July, 1926 b
INDUSTRIAL Ah-D ENGISEERING CHEMISTRY
methods and in this work we have cooperated with the American Society for Testing Materials in making comparative tests. We consider the development of specifications for lime a necessary activity and this year efforts have been made toward a concentration of this activity in Committee C-7 of the American Society for Testing Materials. In the face of the increasing agitation and demand for specifications, the tendency has been, and we believe will continue t o be, toward consolidation and unification with consequent reduction in actual number. 4 classification of uses is gradually being worked out on the basis of the functions of the lime and specifications applied accordingly. Progress along this line is slow, however, owing t o lack of information as t o the relations between properties of the limes and the way they function. Here again we are called upon for more research data.
Dissemination of Literature The digesting and cataloging of technical and scientific lime literature has continued as usual with the added activity involved in selecting and preparing material for the use of the publicity department. The scientific, technical, and trade
755
periodicals carry in almost every issue articles of importance to all our interests and i t is one of the duties of the research department t o direct this material t o those who can use it or to present it in a usable and easily assimilated form. The attention of the manufacturers is called to interesting articles and by means of the press releases of the Publicity Department and through the Agricultural Lime News Bulletin and direct correspondence the more important facts are given wide distribution. The response indicates a genuine interest in this rejuvenated material, lime. The publication of a list of lime research problems in one of the journals brought a large number of inquiries and requests for suggestions concerning cooperative research, and as a result several new investigations have been started. The rapidly increasing use which is being made of the technical literature by lime manufacturers and salesmen and by users and investigators may be considered a favorable index of increased appreciation of lime, and the 50 per cent increase during the past year in the number of lime plants employing chemists indicates the increasing desire to improve products and t o sell service. All such developments must necessarily elevate the plane of the industry and unquestionably react favorably upon both producer and consumer.
AMERICAN CONTEMPORARIES Victor G. Bloede ICTOR G. BLOEDE is a young man of seventy-seven summers. H e is as active now as he ever was, and it is rather difficult to decide just which of the many interesting high lights of his life to record. We shall, however, restrict ourselves mainly to those of his activities which have t o do with his long career in the chemical industry. His story is that of many another American who, through perseverance and struggles in his early days and without the aid of inherited wealth, surmounted difficulties and rose to high repute and esteem as well as to success in his chosen field. He was born in Dresden in 1849 and, as I once heard him state, he was “imported to America under the age of one.” There was no import duty on him, but this country might well have paid one. His father, by education a jurist and later a physician, was obliged to flee with his family from Germany for having taken a leading part in the Revolution of 1848. The scientific urge came naturally t o him, his grandfather having been a n eminent metallurgist and chemist after whom, as discoverer, the semiprecious mineral “bloedite” was named. Chemistry early became the field in which Victor G. Bloede chose his vocation. At the age of seventeen he took out his first patent on an improved method of making dextrin. Interestingly enough, it is this subject of dextrin and hydrolyzed starch products t o which he is still, after sixty years, devoting the major part of his time when civic and charitable activities do not occupy his hours. He received his early training in chemistry a t the night school of the Cooper Union, Xew York. After graduating he was
V
for a while assistant instructor in chemistry there. It developed rather fittingly that in 1918 he received the Cooper Medal in recognition of his work, while in 1920 he was called t o New York to receive from Cooper Institute the honorary degree of chemical engineer. From his early years he addressed himself t o industrial and applied chemistry rather than t o pure science. Although he has spent most of his time in pursuing the study of starch and its hydrolytic conversion and in investigating the science-or shall we say art?-of the myriad methods of producing modified starch products, nevertheless he has had surprisingly broad contacts and intimate experiences in other realms. These include textile chemistry, photographic chemicals and pharmaceuticals, paper-making, b r o m i n e a n d a c i d m a n u f a c t u r e , and the manufacture of 0 Bachrach coal-tar dyes. Regarding this latter phase of his career there was published in THIS JOCTRXAL in April, 1921,an article written by him on “Some Early Attempts to Establish the Aniline Industry in the United States.’ ’ I n 1883 he married Elise Schon, daughter of a civil engineer, and they have had five children. At about this time he disposed of his chemical works in West Virginia, where he made aniline dyes and other products, and located in Baltimore. Here he founded the Victor G. Bloede Co., manufacturing chemists, of which he is still president and general manager. The output of this plant consists for the most part of dextrins, sizing products for the textile and paper industry, adhesives, and vegetable glues. One of Mr. Bloede’s outstanding achievements in this field was the successful produc-
756
INDUSTRIAL AND ENGINEERING CHEMISTRY
tion of the gum used by the U. S. Government on the back of postage and revenue stamps, which he was one of the first t o develop and supply in its present form. H e was also one of the earliest manufacturers and patentees of the now important industrial product known as vegetable glue-a substitute for animal glue used largely in the woodworking industry, his product being known as “viscamite.” In t h e textile industry he contributed a number of products and processes. One of the most important is the method of dyeing absolutely “sunfast” colors on fabrics by the use of mineral pigments, which under the Bloede process has found extensive application in the production of window shades. For this invention he received medals from the Paris Exposition and the Franklin Institute. Perhaps because he realized the obstacles that beset him in his own youthful days when he studied chemistry at night and helped t o support his family by day, Victor G. Bloede established in 1916 through the Chemists’ Club of New York, a n annual scholarship in chemistry. This is open t o all applicants residing in the United States, and its purpose is t o aid young men who have the desire, but not the means, t o specialize in the study of chemistry. He has also presented to Cooper Union a physical laboratory which is named in his honor.
VOl. 18, s o . 7
Victor Bloede’s work has always been characterized by the creative impulse. When he is not working on some improved chemical process or technical compound, he is likely to be found a t his desk writing the specification of a new patent; when he is not in the laboratory he will probably be directing the policies of a hospital or attending a bank board meeting, or giving his time to such problems as a manual training school for blind women founded by him in Brooklyn, in which signally fine results have been achieved. He donated t o the State of Maryland in 1908 its first hospital for the care of advanced cases of tuberculosis, as a memorial to his mother. Victor Bloede today at seventy-seven is hale, genial, and jovial. One of his dominant characteristics is perseverance. He follows his many cultural interests with the vigor and mental alertness of a man twenty-five years younger. H e has the young man’s outlook on things, and he is not satisfied to reminisce although he can narrate delightfully interesting incidents drawn from the memories of a richly filled life. Rather, he prefers to face the problems of the present, and to these contribute his energy and ability. And perhaps, after all, this is the attitude which determines whether one is really old or young. ELMER I,.GREENSRELDER
Report of A. C. S. Committee on Hazardous Chemicals and Explosives T H I S committee was appointed to cooperate with a committee, having the same title, of the National Fire Protection Association, of which A. H. Nuckolls is chairman. Working conjointly these committees have produced the following tentative table, which is submitted for comment and criticism by all interested parties. It received consideration a t the annual meeting of the National Fire Protection Association held a t Atlantic City, M a y . . . . e . . .
10 t o 13, 1926. The adopted table will serve as a guide to insurance underwriters and adjusters, the insured, municipal and inspection authorities, and manufacturers. CHARLESE. MUNROE,Chairman
......
