rinking CHROMIUM" Introdus of 3.2 ug/L. Chromium salts are used extensively in industrial provesses sind may ent fe Supply through th : of wastes. Chromate compounds fregtently are added to cooling water for cor ntrol. Chromium may exist in water sop plies im both the hexavalent and the trivalent state alhcaagh thCHROMIUM (3500-C1)Colarimetric Method 2. Selection of Method Use the colorimetsic methex! for the determination of bex- valent chromjum in « natural or treated water intended to be potable. Use the electrothermal (graphite furnace) atomic ab sorption specttometrie method for determination of low levels of total chromium (< SY) pg/L) in water and wastewater. Use the flame atomic absorption spectrometsic method or the in ductively coupled plasma method to measure concentrations up to millieram-per-iter levels, 359 3. Sample Handling I only the dissolved metal content is desired. filter sample through a (0,45-m membrane filer at the time of collection, After filtration acidiy filtrate with cone nitric acid (HNO,) t© pH <2, W'the total chromium content is desired, acidify until tered sample at time of collection with cone HNO, 10 pH <2. 3500-Cr B. Atomic Absorption Method for Total Chromium See flame atomic absorption spectrometsc method, Sections BITIB and C, and electrothermal tome absorption spectro: metric method. Section 3113, 3500-Cr C. Soe Seetion 3120. Inductively Coupled Plasma Method 3500-Cr D. Colorimetric Method jeneral Discussion «4. Principle: This procedute measures only hexavalent chro: rium (Ce). Therefore. to determing coral chromium convert all the chromium to the hexavalent state by oxidation with po- ‘ssi permanganate. The hexavalent chromium is determined colorimetrically by reaction with diphenylearbazide in acid so: lution. A red-violet color of unkaown composition is produced. The reaction is very sensitive, the absoxptivity based on chto= rium heing about 40 O10 L gem”! at S40) nm, To determine total chromium, digest the sample witha sulfuric-nitrie acid mix: lure and then anidize with potassium permanganate before re ating with the diphenylearbazide. bh. Interfevences: The reaction with diphenylearbzide is nearly specific for chromium. Hexavalent molybdenum and mercury salts will react to form color with the reagent but the intensities fare much lower than that for chromium at the specified pH. Concentrations as high as 200 mg Mo or Hy/L can he tolerated, ‘Vanadium interferes strongly ul concentrations up oH) times that of chromium will not cause trouble, Potential interference from permanganate is eliminated by prior rediction with azide. Iron in concentrations greater than I mg/L may produce a yellow clo but the ferric ion (Fe"*) colors nor strong and ne dificult ‘s eneountered aormally if the absorbance is meastred photo- ‘metrically a the appropriate wavelength. aerfering amounts of inoly dena, vanadium, itor. and copper can be removed by jon of the cupferraies of these metals into chloroform (CHCI,). A procedute fr this exteaction is provided but do not use it unless necessary, because residual cupferron and CHC in the aqueous solution complicate the later oxidation. ‘There fore, follow the extraction by aelditional treatment with acid fuming to decompose these compounds 2. Apparatus 4. Colorimetric equipment: One of the following is required 1) Speerrophotomezer, for use at 54D nm, with a light path of Lom or longer. 2) Filter phorometer, providing a light path of 1 em or longer ‘and equipped with a greenish yellow filter having maximom transmistance near $40 nm. ‘. Separutory funnels, 125-mL, Squibb form. with glass or TPE sopeock and stopper. 8. Reagents Use redistilled water to prepare reagents 4 Stock chromium solution: Dissolve W414 mg K. water and dilute 100 mL; 1.00 mL. = 500 pg Ce 1. Standard chromium solution: Dilute 1.08 ral stock eheo- rium solution to 100 mL: 1.00 mL = 5.00 ap Cr, «. Nitric acid, HNO. cone 4, Sulfuric acid, H.SO,, cone ¢, Sulfurie acid, USO, 1 1 F Sulfuric acid, WSO, 6N. &. Sulfuric acid, H.SO,, 0.2N: Dilute 17 mL 6N H.SO, to 500 mL with water, 1h. Phosphoric acdl, H.PO,, cone i. Methyl orange indicator solution3-60 j, Hydrogen peracid, H.0,- 30% 1. Reed water: Dsled water resid in als ap- ; 1. Ammonium hydroxide, NH,OH, cone. in. Poussin permanganate sotan: Diswolve 4§ KAO, in va mt water Sodom ziesoluton: Dissolve 0.5 NAN, in 100 water ¢. Diphenstwrbacidesoiton: Disolve 250 m1 Sipe. slcrbaade(1iphenletbolyreide) in 80 mi acne Store ina brown tote, Discard when soliton becomes discolored Chloroform, CHCl Avot or testi mater tat comes in contin ith ll oF meta-ined caps 4 Capfemon solution: Dissolve 3 # GHN(NOVONH, in 95, 4, Procedure 4, Preparation of calibration carve: To compensate for possible Slight losses oF chromium during digestion or other analytical ‘operations, great ehromium standards by the same procedure as the sample. Accordingly, pipet measured volumes of standard chromium solution (5 jgimL) ranging from 2,00 t0 20.0 mL. t0 give standards for 