Table of Contents

1. Hydrogen Sulfide
1.1. 1.2. 1.3. 1.4. 1.5. Hydrogen Sulfide (Methylene Blue method): ................................................................................................ 2 Reagents: ...................................................................................................................................................................... 2 Analytical procedure: .............................................................................................................................................. 3 Calibration: .................................................................................................................................................................. 3 Calculation: .................................................................................................................................................................. 3

2. Chlorine and Hydrogen Chloride

2.1. 2.2. 2.3. 2.4. Chlorine and Hydrogen Chloride (Cl2 & HCL) : ............................................................................................. 4 Free Chlorine-o-Tolidine Method:- .................................................................................................................... 4 Reagents: ...................................................................................................................................................................... 4 Analytical Procedure ............................................................................................................................................... 6

3. Chlorides.
3.1. Chlorides:...................................................................................................................................................................... 7

Reference

Hydrogen Sulfide (H2S)

1.1. Hydrogen Sulfide (Methylene Blue method):
Although a number of methods have been described for the determination of H2S, only the most sensitive procedure can be applied for ambient air analysis. This gas is usually present in the community atmosphere in the parts per hundred million our lower concentration range rather than in the parts per million ranges. It can create an odor nuisance at 0.1ppm or less. The best procedure for air pollution control survey and control purpose is absorption in a solution of zinc acetate or some cadmium salt, with subsequent chlorometric estimation as methylene blue. In this method the H2S is absorbed by passing the air sample through an absorption mixture of an alkaline suspension of cadmium hydroxide contained in a standard impinger at a sampling rate of 21cfm or in midget impinger at 0.1cfm. the sulfide ion is reacted with mixture of paminodimethyl aniline, ferric chloride and chloride ions to yield methylene blue. The concentration of H2S is determined by measurement of the optical absorbance of the color sample in comparison with that of standard solution of H2S equivalent, by reference to calibration curve. Spectrometric measures are made at a wavelength of 670 m-microns.

1.2. Reagents:
a. Amine sulfuric acid stock solution 230ml of dist. Water add 50ml of conc. H2SO4. This mixture is cooled and mixefd with the addition of 12g of N, N-dimethyl-p-phenylenediamine until complete solution. b. Amine sulfuric acid test solution Dilute 25ml of above stock solution with 1:1 sulfuric acid to a total volume of 1L. c. Ferric chloride solution Dissolve 100g of FeCl3.6H20 in dist. Water to make up to 100ml solution. d. Absorption mixture Dissolve 4.3g of cadmium sulfate in dist. Water. Mix with the solution containing 0.3g Sodium Hydroxide in water and dilute 1L. This mixture must be stirred well before using.

1.3. Analytical procedure:

After adding 50ml of absorption mixture in a standard impinger the air sample is passed at a measure rate of about 1cfm for 30min or longer. Add 0.6ml of amine sulfuric acid test solution and one drop of ferric chloride solution to impinger and shake after each addition. This mixture is transferred to a 50ml volumetric flask, made up to volume and allows to stand for 30 minutes. A reference reagent blank is prepared by adding above amount of test reagent and ferric chloride solution to 45ml of absorption mixture in a 50ml volumetric flask, making up to volume and allowing the mixture to stand for 30 minutes. The spectrometer is set to zero optical absorbance with 25ml of reference blank at 670m-mocron and absorbance of 25ml of the sample is then determined. By reference to standard calibration curve, the concentration of H2S in the sample measure.

1.4. Calibration:
Calibration is carried out by adding 0, 1,2,3,4 and 5 micro-gram of H2S equivalent on the form of pure reagent to 20ml of absorption mixture contained in 25ml flask. After the addition of 0.6ml of test solution one drop of ferric chloride solution, with stirring to each flask the mixture are diluted to 25ml and allow stand for 30 minutes. The solution without H2S used as reference reagent blank for setting the spectrometer at zero absorbance at 670m-micron.

1.5. Calculation:
The result on air sample may be calculated in parts per thousand million by volume, as follows;
( ) ( ) ( )

H2S (ppb)

Chlorine (Cl2) and Hydrogen Chloride (HCL)

2.1. Chlorine and Hydrogen Chloride (Cl2 & HCL) :
Sources of free chorine emission to the atmosphere are of rare occurrence. Occasionally, chlorine has been reported in areas adjacent to chemical plants manufacturing caustic soda and chlorine from the electrolysis of salt solutions and in the preparation of calcium chloride. Chlorine in very low on centrations may also be formed by atmospheric reactions. Thus

nitrosyl chloride may be formed by the reaction between sodium chloride and nitrogen dioxide. Subsequently, the nitrosyl chloride may decompose photochemicaly to free chlorine and nitric oxide. Another possible mode of formation of free chlorine in the atmosphere is the reaction between chloride ion and ozone. The most sensitive reaction for the determination of free chlorine is given by o-tolidine in acid solution to yield a yellow to orange-colored product. However, this reaction is not specific for chlorine but is given by many other substances that can participate in the oxidation-reduction reaction. Interferences may be caused by the presence of ferric and manganic compounds, nitrites, oxidizing and reducing agents.

