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Dr. D.G. Gajghate Scientist Air Pollution Control Division, NEERI, N a g p u r - 440020
One of the major pollutants produced from man-made sources is sulfur dioxide (SO2), much of which arises from the combustion of fossil fuels used for energy production. Industrial processes such as smelting, sulfuric acid
manufacture, and petroleum refining also produce sulfur dioxide. Sulfur dioxide is a nonflammable, colorless gas that can exist in air either as a gas or dissolved in water droplets. It can be tested by most people at concentrations of about 900 ug/m 3 or greater. Sulfur dioxide partially oxidizes in air to form sulfur trioxide (SO3), which readily combines with water vapor to form sulfuric acid (H2SO4).
Procedures for monitoring SO2 may be of the automatic or manual type, manual techniques may be either static (e.g., sulfation plates) or mechanical (e.g. gas bubbler devices). The two procedures for SO2 monitoring described in this manual are both of the mechanical type and were selected because of their proven reliability and relatively moderate purchase and operating cost. A large number of other methods are available and currently employed to measure SO2 concentrations in ambient air. One manual method involves conversion of SO2 to sulfate, automated techniques for the continuous
measurement of SO2 in air are especially a porosity. The principles involved for the more commonly used continuous techniques are conductivity, colorimetry, electrochemical diffusion, and gas chromatography coupled to flame photometry.
Pararosaniline Method - Comparison Method This method is based on the Schifs Reaction. The reaction was first used as a test for formaldehyde and later modified for use as a test for SO£ by Steigmann and adapted by Kozlyaeva for se in sampling and analyzing ambient air. Many modifications have since been proposed. The method presented here is an adaptation of the procedure used by the Environmental Protection Agency in the U.S.A.
Concentration of SO2 in the range of 25 to 1000 ug/m 3 can be measured with the prescribed absorbing solution volume and sample flow rates.
Concentrations below 25 ug/m 3 can be measured by sampling larger volumes of air but if this is done, the absorption efficiency of the collection system must be checked. Higher concentrations can be analyzed either by collecting a smaller sample of gas or by using a larger volume of solution and only part of the sample for the estimation. Beer's Law is obeyed through the working range from 0.03 to 1.0 absorbance units or 0.8 to 27 ug of sulfite ion in 255 ml of final solution. If 10 ml of tetrachloromercurate solution is used, and twice the standard deviation of duplicate estimations is taken as 0.75 ug, the lower limit of detection of SO2 in an air sample of 30 litres represents a concentration of 25 ug SC>2/m3. The relative standard deviation is 4.6 percent for the analytical procedure using standard samples. Collection efficiency is above 98 percent; efficiency may fall off, however, at concentrations below 25 ug/m 3 The principle substances known to interfere are oxides of nitrogen (NO x ), ozone (O3), manganese (M n ), iron (Fe), and chromium (Cr). In the procedure described here, these interferences have been minimized or eliminated. The interference from NO x is eliminated by sulfamic acid (H2NO3H), and O3 interference is eliminated by a time delay. The use of ethylenedaiamine
tetraacetic acid disodium salt (NaEDTA) and phosphoric acid and (HP3O4) prevents interference by certain metals. At least 60 ug F e , 10 ug M n and 10 ug C r in 10 ml absorbing reagent can be tolerated in the procedure detailed below. No significant interference was found from 10 ug copper ( C u 2 + ) or 22 ug vanadium (V + + ). Ammonia, sulfides, and aldehydes do not interfere.
Apparatus Absorber (30 minute to 1-hour samples) : An all-glass midget impinger or similar equipment.
Absorption tubes : Polypropylene tubes or all glass impingers,
32 mm, equipped with polypropylene two-part closures. Rubber stoppers cause high and varying blanks and should not be used.
Dispersers : A glass tube, approximately 8 mm outside diameter (O.D.), 6 mm inside diameter (I.D.); and 152 mm long with the end drawn out to 0.3 to 0.8 mm O.D.. The glass tube should be positioned so as to allow a clearance of 6 mm from the bottom of the absorption tube.