H. LE& GRAY A. H. NUCKOLLS J. A . RAPPERTY F. C. ZEISBERG
Table of Common Hazardous Chemicals Prepared b y C o m m i t t e e s of N a t i o n a l F i r e P r o t e c t i o n A s s o c i a t i o n and A m e r i c a n C h e m i c a l S o c i e t y on H a z a r d o u s C h e m i c a l s and Explosives I n its present form this i s a tentative report subject to revisions and simply represents progress of the work t o date. More detailed specifications a s to method of storage of t h e chemicals, a s well as additions, will be prepared. M a n y details in regard t o fire-fighting phases of protection remain to be worked out. I. c. c. SHIPPING CONTAINBRLABEL FIREHAZARD LIFE HAZARD STORAGE REMARKS NAME Dangerous in contact with Slightly corrosive ACETICACID Glass carboys and White Safeguard against mechanical chromic acid, sodium perinjury. Isolate from oxibarrels (GLACIAL) oxide, or nitric acid, dizing materials a s noted yields moderately flamunder Fire Hazard mable vapors above flash point 104’ F. Keep in d r y place. I n case Forms flammable a n d exALUMIXUM Barrels or boxes of fire do not use water; i t plosive mixtures with air DUST may cause an explosion Storage should be ventilated Combustible ALUMINUM Wooden barrels and safeguarded a s for oil RESINATE storage building Oxidizing material. May Safepuard against mechanical AMMONIUM Wooden barrels or Yellow explode in a fire. Hazard injury. Isolate from minkegs and glass botPERCHLOeral acids, also from comclasses with potassium tles RATE bustibles chlorate Oxidizing material. HazIsolate Wooden boxes, bar- Yellow BARIUM a r d classes with potasrels or kegs CHLORATE sium chlorate Oxidizing material. Haz- Soluble in water. Do not store with combusWooden boxes; bar- Yellow BARIUM a r d in class with sodium Poisonous when tible materials rels NITRATE nitrate taken internally Do not store with combustiOxidizing material. HazTightly closed metal Yellow BARIUM ble materials ard in class with sodium containers packed PEROXIDE peroxide in wooden boxes or barrels: or in bulk in metal barrels or drums Store in well ventilated comCombustible. Hazard simBORNEOL Barrels, kegs, boxes, None Dartment or building ilar to camphor a n d tins Causes oxidizing effect, re- Corrosive; at ordinary Isolate; safeguard against Bottles should be surBROMINE Glass,bottles; earth- White temperature gives mechanical injury rounded b y incomsulting in heating a n d en jugs bustible packing may cause .fire when in off poisonous suffocating vapors contact with organic material Bronze dust free from When aluminum is present BRONZE DUST Barrels or boxes aluminum not conforms flammable and exsidered dangerous plosive mixtures with air. Composition usually free from aluminum
I. c . c. CONTAINERLABEL Steel cylindf.rs Red
NAME BUTANE
SnIPPING
CAESIUM
Glass bottles
CAESIUM NITRATE
Glass bottles tins
Yellow
and
CAI c Iu M ACETATE CALCIUM CARBIDE
Iron drums and tin cans
CALCIUM NITRATE
Wooden kegs glass bottles
CALCIUM OXIDE
Wooden barrels and bags
Yellow h-one
and
Yellow
Tins
CHINESE WAX
CHROMIC ACID (ANHYDROUS)
or
Burlap bags a n d wooden barrels Iron drums and glass bottles
COBALTOUS Wooden barrels NITRATE COLOPHONY Barrels COPPER NITRATE
Wooden barrels a n d kegs
LIRE H A Z A R D
Oxidizing material. Hazard in class with sodium nitrate Yields acetone on moderate Flammable heating Gives off acetylene gas on Serious under fire concontact with water or ditions moisture Oxidizing material. Hazard in class with sodium nitrate
Spontaneously ignitible when freshly calcined and exposed t o air: hazardous when freshly ground and tightly packed Combustible
Yellow
Oxidizing material; will ig- Poisonous nite o n contact with acetic acid a n d alcohol Oxidizing material. Classes with sodium nitrate Combustible; gives off flammable vapors when heated Oxidizing material. Haz- Poisonous when taken ard classes with sodium internally. Soluble nitrate in water Oxidizing material. Classes with sodium nitrate Oxidizing material
Yellow
DIDYMIUM NITRATE
Wooden kegs
Yellow
FERRIC
Wooden barrels
Yellow
Barrels and carboys
White
FULMIKATE OF
.Detach from other storage
Flammable: gives off flammable vapors which may form explosive mixtures with air High explosive
Corrosive; has caustic effect on t h e skin
SILVER HYDROCHLOTank cars, carboys, RIC ACID and glass bottles
Isolate: may cause explosion in fire See Sodium Nitrate Ventilate storage: avoid dust: keep away from fire or heat Safeguard, against mechanical injury: isolate. See Sodium Nitrate Isolate. See Sodium Nitrate Isolate: safeguard against mechanical injury Safeguard against mechanical injury Explosive restrictions
MERCURY
FULMINATE
Isolate; keep away from fire or heat Store in dry, well ventilated place in accordance with N.F. P. A. Regulations
Isolate: do not store in uncontained mass; prevent dust accumulations; make daily inspections
NITRATE
FORMIC ACID
Isolate: safeguard against mechanical injury; must be immersed in naphtha or kerosene See Sodium Nitrate
Isolate; keep in unheated compartment away from fire or heat Detach from other storage. Keep in well ventilated room remote from fire
Yellow
Yellow
STORAGE Safeguard against mechanical injury
Isolate; store in dry place away from water or moisture when moist and may burst container When heated gives off flammable vapors. Classes with turpentine Flammable; gives off flammable vapors when heated which may form explosive mixtures with air. Flash point 180’ F.
and wooden kegs
CARBOLIC ACID-See Phenol CHARCOAL Boxes, barrels bags (WOOD)
FIREH A Z A R D Flammable gas under pressure. Classes with gasoline vapor in fire hazard Ignites upon contact with water
h’one
CAMPHENE Tins CAMPHOR
757
INDUISTRIAI, AA’D ENGINEERING C H E M I S T R Y
July, 1926
High explosive
Explosive restrictions
OF
White
None
Somewhat corrosive, irritating gas, poisonous Corrosive
None HYDROFLUO-Lead carboys, hard White SILICIC rubber or paraffin bottles LEAD Wooden barrels Yellow Oxidizing material. Classes Poisonous NITRATE with sodium nitrate LIME (UNSLAKED)-see Calcium Oxide MAGNESIUM Tightly closed metal Yellow When powder is dissemi- Serious under fire conor metal lined con- (when in nated in the air explodes ditions ta in er s powdered b y spark; powder liberform) ates hydrogen when in contact u-ith water MAGNESIUM Wooden boxes Yellow Oxidizing material. Classes h’ITRATE with sodium nitrate MURIATICAcI-See Hydrochloric Acid NAPHTHAWhen heated yields flammable vapors. Flash LENE point 125’ F. NICKEL Wooden kegs Yellow Oxidizing material. Classes Poisonous when taken NITRATE with sodium nitrate internally NITRICACID Carboys and glass White M a y cause ignition when in Corrosive; causes sebottles contact with combustible vere burns b y conmaterials; corrodes iron t a c t ; deadly if inhaled or steel; may cause explosion when in contact with hydrogen sulfide and certain other chemicals NITRANILINE Wooden kegs None I n presence of moisture Poisonous O R NITROcauses nitrations of orANILINE ganic materials and may result in spontaneous ignition
Safeguard against mechanical injury; keep away from nitric acid and chlorates Sa!eguard against mechanical injury Isolate; safeguard mechanical iniurv
against
Store remote from water or moisture; avoid dust: safeguard against mechanical injury of containers See Sodium Nitrate Isolate: keep away from fire or heat Safeguard against mechanical injury Safeguard against mechanical injury of containers; isolate from turpentine, combustible materials, carbides, metallic powders, fulminates, picrates, or chlorates Store in dry place: safeguard against mechanical injury
REMARKS Keep cool
INDUSTRIAL A N D ENGINEERING CHEMISTRY
758 I. NAME NITRO-
c. c.
CONTAINER LABEL Wooden kegs None
SHIPPINQ
CHLORO-
BENZINE
PHENOL Hermetically sealed tin cans inside of wooden boxes PHOSPHORUS Wooden boxes, iron SESC!UIdrums, glass botSULFIDE tles PHOSPHORUS, Under water in glass WHITE bottles packed in tin cans PICRIC ACID Wooden kegs, boxes, bottles PHOSPHORUS,
Yellow
RED
None Yellow
POTASSIUMUnder oil or kerosene in glass bottles, tin cans, and iron drums
Yellow
POTASSIUMWooden barrels or
Yellow
CHLORATE
kegs
POTASSIUMWooden b a r r e I HYDROXIDE glass bottles
s,
POTASSIUM Bags, tins, and glass NITRATS bottles
Yellow
POTASSIUMTins PERMANGANATE
Yellow
Tins
Yellow
POTASSIUM
PEROXIDE PorassrwM Glass bottles PERSULFATE atone jars
and
POTASSIUM SULFIDE
Iron drums, cans, glass bottles
Yellow
RUBIDIUM
Metal cans or glass bottles
Yellow
SALTPETER-see Potassium Nitrate SILVER Amber or black glass NITRATE bottles
Yellow
