ANALYTICAL CHEMISTRY
674 Table I.
Magnesiiini Determimations on T u n g Samples (70 Magnesium. D r y Weight BaalsUVolumetric Colorimetric
Sa inpic
0.14 0.29 0.59 0.33 0.33 0.37 0.39 0.46 0.54 0.61 0,376 a
Leaf
0.15 0.27 0.31 0.33 0.34 0 34 0.33 0.45 0.52 0.58 0 364
Mean of triplicnte detrrminationz.
different localities and ranging in magnesium content irom 0.14 to 0.61% by the standard method were used for the comparison. Triplicate determinations were run on each sample by the two methods. The data are given in Table I. The values obtained by the two methods were in close agreement; the mean of the colorimetric determinations was lower than that of the volumetric determinations, but the difference was not statistically significant (Table I). It was noted that the differences between volumetric and colorimetric readings were greatest for high percentages of magnesium. The coefficient of correlation 1% as found to be 1-0.992 and the coefficient of regression of volumetric on colorimetric readings was 1.069 * 0.048 ( 5 ) . As the regression coefficient does not differ significantly from unity, the trend obser;ed in the ten samples of Table I is probably due to chance and one would not be justified in using values calculated from the regression equation. The method was found applicable to the determination of exchangeable magnesium in soils, using a 0.1 S acid solution of the ammonium acetate extract. Eight soil samples from different parts of the tung belt were run for exchangeable magnesium by the method described above and by the standard gravimetric procedure, using 8-hydroxyquinoline. Duplicate determinations were made on each sample by the two method3 (Table 11). The values obtained by the two methods were in good agree0.9985; ment. The coefficient of correlation was found to be and the coc4firient of regression of gravimetric on colorimetric valrir. I\ a c 1.007 * 0 025. n-hich has high statistical qgrific-airct~
+
/
DISCUSSION In addition to the calcium and aluminum in the compensating solution suggested by Peech and English ( 4 ,it was found necessary to add manganese and phosphorus as well. Although hydroxylamine was used to prevent manganese interference a s recommended by Peech and English, some samples high in manganese gave results that were too high. Addition of manganese chloride to the compensating solution corrected this error satisfactorily. Because there was some intensification of color in the presence of phosphate ions, it is necessary to include phosphate in the compensating solution. The amount of phosphate as well as calcium, aluminum, and manganese added in the compensating solution is on the average about five times as much as is present in the aliquot of the ash solution being analyzed, so that the effects of these ions present in the sample are negligible.
Table 11. D e t e r m i n a t i o n s of Exchangeable M a g n e s i u m in Soils Exchangeable hlagnesium per 100 Grams of Snaa
Location hlorriston, Fla.
Soil Type Lakeland fine sand
Hague, Fla.
Ft. hIeade loamy fine sand Orangeburg sandy loam Ora fine sandy loam Pheba fine sandy loam Gainesville fine sandy loam Magnolia, Miss. Ruston fine sandy loam a X e a n of duplicate determinations.
Fairhope, Ala, Folsom, La. Sunnyhill, La. Hague, Fla.
Depth, Inches
Colorimetric, thiazole yellow, m.e.
Gravimetric, S-hydroxyquinoline,
7-14 0-6 0-6
0.05 0.16 0.25
0.05 0.18 0.21
0-6 0-6
0.29 0.32 0.64 1.04
0.27 0.30 0.62 1.22
12-36
2.73
2.96
0-5 0-6
m.e.
LITERATURE CITED
(1) Gillam, W. S., IND.EXG.CHEM.,ANAL.E ~ . , 1 3499-501 , (1941). (2) Kidson, E. B., New Zealand J. Sci. Technol., 27, 411-13 (1946). (3) Mikkelsen, D.S., and Toth, S. J., J. Am. SOC.Agron., 39, 165-6 (1947). (4) Peech, Michael, and English, Leah, Soil Sci., 57,167-95 (1944). (5) Snedecor, G. W., “Statistical Methods,” 4th ed., Amm, Iowa, Iowa State College Press, 1946. R ?:cmvt:n Septeiiihrr 2 , 194i.
Microdetermination of Carbon Monoxide in Air A Portable Instrument . 4 R S O L D 0. BECKMAN, JAMES D. JIcCULLOUGH, AND ROBERT A. CRANE Laboratories of Arnold 0 . Beckman, Pasadena 2 , C a l v . , a n d Cniversity of California,LOS .Ingeles 24,
T
H E instrumelit described was developed in response to a request from the Office of Scientific Research and Development. Three models of the instrument were built; two were intended for laboratory use only, and the third mas designed for field use by inclusion of an internal battery. The instrument makes use of two chemical reactions, both of which go to completion a t 180” C.