Air pump : A pump capable of maintaining a pressure differential of at least 0.7 atmosphere across the flow control device.
Flow control device : Any device capable of maintaining a constant flow through the sampling solution is acceptable. Critical orifices such as calibrated hypodermic needles may be used. A 22 gauge needle (0.394 mm I.D.) 2.5 cm long gives a flow of about 1 litre/minute. A 27 gauge needle (0.191 mm I.D.) 0.9 cm long gives a flow of about 0.2 liter/minute. Needle valves provide good variable control.
Filters : 0.8 to 2.0 um porosity membrane or glass fiber filter. These filters can be used with appropriate holders to remove particulates from the airstream to protect the flow control device.
Flow calibration equipment : A soap bubble flow meter or a wet or dry gas test meter capable of measuring airflow in the range of 0.2 to 1 litre/minute and a stop watch.
Spectrophotometer: A meter suitable for measurement of absorbance at 548 nm with an effective spectral band width of less than 15 nm. Reagent blank problems may occur with Spectrophotometer having greater spectral band width. The wavelength calibration of the instrument should be verified.
Thermometer : Accuracy ± 1°C
Distilled water : Water used must be free of oxidizing agents
A b s o r b i n g Reagent Dissolve 10.86 g HgCl2,
: 0.04M Potassium Tetrachloromercurate (TCM). 0.066 g EDTA (ethylenediaminetetraacetic acid,
disodium salt), and 6.0 g KCL in water and bring to mark in a 1000 ml volumetric flask. (Caution: highly poisonous. If spilled on skin, flush off with water immediately). The pH of this reagent should be approximately 4.0 but it has been shown that there is no appreciable difference in collection efficiency over the range of pH 3 to pH 5.(7) The absorbing reagent is normally stable for 6 months. To avoid disposal problems, mercury (Hg) must be removed from spent or used absorbing reagent (0.8 g/litre) by the following procedure : To each litre of absorbing solution add sodium carbonate (Na2C03) until neutral (about 10g) and
10 g of granular zinc (Zn) (magnesium (Mg) may be used). Stir the solution for 24 hours in a hood. After 24 hours, the solid material will have layered on the bottom of the container despite the stirring. The liquid can be decanted until the brown precipitate begins to pour out. Shake the precipitate into a tube and let it dry. (A test tube brush is useful in freeing material clinging to the walls of the container.) The container may be rinsed clean with water. Pass the rinse water over a filter to catch the precipitate. After rinsing, add the precipitate on the filter to the precipitate in the tube. Allow to dry, then place the contents of the tube into a convenient container. This procedure removes > 99 percent of the Hg in the absorbing solution. Sulfamic acid (0.6 percent) : Dissolve 0.6 g H2NSO3H in 100 ml of distilled water. Prepare fresh daily.
Formaldehyde (0.2 percent) : Dilute 5 ml of formaldehyde (HCHO) solution (36 to 38 percent) to 1000 ml with distilled water. Prepare fresh daily.
Stock iodine solution (0.1 N) : Place 12.7 g iodine (I2) in a 250-ml beaker, add 40 g potassium iodide (Kl) and 25 ml water, stir until dissolved, and make up to 1000 ml in a standard flask with distilled water.
Iodine Solution (0.01 N) : Prepare approximately 0.01 N iodine solution by diluting 50 ml of stock solution to 500 ml with distilled water.
Starch Indicator Solution : Triturate 0.4 g soluble starch and 0.002 g mercuric iodide (Hgl2) preservative with a little water and add the paste slowly to 200 ml of boiling water. Continue boiling until the solution is clear. Cool and transfer the solution to a glass-stoppered bottle.
