I N D U S T R I A L AND E N G I N E E R I N G C H E M I S T R Y
64
Table I contains the results of the analyses of known concentrations of acrylonitrile vapors, prepared in a gas chamber of 1000 liters' capacity by the introduction of measured amounts of liquid acrylonitrile. The various concentrations were chosen to indicate the accuracy of the method over a wide range. Over the entire range of concentrations t,he Only variable is the time of sampling. The large relative error in the analysis of the 25 p.p.m. samples is misleading, since the actual error is only 5 p.p.m. The principal reason for the error in the results of the low concentrations is the difficulty of measuring the exceedingly small amounts of liquid acrylonitrile required in making up these concentrations in the 1000-liter gas chamber available.
Vol. 16, No, 1
ACKNOWLEDGMENTS
The authors gratefully acknowledge the cooperation of v. Migrdichisn of the American Cyanamid Company for his suggestions as to the sampling medium, and of W. P. Tyler, T. R. Steadman, and J. C. McCool of the B. F. Goodrich Company in the development of the analysis. LITERATURECITED
(1) Dudley, N. C.. and Neal. P. A..
J.Id.
Hva. ToZicoL 24, 27-86
(1942).
( 2 ) Proceedings. conferenoeon Health Havards in Rubber Industry, May 29, 1942. (3) Raduisuewski. Bel., 18. 335 (1885).
Spectrophotometric Determination of Iodine Liberated in the Oxidation of Carbon Monoxide by Iodine Pentoxide BERNARD S M A L L E R XtW J Aero Medical Laboratory, A r m y Air For
A spectrophotometric method for measuring tho iodine liberated in tho oxidation of carbon monoxide by iodine pentoxide is described. The iodine concentration was measured at 3 5 0 millimicronsagainst a water blank, using a Coleman photoelectric spectrophotometer. Results in terms of carbon monoxide were calculated by the use of a formula derived from the calibration c u k and the chemical reactions involved. The method is sensitive, convenient (requiring tho preparation of only one reagent, 1 per cent potassium iodide), and reliable for concentrations of carbon monoxide as low as 0.005 to 0.001 per cent. Tho range of applicability is 0.001 to approximately 0.9 per cent. Interfering substances (gasoline vapor, water, etc.) are effectively removed b y the use of chromic acid, silica gel, and phosphorus pentoxide as the absorbing or "scouring" agents. As described, the method has an accuracy of * I 0 per cent in tho,range 0.001 to 0.010 per cent carbon monoxide. For analyses of carbon monoxide concentrations above 0.010 per cent and within the limits of vsofulnori of the apparatus (0.9 per cent) tho accuracy of the method is increased to * 3 to 5 per cent.
0
N E of the standard methods and prohahly the most widely used quantitative procedureat present available for the determination of small amounts of carbon monoxide in air is the iodine pentoxide method. Numerous workers, including Eden ( I ) , Sendroy (31,and Vandaveer and Gregg (4,6) have suggested modifications or have added improvements to the method as originally introduced by de la Harfe and Reverdin (9). I n these methods the gas sample is usually first passed through ehromic acid to remove volatile hydrocarbons, then through potassium hydroxide and phosphorus pentoxide to remove water vapor, andfinallyoverdrysolidiodinepentoxideat150'to 160'C. to produce quantitatively the volatile products carbon dioxide and iodine. These are absorbed or collected in harium hydroxide in case carbon dioxide is measured, or in potassium iodide in case the iodine is to he determined. Iodometric measurement by titration with sodium thiosulfate, using starch as the indicator, has been generally adopted as the method of choice. However, the necessity for frequent determinations in this laboratory of low (0.005 to 0.001 per cent) carbon monoxide concentrations disclosed several difficulties and disadvantages which made desirable some other means of measuring the iodine
lit "eL> y..uyc \"."" o"".yy. l"lyy.vyI "II*yII of a slaw rate of decomposition, require periodic checks upon their concentration; (2) slight overtitration of the end point is a potential source of error; and (3) duplicate titrations on the same sample are sometimes impossible!.
