IS : 228 ( Part 3) - 1987 . ( Reaffirmed 2002 ) Indian Standard METHODS FOR CHEMICAL ANALYSIS OF STEELS PART 3 DETERMINATION OF PHOSPHORUS BY ALKALIMETRIC METHOD (Third Revision) Fourth Reprint NOVEMBER 1998 UDC 669. 144669, 15~194:543.2411 543.847) © Copyright 1987 BUREAU OF INDIAN STANDARDS MANAK BHAVAN, 9 BAHADUR SHAH ZAFAR MARG ‘NEW DELHI 110002 Gr 3 September 1987IS 1 228 ( Part 3) = 1967 Indian Standard METHODS FOR CHEMICAL ANALYSIS OF STEELS PART 3 DETERMINATION OF PHOSPHORUS BY ALKALIMETRIC METHOD (Third Revision) Methods of Chemical Analysis of Ferrous Metals Sectional Committee, SMDG 2 Chairman Representing Da. S$, P. [ren Bhabha Atomic Research Centre, Bombay Members ‘Sarr G. M. APPARAO Steel Authority of India Ltd ( Bhilai Steel Plant ), Bhilai Saaz R. D. Acanwan ( Alternate) " Sua: §.V. Buacwan Khandelwal Ferro Alloys Tad, Nagpur Snax D. N. Gnera ( Alternate) Sunt P, Cuarna Indian Metals & Ferro Alloys Ltd, Koi Cmonsr & Meranconors Ministry of Transport (Department of Assistawr REstaRca O7v10RR (Mer-2), RDSO, Luczxow (Alternate ) Curer Creuset Tata Iron & Steel Co Ltd, Jamshedpur Aseiorant Carer Camseror ( Alternate ) Smet M. K. Cravnavanry Ministry of Defence (DGI) Sari P. K. Sen ( Alternate ) Da M. M, Cuaxnanonty Indian Iron & Steel Co Ltd, Burnpur Suur M. §, Cuarrmnses ( Alternate ) SnarG, K, Dixon? Ordnance Factory Board ( Ministry of Defence ), Calcutta Suni S. N. Morrna ( Alternate) Suar V. B. Kuarora Direstorate General of Supplies & Disposals, ‘New Delhi Sunt J. N. MUxHERsER Steel Authority of India Ltd ( Durgapur Steel Plant ), Durgapur { Continued on page 2) © Copyright 1987 BUREAU OF INDIAN STANDARDS This publication ia protected under the Indian Copyright Act (XIV of 1957) and reproduction in whole or in part by any means except with written permission of the publisher shall be deemed to be an infringement of copyright under the said Act.IS : 228 ( Part 3) - 1987 (Continued from page 1} Members Representing Suet P. Namart Mahindra Ugine Steel Co Ltd, Bombay Suar G. R. Sanaa ( diternate) Sunt N. P. Panna Steel Authority of India Ltd (Rourkela Steel Plant ), Rourkela Sunt B, Mamararra ( Alternate ) Da lL, P. Panpry National Metallurgical Laboratory (CSIR), Jamshedpur Dr D.C. Paaswan National Physical Laboratery (CSIR), New Delhi Sur J. Rat ( Alternate) SuarG. Razarso Ferro Alloys Corporation Ltd, Shreeramnagar SuarK, Ramaxsiennan Essen & Co, Bangalore Da J. Rasanan (Alternate ) Sunt A. P. Sivma Steel Authority of India Ltd (Bokaro Steel Plant ), Bokaro Suni K. ANNIAE ( Alternate ) Sunt N. V. SUBBARAYAPPA Viavesvaraya Iron & Stecl Ltd, Bhadravati Da P, Supmanmaniay Defence Metallurgical Research Laboratory, Hyderabad Sanz T. H. Rao ( Alternate) Da Cw, Ven aTeswaRtv Bhabha Atomic Research Centre, Bombay Sunt K. RaGHAvENDRAN, Director General, BIS ( Ex-oficio Member ) Director ( Struc & Met) Secretary Sunt M. L, Snanma tant Director ( Metals), RIS Ferrous Metals Analysis Subcommittee, SMDC 2: 3 Convener Dn, S, P. Iver Bhabha Atomic Research Centre, Bombay Members ‘Suni S. Basranan Bharat Heavy Electricals Lid, Hyderabad Sant Mara Sanaue ( Alternate 1) Smar B, Raza ( Alternate 11) Sunt U. P. Borr Steel Authority of India Lid ( Bhilai Steel Plant ), Bhil Sumi E. M, Venouson ( Alienate ) Cuver Cueist ‘ata Iron & Steel Co Ltd, Jamshedpur AssiaTant Curr Cramist ( Alternate ) De M, M, Cuaxpanonty Indian Iron & Steel Co Ltd, Burnpur ‘Sunt L. N, Das ( Alternate ) Sum H. K. Das Steel Authority of India Ltd (Rourkela Steel Plant ), Rourkela Smar K, Brsuxor ( Alternate) Sunt A. K, Guerra National Physical Laboratory (CSIR), New Delhi ( Continuad on page 11)1S : 228 ( Part 3) - 1987 Indian Standard METHODS FOR CHEMICAL ANALYSIS OF STEELS PART 3 DETERMINATION OF PHOSPHORUS BY ALKALIMETRIC METHOD ( Third Revision) 0 FOREWORD 0.1 This Indian Standard (Part 3) (Third Revision) was adopted by the Indian Standards Institution on 16 January 1987, after the draft finalized by the Methods of Chemical’ Analysis of ‘Ferrous Metals Sectional Committee had been approved by the Structural and Metals Division Council. 