Stock sodium thiosulfate solution : (0.1 N). Prepare a stock solution by dissolving 25 g sodium thiosulphate (Na2S203-5H20) in 1000 ml freshly boiled cooled, distilled water and add 0.1 g Na2CC>3 to the solution. Allow the solution to stand 1 day before standardizing. To standardize, accurately weigh, to the nearest 0.1 mg 1.5 g primary standard potassium iodate dried at 180°C and dilute to volume in a 500 ml volumetric flask. To a 500 ml iodine flask, pipette 50 ml of iodate solution. Add 2 g Kl and 10 ml of 1 N HCL. Stopper the flask. After 5 min titrate with stock thiosulphate solution to a pale yellow. Add 5 ml starch indicator solution and continue the titration until the blue color disappears. Calculate the normality of the stock solution as follows: W N = V N = Normality of stock thiosulfate solution V= Volume of thiosulphate required, ml W= Weight of potassium iodate, g. 2.80 = 103 (conversion of g to ms) times 0.1 (fraction iodate used) divided by 35.67 (equivalent wt. of potassium iodate) Sodium Thiosulphate Titrant (0.01 N) : Dilute 100 ml of the stock thiosulphate solution to 1000 ml with freshly boiled distilled water. X 2.80
Standardized sulfite solution for preparation of working sulfite - TCM solution Dissolve 0.3 g sodium metabisulfite (Na2S2C>5) or 0.40 g sodium sulfite (Na2S03) in 500 ml of recently boiled, cooled distilled water. The sulphite solution is unstable; it is therefore important to use water of the highest purity to minimize this instability. This solution contains the equivalent of 320 to 400 ug/ml of SO2. The actual concentration of the solution is determined by adding excess iodine and back-titrating with standard sodium sulfate solution. To back-titrate pipette 50 ml of the 0.01 N iodine into each of two 500 ml iodine flasks (A and B) .
To flask A (blank) add 25 ml distilled water, and to flask B (sample) pipette 25 ml sulfite solution. Stopper the flasks and allow to react for 5 minutes. Prepare the working sulfite-TCM. Stopper the flasks and allow to react for 5 min. Prepare the working sulfite-TCM Solution (6.2.9) at the same time iodine solution is added to the flasks. By means of a burette containing standardized 0.01 N thiosulfate, titrate each flask in turn to a pale yellow. Then add 5 ml starch solution and continue the titration until the blue color disappears.
Working sulfite -TCM Solution : Pipette accurately 2 ml of the standard solution into a 100-ml volumetric flask and make up to 100 ml with 0.04 M TCM. Calculate the concentration of SO2 in the working solution by the equation :
(A-B) (N) (32,000) ug S 0 2 / m l = 25 A= B= N= 32,000= 25 = 0.02= Volume thiosulfate for blank, ml Volume thiosulfate for sample, ml Normality of thiosulfate titrant Milliequivalent wt. of SO2, M9 Volume standard sulfite solution ml Dilution factor x 0.02
This solution is stable for 30 days if kept at 5°C. (refrigerator). If not kept at 5°C., prepare daily.
Purified Pararosaniline Stock
Solution (0.2 percent nominal) - The
pararosaniline dye must meet the following performance specifications: (a) the dye must have a wavelength of maximum absorbance at 540 nm when assayd in a buffered solution of 0.1 M sodium acetate-acetic acid; (b) the absorbance of the reagent blank, which is temperature sensitive (0.015 absorbance unit/°C). should not exceed 0.170 absorbance unit at 22°C with a 1-cm optical path length, when the blank is prepared according to the prescribed analytical procedure and to the specified concentration of the dye; (c) the calibration curve (Section 8.2.1) should
have a slope of 0.030±0.002 absorbance units/pg SO2 at this path length when the dye is pure and the sulfite solution is properly standardized. A specially
purified solution of pararosaniline, which meets the above specifications, is commercially available in the required 0.20% concentration. Alternatively, the dye may be purified, and a stock solution prepared and then assayed by standard procedure.
