stopper in the bottle; be sure that no air becomes entrapped. Invert the bottle several times to distribute the precipitate uniformly. When the precipitate has settled leaving the supernat clear, shake again. When the precipitate has settled at least 3 cm below the stopper, introduce 1 ml of concentrated (18 M) H SO well below the surface. (Care should be taken to avoid exposure to the overflow, as the 2 4 solution is quite alkaline.) Replace the stopper and mix until the precipitate dissolves. Pipet 50 ml of the acidified sample into a 500 ml conical flask. Titrate with 0.050 M Na S O until the iodine 2 2 3 color becomes faint. Analyze triplicate samples. Special Solutions That You Will Need a. KI-NaOH solution. 15 g of Kl is dissolved in 25 ml of water plus 66 ml of saturated NaOH, then diluted to 100 ml. b. Manganese(II) Sulfate. 48 g of MnSO .4H O in sufficient deionized water to make 100 ml. 4 2 Report A full report is not necessary. Each boat group should generate a spreadsheet showing results, and calculations, and answer the questions below. Report the concentration of dissolved oxygen in mM and mg/L for sample. Compare your results to the YSI probe results. How confident are you that the two techniques produce the same result? Comment on the various uncertainties and biases involved in this analysis. What do you think the limit of accuracy is in this experiment (that is, estimate the cummulative value of the random and determinant errors)? Source: Fundamentals of Analytical Chemistry, 3rd Ed., Douglas A. Skoog and Donald M. West, 1976, Holt, Rinehart and Winston.


Analysis of Water Chemistry

Analysis of Water Chemistry

  • Urban Stream Restoration Project

  • Outline

  • Water Chemistry Background

  • Chemistry in Urban Streams

  • Methods

  • 2003 Results

  • Comparison to 2002

  • Conclusions

  • Outline

  • Water Chemistry Background

  • Chemistry in Urban Streams

  • Methods

  • 2003 Results

  • Comparison to 2002

  • Conclusions

  • Temperature

  • Most aquatic organisms are cold-blooded and have an ideal temperature range, specific to the organism:

  • Diatoms 15-25 degrees C

  • Green algae 25-35 degrees C

  • Blue greens 30-40 degrees C

  • Salmonids – cold water fish

  • Temperature, continued

  • Affects development of invertebrates, metabolism of organisms

  • Affects dissolved oxygen (warm water holds less oxygen)

  • Warm water makes some substances more toxic (cyanide, phenol, xylene, zinc) and, if combined with low DO, they become even more toxic

  • Dissolved Oxygen

  • Oxygen that is dissolved in water

  • DO increases with cooler water and mixing of water through riffles, storms, wind

  • Nutrient loading can lead to algal blooms which result in decreased DO

  • 4-5 ppm DO is the minimum that will support large, diverse fish populations. Ideal DO is 9 ppm. Below 3 ppm, all fish die.

  • Dissolved Oxygen, continued

  • Dissolved oxygen can also be expressed as % saturation

  • 80-124% = excellent

  • 60-79% = ok

  • < 60% = poor

  • Conductivity

  • Measures the ability of water to carry an electric current

  • Measures the ions such as Na+, Cl- in the water

  • Differences in conductivity are usually due to the concentration of charged ions in solution (and ionic composition, temp.)

  • Reported as microsiemens per cm

  • pH

  • pH measures the degree of acidity or alkalinity of the water (each number is a 10-fold difference)

  • 0-6 = acid; 7 = neutral; 8-14 = base

  • Ideal for fish = 6.5 –8.2

  • Ideal for algae = 7.5 – 8.4

  • Acid waters make toxic chemicals (Al, Pb, Hg) more toxic than normal, and alter trophic structure (few plants, algae)

  • Turbidity

  • Measures the cloudiness of the water

  • Turbidity caused by plankton, chemicals, silt, etc.

