3 ape A Del 'Hethoas of Bil Anglows BORE BREET? q eo ef TEC ABlock. (Eder -. Ge. i 0-274. coknénts wie S ~ {Drying of extracts is best accomplished in 100-ml. fale of Tie Kjeldaht ee ype. A 2-liter beaker conveniently holds 4 flasks. Drying in this manner 4 is tt ‘more any than bs dried samples can be ge for, | 90-3 WAIKLEY-BLACK METHOD ~¢<4 atu \ - 90-3.1. Introduction 2 Oxidizable matter in a soll sample is oxidized by Cr.O; = tion is facilitated by the heat generated when 2 volumes of H.SO, are mixed with f volume-of iN KsCr.O; solution. The excess CrO;?~ is determined by titration with standard FeSO, solution, and the quantity of substances ‘oxidized is ealeul=ted from the arhount of Cr.0;2~ reduced. jenberger (1927, 1945) and Allison (1935) used di- entrated H.SO, as indicator, Peech et al. (1947) found that aqueous barium diphenylamine sulfonate is much more stable, equally effectie, and he> the same blue-to-green color change as diphenylamine. With these indic=tors, HyPO, is used to sharpen the color change at the endpoint. The o-ahenanthroline-ferrous complex indicator (Ferroin) gives. <~ a color change from blue to red at a muck higher oxidation-Feduction po- U2 tential than eithe> of the diphenylamines and, consequently, itis considered °° superior to the Iztter. The use of H;PO, with this indicator appears to be ‘optional: Jacksor (1958, p. 211) advises its use, but others (U. S. Salinity Laboratory, 195+) have found.it unnecessary. A criticism of o-phenanthro- Tine is that some vara : ORGANIC CARBON Carbon in Sil, % = (Apparent % C in soil) — (% CI-/12). - ‘The higher oxides of Mn occur in many forms, but the extent of their ‘occurrence in soils is unknown. The fnost active type (Walkley, 1946), corresponding to fresbly precipitated soil Mn, will take part in oxidation » reactions, Active MnO, competes with K-Cr,O; when heated ia acid media Containing oxidizable substances, and thereby induces a negative error of analysis, depending on the quantity present andthe extent of its activity. Based on extensive studies of the effect of higher oxides of Mn on the ‘Walkley-Black procedure, Walkley (146) concluded that in normal soils ‘the quantity of reducible oxides of Mn is invariably small, and that in highly manganiferous soils only a small fraction of all oxides present is in the active state Eapable of competing with Cr,0;?~ oxidation. Moreover, ‘all errors observed in this study from the effect of soil Mn on the C de- _ ‘termination were, <6%. Walksy (1946) devised 2 prosedure for deter- mining the quantity of reactive oxygen in sols if large quantities of reactive Mn are |. Ferrous irom, if present in the soil sample, would be oxidized by Cr:0; and thereby would give a positive error in the analysis, i.e. high values of | organic-C. Traces of Fe? are known to exist in well-aerated soil, and ap- preciable amounts of this constituent may be found in sols rich in organic ister oF in paddy soils, Lee (1939) obtained highly erroneous C values on feed subsoils from paddy land by the rapid titration method, However, Walkley (1946) obtained normal C recovery from gleied soils that were thoroughly air dried for 1 or 2 days before analysis, in which case the amount of soluble Fe?~ compounds is trifling compared to the qual organic-C present, It is advisable to avoid grinding soll samples, particularly coarse-textured sols, in iton or steel equipment t0 avoid the positive errors of analysis that will result from contaminating the samples with metallic (reduced) iron. 90-32 Method? 90-321 REAGENTS 1, Potassium dichromate (K.Ct:0;), 1N: Dissolve 49.04, g. of reagent- grade K,Cr0; (dried at 105°C.) in water, and dilute the solution to a ‘olume of 1,000 ml. 2, Sulfuric acid (H,S0,), concentrated (not Tess than 96% ). If CL” is present in the soil, add Ag.SO, to the acid at the rate of 15 g. per liter. 3. Orthophosphoric acid (H.PO.), concentrated, “4, o-phenanthroline-ferrous- complex, °0.025M: Dissolve 1485 g. of Firenamthroline monohydrate and 6.95 v. ot FeSO, -7H.O in wate “A dilute the solution to 2 volume of 1.000 ml. o-phenanthroline *Walhley, 1946; Peeeh-et al, 194%. Greweling and Peech. (960.OO - plex is available under the name of “Ferroin” fromghe U- ‘Smith Chemical Co., Station D, Box 5906, 867 McKinley ‘Columbus 22, Ohio. diphenylamine sulfonate: Prepare a 0.16% aqueous solution. s reagent is an optional substitute for No. 4. sulfate (FeSO.-7H.0) solution, 0.5N: Dissolve 140 g. of de FeSO,-7H,0 in water, add 15 ml. of concentrated H:SO., the solution, and dilute it to a volume of 1,000 ml. Standardize ‘reagent daily by titrating it against 10 ml. of 1N K;Cr,Or, as ted below. (For routine use, this reagent in larger quantities may ored under hydrogen from a Kipp generator with negligible change er from day to day.) ‘pROcEDURE ‘ d the soil to pass a 6.5-mriz sieve, avoiding iron or steel mortars. ‘a weighed sample, containing 10 to 25 mg.vof organic-C, but not of 10 g. of soil, into a 500-ml. wide-mouth Erlenmeyer flask. Add W-INKCi.0,, and swirl the flask gently to disperse the soil in the ‘Then rapidly add 20 mi. of concentrated H.SO,, directing the nto the suspension. Immediately swirl the flask gently until soil and are mixed, then more vigorously for a total of 1 minute. Allow ask to stand on a sheet of asbestos for about 30 minutes. Then add ‘of water to the flask, and filter the suspension if experienge shows ‘endpoint of the titration cannot otherwise be clearly discerned. Add drops of o-phenanthroline indicator, and titrate the solution with SO,. As the endpoint is approached, the solution takes on a green- st and then changes to dark green. At this point, add the ferrous sul- irop by drop until the color changes sharply from blue to red (maroon in reflected light against » white background). Make a blank determi- nin the samé manner, but without soil, to standardize the Cr.0;*~. the determination with less soil if more than 75% of the di- cis reduced, ; ulate the results according to the following formula, using a correc itable value found experimental C Cle) de am Proceed in the mantter-deseribed in section"90-3.2.2 through the opera on of adding 20 ml. of concentrated H.SO;> Tnsert-i>2U0..C.thermomerer the reaction mixture, and-gently-heat the flask over a low Mame-to. cain a température of 150°C. in a heating period of approximately 1 \ Ve = as jp welfe eeeFactor de VAN BEMMELEN | Fi Porcentaje de materia orgénica total o facimente oxidable se determin, Tanacando el carbon (total u oxidable) por un factor empitico (factor de Factor de VAN BEMMELEN = 100/58 = 1.724 | Procedimientos Normalizados de Trabajo (PA-002) Determinacién de materia orgénica en suelos (Método de Walkley,1934 y Walkigy. 1947)