10 10 100 yg Cr, into 250-mL beakersor conical flasks. Depending on pretreatment used in 4b below, proceed \with subsequent treatment of standards asif they were samples, also carrying out cupterron treatment of standards if this ise quired for samples. Develop colar as for samples. transfer a suitable portion of each colored solution to a em absorption ell, and measure absorbance at 540 1m, As reference. use distilled water. Correct absorbance readings of standards by subtracting absorbance of i reagent blank curried through the method, Construct a calibration curve by plotting corrected absorbance values against micrograms chromium in 102 mL final volume, . Treamnent of sample: f sample has been filtered and act ified and only hexavalent chromium is desited, proceed to 4 4e 1 total dissolved chromium is desired and there are interfering amounts of molybdenum, vanadium, copper. or irom present. proceed to 4c, I imerferences ure not present, proceed to dd, It sample is unfiltered and total chromium is desired, digest with HINO, and H.SO, as in Section 3030G, If interferences are pre- sent, proceed to $s 4e. dd, und 4e, If there ate no interferences, proceed to $5 4d and de 6 Removal of molybdenum, vanadium, iron, and copper with cupferron: Pipet a postion of digested sample containing 10 to 100 jap Cr into 125-mL separatory funnel, Dilute to about 40 mL with distilled water and chillin an ice bath, Add 5 mL ice cold cupferron solution, shake well, and let stand in ice bath for |Umin. Extract in separatory funnel with three successive S-mL. portions of CHCl. shake each portion thoroughly with aqueous. solution, let layers separate, and withdraw and discard CHC), extract. Transfer extracted aqueous solution 102 125-mL_ conical Task. Wash separatory funnel with a small amount of distilled water and add wash water t@ flask, Boil for about 5 min to volatiize CHCl, and cool. Add 5 mL HNO, and 3 mL H.SO, Boil samples t che appearance of SO, fumes. Cool slight carefully add 5 ml. HNO,, and again boil to fumes to complete decomposition of arganie matter, Cool, wash sides of flask, and boil once more t» SO, fumes to eliminate all HNO,. Cool and adel 25 ml. water METALS (8000) 4. Oxidation of rivalens chromium: Pipet a portion of digested sample with or without interferences removed, and containing 10 to 100 jg Cr, into a 125-ml. conical flask. Add several drops ‘of methyl orange indicator, then add cone NH,OH until solution just begins 10 tum yellow, Add 1 + 1 H.SO, dropwise until it is acidic, plus | mL. (20 drops) in excess. Adjust volume to about 40) mL, add a boiling chip. and heat to boiling, Add 2 drops KMno, solution to give a dark red color. If fading occurs, add KMnO, dropwise to maintain an excess of about 2 drops. Boil for 2 min longer. Add | ml. NaN, solution and continue boiling gently. If red color does not fade completely after boiling for Approximately 30 s, add anther 1 mL NaN, solution, Continue biting for 1 min after cofor has faded completely, then cool ‘Ada 0.25 mi. (5 drops) HPO, & Color development and measurement: Use 0.2N H.SO, and pH meter to adjust solution to pH 1.0 + 0,3. Transfer solution to a 10m. volumetric flask, dilute (© 100 mL, and mix. Add 2.0 mL diphenylearbazide solution, mix, and let stand 5 t0 10 min for fll color development. Transfer an anpropriate portion to.a Lem absomption cell and measure its absorbance at 540 nm. Use distilled water as reference. Correct absorbance reading of sample by subtracting absorbance of a blank carried through the method (see also note below). From the corrected absorbance. determine micrograms chromium present by reference to the calibration curve NoTE: Ifthe solution is turbid after dilution to 100 min Ye above, take an absorbance reading before adding carbazide re ‘agent and correct absorbance reading of final colored solution by subtracting the absorbance measured previously. 5. Calculation sm Cun. = MECN HOD mt final volume) yy 1p Cu a 100 where: ‘A= ml original sample, and 1H = mi. portion from 100 mi. digested sample. 6. Precision and Bias The dissolved (trivalent plus hexavalent) chromium was de termined in 31 laboratories in a synthetic sample containing 110, hg CriL, 500 wg AUL, 50 wg Ca, 470 pg Cail, 300 wg Fell, 70 yg POL, 120 pg MniL, 150 pg Ag/L. and 650 wg ZavL in istilled water. The relative standard deviation was 47.8% and the relative error 16.3% 7. Bibliography ROWLAND. GP... 1939. Photostctriccolorimetry—Opticl study of permanganate ion and of chromiamtdiphenscarbacde system, Ana Chem, 11482 Satr2man. BE, 1952, Mierodetermination of eheomium with diphen: leatbazide by permanganate oxidation. Aral, Chem, 241016 UnoNe, P.F, 1985, Stability of colorimetric reagent for chromium. 5 iphenylearbazid. in various solvents. Anal Chem. 27.1331, ALLEN. TL. 198K, Micotermination of chromium with 1.5-diphen leathohydrazide. Anal. Cher. W887 SANDELL, E.B. 1959, Colorimetsic Determination of Traces of Metals. Sided. Interscience Publishers, New York, N.Y.