...,
"/)--)
".A"""Io.yI
APPARATUS AND REAGENTS
Iodine pentoxide ap aratus. Coleman photoelectric spectraphotometer, Model 108 One per cent potassium iodide solution (Merck's C.P. granular potassium iodide is satisfactory). Pipets, 10.0, 1.0, and 0.2 cc. METHODS AND PROCEDURE
The above-mentioned difficulties could he eliminated, i t was found, by the use of a spectrophotometric method of measuring the iodine ooncentrrttian. For this purpose a Coleman double monochromator photoelectric spectrophotometer. (Model 10s) having's. range of 350 to 1000 millimicrons wm used. Determinations of the spectral transmittance of iodine in 1 per cent potassium iodide, the calibration curve relatins concentrations to 1ogaritG of the percentage transmi6 tance, as well as all measurements of iodine concentration in blanks and unhmown samples were perf armed with this instr'ument.
1
I
Figure 1.
Absorption Tube
method : ok measuring the mount*of iodine in a 1 per cent potassium iodide solution requires no chemical reaction of the iodine but is dependent only upon the absorption of light by the iodine in solution. For the range of iodine cancentrations used this ahsorption has been observed to follow Beer's law, in that the relationnhin hetween t h e logarithm of the percentage transmittance and the con-
January 15, 1944
ANALYTICAL EDITION
65
Blank analyses are carried out by filling calibrated containers with nitrogen (commercial), passing the gas through the apparatus, and flushing exactly as with unknown samples. From the amount of iodine measured the equivalent carbon monoxide is then calculated. Blank analyses are always performed prior to the analysis of unknown samples and the blank value in terms of percentage carbon monoxide is always subtracted from the unknown value to obtain the true or Licorrected”carbon monoxide percentage concentration. The only reagent required for an analysis is the 1 per cent potassium iodide solution. This should be prepared from a pure grade of potassiilm iodide (since impure preparations readily liberate appreciable iodine) and should be renewed about once a week. The solution should be stored in a dark glass bottle. RESULTS
350
450
550
WAVE LENGTH Figure 2.
650
750
- MILLIMICRONS
Spectral Transmission Curve of Iodine
(5
x
i o - 5 ~ )
In 1 per cent potassium iodide solution as determined with Coleman photoelectric spectrophotometer (Model 1 OS) using a 5-mm. slit. Cuvettes were circular tubes of 16.5-mm. diameter and comparison tube was a blank solution (IO cc.) of 1 per cent potassium iodide
centration of absorbing material (iodine in 1 per cent potassium iodide) is linear and the calibration curve is a straight line. This may be expressed as: Concentration
log To =K’X
7-
where To equals the intensity of incident light, T equals the intensity of transmitted light (after passing through sample), and K‘ equals the calibration constant expressing the relationship between concentration of iodine in 1 per cent potassium iodide solution and the logarithm of the percentage transmittance. Absorption of light by iodine ( 5 X lO-6N)in 1 per cent potassium iodide increases as the wave length of light used decreases into the ultraviolet. As a result of this observation all measurements were made a t 360 millimicrons, the point of greatest absorption of the wave-length range available with this type spectrophotometer. Gas samples are collected in calibrated metallic containers of approximately 1600- to 1700-cc. (STP) capacity; smaller 200to 250-cc. (STP) glass tonometers may be used for sampling purposes, but give less satisfactory results. The samples are then passed through the iodine pentoxide apparatus by displacement with water, this method being preferable from the standpoint of safety, ease of adjustment, and convenience to the suction method usually employed. I t was experimentally observed that the displacement of the 1600- to 1700-cc. sample in 60 minutes followed by a 30-minute flushing with nitrogen gas a t the same rate of flow gave most accurate results. However, size of sample, its concentration, and degree of accuracy demanded are all factors which may modify the time necessary to complete an analysis. For the collection of the liberated iodine the original Gomberg tube used routinely with the iodine pentoxide apparatus was replaced by an absorption tube designed and adapted by J. W. Heim of this laboratory for the present method of analysis (Figure 1). The iodine passes through the collecting tube, which extends almost to the bottom of the absorption vesspl, and bubbles out through the sintered-glass filter at its end. The amount of iodide solution used (10 cc.) is sufficient, of course, to keep the filter well below the liquid level. This tube has marked advantages over the Gomberg type, in that its wide-mouthed ground-glass stopper permits ready access to the iodide solution for sampling a t the completion of an analysis; it is easily washed out or cleansed; and quantitative results obtained with its use have proved it an efficient type of absorption vessel.