Pararosaniline Reagent - To a 250 ml volumetric flask, add 20 ml stock pararosaniline solution. For each percentage the stock assays below 100% and an additional 0.2 ml of stock solution. Then add 25 ml 3M H3PO4 and dilute to volume with distilled water. This reagent is stable for atleast 9 months.
Sampling Procedure This method is generally used for sampling for 30 minutes, for 1 hour, and 24 hours. To meet special needs, one can select different combinations of sampling rate and sampling time. Sample volumes should be adjusted in order that the relation between absorbance and concentration remains linear. All airflow measurement and control devices to standard atmospheric conditions (760 mm and 25°C) may be desirable if extremes in ambient pressure and temperature are encountered. If the sample must be stored for more than a day before analysis, keep it at or below 5°C in a refrigerator.
Sampling for 30 min and 1 hour- Insert a midget impinger into the sampling system. Add 10 ml TCM solution to the impinger. Aspirate the air at 1 l/m or at 0.5 l/m, controlling the flow with a critical orifice or with a needle valve and glass rotameter. During and after sampling, shield the absorbing reagent from direct sunlight. Determine the volume of air sampled by multiplying the flow rate by the time in min and record the atmospheric pressure and temperature.
Sampling for 24 hour - Place 50 ml TCM solution in a large absorber and collect the sample at 0.2 l/m with a sampling train. Protect from direct sunlight throughout collection and storage. Determine the total air volume by multiplying the airflow rate by the time in minutes, and record this and also the atmospheric pressure and temperature.
Analytical Procedure If after collection a precipitate is observed in the sample, remove it by centrifuging.
30 min and 1 hour Samples - Transfer the sample quantitatively to a 25 ml volumetric flask ; use about 5 ml distilled water for rinsing. Delay analyses for 20 min to allow any O3 to decompose.
24 hour sample - Dilute the entire sample to 50 ml with absorbing solution. Pipette 5 ml of the sample into a 25 ml volumetric flask for chemical analyses. Bring volume to 10 ml with absorbing reagent. Delay analyses for 20 minutes to allow any ozone to decompose. For each set of determinations prepare a reagent blank by adding 10 mi unexposed TCM solution to a 25 ml volumetric flask. Prepare a control solution by adding 2 ml of working sulfite-TCM solution and 8 ml TCM solution to a 25 ml volumetric flask. To each of these flask and also that containing the sample, add 1 ml 0.6 percent sulfamic acid and allow to react 10 min to destroy the nitrite from oxides of nitrogen. Accurately pipette in 2 ml 0.2% formaldehyde solution, then 5 ml pararosaniline solution. Start a laboratory timer that has been set for 30 min. Bring all flasks to volume with freshly boiled and cooled distilled water and mix thoroughly. Between 30 min and before 60 min, determine the absorbance of the sample (denote as A), reagent blank (denote as A) and the control solution at 548 nm using 1 cm optical path length cells. Use distilled water, not the reagent blank, as the reference. (Note This is important because of the sensitivity of the color reagent blank to temperature changes which can be induced in the cell
compartment of a spectrophotometer.) Do not allow the colored solution to stand in the absorbance cells, because a film of dye may be deposited. Clean cells with alcohol after use. If the temperature of the determinations does not differ by more than 2°C. from the calibration temperature, the reagent blank should be within 0.03 absorbance unit of the y-intercept of the calibration curve. If the reagent blank differs by more than 0.03 absorbance unit from that found in the calibration curve, prepare a new curve.
If the absorbance of the sample solution ranges between 1.0 and 2.0 the sample can be diluted 1:1 with a portion of the reagent blank and read within a few min. Solutions with higher absorbance can be diluted upto six fold with reagent blank in order to obtain onscale readings within 10% of the true absorbance value.