  • Most common causes of excess turbidity are plankton and soil erosion (due to logging, mining, farming, construction)

  • Turbidity, continued

  • Excess Turbidity can be a problem:

  • Light can’t penetrate through the water – photosynthesis may be reduced or even stop – algae can die

  • Turbidity can clog gills of fish and shellfish –can be fatal

  • Fish cannot see to find food, but can hide better from predators

  • Phosphorus (Reactive)

  • Is necessary for plant and animal growth

  • Natural source = phosphate-containing rocks

  • Anthropogenic source = fertilizer and pesticide runoff from farming

  • Can stimulate algal growth/bloom

  • Nitrates

  • Formed by the process of nitrification (addition of O2 to NH3 by bacteria)

  • Used by plants and algae

  • Is mildly toxic, fatal at high doses

  • Large amounts (leaking sewer pipes, fertilizer runoff, etc.) can lead to algal blooms, which can alter community structure, trophic interactions and DO regimes)

  • Below 90 mg/L seems to have no effect on warm water fish, but cold water fish are sensitive

  • Alkalinity

  • A measure of the substances in water that can neutralize acid and resist changes in pH

  • Natural source = rocks

  • Ideal water for fish and aquatic organisms has a total alkalinity of 100-120 mg/L

  • Groundwater has higher alkalinity than surface water

  • Hardness

  • The amount of Calcium and Magnesium in the water (the two minerals mostly responsible)

  • Natural source = rocks

  • Limestone = hard water, granite = not hard water

  • Hardness, continued

  • Soft water can be a problem: in soft water, heavy metals are more poisonous, some chemicals are more toxic, drinking soft water over long periods can increase chance of heart attack

  • 0 – 60 = soft water

  • 61-120 = moderately hard water

  • 121-180 = hard water

  • 181+ = very hard water

  • Hardness and alkalinity are related

  • Outline

  • Water Chemistry Background

  • Chemistry in Urban Streams

  • Methods

  • 2003 Results

  • Comparison to 2002

  • Conclusions

  • Physical Effects of Urbanization Related to Water Chemistry

  • Riparian Vegetation Removal

  • Decreased Groundwater Recharge

  • Heat Island Effect

  • Increased Surface Runoff / Impervious Surfaces

  • Leaky Storm-water / Sewage Pipes

  • Point Source Pollution

  • Trends in Water Chemistry

  • Temperature increases

  • Nitrate increases

  • Phosphorus increases

  • Conductivity increases (Increased ion concentration)

  • O2 demand increases

  • Outline

  • Water Chemistry Background

  • Chemistry in Urban Streams

  • Methods

  • 2003 Results

  • Comparison to 2002

  • Conclusions

  • Field Measurements

  • Dissolved Oxygen

  • Temperature

  • Conductivity

  • pH

  • Water Collection For Laboratory Analysis

  • Grab Samples

  • Three replicates (from multiple samples)

  • Measured within 24 hours (few exceptions)

  • Laboratory Analysis

  • Nitrate

  • Reactive

Phosphorus

  • Alkalinity

  • Hardness

  • Turbidity

  • Outline

  • Chemistry in Urban Streams

  • Water Chemistry Measurements and Theory

  • Methods

  • 2003 Results

  • Comparison to 2002

  • Conclusions

  • Field Measurements 2003

  • Turbidity

  • All values for 2003 <5 jtu

  • For 2002, all but one sampling date <5 jtu

  • The one date for 2002 >5 was during a storm event

  • Reactive Phosphorus 2003

  • Nitrate 2003

  • Alkalinity 2003

  • Hardness 2003

  • Outline

  • Chemistry in Urban Streams

  • Water Chemistry Measurements and Theory

  • Methods

  • 2003 Results

  • Comparison to 2002

  • Conclusions

  • Field Measurement PB

  • Field Measurement For SAL

  • Paint Branch

  • Stewart April Lane

  • Outline

  • Chemistry in Urban Streams

  • Water Chemistry Measurements and Theory

  • Methods

  • 2003 Results

  • Comparison to 2002

  • Conclusions

Between Site Differences

  • Land use – increased runoff cause increased input of particular constituents

  • Natural site variation – Substrate type

Between Years

  • Increased snow caused more runoff increased use of road-salt

  • Drought (temperature, DO)

“. . . Rivers and the inhabitants of the watery element were made for wise men to contemplate, and fools to pass by without consideration, . . . for you may note, that the waters are Nature’s storehouse, in which she locks up her wonders.”

  Izaak Walton

  (from Ward, 1992)