CO (gas)
+ HgO (s, red) = C o n (gas) + Hg (gas, + SeSz (s) = PHgS is) + HgSe (s’l
3Hg (gas)
11)
(2) Although neither of these reactions is new, the conditions and method of application are radically different from those used by previous investigators. Both reactions have been evtensively
calv.
studied during the present investigation. In the case of Reaction 1 this study led to an accurate gravimetric method for the determination of carbon monoxide in air, based on the loss in weight of the mercuric oxide. The analytical procedure as well as the study of Reaction 1 has been described in an earlier communication (4). Sordlander (5) using Reaction 2 developed an instrument for the detection and semiquantitative determination of mercur) vapor in air by use of a selenium sulfide paper prepared by coating the precipitated material onto white bond paper. The air stream being tested for mercury was heated to 70” C. and caused to impinge normally on the coated surface. The intensity of blackening as measured by photometry of the exposed paper gave an approximation of thP mercury concentration in the air.
V O L U M E 20, NO. 7, J U L Y 1 9 4 8
675
i portable instrument for the determination of carbon monoxide in air makes use of two reactions, one between carbon monoxide and red mercuric oxide t o gibe mercury bapor and carbon dioxide, the other between mercury tapor and selenium sulfide. The mercury -containing air flows slowl? along a selenium sulfide test strip. and produces a black coloration o\er a length which is a direct measure of the quantity of carbon monoxide in the original sample. Determinationq can be made in a few minutes with an aterage error of less than 10%. The instrument may he used over wide ranges of carbon monoxide concentration from a few parts per million up to about 3 7 ~ .
Improvenients in the method employid both in niaking the selenium sulfide papers and in their usif: were dwcloped during the present investigation. I n the preparation of the papers a better result from every standpoint was ohtained if the selenium sulfide was precipitated in the pores of the paper. This was accomplished by impregnating a good quality of smooth filter paper with aqueous selenious acid solution, fOllCJ\\f’tihy exposure to hydrogen sulfide gas. The improvcd method oJ using the papers is an adaptation of that described hy Sanger and Black ( 6 ) ,n h o used mercuric chloride test paperr in the microwtimation of nrsenic by the Gutzeit method. Instead of impinging nurnially upoil the> test paper as in the f l o ~ r rh~ngthnisealong a Nordlander method, the gas sti~t~aiii narroir strip of the test paper. The mercury vapor produces a black coloration which extends progrcwivrly along the strip in substantially linear relation iritli tht, nitLiwny-i.e., carbon monoxide-concentration. The carbon Inonuxide concentration in the original gas samplc is accordingly detcrmined by the length of the blackened portion of the test strip. and the necessity For photometry is avoided. REAGENTS .&&I) l\IATERIA LS
Red Mercuric Oxide. A granular (8- to 14-mesh) form of thr oxide must be used. Its preparation from mercuric nitrate has been fully described ( 1 ) . Selenium Dioxide. Commercial selenium powder was purified as described by Campbell and AIcCullough ( 2 ) . The pure seleniuni was then dissolved in C.P. nitric acid and the resulting solution evaporated to dryness over a sand bath or hot plate in a hood.
S
Final heating to about 140‘ pure, XThite product.