0.2 IS: 228, which was issued as a tentative standard in 1952 and revised in 1959, covered the chemical analysis of pig iron, cast fron and plain carbon and low alloy steels. For the convenience it was decided to publish a comprehensive series on chemical analysis of steels including high alloy steels. Accordingly, revision of IS: 228 was taken up again and new series on methods of chemical analysis of steels including high alloy steels was published in various parts as IS : 228 (Parts 1 to 13) (see Appendix A ) covering separate method of analysis for each constituent in steels. However, IS ; 228-1959* version has been retained for the analysis of pig iron and cast iron till a separate standard for analysis of pig iron and cast iron is published. 0.2.1 This revision of IS ; 228 (Part 3 )-1972t- has been undertaken on the basis of experience gained during the implementation of the standard by the manufacturers and testing laberatories. 0.3 In this revision method for determination of phosphorus in following alloy steels has been incorporated: a) Stainless steel, high chromium, nickel chromium and similar alloy steels without tungsten or vanadium, *Methods of chemical analysis of pig iron, cast iron and plain carbon and low alloy steels (revised). tMethods for chemical analysis of steels: Part 3 Determinatit f phosph« alkalimetric method (second revivon ation of Phosphorus ByIS : 298 ( Part 3) - 1987 b) Steel containing high silicon, titanium or zirconium, ¢) Chromium vanadium steels or other steels containing vanadium but no tungsten, 4) High speed steels or other steels containing tungsten with or without vanadium, e) Austenitic manganese steels, and f) Steels containing arsenic up to 0°l percent. 0.4 In reporting the result of a test or analysis made in accordance with this standard, if the final value, observed or calculated, is to be rounded off, it shall be done in accordance with IS : 2-1960*. 1, SCOPE 1.1 This standard (Part 3) covers method for determination of phosphorus content of plain carbon steel and alloy steels by alkali- metric method. 2. SAMPLING 2.1 The samples shall be drawn and prepared as prescribed in the relevant Indian Standard, 3. QUALITY OF REAGENTS 3.1 Unless specified otherwise, analytical grade reagents and distilled water (see IS : 1070-1977 ) shall be employed in the test. 4. OUTLINE OF THE METHOD 4.1 Phosphorus is converted to orthophosphoric acid and precipitated as ammonium phosphomolybdate. The precipitate is dissolved in known excess of standard sodium hydroxide solution and the excess is titrated against standard nitric acid solution. 42 Reagents 4.2.1 Dilute Nitric Acid —1:1, 1:3, 1:5 and 2 : 98 (ajo). 4.2.2 Potassium Permanganate Solution— Dissolve 2 g of potassium permanganate in 100 ml of water. ‘Rules for rounding off numerical values (révissd). ‘Specification for water for general laboratory use ( second revision ). 4IS : 228 ( Part 3) - 1987 4.2.3 Sodium Nitrite Solution —5 percent (mv). 4.2.4 Concentrated Ammonium Hydroxide — Relative density 0°90. 4.2.5 Concentrated Nitric Acid — Relative density 1°42 (conforming to TS : 264-1076* ) 4.2.6 Ammonium Molybdate Solution — Add solution A (see 42.6.1) slowly and with constant stirring to solution B ( see 4.2.6.2 ) kept cool in a cold waterbath. Add 10 ml of ammonium phosphate solution (1 g/l) and keep the solution at least for 24 hours. Filter the solution through Whatman filter paper No. 040 before use. 4.2.6.1 Solution A ~ Dissolve 100 g of molybdic acid (MoOs, 85 percent ), or 118 g of ammonium molybdate in a mixture of 145 ml of ammonium hydroxide (rd = 0°90) and 270 ml of water. Cool the solution. 