Microdetermination of Sulfuric Acid Aerosol EARL R. GERHARD' and H. F. JOHNSTONE University of Illinois, Urbana, 111. washed with distilled w e t s , and dried. Two grams of thymol blue wm dissolved in 90 ml. of 0.05N sodium hydroxide in a n agate mortar, filtered through No. 1 Whatman filter paper, and diluted with distilled water to 1 liter t o give approximately 0.2% by weight. The solution was adjusted with 0.1N sulfuric acid to a pH of 3.3. Two-foot strips of the film were immersed in the solution and stirred for 2 minutes. The film w88 dipped in distilled water, and rinsed once on each side with a stream of distilled water. It wais then dried and stored in filtered air in a
An analytical technique for the miorodetermination of sulfuric acid aerosol was developed in wbioh the aerosol particles were collected by a high velocity impactor on a film impregnated with thymol blue. The color change from yellow to red, resulting from the action of the sulfuric acid drops, was measured by a photoelectric colorimeter attached to a low power microscope. The film was calibrated by impaction of known quantities of sulfuric acid aerosol. The method was used to determine from 0.01 to 0.2 y of sulfuric acid. It was reliable when the quantity of acid collected was controlled to give essentially uniform acid trace#. The method detects the presence of any acid aerosol, but is not sensitive to acidic gases. Alkaline gases which tend to neutralize the droplets affect the accuracy of the results.
hnu
. . 1 " _
The mme techniqut : was used to prepare the bromocresol green film. For this fi Im, the solution concentration was 0.1% byweightanditwasad,iusted topH 4.4. PHOTOELECTRIC C O M R MEASUREMENTS
A section of the indicator film was attached by Scotch tape to a small microsco~eslide.
c
ONSIDERABLE difficulty has been experienced in air pollution work both in the field and in the laboratory hecame of the small quantities of materials availahle for analysis. T h e analytical technique described here was developed while studying the rate of formation of sulfuric acid aerosol from the photochemical oxidation of sulfur dioxide in the presence of water vapor. It was desired to sample the sulfuric acid aerosol formed in an 8-liter reaction chamber when 1 t o 30 p.p,m, of sulfur dioxide was used. At 1 p.p.m. of sulfur dioxide in air the concentration of sulfur dioxide is 2.85 y per liter. Even if all the sulfur dioxide is converted to sulfuric acid, 1 liter would contain only 4.37 y of sulfuric acid. Ordinary methods of acid analysis, such as acid-base or amperometric titrations, could not he used to determine less than 100 y of sulfuric acid, At first, an attempt was made to count and measure, under the microscope, the particles collected on an imprtetor slide, hut this w m impossible because of the presence of many small partielea about 0.5 micron in diameter, even in filtered air. By dissolving the acid collected on the impactor slides in small quantities of water and measuring the electrical eonduotivity, quantities as low as 5 y could be determined. The method possibly could he extended to determine as little as 1 y of acid. The work led to the development of a method using indicator films. Strips of film vere impregnated with solutions of methyl red, neutrd red, methyl orange, bromocresol green, and thymol blue. Best results were obtained with the bromocresol green and thymol blue. Further tests were made with these two indicators to determine the optimum concentration and pH of the indicator solution and the time of immersion of the film in the solution. The selection was based on the maximum light transmittance difference between the acid and base colors. The aerosol was sampled by jet impaction, a method originally developed by May ( 1 ) . The particular jets used in this work and their calibration me described by Ranz and Wong (a). With a round jet 0.353 mm. in diameter and a t sonic velocity through the throat, it was possible t o obtain essentially 100% removal of 0.20-micron droplets and larger, and 50% removal of 0.11-micron droplets.
The sulfuric acid aerosol particles were
colored trace and an adjrtceit base colored part of the film was then determined. For this purpose, a photosensitive element from a Ceneo photelometer which had an inside diameter of 2.5 cm. waa used. In order to obtain sufficient sensitivity and significant differences in light transmittance, it was necessary t o
Figure 1. Apparatus used for miorodetermination of sulfuric acid aerosol
-
\"IF;*
PREPARATION OF FILMS
Eastman positive, fine-grained, 35-mm. photographic film was immersed in a hypo solution to remove the silver salts, then
__
I Present address, Department of Chemical Engineering, University of Loumville, Louisville, Ky.
702
VOLTACE IIEGULATOR IIOVAC.
VOLTMETE* "ARIAC
V O L U M E 2 7 , NO. 5, M A Y 1 9 5 5
703 43X objective and 1.75-cm. disk as described above. The calibration curve for these results is shown in Figure 3. Readings on larger dots having a uniform distribution of acid showed that in the range 0.41 to 0.535 mm. the transmittance difference depended only on the amount of acid collected per unit area. Thus, a uniform trace 0.535 mm. in diameter gave the same transmittance difference with a 2.3-cm. beam of light as with a 1.75-cm. beam, but contained more acid in proportion to the larger area. Based on these results, a calibration curve for 43X and 2.3 cm. was calculated from the experimental curve for 43X and 1.75 cm. This is also shown in Figure 3.
SULFURIC ACID, MICROGRAM
Figure 3.
Calibration of indicator film
magnify the trace or dot size. This was accomplished by use of a 43X objective on a Bausch & Lomb microscope in which the eyepiece was replaced by the photocell.