Calibration Procedure with Sulfite Ion Accurately pipette graduated amounts of the working sulfite-TCM solution (such as 0,0.5, 1, 2, 3, and 4 ml) into a series of 25 ml volumetric flasks. Add sufficient TCM solution to each flask to bring the volume to approximately 10 ml. Then add the remaining reagents as described. For maximum precision use a constant-temperature bath. The temperature of calibration must be maintained within 2°. Plot the absorbance against the total concentration in ug SO2 for the corresponding solution. The total ug SO2 in solution equals the concentration of the standard in ug SC^/ml times the ml sulfite solution added (ug 5 0 2 =
SO2 x ml added). A linear relationship should be obtained and the y-intercept should be within 0.03 absorbance unit of the zero standard absorbance. For maximum precision determine the line of best fit using regression analysis by the method of least squares. Determine the slope of the line of best fit. calculate its reciprocal and denote as Bs. This calibration factor can be used for calculating results provided there are no radical changes in temperature or pH. At least one
control sample containing a known concentration of SO2 for each series of determinations, is recommended to insure the reliability of this factor.
Calibration Procedure with SO2 Permeation Tubes Atmospheres containing accurately known amounts of SO2 at levels of interest can be prepared using permeation tubes. In the systems for generating these atmospheres, the permeation tube emits SO2 gas at a known, low, constant rate, provided the temp, of the tube is held constant (+01 °C) and provided the tube has been accurately calibrated at the temperature of use. The SO2 gas permeating from the tube is carried by a low flow of inert gas to a mixing chamber where it is accurately diluted with SO2 free air to the level of interest and the sample taken. Permeation tubes may be prepared or purchased. Tubes with a certified permeation rate are available from the National Bureau of Standards USA. Tube permeation rates from 0.2 to 0.4 ug/min, inert gas flows of about 50 ml/min and dilution air flow rates from 1.1 to 15 l/m conveniently give standard atmospheres containing desired levels of SO2 (25 to 390 ug/m 3 : 0.01 to 0.15 ppm SO2). The concentration of SO2 in any standard atmosphere can be calculated as follows :
P x 103 C = Where, R d + Ri
C = Concentration of SO2, ug/m 3 at reference conditions, P = Tube permeation rate, ug/min Rd = Flow rate of dilution air, l/m at reference conditions Rj = Flow rate of inert gas l/m at reference conditions Prepare a series (usually six) of standard atmospheres containing SO2 levels from 25 to 390 ug SC^/m 3 . Sample each atmosphere using similar
apparatus and taking exactly the same air volume as will be done in atmospheric sampling. Determine absorbance as directed in earlier. Plot the concentration of SO2 in ug/m 3 (x-axis) against A-Ao values (y-axis), draw the straight line of best fit and determine the slope. Alternatively, regression analysis by the method of least squares may be used to calculate the slope, calculate the reciprocal of the slope and denote as Bg.
Calculations : Convert the volume of air sampled to the volume at reference conditions of 25°C and 760 mm Hg. (On 24-hour samples this may not be possible.)
P Vr = V x 760 where, x
298 (t + 273)
Vr = volume of air at 25°C and 760 mm Hg litres V = volume of air sampled, litres P = atmospheric pressure during sampling, mm Hg t = temperature of air sample, °C When sulfite solutions are used to prepare calibration curves, compute the concentration of SO2 in the sample:
(A-Ao) (103) (Bs) ug S0 2 /m = — Vr
where, A = A0 = 10 3 = V = Bs = D = D=1 sample absorbance reagent blank absorbance Conversion of liters to cubic meters . the sample volume corrected to 25°C and 760 mm Hg, litres Calibration factor, ug/unit of absorbance Dilution factor: For 30-min and 1-hour samples, For 24-hour samples,
When SO2 gas standard atmospheres are used to prepare calibration curves, compute the SO2 in the sample by the following formula:
S 0 2 ug/m 3 = (A - A 0 ) x B g
where, A = Sample absorbance A 0 = Reagent blank absorbance Bg = Calibration factor, ug/m 3 absorbance unit If desired, the concentration of SO2 may be calculated as ppm SO2 at reference conditions as follows : ppm S 0 2 = ug S02/m 3 x 3.82 x 10"4.pa
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