4.2.6.2 Solution B— Add 490 ml of concentrated nitric acid to 1 150 ml of water and cool. 4.2.7 Potassium Nitrate Solution ~ 1 percent (mv). 4.2.8 Phenolphthalein Solution—1 percent. Dissolve 1 g of powder phenolphthalein in 100 ml of rectified spirit or methyl alcohol. 4.2.9 Sodium Hydroxide Solution —0'1 N, dissolve 45 g of sodium hydroxide in one litre of freshly boiled and cooled distilled water, and standardize against standard nitric acid { 4.2.10 ). 4.2.10 Standard Nitric Acid Solution —0°1 N, dilute 7 ml of concentrated nitric acid to one litre with freshly boiled distilled water. Standardize against sodium carbonate previously ignited at 350°C and cooled. AQ Lilute Hydrochloric Acid —1 + 1 (2/0) and 2 percent (2/2). A232 Hydrofluoric Acid — 40 percent 4.2.13 Perchloric Acid — 70 percent. 4.2.14 Sodium Carbonate — 5 percent (m/v). 4.2.15 Ferrous Sulphate Solution — Dissolve 100 g of ferrous sulphate crystals ( FeSQ,, 7H,O ) in one litre of dilute sulphuric acid (5 : 95). 4.2.16 Dilute Ammonium Hydroxide — 1:1, 1: 20 (v/v). 4.2.17 Sulphurous Acid — Saturate water with sulphur dioxide gas. ‘Specification for nitric acid ( second reowsion ). 5IS + 228 (Part 3) - 1987 4.2.10 Concentrated Hydrochloric Acid — Relative density 1°16 ( conform- ing to 1S: 265-1976* }. 4.2.19 Dilute Hydrobromic Acid — \ : 4 (v/v). 5. PROCEDURE FOR PLAIN CARBON STEEL AND LOW ALLOY STEEL WITHOUT VANADIUM 5.1 Transfer 2 g of the sample in a 250-ml conical flask. Add 30 ml of dilute nitric acid (1 : 1) till the vigorous reaction subsides. Keep the flask at low heat till it dissolves. 5.2 Add 5 to 10 ml of potassium permanganate solution and boil for few minutes. If manganese dioxide does not precipitate add further permanganate solution till a precipitate of manganese dioxide appears and boil for few minutes. Add sodium nitrite solution dropwise till the brown precipitate is dissolved. Buil tv expel oxides of nitrogen. 5.3 Add ammonium hydroxide till brown precipitate of ferric hydroxide appears. Dissolve the precipitate adding dilute nitric acid (1: 1) dropwise and add 2 to 3 ml of concentrated nitric acid. Nore — Quantity of nitric acid added at this stage will depend upon the actual volume of the solution. The analyst will ensure that the acidity of the solution belore precipitation of phosphomolybdate complex 1s maintamed at -1U percent. 5.4 Warm the solution to about 60-80°C and add 50 ml of ammonium molybdate solution, stopper the flask, shake vigorously for a few minutes and allow to stand for half an hour. 5.5 Filter the precipitate through a filter paper pulp pad by suction, Wash the flask, precipitate and filter pad twice with 5 ml portions of dilute nitric acid (2 : 98) and five times with 5 ml portions of potassium nitrate. Continue washing of the precipitate and filter pad with potassium nitrate solution until the washings are acid free (10 ml Portion of the washings in presence of phenolphthalein should turn pink on adding one drop of 0"1 N sodium hydroxide solution ). 5.6 Transfer the pulp along with the precipitate to the flask. Add about 25 ml of water, few drops of phenolphthalein and a known volume of sodium hydroxide solution (which should be 1-2 ml in excess) and shake to dissolve the precipitate. Dilute to about 100 mi and titrate with standard nitric acid solution to the disappearance of pink colour. “Specification for hydrochloric acid ( second revision ). 