10
150’ C’, tur an hour or twi yiiBlils a
PREPARATIOh~ OF SELENIU\I SULFIDE PAPERS
Choice of Paper. Best results have been obtained with Whatman S o . 1, Pchleicher and Schuell (American) No. 602 Extra Dense and S o . 598. -4heavy paper such as S. and S. No. 598 takes a heavier deposit of selenium sulfide and is accordingly more useful in the higher concentrations. Selenious Acid Solution. The areal concentration of selenium aulfide in the test papers is directly proportional to the concentration of selenious acid solution used. For carbon monoxide concentmtions in the range 0 to 200 p.p.in. a solution 0.025 formal in selenious acid is satisfactory when Whatman S o . 1 paper is used. In the range 10,000 to 30,000 p.p.m. of carbon monoxide, 1.0 F selcnious acid on S. and S. ?To. 598 was used with success. The selenious acid concentration most satisfactory for any particular range may be estimated with sufficient accuracy from these figures; Y. and d. S o . 598 paper is about 2.5 times as thick as Khatinan S o . 1 and accordingly takes up proportionally more uf the solution. Impregnation of Papers with Selenium Sulfide. Large sheets of the paper are cut into pieces about 20 em. (8 inches) square, and a strip about 0.5 inch nide is folded doxn on one edge and fastenec! with three staples. A stiff Chrome1 n-ire about 10 iiyhes long is inserted under the folded part of each paper to give a suitahlr, handle and also to keep the papers straight when wet. In groups of eight the papers are immersed in the selenious acid solution for about 10 to 15 minutes. They are then hung up to drain for about 5 to 10 minutes, the time depending on the temperature and humidity of the air, until they are v-ell beyond the dripping stage but, not dry. After exposure to Eiytirogrn sulfide gas for ahout 10 to 15 minutes in a large glass tank, the papers are hung up in a well ventilated place to dry. When completely dry thes are stacked and pressed flat. Baking Selenium Sulfide Papers. The stability of the selenium sulfide papers is increased by baking for about 30 minutes a t 140 C. If forced air circulation is not provided in the oven, the papers must be rotated or turned frequently to prevent uneven sublimation of the active material During baking the color deepens from yellon--orange to red-orange and the colloidal particles of selenium sulfide fusp into larger glassy, amorphous beads. X-ray diffraction patterns of the material hoth before and after baking show no evidence of crvstallinity. Cutting of Test Strips. rifter ahout 1.5 inches from top and bottom and 0.5 inch from each side aye trimmed avay, the papers are cut into strips 0.125 by 4.5 inches. Because the accuracy of the analyses depends on the uniformity of width of the strips, the cutting must be done carefully. A metal spacing gage fastened to the cutting edge of a good quality photographic trimming board has been found satisfactory. The strips from a given square are fairlj- uniform, but there is often considerable variation from one q u m ’ t o another. The strips are therefore segregated according to thc squares from which they are cut and stored in s t o p p e l d rials. Thev are stable if kept in the dark, especially if kept cold. Paptars stored in a refrigerator for over a year have kept theii. original i7alibrariun. Under ordinary laborator!- tcmperaturt.s t hi. pnpc’r. retain tlit’ir calibration values for several rnontlrs if ictLpt tlarli. THE INSTRt‘hIEYT
.I wlwiii;ttic diaxram of the instrument, is shown iii E’iguw 1; Figure 1. 4.
Schematic Diagram of Carbon \Ionoxide Instrument Vent to atmosphere. C . charcoal trap. H . heater coil. L.
pilot lamp. thermosnitck?’
P!‘?&r-uay
R . reaction tube.
5’. sample intake. T. valve with positions S to P , P to A . P t o C and S to C
Figures 2 :tnd 3 are photographs of two models of the instrument’. The pump and valve mechanism are critical parts and rcquired wnsiticral)lr t.sperimenta1 work in their development, The pump body consists of a stainless-steel tube 1 inch in insidr diainrter hy 1 inches lung, the. inner surfacts of n-hirh is
ANALYTICAL CHEMISTRY
676
te&;er&ure i s maintahed by use ifan electric heater controlled by an Edison thermosn*itch. The reaction tube, heating coil, ,pilot light, and tbermoswitch are eontaincd In a half-pint Thermos bottle and w e held in place by asbestos fiher insulation. The pilot light is B small neon lamp, which is placed next to the upper end of the exhaust tube, so that its glov may he Been through the tube. OPERATION O F THE INSTRUMENT
Detailod instructions for use of the instrument are contained in the final report ( 1 ) by the authors to the office of Scicntifie Research and Dcvclopmcnt; hcnceanly anoutlineisgiven here.
co
Conoentra. tion
P.p.m.
Length of Blaokening Front Bhok
Mm.
Mm. 14.0 13.5 13.5 13.2 13.0
Av.
Mea" Deviation from Av.
Mm.
Mm.
13.7
0.3
Calibra.
tion Mm./100 P.P.~.
13.0
13.7 12.0
14.0 14.7
14.0
11.0 12.2 12.o
11.5
12.7
33.0
34.0 35.0 34.5 35.0
Testing Air Blank. Because mercuric oxidedissocistes to a meawrahle extcnt. even a t 175" C., the instrument will always show a small amount (1 to 2 mm.) of blackening with carbon monmidc-frec air. As mercuric oxide tends to absorb free mercury a t room temperature, the air hlsnk should always he tested before making malyses. This is done by allowing the instrument to heat to the reaction temperature, a t which time the pilot light, comes on. With the valve at the sample position, a sample of pure air is drawn in hy slowly raising the pump to the top of its stroke. The valve IS turned momentarily to the vent position, then on to the run position. A right-angle bend is made in a test strip about 0.5 inch from one end and the other end inserted in the reaction tuhe. The catch on the pisban rod is released, permitting tho piston to fall slowly. The piston is timed t o fall in about 3 minutes. If the fall is too rapid, the boundary of the black coloration on the test strip is not sharp. If the first air blank is more t,hm 2 mm. (as it. may he if the instrument h m not been used for several days), two or three more determinations should he made. This will bring the blank down unless the reaction tube has been unused for a long period or is contaminated. In this case the tube should be conditioned bp passing a slow stream of pure air through it for several hours at about 250' C. Makine an Analvsis. The container holding the sample to he
"--. ..~__ ..... ~~~
.