A photograph of the apparatus used is shown in Figure 1. The optical arrangement is shown in Figure 2. A light source of constant intensity was adjusted to give a narrow beam of parallel light by means of a lens and diaphragm. The distance from the light source to the microscope was set a t 45-cm. to permit adjustment of the size of the beam to the proper diameter. The photosensitive element was connected to a Leeds and Northrup Type R galvanometer which had a sensitivity of 0.005 fia. per mm. a t 1meter. In order to increase the transmittance difference between the acid and the base color, Wratten filters 58B and l5G were placed in the light beam between the mirror and substage of the microscope. The acid trace or dot could be observed and focused by placing a frosted 'disk on top of the microscope barrel. For maximum transmittance differences, it was necessary to use a light beam of approximately the same size as the acid dot. For this purpose a series of brass disks with circular holes was used. One of these was placed on top of the frosted disk. For each reading, a disk which just enclosed the magnified projection of the acid dot was selected, and the substage diaphragm was adjusted to give a beam of light of the same diameter as the disk. Before readings were taken, the mirror was adjusted to give a uniform and centered field of illumination as observed on the frosted disk; the galvanometer was set at zero with no light on the photocell. The substage condenser was adjusted to focus the substage diaphragm on the frosted disk and the diaphragm was closed to give the proper size light beam. For each film, the light intensity was set to give a galvanometer reading of 50.0 cm. for the base color of the thymol blue film. Transmittance readings were obtained betxeen 20.0 and 45.0 cm. for the acid dots, This procedure gave reproducible transmittance readings. C4LIBRATIOh O F FILMS
The thymol blue indicator films were calibrated by impaction of a known quantity of sulfuric acid aerosol on the films. A condensation aerosol generator similar to that used by Sinclair and LaMer ( 3 ) for aerosol research was used to produce homogeneous sulfuric acid aerosols with particles about 0.6 micron in diameter. The aerosol stream from the generator was diluted with filtered air and passed through two mixing chambers. All of the particles in the stream weie then collected in the impactor cup and analyzed for sulfuric acid. The volume of gas passing the impactor was measured. During each run, I- to 30-ml. samples of the air containing the aerosol droplets were removed from the mixing chamber and injected into a second filtered air stream, where the acid particles were impacted on the indicator films through a round jet. From the known concentration of the aerosol and the volume of the sample, the amount of acid deposited on the film was calculated. In this way, acid traces containing 0.015 to 0.3 y of sulfuric acid were obtained. The light transmittance differences of the acid traces, 0.35 to 0.41 mm. in diameter, were measured with the
For example, assume that we have a dot 0.535 nun.in diameter which contains a uniform acid color over its entire surface. When this dot is read with the 43X objective lens and a 2.3-cm. beam of light, a difference of 250 mm. is obtained on the galvanometer. If now the size of the light beam is reduced to 1.75-em. diameter, and the voltage to the light source readjusted to give a reading of 500 for the base color, the dot will again give a difference of 250 mm. on the galvanometer. The calibration obtained for the 1.75-cm. size gives a value of 0.24 y of acid. Hence, when the 2.3-cm. beam of light is used, a reading of 250 would correspond to a total acid content of (0.24) (2.3/1.75)2 = 0.41 mg. This procedure was substantiated when experimental dots gave approximately the same total amount of sulfuric acid when measured by either of the two calibration curves. APPLICATIONS AND LIMITATIONS OF INDICATOR FILM ANALYSIS
Use of these thymol blue indicator films permitted determination of 0.10 to 0.50 y of sulfuric acid aerosol and detection of quantities as small as 0.01 y . This is equivalent to 2 X 10-3 p.p.m. by volume of sulfuric acid vapor from a 1-liter sample. For many test runs an analysis could be made by removing less than 250 ml. of aerosol from the reaction chamber. To ascertain the effect of filtered air on the fiIm, 25 Iiters of airsulfur dioxide mixtures containing up to 300 p.p.m. of sulfur dioxide, with and without sodium chloride nuclei, and gases such as nitrogen dioxide and hydrogen chloride, were drawn through the impactor a t sonic velocity. KOvisible trace or color was observed under these conditions. The presence of other acidic or basic impurities dissolved in the aerosol of course modifies the color change caused by sulfuric acid alone. Furthermore, soluble salts might crystallize in the trace on the film with a decrease in light transmittance caused by the solid particles. Test runs in which a trace of ammonia gas was added to the air showed a marked decrease in the color of the aerosol trace and the presence of solid white crystalline particles on the film. In general, the light transmittance readings of the films were made within 10 minutes after the sample was collected, and often within 2 minutes. Readings on several dense acid traces showed no significant change in transmittance for several days when the film was stored in a closed container in the dark. However, fading occurred after storage of several weeks. Before use, the films were perfectly stable and gave reproducible transmittance readings after storage for months. The most serious difficulty was the tendency of the acid to splash or spread into irregular shapes, especially when large quantities were collected by impaction near sonic velocity. Occasionally, the high velocity of the jet blew the acid into streamers several millimeters from the central dot. When possible, these runs were repeated and smaller quantities of acid were collected. Traverses of traces having irregular shapes or slight spreading usually gave satisfactory results. ACKNOWLEDGMEKT
This work was a part of the program in the University of Illinois Engineering Experiment Station on a study of stack gases. It was supported in part by the Smoke and Fumes Committee of the American Petroleum Institute as Contract SF-9. LITERATURE CITED
(1) l\lay, K. R., J . Sci. Tnstr., 22, 187 (1945). (2) Ranz, W. E., and Wong, J. B., Ind. Eng. Chem., 44, 1371 (1952). (3) Sinclair, D., and LalIer, V. K., Chem. Reus., 44, 245 (1949). RECEIVED for review September 3, 19.54,
Accepted December 21, 1954.