6IS : 228 (Part 3) - 1987 6. PROCEDURE FOR ALLOY STEELS 6.1 Stainless Steel, High Chromium, Nickel Chromium and Similar Alloy Steel Without Tuvgsten or Vanadium — Transfer 2 g of the sample in a 400-ml beaker. Add 50 ml of a 1:1 mixture of concentrated hydrochloric acid and nitric acid and a few drops of hydrofluoric acid. Place the Leaker at low heat uuuil dhe reaction subsides and then add 15 ml of perchloric acid. Evaporate to copious fumes and fume for a few minutes. Cool, take up with 40 ml of water and 10 ml cf concentrated nitric acid, boil for few minutes, filter through paper pulp and wash with hot dilute nitric acid (1:5). Collect the filtrate in 500-ml conical flask and proceed as in 5-2 to 5. 6.2 Steel Containing High Silicon, Titanium or Zirconium 6.2.1 Follow the procedure given in 61 up to filtration and proceed as follows. 6.2.2 Collect the filtrate in a 500-ml conical flask and preserve it. ‘Vake the precipitate and pulp (as in 6.1) in a platinum crucible and ignite, fume with 1 ml hydrofluoric acid and a few drops of concentrated nitric acid at low temperature. Fuse the residue with sodium carbonate. Dissolve the melt in water, filter through paper pulp and wash with sodium carbonate solution. Acidify the filtrate with concentrated nitric acid and add to the main filtrate, Proceed further as in 5.2 co 5.6. 6.3 Chromium Vanadium Steels or Other Steels Containing Vanadium But No Tungsten 6.3.1 Proceed as in 6.1 when the solution is ready for the precipitation of phosphomolybdate complex. 6.3.2 Cool the solution to 10-20°C, add 5 ml of ferrous sulphate solution and 2 to 3 drops of sulphurous acid, and shake to mix well. Add 50 ml of ammonium molybdate solution, stopper the flask, shake vigorously for a few minutes and allow to stand overnight. Proceed further as in 5.5 to 5.6. 6.4 High Speed Steels or Other Steels Containing Tungsten with or Without Vanadium 64.1 Transfer 2 g of the sample to 2 400-ml beaker. Decompose the sample in 60 ml of dilute nitric acid (1:3) and a few drops of hydrofluoric acid, if required. Add 20 ml concentrated hydrochloric acid, 60 ml concemrated nitric acid and few drops of hydrofluoric acid’ and evaporate to dryness. Digest with 20 ml of concentrated 7IS : 228 ( Part 3) - 1987 hydrochloric acid, dilute to 50 ml with water and boil. Filter through a paper pulp as far as possible by decantation, keeping back the precipitate of tungstic acid in the beaker. Wash twice with hot dilute hydrochloric acid (2 percent). Collect the filtrate in a 500-ml conical flask and evaporate to a small volume. Add 30 ml concentrated nitric acid, and evaporate to syrupy liquid. Add 5 ml concentrated nitric acid, dilute to about 29 ml and boul for a few minutes. 6.4.2 To recover phosphorus from the precipitate of tungstic acid, dissolve the precipitate in the beaker with minimum quantity of dilute ammonium hydroxide (1:1) and pour it through the filter pad collecting the solution in a beaker, wash the beaker and the filter pad with dilute ammonium hydroxide (1:1) until all of the tungstic acid has heen dissolved and collected. Add a few ml of the main filtrate . (end of 6.4.1) to this solution and slightly acidify with dilute nitric acid (1:1). Add dilute ammonium hydroxide (1: 1) in clight excess and heat to flocculation, Filter through Whatman filter paper No. 42 and wash with dilute ammonium hydroxide (1 : 20). Dissolve the precipitate in imum hot dilute nitric acid (1:5) and add to the main filtrate (see 6.4.1 ). 6.4.3 Treat the filtrate as in 5.2 and 5.3. If the sample contains vanadium, proceed further as in 6.3.2. In the absence of vanadium, complete the determination as in 5.4 to 5.6. 6.5 Austenitic Manganese Steels — Decompose 2 g of the sample in a 400-ml beaker in 40 ml of dilute nitric acid (1:3), Add 15 ml of perchloric acid and evaporate just to white fumes. Add hydrofluoric acid drop by drop until all the hydrated silica is dissolved and a few drops in excess. Heat so that perchloric acid refluxes on the sides of the beaker for about 25 minutes. Cool, add about 40 ml of water and 10 mt concentrated nitric acid and boil for few minutes. Proceed further as in 5.2 to 5.6. 