FIR&HAZARD LIFE HAZARD STORAGE REMARKS Gives off flammable vapors Serious under fire con- Isolate, preferably in the open, if inside should be in when heated, which may ditions building compartment or unheated form explosive mixtures with air When heated yields flam- Poisonous Soluble in water. Never store with or above food mable vapors. Flash products point 172.4' F. Flammable Explosive Fumes in fire toxic Isolate from chemicals, safemixed with oxidizing maguard against mechanical terials injury of container Highly flammable. Ignites Fumes in fire toxic Isolate from chemicals. Safeguard container against b y friction shock Ignites spontaneously on Poisonous. Serious Isolate from chemicals. safecontact with air under fire conditions guard against mechanical injury of container Isolate or store under water, Flammable, explosive. Ox- Classes with high exidizing material plosives in respect keep away from other t o life hazard material, including metals with which it forms sensitive and explosive picrates Inflames and may explode Dangerous under fire Isolate; store in dry place spontaneously on contact away from water or moisconditions ture: safeguard against with water mechanical injury of containers Oxidizing material; explo- Dangerous under fire Isolate from combustible sive when in contact with material, acids, and sulconditions combustible material fur Generates heat on contact Store in dry place; keep rewith water. Classes mote from water or moiswith calcium oxide (lime) ture in hazard I n contact with organic ma- See Sodium Nitrate Store in d r y place; prevent See Sodium Nitrate terials causes violent contact with organic matecombustion on ignition. rial Classes with sodium nitrate Isolate from other chemicals, Oxidizing materia& Exespecially those noted unplosive when treated with der fire hazard sulfuric acid, and in contact with alcohol, ether, flammable gases, and combustible materials M a y cause explosion on Dangerous under fire Store remote from water See Sodium Peroxide contact with water. conditions Classes with sodium peroxide Keep dry; safeguard against Oxidizing material. M a y mechanical injury of concause explosion in a fire tainers Yields irritating a n d Safeguard against mechanModerately flammable, corrosive gases ical injury of containers yields flammable hydrowhen burning gen sulfide on contact with mineral acids and sulfur dioxide when burning Explodes on contact with Serious under fire con- Note precautions under Fire ditions Hazard; safeguard against air or moisture; must be mechanical injury; isolate kept immersed in kerofrom water or moisture sene or naphtha Oxidizing material
SODA,cAwsTIc-See Sodium Hydroxide SODIUM I n h e r m e t i c a l l y Yellow sealed tin cans or iron drums
SODIUM CHLORATE
Wooden b a r r e 1 s, glass bottles
Yellow
SODIUM Iron drums HYDROXIDE SODIUM NITRATE
Bags, tins, and glass bottles
Yellow
SODIUM
Yellow
RATE SODIUM PEROXIDE
Iron canisters, glass bottles Tins
Yellow
SODIUM SULFIDE
Iron drums and bottles
Yellow
SrRoNrruM NITRATE
Barrels a n d boxes
Yellow
PBRCHLO-
VOl. 18, No. 7
Corrosive and poisonous
Store in dark place: keep cool and away from combustible material
Dangerous
Do not away guard injury
hazard Oxidizing material. Classes See Potassium Chlorate with potassium chlorate. See Potassium Chlorate Classes with potassium hydroxide and calcium oxide Oxidizing material. Ab- I n case of fire keep water away. It sorbs moisture, bags bemay produce an excome impregnated with plosion. It is, hownitrate. I n contact with ever, intended t h a t combustible materials water should be apwill cause violent complied t o surroundbustion on ignition ing material where necessary t o prevent extension of fire or conflagration Oxidizing material. Classes Dangerous under fire conditions with potassium chlorate in respect t o fire hazard Dangerous
Moderately flammable. Classes with potassium sulfide Oxidizing material. Classes with sodium nitrate
See Potassium fide
tier; isolate. Keep from water; safeagainst mechanical of container
See Potassium Chlorate Isolate from heat and water. See Calcium Oxide and Potassium Hydroxide Store in dry place; prevent Fire hazard less if recontact with organic or moved from bags and stored in noncombustible material combustible bins
Isolate. safeguard against mecianical injury of container Store remote from water
SUI- See Potassium Sulfide
See Sodium Nitrate
Safeguard against mechanical injury; keep away from other materials
I. c. c. SAME SHIPPING COHTAINBRLABEL SULFUR Box cars, barrels, and boxes SULFURIC Carboys,iron drums, White ACID glass bottles, a n d tank cars
THORIUM NITRATE URANIUM
Wooden kegs
Yellow
Glass bottles, boxes
Yellow
Glass bottles, iron drums
Yellow
NITRATE
ZINC CHLORATE
759
IXDUSTRIAL A N D E,VGINEERING CHEMISTRY
July, 1926
FIREHAZARD Flammable
LIFE HAZARD Suffocating fumes
May cause ignition b y con- Corrosive; dangerous fumes under fire tact with combustible conditions materials. Corrodes metal Oxidizing material. Classes See Sodium Nitrate with sodium nitrate Oxidizing material. Classes with sodium nitrate R'hen in contact with or- Serious under fire conditions ganic material explodes b y slight friction, percussion or shock. Classes with potassium chlorate
STORAGE Provide good ventilation: do not store on wooden fioor Safeguard against mechanical injury, isolate from saltpeter, metallic powders, carbides, picrates, fulminates chlorates, and combusiible materials Store in dry place remote from water or moisture See Sodium Nitrate
REMARKS
Safeguard against mechanical injury; avoid tiering: isolate
Recommended Specifications for Analytical Reagent Chemicals Part 11' Ferric Ammonium Sulfate, Ferrous Ammonium Sulfate, Potassium Carbonate Anhydrous, Potassium Chloride, Potassium Permanganate, Potassium Sulfate, Sodium Bicarbonate, Sodium Carbonate Anhydrous, Sodium Cyanide, Sodium Sulfate Anhydrous, Sodium Thiosulfate By W. D. Collins, H. V. Farr, Joseph Rosin, G. C. Spencer, and Edward Wichers COXMITTBEO N GUARANTEED REAGENTS,AMERICANCWBMICAL SOCIETY
Ferrous Ammonium Sulfate (Not a Primary Standard)
Ferric Ammonium Sulfate REQUIREMENTS Appearance-Pale violet crystals. Insoluble Matter-Not more than 0.010 per cent. Chloride (C1)-To pass test (limit about 0.001 per ceni). Copper (Cu)-To pass test (limit about 0.005 per cent). Ferrous Iron-To pass test (limit about 0.001 per cent.). Material N o t Precipitated by Ammonium Hydroxide-Not 0.05 per cent. Zinc (Zn)-To pass test (limit about 0.005 per cent).
REQUIREMENTS
more than
Insoluble Matter-Not more than 0.010 per cent. Phosphate (Pod-Not more than 0.003 per cent. Copfiev (Cu)-To pass test (limit about 0.005 per cent). F e v r i c Iron-Not more than 0,010per cent. Manganese (Mn)-Not more than 0.015 per cent. Material Not Precipitated by Ammonium Hydroxide-Not 0.050 per cent. Zinc (Zn)-To pass test (limit about 0.005 per cent).
more than
TESTS TESTS Blank tests must be made on water and all reagents used in the methods unless t h e directions provide for elimination of errors due to impurities. Solutions of the sample must be filtered for tests in which insoluble matter would interfere. Insoluble Matter-Dissolve 10 grams in 100 cc. of water containing 1 cc. of hydrochloric acid, Filter through asbestos in a Gooch crucible, wash thoroughly, dry at 105' C., and weigh. The weight of the residue should not exceed 0,0010 gram. Chloride (Cl)-Dissolve 1.0 gram in a mixture of 20 cc of water and 4 cc. of nitric acid. Filter if necessary and divide into two equal portions. T o one portion add 0.5 cc. of 0.1 N silver nitrate. At the end of 5 minutes the two portions should be equally clear. Copper-See test for zinc and copper. Ferrous Iron-Dissolve 1 gram in a mixture of 20 cc. of water and 1 cc. of hydrochloric acid; add 1 drop of a freshly prepared 5 per cent solution of potassium ferricyanide, N o blue or green color should be produced in 1 minute. Material Not Precipitated b y Ammonium Hydroxide--T)issolve 5 grams in 70 cc. of water, heat to boiling a n d pour into a mixture of 40 cc. of water a n d 10 cc. of ammonium hydroxide. Filter through a folded filter while hot a n d wash with hot water till the filtrate measures 150 cc. Evaporate 60 cc. of the filtrate t o dryness, ignite, and weigh. The weight of the residue should not exceed 0,0010 gram. Zinc and Copper-Neutralize with acetic acid t h e remaining 90 cc. of the filtrate obtained in the test for material not precipitated b y ammonium hydroxid;, add a n excess of 1 cc. of glacial acetic acid and 2 cc. of a freshly prepared 10 per cent solution of potassium ferrocyanide. N o turbidity or pink color should appear in 30 minutes. For P a r t 1 see THISJOURNAL, 18, 636 (1926).
Blank tests must be made on water and all reagents used in the methods unless the directions provide for elimination of errors due to impurities. Solutions of the sample must be filtered for tests in which insoluble matter would interfere. Iizsoluble Matter-Dissolve 10 grams in 100 cc. of freshly boiled water containing 1 cc. of sulfuric acid. Filter through asbestos in a Gooch crucible, wash thoroughly, dry a t 105' to 110" C.,and weigh. The weight of the residue should not be more than 0.0010 gram. Phosphale-Dissolve 5 grams in 50 cc. of water, add 10 cc. of nitric acid, and beat on the steam bath for one-half hour. Nearly neutralize the nitric acid with ammonium hydroxide, add 50 cc. of ammonium molybdate solution, shake for 5 minutes a t about 40' C., and allow t o stand for 1 hour. If a yellow precipitate forms i t should not be greater than is formed from 0.15 mg. of PO, in an equal volume containing a s nearly a s possible the quantities of nitric acid, ammonium hydroxide, and ammonium molybdate used in the test. The ammonium molybdate solution is prepared a s directed under t h e test for phosphate in acetic anhydride. Copper-See test for zinc and copper. Ferric Iron-Dissolve 1 gram in a mixture of 48 cc. of freshly boiled and cooled water and 1 cc. of sulfuric acid and add 1 cc. of 10 per cent ammonium thiocyanate solution. The color should not be greater than is obtained in a standard prepared a s follows: Dissolve 0.14 gram of iron in 50 cc. of 20 per cent sulfuric acid in a 125-cc. Erlenmeyer flask closed b y a funnel tube sealed with water. After the reaction stops add 0.1 mg. of ferric iron as sulfate and 1 cc. of 10 per cent ammonium thiocyanate solution. Manganese-Dissolve 1 gram in a mixture of 15 cc. of nitric acid and 45 cc. of water and boil t o oxidize the iron a n d expel oxides of nitrogen. Cool to 15' C., a d d 0.5 gram of sodium bismuthate, agitate, and allow t o stand 5 minutes. Add 50 cc. of water, filter through asbestos or alundum, and compare a t once with a standard prepared b y treating a quantity of potassium permanganate containing 0.15 mg. of manganese with the quantities of nitric acid and sodium bismuthate used with the sample.