2.2. Free Chlorine-o-Tolidine Method:The following method is based on the procedure adopted for the analysis of free chlorine in water. For air analysis, the sample is passed through a standardimpinger containing 75 ml of 0.0125 N sodium hydroxide solution at a measured rate for a sufficient time to scrub at least 1 m3 of air.

2.3. Reagents:
a. O-Tolidine Reagent Dissolve 1 gm of o-tolidine (mp 120 C) by placing it in a mortar and add 5 ml of hydrochloric acid solution (100 ml of concentrated acid to 400 ml of distilled water).

Grind to a thin paste and add 150-200 ml of water. Transfer to a 1-liter by adding the hydrochloric acid solution. 1:4.This reagent is stored in amber bottles and has a shelf life of about 6 months. b. Color Comparison Standards Permanent color standards may be prepared from potassium dichromate and copper sulfate. Potassium Dichromate Solution. Dissolve 0.25 gm of potassium dichromate and 1 ml of concentrated sulfuric acid in distilled water and dilute to 100 ml. Copper Sulfate Solution. Dissolve 1.5 gm of copper sulfate, CuSO4.5H2O and 1 ml of concentrated sulfuric acid in water and dilute to 100 ml. When the color comparison is made in Nessler tubes of 100 ml, having the graduation mark at 300 mm from the bottom of the tube the following standards may be used to determine the chlorine comment with o-tolidine. After mixing the quantities of copper sulfate and potassium dichromate solutions indicated in Table dilute with distilled water to 100 ml. Table 1. Color comparises standards. Chlorine, equivalent in microorganism per 100 ml of standard 1 2 3 5 7 10 20 30 40 50 60 70 80 100

Copper sulfur solution (ml) 0.0 0.0 0.0 0.4 1.2 1.8 1.9 1.9 2.0 2.0 2.0 2.0 2.0 2.0

Potassium dichromate (ml) 0.8 2.1 3.2 5.5 7.5 10.0 20.0 30.0 38.0 45.0 51.0 58.0 63.0 72.0

2.4.

Analytical Procedure
The sample solution in the standard impinger is brought to a temperature of 20-40C by

warming in a water bath. Sufficient sulfuric acid (1 N) is added to neutralize the sample. Transfer the sample to a 300mm Nessler tube and dilute with distilled water to 100 ml. Add 1.0 ml of the o-tolidine reagent, mix, and place in the dark for about 5-15 minutes to allow for color development. Compare the color, at maximum color development, with that of the standards prepared as directed above in a similar size Nessler tube, under a daylight lamp or against a white background in ordinary daylight, not in direct sunlight. The permanent standard in the comparison tubes may be protected from evaporation and dust by sealing on microscope cover glasses with a transparent sealing compound. Color comparison may also be conducted with a spectrophotometer at 435 and 490 m with cuvettes providing a light path of 1 cm or longer. The method is also applicable to chlorine dioxide.

Chlorides
3.1. Chlorides:
Hydrochloric acid as a gaseous contaminant occurs rarely in significant concentrations in community atmospheres. Occasionally, it may be discharged as an emission product from chemical processes, such as those involved in the manufacture of calcium chloride, Freon refrigerant. etc. This acid cannot be distinguished from other acid gases by direct titration methods with standard bases. If the air sample is passed through a water solution containing a known amount of dilute hydrogen peroxide (0.003 M) and dilute sulfuric acid (2 10-5 N), the sulfate due to the presence of sulfur oxides may be removed by precipitation and the filtrate titrated with standard alkali or sodium tetraborate to determine the .hydrochloric acid content. A better way is to determine the chloride concentration by one of the following methods. However, these methods for chlorides will also include soluble salt particles and other atmospheric chlorides. Well-known methods for the estimation of chforides are those described by Mohr, Fajans, Kolthoff and Volhared, as modified by Jacobs (41), Certzzain dyes, such as dichloro.

Reference:
1. Techniques in Environmental Engineering & Management, Dr. Khurshid Ahmad, 2nd edition, AOne Publisher, 2009.