~~~~
~~
20 and 40 mm. The first determination for each new sample should be discarded, hecausc the reaction tube will contain some of the previous samplr (or sir). Five additional strips are usually
accurately ground axid honed. An dliminum piston about 0.75 inch long is carefully turned to a ,iia.meter 0,001inch less than the hare of the tube. It is operated 1vit,bout lubricant. As the gas pressure within the pump is only dig,ht mre (being determined by the wei gb leakage past the piston is small andI S leakaee is nealieible. The viston a.nCI ;ad are made as light as I t he line suffices to slow the !"t , t o the desired rate of 15 to
ts
Thi'faur-wai rotary valve consis of two flat, circular platcs held tightly together by spring ten!310n. Each plate has appropriately located grooves and ports 1tor propcr routing of thc gas stream. The routes followed in ea.ch of the four positions arc noted on Figure 1. To remove unsaturated h y d r o a.rhons apd higher saty+?d hvdrocarhons (butane and above) a charcoal trap 1s inciuaea DP"he. This trap consists of a ng containing 8- to 14-mesh ;lass-wool plugs. The Pyrcx reaction tube serves as the harder 03 both the mercuric oxide and le tubing into which the test sen, so thatitsinside diameter ne test strips. nre of the instrument is 175' t o 180" 'c. At l o b te6peradures the reaction between carbon monoxide and red mercuric oxide is incomplete and a t higher
rigure a. Larnon wonoxide Analyzer
677
V O L U M E 20, NO. 7, J U L Y 1 9 4 8 Table 11.
Concentrations of Carbon \\Ionoxide in Eight Carbon >Ionoxide-Air Samples
(Deteririined by Beckman-hfcCullough method in order of analysis compared rvith 1 2 0 6 reference method) Analysis 1 9 0 5 h l e t hod
JIlU.
Carbon 90 5 1 8 4 . 0 44 8 40 95 184 54 202 96 42 215 9" 49 204 102 44 195 103 42 201 93 50 201 101 47 92 169 44 182 95 192 43 YO 95.9 1 9 4 . 3 4 5 . 5 103 204 .54 40 92 169
A r. Mas. Slin.
Per 106.0 113.8 101.7
Bechman.\lcCullo11 method
hv. Ala-..
Monoxide, P a r t s per Million 360 2 4 4 . 7 2 3 . 8 66 2 1 3 7 . 8 1 3 7 . 8 155 215 261 26 128 56 142 2i9 2 14 55 119 23 281 25 146 61 197 119 149 25 278 57 123 21 149 60 269 117 '2 146 57 122 208 264 152 65 17 127 220 206 159 55 27 208 201 121 12'2 216 266 60 ... 214 119 ... 61 276 270 212 '24.2 5 8 . 7 1 2 1 . 7 1 4 8 . 5 279 220 27 65 128 155 261 197 21 55 119 142
;;
Cent Recovery of Carbon llonoaide 1 0 5 . 4 1 0 1 . 6 8 4 . 4 8 6 . 6 9 3 . 8 8 8 . 7 8 8 . 7 107.6 110.5 120.5 8 7 . 2 9 0 . 0 1 0 4 . 7 9 8 . 2 Y2.Y 112.5 82.9 8 9 . 3 81.6 8 0 . 5 8 1 . 4 8 3 . 1 8 6 . 4 1 0 3 . 0
prepared, the traces on both sides nieasuied, and the ten resulting values averaged. PERFORIIAhCE
The accuiacy of the instrument may be judged from the data given in Tables I and 11. Table I shoss typical re- ilts obtained in the authors' laboratories in the calibration of five lots of selenium sulfide test papers. The data in Table I1 were obtained during comparative tests ( 3 )of five methods for the determination of carbon monoxide in air a t S a v a l Medical Research Institute. Table 11,which is taken directly from Consolazio's report, com-
pares the results obtained with the mercuric oxide instrument with those obtained n i t h an iodine pentoxide train. The mean deviation of the instrument values from those obtained by the iodine pentoxide method is S.S%, which is good a t these low concentrations. Some of the deviation is without doubt due to errors in the iodine pentoxide method, which was said by the author of the report to be perhaps as high as 5%. That the instrument error is almost entirely in the selenium sulfide step is shown by the high accuracy of the gravimetric method based on the mercuric oxide reaction ( 1 ) . Instrument accuracy is high enough for many laboratory and most field requirements and the instrumrnt has the distinct advantages of speed and simplicity. In over five hundred determinations with one of these instruments in the writers' laboratory in the calibration of papers no servicing of the instrument n as required. LITER.4TURE CITED