760
INDUSTRIAL A N D ENGINEERING CHEMISTRY
lMateria1 Not Precipitated by Ammonium Hydroxide-Dissolve 5 grams in a mixture of 10 cc. of nitric acid a n d 70 cc. of water. Boil to oxidize the iron and expel the excess gases and pour into a mixture of 40 cc. of water and 20 cc. of ammonium hydroxide. Filter through a folder filter while hot and wash with hot water till the filtrate measures 150 cc. Evaporate 60 cc. of the filtrate to dryness, ignite, a n d weigh. The weight of the residue should not exceed 0.0010 gram. Zinc and Copper-Neutralize with acetic acid the remaining 90 cc. of the filtrate obtained in the test for material not precipitated b y ammonium hydroxide, add a n excess of 1 cc. of glacial acetic acid and 2 cc. of a freshly prepared 10 per cent solution of potassium ferrocyanide. N o turbidity or pink color should appear in 30 minutes.
Potassium Carbonate, Anhydrous REQUIREMENTS Insoluble Matter-Not more than 0.020 per cent. Loss on Ignition-Not more than 1.0 per cent. Chloride and Chlorate-To pass test (limit about 0.003 per cent as CI). Sulfur Compounds (as SOS-Not more than 0.004 per cent. Nitrogen Compounds (as W-iVot more than 0.001per cent. Phosphate (Pod-Not more than 0.005 per cent. Silica and Ammonium Hydroxide Precipitate-Not more than 0.010 per cent. Not more than 0.005 per cent SiOn. Calcium and Magnesium Precipitate-Not more than 0.015 per cent. Arsenic (Ad-Not more than 0.0003 per cent. Heavy Metals-To pass test (limit about 0.0005 per cent lead, about 0.001 per cent iron). Sodium (Na)-To pass test (limit about 0.02 per cent).
TESTS Blank tests must be made on water a n d all reagents used in the methods unless the directions provide for elimination of errors due t o impurities. Solutions of the sample must be filtered for tests in which insoluble material would interfere. Insoluble Matter-Dissolve 10 grams in 100 cc. of hot water and allow t o stand on the steam bath for 1 hour. Filter on asbestos in a Gooch crucible, wash, dry at 105' t o 110' C., a n d weigh. The residue should not weigh more than 0.0020 gram. Loss on Ignition-Ignite 2 grams a t a temperature not over 300° C. The loss in weight should not be more than 0,0200 gram. Chloride and Chlorate-Ignite 2 grams a t a low red heat. Dissolve in a small amount of water, add 3 CC. of nitric acid, filter if necessary, and dilute to 100 cc. Add 1 cc. of approximately 0.1 N silver nitrate. The turbidity should not be greater than is produced b y 0.06 mg. of chloride ion in an equal volume of solution containing 1 cc. of nitric acid and 1 cc. of 0.1 N silver nitrate. Sulfur Compounds-Dissolve 10 grams in 100 cc. of water, add 5 drops of saturated bromine water, a n d boil. Cool, neutralize with hydrochloric acid, a d d a n excess of 1 cc., a n d filter. Boil the filtrate, add 5 cc. of 10 per cent barium chloride solution, a n d allow to stand overnight. Filter, wash, ignite, and weigh. The weight should not be more than 0,0010gram. Nitrogen Compounds-Dissolve 2 grams in 50 cc. of ammonia-free water; add 10 cc. of 10 per cent sodium hydroxide solution and about 0.5 gram of aluminum wire or foil. Protect from absorption of ammonia a n d allow t o stand 3 hours with occasional agitation. Dilute with water to 100 cc. Decant 50 cc. of the liquid and add 2 cc. of Nessler's solution. The color produced should not be greater than t h a t in a blank containing the same quantity of sodium hydroxide and a quantity of ammonium salt correspond. ing to 0.010 mg. of nitrogen. Phosphate-Dissolve 5 grams in 50 cc. of water and add 15 cc. of nitric acid (first 5 cc. cautiously). Nearly neutralize with ammonium hydroxide add 50 cc. of ammonium molybdate solution, shake (at about 40' C.) for 5 minutes, a n d allow to stand for 1 hour. Any yellow precipitate should not be greater than is formed from 0.25 mg. of Po4 in a n equal volume of solution containing a s nearly a s possible the quantities of nitric acid, ammonium hydroxide, and ammonium molybdate used in the test. The ammonium molybdate solution is prepared a s directed under the test for phosphate in acetic anhydride. Silica and Ammonium Hydroxide Precipitate-Dissolve 10 grams in 50 cc. of water, a d d an excess of sulfuric acid, evaporate, and drive off the fumes of sulfuric acid until the residue is nearly dry. Cool, take up in about 100 cc. of water, a d d a few drops of methyl red solution, and add ammonium hydroxide carefully until the solution is just alkaline. Boil, filter, reserving t h e filtrate for the calcium and magnesium test; wash, rejecting the washings; ignite; and weigh the precipitate. The weight should not exceed 0.0010 gram. If the weight of the residue exceeds 0.0005 gram, treat with a few drops of sulfuric acid a n d hydrofluoric acid a n d ignite. The loss should not exceed 0.0005 gram. Calcium and Magnesium Precipitate-To the filtrate from the test for silica and ammonium hydroxide precipitate a d d 0.5 cc. of hydrochloric acid, 5 cc. of 4 per cent ammonium oxalate solution, 2 cc. of 10 per cent ammonium phosphate solution, and 10 cc. of ammonium hydroxide. Allow t o stand overnight. If any precipitate is formed, filter, wash with water containing 2.5 per cent of ammonia, and dry. Mix the residue with about
Vol. 18, No. 7
0.02 gram of sucrose, ignite, and weigh. The weight of the ignited residue should not exceed 0.0015 gram. Arsenic-Dissolve 2 grams in a small volume of water and acidify with sulfuric or hydrochloric acid. Determine arsenic b y the modified Gutzeit method. Special care in making blank tests is necessary in this determination. Heavy MetaZs-Dissolve 2 grams in 10 cc. of water, a d d 5 cc. of hydrochloric acid, a n d evaporate t o dryness. Take up in 1 CC. of hydrochloric acid and 50 cc. of water. Pass hydrogen sulfide through t h e solution a n d make just alkaline with ammonium hydroxide. N o brown color should be observed. Any green color should n o t be more than is produced by 0.02 mg. of iron in alkaline solution t o which ammonium sulfide is added. Sodium-A 20 per cent solution tested with a platinum wire in the flame should give no distinct yellow color to the flame.
Potassium Chloride REQUIREXENTS Insoluble Matter-Not more than 0.010 per cent. Neutrality-To pass test. Chlorafe and N i t r a f c T o pass test (limit about 0.006 per cent a s Clod. Nitrogen Compounds (as N)-Not more than 0.001 per cent. Phosphate (Pod-Not more than 0.002 per cent. Sulfate (SO&-Not more than 0.005 per cent. Barium (Ba)-To pass test (limit about 0.001 per cent). Calcium, Magnesium, and Ammonium Hydroxide Precipitate-Not more than 0.005 per cent. Heasy M e t a l s T o pass test (limit about 0.0006 per cent lead). Iron (Fe)-To pass test (limit about 0.0003 per cent). Sodium (Na)-To pass test (limit about 0.02 per cent).