I n Figure 2 the spectral transmittance curve of iodine ( 5 X 10-6N) in 1 per cent iodide solution is presented. RIaximum absorption of light by iodine ( 5 X 10-6-V) in 1 per cent potassium iodide solution occurs in the region of the ultraviolet. However, a t 350 millimicrons (the lower limit of the Coleman instrument) the absorption is sufficiently great (90 per cent) to provide a means of measurement that is as sensitive and accurate as the routine sodium thiosulfate titration method. Both the titration method and that described here have been employed in this laboratory for determining carbon monoxide in air samples. However, the authors have found the titration method less satisfactory for concentrations of carbon monoxide below 0.005 per cent. Below this value the titration method was less convenient and more time-consuming than the spectrophotometric. The relationship between the concentration of iodine over a wide concentration range and the logarithm of percentage transmittance is linear. The value of the calibration constant, K’, which expresses this relationship between concentration in equivalents per liter and logarithm of percentage transmittance, is 5.1 X
z
0 IO,
I
I
I
1
2
3
I
I
1
I
v)
f
3
0
4
5
2
3
TIME -HOURS Figure 3. Chan es in Percentage Transmission of Iodine in 1 Per Cent%otassium Iodide as a Function of Time
The change in the percentage light transmission of iodine in 1 per cent potassium iodide solution as a function of time is illustrated in Figure 3 and the quantitative effects of such changes are presented in Table I. Dilutions of 1 to 50 showed changes equivalent to only a 6 per cent decrease in the percentage of carbon monoxide after one hour. If spectrophotometric readings are made within 5 to 10 minutes following the completion of the sample run, the error due to any change in light transmission may be considered negligible. Blank analyses using nitrogen gas (commercial) and performed as previously described gave fairly consistent values, the average being equivalent to a carbon monoxide concentration of 0.0004 per cent. These results are summarized in Table 11.
Vol. 16, No. 1
INDUSTRIAL AND ENGINEERING CHEMISTRY
66
Effect of Changes in Percentage Transmission OF Iodine in 1 Per Cent Potassium Iodide Solution with Time Original Concentration 1 Hour 5 Hours 23 Hours Dilution CO CO Change CO Change CO Change % % % % % % % 1:lO 0.0137 0,0120 -12.4 0.0109 -20.4 0.0103 -24.8 1:20 0.0136 0.0120 -11.8 0.0112 -17.6 0,0107 -21.4 1:50 0.0116 0.0109 6.0 0.0091 -21.6 0.0085 -26.8
Table I.
-
Date
Table II. Blank Analyses [Nitrogen (Commeroial) Gas Samples] Sample Volume CO (as Iodine Equivalent)
cc.
%
12/5/42 12/5/42 12/8/42 12/12/42 12/12/42 12/12/42 12/19/42 1/2/43 1/6/43
From the chemical reactions involved 1.0 ml. of 0.001N iodine solution is equivalent to 0.056 ml. of carbon monoxide measured a t 0" and 760 mm. The volume of carbon monoxide a t Oo and 760 mm. is then calculated as follows: %CO =
-
(*)0.0001
An opportunity to check the accuracy and sensitivity of this method was offered when known standard samples of carbon monoxide mixtures prepared and analyzed by the National Bureau of Standards, Washington, D. C., were sent to Wright Field for check analyses. The comparative results are presented in Table 111. In general, values with the spectrophotometric method varied from 4 to 18 per cent below those reported by the Bureau of Standards, with results averaging 10 to 11 per cent lower. While the method is capable of detecting concentrations as low as 0.001 per cent, the limit of accuracy is approximately 5 to 10 per cent for concentrations below 0.010 per cent.