6.6 Steela Containing High Arsenic Up to 0'1 Percent 6.6.1 Decompose 2g of the sample in 400-ml beaker in 40 ml of dilute nitric acid (1:3). Add 20 mil of perchloric acid and fume to expell nitric acid. Gool, add about 80 ml of dilute hydrobromic acid and evaporate to copious fumes. Cool, add about 40 ml of water ard 10 ml nitric acid. Proceed further as in 5.2 to 5.6. 7. RLANK DETERMINATION 7.1 Make a blank determination following the same procedure and using the same quantity of all reagents. 81S : 228 ( Part 3) - 1987 8. CALCULATION 8.1 Calculate phosphorus, percent, as: Phosphorus ( percent ) = BaDxe x 100 where A = nillilitres of standard nitric acid solution required in the sample in the titration of the excess sodium hydroxide (see 5.6), B = niillilitres of standard nitric acid solution required in the blank determination (cee 7.1), C = phosphorus equivalent of 1 ml standard nitric acid solution, and D = quantity of sample in g. 8.2 Reproducibility — + 0°001 5 percent. APPENDIX A ( Clause 0.2) IS : 228 Methods for chemical analysis of steels: (Part 1)-1972 Determination of carbon by volumetric method (for carbon > 0'l percent ) ( second revision ) (Part 2)-1972 Determination of manganese in plain carbon and low alloy steels by arsenite method ( second revision ) (Part 3)-1972 Determination of phosphorus by alkalimetric method ( second revision ) (Part 4)-1974 Determination of carbon by gravimetric method (for carbon > 0°1 percent ) (second revision ) (Part 5)-1974 Determination of nickel by dimethylglyoxime (gravimetric) auethud (for nickel > 0°S percent) (second revision ) (Part 6)-1974 Determination of chromium by _ persulphate oxidation inethod (for chromium > 0°5 percent) (second revision ) 9IS : 228 (Part 3) - 1987 (Part 7)-1974 Determination of molybdenum by a-benzoinoxime method (for molybdenum > 1 percent } ( second revision ) (Part 8)-1975 Determination of silicon by the gravimetric method (for silicon > 0'l percent ) ( second revision (Part 9)-1975 Determination of sulphur in plain carbon steels by evolution method (second revision ) (Part 10)-1976 Determination of molybdenum by thiocyanate (photometric ) method (for molybdenum up to | percent ) in low and high alloy stecls (second revision ) (Part 11)-1976 Determination of silicon by photometric method in _ carbon steels and low alloy steels (for silicon U'UI to 0°05 percent ) ( second revision ) (Part 12)-1976 Determination of manganese by periodate (photometric) method in low and high alloy steels ( for manganese up to 2 percent ) ( second revision ) (Part 13 )-1982 Determination of arsenic 10IS : 228 ( Part 3) - 1987 ( Continued from page 2) Mantes Representing Sxau J. Muxasisen, Steel Authority of India Ltd (Durgapur Steel Plant ), Durgapur Sunt P. K. Bawensee ( Alternate ) Sunt P. NaRatn Mahindra Ugine Steel Co Ltd, Bombay Sunt G. K. SanMa ( Alternate ) Sam R. 3, Nara Steel Authority of India Ltd (Bokaro Steel Plant), Bokaro Suni N. Goxparra ( Alternate) Dr L. P. PANvEY National Metallurgical Laboratory (CSIR), ‘Jamshedpur Susi G. Rampas Visveavaraya Iron & Steel Lid, Bhadravati Sunt B.D, Vasmnaswarrs Tralah Pur Tad, Rombay Sunt J. C. Dey ( Alternate) ulBUREAU OF INDIAN STANDARDS Headquarters: Manak Bhavan, 9 Bahadur Shah Zafar Marg, NEW DELHI 110002 Telephones: 323 0131, 323 3375, 323 9402 Fax : 91 113234062, 91 11 3239399, 91 113239982 Telegrams : Manaksanstha (Common to all Offices) Contral Laboratory: Teeptone: Plot No. 20/9, Site IV, Sahibabad Industrial Area, SAHIBABAD 201010 8-77 00 32 Regional Offices: Central : Manak Bhavan, 9 Bahadur Shan Zafar Marg, NEW OELHI 110002 323 76 17 “Eastern : 1/14 CIT Scheme Vil M, V.LP. 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