TESTS Blank tests must be made on water a n d all reagents used in the methods unless the directions provide for elimination of errors due to impurities. Solutions of the sample must be filtered for tests in which insoluble matter would interfere. Insoluble Matter-Dissolve 10 grams in 50 cc. of hot water, filter through asbestos in a Gooch crucible, wash with hot water, dry at 105' C., a n d weigh. The weight of the residue should not exceed 0.0010 gram. Neutrality-Dissolve 5 grams in 50 cc. of carbon dioxide-free water and add 3 drops of phenolphthalein indicator solution. N o pink color should be produced. Add 1 drop of 0.1 N sodium hydroxide solution. A pink color should be produced. Chlorate ond Nitrate-Dissolve 1 gram in 10 cc. of water a n d overlay on 10 cc. of diphenylamine solution (0.5 gram in 100 cc. of sulfuric acid a n d 20 cc. of water). No blue ring should develop at the line of contact of the two solutions in 20 minutes. Nitrogen Compounds-Dissolve 2 grams in 40 cc. of water in a flask. Add 10 cc. of 10 per cent sodium hydroxide solution a n d about 0.5 gram of aluminum wire in small pieces. Allow to stand for 3 hours protected from loss or access of ammonia. Decant half the solution a n d a d d 2 cc. of Nessler's solution. The color should not be greater than is produced by a quantity of ammonium salt corresponding to 0.01 mg. of nitrogen. Correction must be made for the nitrogen obtained from the water and reagents used. Phosphate-Dissolve 5 grams in 20 cc. of water and 10 cc. of nitric acid and evaporate t o dryness. Take up in 5 cc. of water and 5 cc. of nitric acid a n d evaporate t o dryness again. Take up with 10 cc. of nitric acid, dilute with 50 cc. of water, and nearly neutralize with ammonium hydroxide. Add 50 cc. of ammonium molybdate solution and shake the solution (at about 40° C.) for 5 minutes a n d allow to stand one-half hour. Any precipitate formed should be less than is produced when a quantity of an alkaline phosphate containing 0.10 mg. of phosphate ( P o d is treated according t o the above procedure. The ammonium molybdate solution is prepared as directed under the test for phosphate in acetic anhydride. Sulfate-Dissolve 10 grams in 150 cc. of water, a d d 1 cc. of hydrochloric acid, heat t o boiling, add 5 cc. of 10 per cent barium chloride solution, and allow to stand overnight. If a precipitate is formed, filter, wash, ignite, a n d weigh. The weight should not exceed 0.0012 gram. Barium-Dissolve 4 grams in 20 cc. of water, filter if necessary, and divide in 2 portions. To one portion add 2 cc. of 10 per cent sulfuric acid and to the other add 2 cc. of water. The solutions should be equally clear a t the end of 2 hours. Calcium, Magnesium. and Ammonium Hydroxide Precipitate-Dissolve 10 grams in 75 cc. of water, a d d 5 cc. of 4 per cent ammonium oxalate solution, 2 cc. of 10 per cent ammonium phosphate solution, and 10 cc. Of ammonium hydroxide. Allow to stand overnight, Filter, wash with water containing 2.5 per cent of ammonia, and dry. Mix the re-idue with 0.02 gram of sucrose, ignite, and weigh. The weight should not exceed 0.0006 gram. Heavy Metals-Dissolve 2 grams in 20 cc. of water and pass hydrogen sulfide through the solution. N o brown color should be produced. Iron-Add ammonium hydroxide to make alkaline the solution tested for heavy metals. If a greenish color is produced i t should not be greater than is produced b y 0.006 mg. of iron in 20 cc. of an alkaline sulfide solution. Sodium-Test a 10 per cent solution of the sample on a platinum wire in the flame. N o pronounced yellow color should be Dmduced.
INDUSTRIA I, A N D ENGINEERING CHEMISTRY
July, 1926
Potassium Permanganate REQUIREMENTS A ppearance-Dark purple lustrous crystals. Chloride and Chlorafe (as C1)-To pass test (limit about 0.003 per cent). h'ifrogen Compounds (as N)-Not more than 0.003 per cent. Sulfate (Sod-Not more than 0.004 per cent.
TESTS Blank tesfs must be made on water and all reagents used in the methods unless t h e directions provide for elimination of errors due to impurities. Solutions of the sample must be filtered for tests in which insoluble matter would interfere. Chloride and Chlorate-Dissolve 1 gram in 25 cc. of warm water. Add gradually 4 grams of oxalic acid, a n d after the reduction is complete a d d 5 cc. of nitric acid a n d 1 cc. of 0.1 N silver nitrate. The turbidity should not be greater than is produced b y 0.03 mg. of chloride ion in a n equal volume of solution containing the quantity of reagents used in the test. Nifrogen Compounds-Dissolve 1 gram in 100 cc. of water in a flask; a d d 1 cc. of sulfuric acid and 2.5 grams of oxalic acid. When clear, add 20 cc. of 20 per cent sodium hydroxide solution and about 0.5 gram of aluminum wire in small pieces and allow io stand for 3 hours protected from access or loss of ammonia. Distil off 50 cc. and nesslerize. The color should not be greater than is produced b y a quantity of a n ammonium salt corresponding to 0.03 mg. of nitrogen. Correction must be made for nitrogen derived from the reagents used. Sulfate-Dissolve 5 grams in 75 cc. of water; add 10 cc. of alcohol a n d 10 cc. of hydrochloric acid. Heat until colorless, adding more alcohol and a little hydrochloric acid if necessary. Evaporate t o dryness. Take up with 1 cc. of hydrochloric acid a n d 100 cc. of water, filter, and add to the filtrate 5 cc. of 10 per cent barium chloride solution. Allow to stand overnight. The weight of precipitate formed should not be more than 0.0005 gram.
Potassium Sulfate REQUIREMEKTS Insoluble Matter-Not more than 0.010 per cent. Neufralify-To pass test. Chloride (Cl)-Not more than 0.001 per cent. Nitrogen Compounds (as N)-Not more than 0.0005 per cent. Arsenic (As)-Not more than 0.0002 per cent. Calcium, Magnesium, and Ammonium Hydroxide Precipifufe-Not more than 0.020 per cent. Heavy M e f a l s T o pass test (limit about 0.0005 per cent lead). Iron (Fe)-To pass test (limit about 0.0005 per cent). Sodium (Na)-To pass test (limit about 0.03per cent).
TESTS Blank fesfs must be made on water a n d all reagents used in the methods unless the directions provide for elimination of errors due t o impurities. Solutions of the sample must be filtered for tests in which insoluble matter would interfere. Insoluble Matfer-Dissolve 10 grams in 150 cc. of hot water a n d allow t o stand on t h e steam b a t h for 1 hour, Filter through asbestos in a Gooch crucible, wash, dry a t 105' t o llOo C . , a n d weigh. T h e residue should not weigh more than 0.0010 gram. N e u f r a l i f p T o a solution of 5 grams in 50 cc. of carbon dioxidefree hot water a d d 3 drops of phenolphthalein. N o pink color should be produced (alkali) a n d on the addition of 1 drop of 0.1 .V sodium hydroxide a pink color should be produced (acid). Chloride-Dissolve 2 grams in 45 cc. of water, add 4 cc. of nitric acid and 1 cc. of 0.1 N silver nitrate. Any turbidity produced should not be greater than is produced b y 0.02 mg. of chloride ion in 4 5 cc. of water after t h e addition of the quantities of nitric acid a n d silver nitrate used in t h e test. Nitrogen Compounds-Dissolve 3 grams in 35 cc. of warm water in a flask, cool, add 10 cc. of 10 per cent sodium hydroxide solution and about 0.5 gram of aluminum wire in small pieces, a n d allow t o stand for 3 hours, the flask being suitably protected t o prevent access or escape of ammonia. Decant 30 cc. and add 1 cc. of Nessler's solution. The yellow color should not be greater t h a n is produced b y the same treatment of a quantity of ammonium chloride corresponding to 0.01 mg. of nitrogen. A r s e n i e T e s t 1 gram by the modified Gutzeit method.- Special care in making blank tests is necessary in this determination. Calcium, Magnesium, and Ammonium Hydroxide Precipifafe-Dissolve 5 grams in 75 cc. of water, add 5 cc. of 4 per cent ammonium o x d a t e solution, 2 cc. of 10 per cent ammonium phosphate solution, and 10 cc. of ammonium hydroxide. Allow t o stand overnight. If a n y precipitate is formed, filter, wash with water containing 2.5 per cent of ammonia, and dry. Mix t h e residue with about 0.02 gram of sucrose, ignite, and weigh. The weight of the ignited residue should not exceed 0,0010gram. Heavy Mefals-Dissolve 2 grams in 25 cc. of warm water a n d pass hydrogen sulfide through the solution. N o brown color should be produced (lead). Iron-Add ammonium hydroxide t o make alkaline the solution tested for heavy metals. If a green color is produced, i t should not be greater than
is produced b y 0.01 mg. of iron in a n equal volume of alkaline solution through which hydrogen sulfide has been passed. 10 per cent solution tested with a platinum wire in the Sodium-A flame should give no distinct yellow color t o the flame.
Sodium Bicarbonate REQUIREMENTS Insoluble Matter-Not more than 0.020 per cent. Assay and Carbonafe-To pass test. Chloride (Cl)-Not more than 0.003 per cent. Sulfur Compounds (as Sod-Not more than 0.003 per cent. Phosphafe (PO,)-Not more than 0.002 per cent. Calcium, Magnesium, and Ammonium Hydroxide Precipitafe-Not more than 0.010 per cent. Potassium (K)-Not more than 0.02 per cent. Ammonia (NHa)-Not more than 0.0003 per cent. Heavy Mefals-To pass test (limit about 0.0006 per cent lead, about 0.001 per cent iron).