(1) Beckman, A . O., hIcCullough, J. D., and Crane, R. .1.,Report
PB 5921, Office of Publication Board, Department of Cornmerce, Washington 2 5 , D. C. (2) Campbell, T. W., and McCullough, J. D., J . Am. Chem. Soc., 67, 1965 (1945). ( 3 ) Consolaeio. W. V.. and eo-workers. Remaort 5. Proiect X-417,
h'aval Medical Research Institute, Naval Medical Center, Bethesda, Md., 1944. (4) McCullough, J. D., Crane, R. A., and Beckman, 9.O., ,1N.4L. CHEM.,19,999 (1947). ( 5 ) h'ordlander, B. W., Ind. Eng. Chem., 19, 518 (1927). (6) Sanger, C. R., and Black, 0. F., Proc. Am. Acad. Arts Sci., 43, 295 (1907-8). RECEIVED October 27, 1947. Based on research done for the Office of Scientific Research and Development under Contract KO. OEMsr 674 with Arnold 0. Beckman.
Argentometric Microdetermination of Organic Chlorine KEIITI SISIDO AND HIROSI Y.AGI Depurtment of Industria: Chemistry, Fuculty of Engineering, Kyoto Cnicersity, Iiybto, Japan
A sample containing about 2 mg. of chlorine is digested with an excess of metallic sodium in butyl or amyl alcohol according to the method of Stepanow. The resulting chloride ion is titrated with 0.01 ,V silver nitrate solution and bromophenol blue is used as an adsorption indicator.
I
S T E R E S T in organic chlorine compounds has made necessary the establishment of a suitable method for the determination of chlorine. llost of the micromethods listed in testbooksPregl-Roth ( 11 ), Siederl-Siederl ( 9 ) , and Ochiai-Tsuda (10)as well as in the literature could not be performed because of the postwar shortage of equipment. Even the Carius micromethod, which is perhaps the most universal, could not be carried out because of the lack of suitable glass tubing and fuel gas for sealing the Carius tubes and heating the Carius oven. Other methods required special equipment or rare reagents or were too coniplicatcd or time-consuming. In the authors' laborator?, carbon and hydrogen analyses are performed by specialists and the research chemist need only purify and submit the saniplr. Sulfur and halogen determinations must always be done by the research chemist himself. .Xccording to the prcn-ar literature available to the authors, no simple method of analysis exists. In order to determine the chlorine in organic combination, it must first be converted into the ionic form. For this purpose, chlorine compounds with the exception of hydrochlorides and alkyl chloride addition products of organic bases (13, 16) must be decomposed by the Carius, oxidation, reduction, combustion, fusion, or other method. The Stepanow method ( l q ) , in which the compound is digested
15 ith metallic sodium to convert the chlorine to chloride ion, dispenses with special apparatus, is free from explosion, and is rapid and as in the Kjeldahl method for nitrogen, many analyses can be carried out in parallel a t the same time. As the result of recent developments, the method is now improved in accuracy and reliability. Indeed, the analysis of a compound, for which even the Carius method failed to give a correct value, has been successfully carried out (1, S, 4,5, 6,8, 12, 16). Chloride ion is best determined by means of the silver salt. Both volumetric and gravimctric procedures are used. illthough Rauscher (12), in modifying the Stepanow method, emplo! ed gravimetric analysis on a micro scale, a volumetric modification is preferred because of its simplicity, even though it is less accurate than the gravimetric procedure. The errors aie attributable to the buret and to the indicator. The backtitration (of the Volhard method), which doubles the largest error, must be avoided and the nature of the color change must be carefully studied. The original Stepanow method and many of its improvements, in nhich the Volhard back-titration is used, are unsatisfactory \Then applied to microanalysis. iinother objection to the Volhard method is the fact that the reddish brown color of ferric thiocyanate often becomes indistinguishable from that of the solution titrated and is influenced by tempera-