Table 111. Carbon Monoxide (Comparison of Bureau of Standards and Wright Field Analyses) Bureau of Wright Field Standards Analyaes Date Analyaea Difference
%
5%
0.0076
4/12/42 4/12/42 4/12/42 4/12/42
0.0070 0,0065 0.0068 0.0069
0,0050
4/11/42
0.0041 0.0048
7.9 -14.5 -10.5 - 8.1 Av. -10.5 -18.0 - 4.0 Av. -11.0
%
9
cc. of sample (STP)
where K' is 5.1 X 10-6 and 10 ml. of 1% potassium iodide a used. substituting, %CO =
5.1 X lo-' X (0.056 X 1000) X 1000 X (2 cc. of sample (STP)
or
%CO =
Finally Av. O.OO04MD
K' X (0.056 X 1000) X 100 X 10 X (2 - log %
% CO
5.1 X
- log % 7')
X 56,000 X (2 - log % 2') cc. of sample (STP)
2*86 x (2
- log % T, x dilution used
= cc. of sample (STP)
The value 2.86 is termed K in the final equation below and is determined as indicated from both the calibration curve and the quantitative relationship between the concentration of carbon monoxide and iodine released in the oxidation reaction. The final general equation is then: %CO =
x (2 - log % cc. of sample (STP)
x dilution
As an example of the use of the above equation in calculating results, the following analytical data are presented:
A 10-cc. portion of the 1 per cent potassium iodide was used to collect the iodine liberated when a gas sample of 2360 cc. (STP) was passed through the apparatus. A 1 to 100 dilution of the iodine collected in the 10-cc. portion of the 1 per cent potassium iodide solution was made and when measured (at 350 millimicrons) with the spectrophotometer against a 10-cc. 1 per cent potassium iodide blank set a t 100 per cent light transmission, gave a percentage light transmission of 44.5. The calculation, by substitution of the above data, is illustrated as follows:
-
Table IV. Standard Carbon Monoxide Mixture [Comparison of Analyses Using Small and Large Sample Volumea of Standard CO (0.012 per cent)] Date Gas Volume CO Found Deviation
The analysis of samples whose concentration is below 0.010 per cent requires consideration of several factors. As previously mentioned, rate of sample flow should be sufficiently slow to ensure complete oxidation of all carbon monoxide by the iodine pentoxide. For concentrations of 0.010 per cent and below total sampling periods of 80 to 90 minutes gave satisfactory results. Sample volume is another factor to be given consideration when accurate results are desired. Comparative results of analyses of a standard carbon monoxide mixture when using small and large sampling volumes are shown in Table IV. Accuracy and dependability of analysis are obviously increased when larger volumes are used, particularly when the concentration of carbon monoxide is below 0.010 per cent. The photoelectric colorimeter used with a filter which transmits the greater portion of its light as nearly as possible within the region of the maximum absorption of iodine in 1per cent potassium iodide solution-Le., about 350 millimicrons-can be used if the spectrophotometer is not available. A calibration curve must be determined and the sensitivity of the photoelectric colorimetric procedure is somewhat less than that obtained with the spectrophotometer.
5%
%
Cc.
0.011 0.009 0.013 0.006 0.010 0.006 0.015 Av. 0.010
-0.004 $0.005 MD
0.013 0.010 0.011 0.012 0.011 0.013 0.011 0.011 0.012 Av. 0.011
$0.002 -0.001 0.000 $0.001 0.000 +0.002 0 IO00 0.000 +0.001 MD (I 0.0008 )
+0.001 -0.001 +0.003 -0,004
0.000
-
(k)
0.0026
-
W
LITERATURE CITED
(1) Edell, G. M., IND. ENQ.CHBM., 20,275 (1928). (2) Harfe, C. d e la, a n d Reverdin, F., Chem.-Ztg. 12,1726 (1888). (3) Sendroy, J., in P e t e r s and V a n Slyke, "Quantitative Clinical Chemistry, Vol. 11, Methods", Baltimore, Williams & W i l k h Co., 1932. (4) Vandaveer, F. E., Gas, 18, 24 (1942). (5) Vandaveer, F. E., and Gregg, R. C., IND.ENQ.CHEM., ANAL. ED., 1, 129 (1929).