TESTS Blank fesfs must be made on water and all reagents used in the methods unless t h e directions provide for elimination of errors due t o impurities. Solutions of the sample must be filtered for tests in which insoluble material would interfere. Insoluble Matfer-Dissolve 10 grams in 100 cc. of hot water, boil a few minutes, and allow t o stand on the steam bath for 1 hour. Filter on asbestos in a Gooch crucible, wash, dry a t 105'' to 110' C., and weigh. The residue should not weigh more than 0.0020 gram. Assay and Carbonate-Dry about 3 grams over sulfuric acid for 24 hours, weigh accurately, dissolve in 50 cc. of water, and titrate with normal acid, using methyl orange indicator. The sodium bicarbonate calculated from the total alkalinity a s determined by the titration should be between 99.8 and 100.3 per cent of the weight taken. Chloride-Dissolve 3.3 grams in 30 cc. of water; add a slight excess of nitric acid and 1 cc. of 0.1 N silver nitrate. The turbidity should not be greater than is produced b y 0.1 mg. of chloride ion in a n equal volume of solution containing the quantities of nitric acid a n d silver nitrate used in the test. Sulfur CompoundsDissolve 10 grams in 100 cc. of hot water, a d d 5 drops of saturated bromine water, and boil. Cool, neutralize with hydrochloric acid, a d d an excess of 1 cc., and filter. Boil t h e filtrate, a d d 5 cc. of 10 per cent barium chloride solution, a n d allow t o stand overnight. Filter, wash, ignite, a n d weigh. The weight should not be more than 0.0008 gram. Phosphate-Dissolve 5 grams in 50 cc. of water a n d a d d 15 cc. of nitric acid (first 5 cc. cautiously). Nearly neutralize with ammonium hydroxide, a d d 50 cc. of ammonium molybdate solution, shake (at about 40' C.) for 5 minutes, and allow t o stand for 1 hour. Any yellow precipitate should not be greater than is formed from 0.1 mg. of PO1 in a n equal volume of solution containing as nearly a s possible the quantities of nitric acid, ammonium hydroxide, a n d ammonium molybdate used in t h e test. The ammonium molybdate solution is prepared a s directed under the test for phosphate in acetic anhydride. Calcium, Magnesium, and Ammonium Hydroxide Precipitate-Dissolve 10 grams in 100 cc. of water with hydrochloric acid a n d a d d a n excess of about 0.5 cc. of the acid. Filter if necessary. Add 5 cc. of 4 per cent ammonium oxalate solution, 2 cc. of 10 per cent ammonium phosphate solution, and 10 cc. of ammonium hydroxide. Allow t o stand for 3 hours. If a n y precipitate is formed, filter, wash with water containing 2.5 per cent of ammonia, a n d dry. Mix the residue with about 0.02 gram of sucrose, ignite, and weigh. T h e weight of the ignited residue should not exceed 0.0010 gram. Pofassium-Dissolve 2 grams in a small volume of water a n d neutralize with hydrochloric acid, using a suitable indicator. Evaporate this solution t o dryness on the steam bath a n d redissolve the residue in 15 cc. of water (to concentrate the solution a n d remove a n y free acid). Add 5 cc. of sodium cobaltinitrite solution and allow to stand overnight. (The sodium cobaltinitrite solution is made by dissolving 25 grams of NaNOz in 50 cc. of water and then adding 15 cc. of 6 N HCzH302 a n d 2.5 grams of Co(CzHa02)~.4HzOor a n equivalent amount of nitrate or chloride, The solution is allowed to stand overnight, filtered, and diluted t o 100 cc.) Any precipitate formed should not be greater t h a n is produced b y an amount of potassium chloride equivalent t o 0.40 mg. K dissolved in 15 cc. of water, treated with 5 cc. of sodium cobaltinitrite solution, a n d allowed t o stand overnight. Ammonia-Dissolve 2 grams in 40 cc. of ammonia-free water; add 10 cc. of 10 per cent sodium hydroxide a n d 2 cc. of Nessler's reagent. T h e yellow color produced should not exceed t h a t produced by a quantity of ammonium salt corresponding to 0.01 mg. NH3 in a n equal volume of solution containing t h e quantities of sodium hydroxide a n d Nessler's reagent used in the test. Heavy Metals-Dissolve 2 grams in 50 cc. of water. Neutralize with hydrochloric acid and a d d a n excess of 1 cc. Pass hydrogen sulfide through the solution and make just alkaline with ammonium hydroxide. N o brown color should be observed. Any green color should not be greater than is produced by 0.02 mg. of iron in alkaline solution t o which ammonium sulfide is added.
762
INDUSTRIAL S N D EYGINEERING CHEiVISTRY Sodium Carbonate, Anhydrous REQUIRBMENTS
Insoluble Muller-Not more than 0.020per cent. LOSSon Ignition-Not more than 1.0 per cent. Chloride ('21)-Not more than 0.006 per cent. Sulfur Compounds (as S04)-Not more than 0.004 per cent. Nitrogen Compounds (as N)-Not more than 0,001 per cent. Phosphale (PO4-Not more than 0.002 per cent. Silica and Ammonium Hydroxide Precipitate-Not more than 0.010 per cent. Not more than 0.005 per cent SiOz. Calcium and Magnesium Precipifate-Not more than 0.015 per cent. Polassium (K)-Not more than 0.02per cent. Arsenic (AsI-Not more than 0.0003 per cent. Heavy Metals-To pass test (limit about 0.0005 per cent lead, about 0.001 per cent iron).
TESTS Blank fesls must be made on water and all reagents used in the methods unless the directions provide for elimination of errors due t o impurities. Solutions of the sample must be filtered for tests in which insoluble matter would interfere. Insoluble Mafter-Dissolve 10 grams in 100 cc. of hot water and allow t o stand on the steam bath for 1 hour. Filter through asbestos in a Gooch crucible, wash, d r y a t 105' t o llOo C., and weigh. T h e residue should not weigh more than 0.0020 gram. Loss on Ignition-Ignite 1 gram a t a temperature not over 350' C. The loss in weight should not be more than 0.010 gram. ChlorideDissolve 2 grams in 30 cc. of water; a d d a slight excess of nitric acid and 1 cc. of 0.1 N silver nitrate. T h e turbidity should not be greater than is produced by 0.1 mg. of chloride ion in a n equal volume of solution containing the quantities of nitric acid and silver nitrate used in the test. Sulfur Compounds-Dissolve 10 grams in 100 CC. of water, add 5 drops of saturated bromine water, and boil. Cool, neutralize with hydrochloric acid, add a n excess of 1 cc., and filter. Boil the filtrate, add 5 cc. of 10 per cent barium chloride solution, a n d allow to stand overnight. Filter, wash, ignite, and weigh. T h e weight should not be more than 0.0010 gram. Nitrogen Compounds-Dissolve 5 grams in 50 cc. of ammonia-free water; add 20 cc. of 10 per cent sodium hydroxide solution and about 0.5 gram of aluminum wire or foil. Protect from absorption of ammonia and allow to stand 8 hours with occasional agitation. Dilute with water t o 100 CC. Decant 50 cc. of the clear liquid and a d d 2 cc. of Nessler's solution. The color produced should not be greater than t h a t in a blank containing the same quantity of sodium hydroxide and a quantity of ammonium salt corresponding to 0.025 mg. of nitrogen. PhosphatcDissolve 5 grams in 50 CC. of water and add 15 cc. of nitric acid (first 5 cc. cautiously), Nearly neutralize with ammonium hydroxide, add 50 cc. of ammonium molybdate solution, shake (at about 40' C.) for 5 minutes, and allow t o stand for 1 hour. Any yellow precipitate should not be greater than is formed from 0.1 mg. of Po4 in a n equal volume of solution containing a s nearly a s possible the quantities of nitric acid, ammonium hydroxide, and ammonium molybdate used in the test. T h e ammonium molybdate solution is prepared a s directed under the test for phosphate in acetic anhydride. Silica and Ammonium Hydroxide Precipitafe-Dissolve 10 grams in 50 cc. of water, add a n excess of sulfuric acid, evaporate, and drive off the fumes of sulfuric acid until the residue is nearly dry. Cool, take up in about 100 cc. of water, add a few drops of methyl red solution, and add ammonium hydroxide carefully until the solution is just alkaline. Boil, filter, reserving the filtrate for the calcium and magnesium test; wash, rejecting the washings; ignite and weigh the precipitate. The weight should not exceed 0.0010 gram. If the weight of the residue exceeds 0.0005 gram treat with a few drops of sulfuric acid and hydrofluoric acid and ignite. The loss should not exceed 0.0005 gram. Calcium and Magnesium Precipifate-To the filtrate from the test for silica and ammonium hydroxide precipitate add 0.5 CC. of hydrochloric acid, 5 cc. of 4 per cent ammonium oxalate solution, 2 cc. of 10 per cent ammonium phosphate solution, and 10 cc. of ammonium hydroxide. Allow t o stand for 3 hours. If a n y precipitate is formed, filter, wash with water containing 2.5 per cent of ammonia, and dry. Mix the residue with about 0.02 gram of sucrose, ignite, and weigh. The weight of the ignited residue should not exceed 0.0015 gram. Potassium-Dissolve 2 grams in a small volume of water and neutralize with hydrochloric acid, using a suitable indicator. Evaporate this solution t o dryness on the steam bath and redissolve the residue in 15 cc. of water (to concentrate the solution and remove any free acid). Add 5 CC. of sodium cobaltinitrite solution and allow t o stand overnight. (The SOdium cobaltinitrite solution is made by dissolving 25 grams of NaNOz in 50 cc. of water and then adding 15 cc. of 6 N HCzHaOt and 2.5 grams of Co(CzHa02),.4Ha0 or an equivalent amount of nitrate or chloride. The solution is allowed to stand overnight, filtered, and diluted to 100 cc.) Any precipitate formed should not be greater than is produced by a n amount of potassium chloride equivalent t o 0.40 mg. K dissolved in 15 cc. of water, treated with 5 cc. of sodium cobaltinitrite solution, and allowed t o stand overnight.
vol. 18, S o . 7
Arsenic-Dissolve 2 grams in a small volume of water and acidify with sulfuric or hydrochloric acid. Determine arsenic by the Gutteit method. Special care in making blank tests is necessary in this determination. Heavy Metals-Dissolve 2 grams in 10 cc. of water, add 5 cc. of hydrochloric acid, and evaporate t o dryness. Take up in 1 cc. of hydrochloric acid and 50 cc. of water. Pass hydrogen sulfide through the solution a n d make just alkaline with ammonium hydroxide. N o brown color should be observed. Any green color should not be more than is produced by 0.02 mg. of iron in alkaline solution t o which ammonium sulfide is added.
Sodium Cyanide RRQUIREXENTS Assay-Not less than 95 per cent NaCN. Chloride (CI)-Not more than 0.020 per cent. Ferrocyanide [Fe(CN)z]-To pass test (limit about 0.010 per cent), Sulfate (Sod-To pass test (limit about 0.010 per cent). Sulfide (S)--Not more than 0.003 per cent. Thiocyanate (SCN)-To pass test (limit about 0.020 per cent).
TESTS Caution-On account of the extremely poisonous nature of this reagent itself and of the gas evolved on treatment with acid, all tests must be made in a hood with a strong draft and special care must be taken to avoid inhaling the fumes. Pipets will not be used in measuring solutions. Blank tests must be made on water and all reagents used in the methods unless the directions provide for elimination of errors due t o impurities. Solutions of the sample must be filtered for tests in which insoluble matter would interfere. Sample Solution (Solution A)-Dissolve 10 grams in water, filter if necessary, and make up to 200 cc. Use portions of this solution for all tests except assay. A s s a w w e i g h accurately about 0.4 gram of the sample and dissolve in 30 cc. of water. Add 2 drops of 20 per cent potassium iodide solution a n d 1 cc. of ammonium hydroxide. Titrate with 0.1 N silver nitrate to a slight permanent turbidity. 1 cc. equals 0.0098 gram of N a C N . Chloride-Measure 20 cc. of Solution A in a graduated cylinder and pour into a long-necked flask. Add 10 cc. of water and 25 cc. of dilute sulfuric acid, and evaporate in the hood t o half the original volume. Replace t h e water lost and evaporate again t o half the original volume. Cool, filter, dilute t o 50 cc., and add 2 cc. of nitric acid and 1 cc. of 0.1 N silver nitrate. T h e turbidity should not be greater than is produced by 0.2 mg. of chloride ion in 50 cc. of water upon the addition of the quantities of nitric acid and silver nitrate used in the test. Ferrocyanide-To 20 cc. of Solution A (measured in a graduated cylinder) add 3 cc. of hydrochloric acid and a drop of freshly prepared 10 per cent ferric chloride solution. N o blue or green color should develop in 1 hour. Sulfafe-To 20 cc. of Solution A (measured in a graduated cylinder) add 2.5 cc. of hydrochloric acid and 2 cc. of a 10 per cent solution of barium chloride. At the end of 10 minutes the solution should have no greater turbidity than a similar solution without the barium chloride. Sulfide-To 2 0 cc, of Solution A (measured in a graduated cylinder) add a few drops of alkaline lead solution (made by adding sodium hydroxide to a 10 per cent solution of lead acetate till the precipitate is redissolved). The color should not be greater than is produced b y 0.03 mg. of sulfide ion in the same volume of solution when treated with alkaline lead solution. Thiocyanal+To 20 cc. of Solution A (measured in a graduated cylinder) add 4 cc. of hydrochloric acid and 4 drops of a 10 per cent solution 06 ferric ammonium sulfate. At the end of 5 minutes the solution should show no reddish tint when compared with 20 cc. of distilled water to which have been added the quantities of hydrochloric acid and ferric ammonium sulfate used in the test.
Sodium Sulfate, Anhydrous REQUIREMENTS Insoluble Matter-Not more than 0.010 per cent. Loss on Innifion-Not more than 0.50 per cent. NeufraZify-To pass test. Chloride (Cl)-Not more than 0.008 per cent. Nitrogen Compounds (as N)-Not more than 0.0005 per cent. Arsenic (As)-Not more than 0.0003 per cent. Calcium, Magnesium, and Ammonium Hydroxide Precipilate-Not more than 0.030 per cent. Heavy Mefals-To pass test (limit about 0.0005 per cent lead). Iron-To pass test (limit about 0.001 per cent).
TESTS Blank tesfs must be made on water and all reagents used in the methods unless the directions provide for elimination of errors due t o impurities. Solutions of the sample must be filtered for tests in which ipsoluble matter would interfere.
July, 1926
INDUSTRIAL AND ENGINEERING CHEMISTRY
I>rsolubleMatter-Dissolve 10 grams in 100 cc. of hot water and allow to stand on the steam b a t h for 1 hour. Filter through asbestos in a Gooch crucible, wash, d r y a t 105’ C., a n d weigh. T h e weight 01 the insoluble residue should not exceed 0.0010 gram. Loss o n Ignition-Weigh out about 2 grams, ignite a t low red heat, a n d weigh. T h e loss in weight should not be more than 0.50 per cent. Seutrality-To a solution of 5 grams in 50 cc. of carbon dioxide-free water add 3 drops of phenolphthalein indicator solution. No pink color should be produced (alkali), a n d on t h e addition of 1 drop of 0.1 N sodium hydroxide a pink color should be produced (acid). Chloride-Dissolve 1 xram in 45 cc. of water: a d d 4 cc. of nitric acid a n d 1 CC. of approximately 0.1 N silver nitrate solution. T h e turbidity should not be greater than is produced by 0.03 mg. of chloride ion in 45 cc. of water after the addition of t h e quantities of nitric acid a n d silver nitrate used in the test. -Vitrogen Comfiounds-Dissolve 3 grams in 3 5 cc. of water in a flask; a d d 10 cc. of 10 per cent sodium hydroxide a n d about 0.5 gram of aluminum mire in small pieces. Allow t o stand for 3 hours, protecting the flask from access or loss of ammonia. Decant 30 cc. of the clear liquid a n d a d d 1 cc. of Nessler’s solution. T h e color should not be greater than is given b y a quantity of ammonium chloride containing 0.01 mg. of nitrogen. Allowance m a y be made for nitrogen in t h e sodium hydroxide by treating 0.015 mg. of nitrogen in a n ammonium salt with the quantities of water a n d reagents used in t h e test. Arsenic-Determine t h e arsenic in 1 gram of t h e sample b y the modified Gutzeit method. Special care in making blank tests is necessary in this determination. Calcium, Magnesium, and Ammonium Hydroxide Precifiitate-Dissolve 5 grams in 7.5 cc. of water: a d d 5 cc. of 4 per cent ammonium oxalate solution, 2 cc. of 10 per cent ammonium phosphate solution, a n d 10 cc. of ammonium hydroxide. Allow t o stand for 3 hours. If a n y precipitate is formed, filter, wash with water containing 2.5 per cent of ammonia, and dry. Mix the residue with about 0.02 gram of sucrose, ignite, and weigh. The weight of the ignited residue should not exceed 0.0015 gram. Heaus Jlefals-Dissolve 2 grams in 25 cc. of warm water, add 2 cc. of hydrochloric acid, a n d boil gently for 10 minutes, Cool, neutralize t o litmus paper with ammonium hydroxide, a d d 0.1 cc. of N hydrochloric acid, and pass hydrogen sulfide. N o brown color should be produced (lead). Iron--Sdd ammonium hydroxide to the solution tested for heavy metals till i t is slightly alkaline. Any green color produced should not he greater than is produced b y 0.02 mg. of iron in a n equal volume of slightly alkaline solution t o which hydrogen sulfide has been added.
763
S o d i u m Thiosulfate REQUIREMENTS Insoluble Matter-Not more than 0.010 per cent. Sulfate and Sulfife-To pass test (limit about 0.020 per cent a s 503. Sulfide @)-To pass test (limit about 0.0001 per cent). N e u l r a E i l y T o pass test.
TESTS Blank tesfs must be made on water and all reagents used in the methods unless the directions provide for elimination of errors due t o impurities. Solutions of t h e sample must be filtered for tests in which insoluble matter would interfere. Insoluble Matter-Dissolve 10 grams in 100 cc. of hot water a n d allow to stand on the steam b a t h for 1hour. Filter on asbestos in a Gooch crucible, wash, dry at 105’to llOo C., a n d weigh. The residue should not weigh more than 0.0010 gram. Sulfate and Sulfite-Dissolve 2 grams in 50 cc. of water and add approximately 0.1 N iodine until t h e liquid has a faint yellow color. Add 2 drops of hydrochloric acid a n d 2 cc. of 10 per cent barium chloride solution. No turbidity should be produced in 5 minutes. Sulfide-Dissolve 1 gram in 10 cc. of water a n d add 0.5 cc. of alkaline lead solution (made b y adding su5cient 10 per cent sodium hydroxide solution to 10 per cent lead acetate solution to redissolv? the precipitate). No dark color should be produced in 1 minute. Neutrality-Dissolve 5 grams in 50 cc. of stricfly carbon dioxide-frcc water and a d d 3 drops of phenolphthalein solution. If no color is produced the addition of 1 drop of 0.1 N sodium hydroxide should produce a reddish t i n t (limit of acidity). If a pink color is produced, i t should be discharged by 1 drop of 0.1 N acid (limit of alkalinity)
Corrections for P u b l i s h e d Specifications2 ACID, NITRIC Suljale-Take
18 cc. instead of 20 cc. for the test.
AMMONIUM OXALATB requirement should be “ N o t more than 0.002 per cent.” POTASSIUM HYDROXIDE Chloride-In the test a d d 5 cc. of dilute nitric acid instead of 1 cc. SODIUMHYDROXIDE Chloride-In the test a d d 5 cc. of dilute nitric acid instead of 1 cc.
Chloride-The
2
THISJOURNAL, 17, 756 (192.5).
NOTES AND CORRESPONDENCE Determination of Aniline Editor of Idustrial and Engineering Chemistry: In THISJOURNAL, 17, 62 (1925), C. M. Carson described the acidimetrical determination of aniline, preferring this method t o titrimetric diazotization and the bromometrical method and pointing out t h e inexactness of the latter. In my laboratory a series of methods for the quantitative determination of aniline has been worked out which is applicable t o very dilute solutions, such as 20 t o 0.2 mg. of aniline in 200 cc. of 10 t o 20 per cent sulfuric acid. I cannot agree with Carson’s criticism of the bromometrical method, which according t o our results is as accurate and convenient as the others. The method of diazotization, however, is cumbersome and not applicable t o concentrations below 0.1 molar, although for concentrations above this i t gives comparatively good results. 4 s for the acidimetrical method described by Carson, I can, in general, confirm the results of t h e author, but I cannot agree with him a s t o t h e unsuitability of methyl orange as indicator, This indicator is a little less precise than p-dirnethylarninoazobenzene and is much more convenient than Congo red, because its color changes are very gradual. With practice good results can be obtained t o concentrations not lower than 0.007 molar, with a n error of not more than 5 per cent for lower concentrations. The practical value of this method is limited by the necessity of ha!-ing a solution free from other materials t h a t give a non-
neutral reaction, as if such should be present it would be necessary t o extract the aniline previously. In the determination of very small quantities of aniline, such as t h a t absorbed from the air, acid solutions are unavoidable, as sulfuric acid must be used as solvent. T h e bromometrical method using starch-iodide paper, a n outside indicator, has indeed all the deficiencies of the “dipping” method, and is especially complicated by t h e volatility of bromine. For this reason i t is inapplicable t o the low concentrations. A direct titration using a solution of bromine in potassium bromide or bromate with indigo carmine as inconvertible indicator, has proved t o be accurate within 1 t o 3 per cent for the determination of aniline in very dilute concentrations, approximately to 0.00002 molar. The acidity of the medium, as long as it does not exceed approximately 5 per cent, does not affect the titration. For nearly the same concentrations with a little less exactness the colorimetric method of Elvovel is quite suitable. This investigator has been successful in choosing the order of mixing the components of the reaction, adding to the solution of aniline first the solution of hypochlorite and then, after 2 minutes, the alkali. The yellow color obtained does not change its hue perceptibly for a long time. But if we apply Christiansen’sz working order-that is, if we add hypochlorite and alkali togetherthen the solution in dilute concentrations either remains colorless, 1 2
THISJOURNAL, 9, 953 (1917). Ibid., 11, 763 (1919).
INDUSTRIAL AhTD ENGINEERING CHBMISTRY as it was already pointed out by Elvove, or appears as a rapidly disappearing greenish lilac. A t high concentrations (0.5 t o 0.1 per cent) the color OF the products obtained by Christiansen’s method is not constant. In m y opinion, therefore, for the determination of low concentrations of aniline bromometrical determination b y direct titration and the colorimetric method of Elvove are the most convenient methods. A. v. PAMPILOV POLYTECHNICAL INSTITUTE IVANOVO-VOSNESSENSK, RUSSIA April 21, 1926
....... . ..... .
Editor of Industrial and Engineering Chemistry: The use of indigo carmine as suggested by Mr. Pamfilov seems t o be the means of putting t h e bromate-bromide method on a workable basis. Certainly the use of starch-iodide paper as an indicator was far from satisfactory. The acidimetric titration t o which Mr. Pamfilov objects was definitely stated t o be limited to aqueous solutions of aniline and t o concentrations above 0.1 per cent aniline. As no claims for accuracy in lower concentrations were made in my paper, his criticism of the method as applied to his solutions is hardly justifiable. The use of methyl orange as a n indicator for aniline titrations has not been found t o be accurate, in our laboratories, owing to slow change of color and t o the fact t h a t the color change does not occur at the neutralization point of aniline in solutions of known strength. Our findings are substantiated by Sutton’s “Volumetric Analysis,” which states t h a t methyl orange is not suited to titrations of aniline hydrochloride. C . M. CARSON THE GOODYEAR TIRE& RUBBERCOMPANY AKRON,OHIO M a y 18, 1926
“
Experts ”
Editor of Industrial and Engineering Chemistry: May I use your columns t o comment on two of your editorial utterances in your May issue. On page 442 you consider the broad question of “experts,” and on page 547 you express the opinion t h a t differences of opinion “contribute t o the wealth of the attorney and the poverty of the chemist.” M y fellow attorneys consider me an engineer and chemist, and my fellow engineers consider me a lawyer. Since they are both essentially wrong, I am on a par with the editors and in a position t o speak authoritatively on both law and chemistry. Now as t o this wealth and poverty business-I personally know several chemists who have attained considerable wealth due to their ownership in patents on which there have always been decided differences of opinion as to their validity and scope and in regard to which protracted litigation has been necessary. The attorneys did not make this difference of opinion, and while they undoubtedly were paid for the time they spent in this litigation, I do not think they received collectively one-half of one per cent of the amounts received by the chemist-inventors. Yet, had they not used their time and trained brains the chances are the inventors would have received nothing. It is a common habit t o sneer a t the lawyer on the theory that he is a sort of parasite, fattening on the body politic, losing entire sight of the fact that his work is just as essential as t h a t of the chemist. H e is an absolutely necessary part of the machinery of civilization. If you doubt it, hire a n incompetent lawyer in your next patent suit and see what happens t o you. We have built a complicated civilization, governed by complicated laws, and it takes brains to understand and interpret these laws. The average scientist thinks he has a better brain than the average lawyer, whereas all t h a t he has is a differently
Vol. 18, No. 7
trained brain. H e is disposed to despise the lawyer because the lawyer does not fully understand Einstein and to ignore the technical man’s absolute ignorance on the fundamentals of our law, which in the last analysis are the fundamentals of our civilization, It is also a pose of the scientist t o scorn the ethics of the lawyer, and that brings us t o the question of expert witnesses. It is true t h a t some lawyers will go t o considerable length in misrepresentation in arguing a case and in suppressing or distorting facts in presenting it. But the lawyer is not under oath; he is a recognized partisan and he is paid t o present his client’s case, not t o judge i t or to bring out facts in rebuttal. I n almost every patent case we feel it desirable t o call on experts whose sole duty is to elucidate the laws of nature or the like, so that the court can understand the fundamental theories involved. Such experts should be amicus curiae, or “friends of the court.” After years 01 experience I have developed a hearty contempt for the professional expert. H e is in most cases a professional perjurer. The important thing for the scientific fraternities to consider is that, however bad a case a lawyer may have, and however badly his contentions may be refuted by the laws of nature, he can always find a scientist who will go on the witness stand and under oath pervert those laws or suspend their operation entirely. I have in mind one engineer who makes it his business to speak very disparaging of the ethics of the lawyers, who is under contract with a firm of lawyers and who has never yet refused t o testify stoutly on their side of any case. H e also never hesitates t o ignore the laws of gravity or thermodynamics if necessary t o win a case. In one historic case he testified in regard to steam a t 210’ F. and 90 pounds gage pressure, and the pathetic thing was that the federal judge saw nothing unusual about such steam, nor did the lawyer on the other side. And this expert is not a sporadic case. I will undertake to produce in any case three reputable scientists who will make out an excellent showing of the facts on either side. This is something for engineers and chemists to think about, since i t is primarily their scandal, and while they are thinking they might “lay off” the ethics of the lawyers, since for every crooked lawyer conducting a case there are three crooked experts, perhaps chemists, doing some high and fancy perjury. And while it may be t h a t the lawyers have seduced the scientists, i t does not speak well for the moral fiber of the latter t h a t they can be persuaded t o lie for a little money, for such experts are rarely very expensive t o hire. As a matter of fact, the whole system of expert testimony is wrong. X o man who has a personal bias in the case ought t o go on the stand t o testify as to the laws of nature or the like. Experts should be appointed by the judge if he thinks he needs them. They should sit in a semijudicial capacity as t o the facts and should be real experts. If our national technical societies were properly organized, they might furnish the machinery by which a judge could draft technical assistance, the judge applying t o the society for a man having the knowledge necessary t o assist him. For example, the technical society might name ten men competent t o pass on the facts and the litigants might be required t o elect one or more from this list, leaving the judge the right t o appoint if no agreement could be reached by litigants. Or if our Patent Office were properly organized, the judge might call a n expert from the office t o sit with him and advise him. Until t h a t happy day arrives, let us all be a s honest as we can and avoid innuendos as t o the other fellow’s honesty. AS a matter of fact, most men are willing t o lie a little for a little money.
FORDW. HARRIS 471 CHAMBrtR O F COMMERCB BLDO. Los ANGELES,CALIF. M a y 11,1926
