Reagents
For the purposes of the following specifications,these definitions apply:Ablankconsists of the same quantities of the same reagents treated in the same manner as the specimen under test.Acontrolis a blank to which has been added the limiting quantity of the substance being tested for,or is a specified comparison solution prepared as directed in the particular test.
The values given in boldface type following chemical symbols and formulas represent,respectively,atomic and molecular weights of the substances concerned.
Color and turbidity comparisons are to be made in color-comparison tubes that are matched as closely as possible in internal diameter and in all other respects,as directed for Visual Comparisonunder Spectrophotometry and Light-scattering á851ñ.Such tubes frequently are called Nessler tubes.
In making visual comparisons of the densities of turbid fluids,compensate for differences in color,if necessary,by viewing the turbidity through a column of water,the depth of which is determined by the volume specified in the individual reagent specification.Place the water in color-comparison tubes,and hold one of the tubes above the control tube and the other below the specimen tube.
Where an expression such as Retain the filtrateappears it is to be understood,unless otherwise indicated,that the washings of the residue are not to be added to the filtrate obtained.In the test heading,Calcium,magnesium,and R2O3precipitate,the expression R2O3is intended to indicate the residue on ignition from compounds precipitated upon the addition of ammonium hydroxide,such as Fe2O3and Al2O3.
GENERAL TESTS FOR REAGENTS The following general test methods are provided for the examination of reagents to determine their compliance with the specifications of the individual reagents and are to be used unless it is otherwise directed in such specifications.
Boiling or Distilling Range for Reagents
Use the following procedure for determining the boiling or distilling range of reagents,unless otherwise directed in the individual specifications:
APPARATUS
Use apparatus similar to that specified for Distilling RangeMethod Iá721ñ,except that the distilling flask is to be of 250-mLcapacity,to have a short neck,and to be connected to the condenser by means of a three-way connecting tube fitted with standard-taper ground joints.
PROCEDURE
Place the distilling flask in an upright position in the perforation in the asbestos board,and connect it to the condenser.
Measure 100mLof the liquid to be tested in a graduated cylinder,and transfer to the boiling flask together with some device to prevent bumping.Use the cylinder as the receiver for the distillate.Insert the thermometer,and heat so as to distil at the rate of 3mLto 5mLper minute.Make a preliminary trial,if necessary,to determine the adjustment for the proper rate of heating.Read the thermometer when about 20drops have distilled and thereafter at volumes of distillate of 5,10,40,50,60,90,and 95mL.Continue the distillation until the dry point is reached.
The Boiling or Distilling Rangeis the interval between the temperatures when 1mLand 95mL,respectively,have distilled.
Arsenic in Reagents
Select reagents for this test for a low arsenic content,so that a blank test results in either no stain or one that is barely perceptible.
APPARATUS
Prepare a generator by fitting a 1-hole rubber stopper into a wide-mouth bottle of about 60-mLcapacity.Through the perforation insert a vertical exit tube about 12cm in total length and 1cm in diameter along the entire upper portion (for about 8cm)and constricted at its lower extremity to a tube about 4cm in length and about 5mm in diameter.The smaller portion of the tube should extend to just slightly below the stopper.Place washed sand or a pledget of purified cotton in the upper portion to about 3cm from the top of the tube.Moisten the sand or cotton uniformly with lead acetate TS,and remove any excess or adhering droplets of the latter from the walls of the tube.Into the upper end of this tube fit a second glass tube 12cm in length,having an internal diameter of 2.5to 3mm,by means of a rubber stopper.Just before running the test,place a strip of mercuric bromide test paper (see under Indicator and Test Papers)in this tube,crimping the upper end of the strip so that it will remain in position about 2cm above the rubber stopper.Clean and dry the tube thoroughly each time it is used.
TEST PREPARATION
Add 1mLof sulfuric acid to 5mLof a solution of the chemical substance (1in 25),unless another quantity is directed in the individual reagent specification.Omit its addition entirely in the case of inorganic acids.Unless especially directed otherwise,add 10mLof sulfurous acid.Evaporate the liquid in a small beaker,on a steam bath,until it is free from sulfurous acid and has been reduced to about 2mLin volume.Dilute with water to 5mLto obtain the Test Preparation.Substances subjected to special treatments specified in the individual reagent specification may be used directly as the Test Preparation.
NOTESolutions prepared by the dissolving of the chemical substances in dilute acids are not considered to have undergone special treatment.
STANDARD STAIN
Place in the generator bottle 5mLof potassium iodide TS,2.0mLof Standard Arsenic Solution,5mLof acid stannous chloride TS,and 28mLof water.Add 1.5g of granulated zinc (in No.20powder),and immediately insert the stopper containing the exit tube.Keep the generator bottle immersed in water at 25during the period of the test to moderate the reaction so that the stain will take the form of a distinctive band to facilitate the comparison of color intensity.When evolution of hydrogen has continued for 1hour,remove the mercuric bromide test paper for comparison.This stain represents 2µg of arsenic.
PROCEDURE
Pipet into the generator bottle 5mLof potassium iodide TSand 5mLof the Test Preparation,and add 5mLof acid stannous chloride TS.Set the apparatus aside at room temperature for a period of 10minutes,then add 25mLof water and 1.5g of granulated zinc (in No.20powder),and proceed as directed under Standard Stain.Remove the mercuric bromide test paper,and compare the stain upon it with the Standard Stain:the stain produced by the chemical tested does not exceed the standard stain in length or in intensity of color,indicating not more than 10parts of arsenic per million parts of the substance being tested.Since light,heat,and moisture cause the stain to fade rapidly,place the papers in clean,dry tubes,and make comparisons promptly.
INTERFERING CHEMICALS
Antimony,if present in the substance being tested,produces a gray stain.Sulfites,sulfides,thiosulfates,and other compounds that liberate hydrogen sulfide or sulfur dioxide when treated with sulfuric acid must be oxidized by means of nitric acid and then reduced by means of sulfur dioxide as directed under Test Preparationbefore they are placed in the apparatus.Certain sulfur compounds,as well as phosphine,give a bright yellow band on the test paper.If sulfur compoundsare present,the lead acetate-moistened cotton or sand will darken.In that case,repeat the operation as directed under Test Preparationupon a fresh portion of the solution being tested and use greater care in effecting the complete removal of the sulfurous acid.In testing hypophosphites,observe special care to oxidize completely the solution being tested as directed,otherwise the evolution of phosphine may result in a yellow stain which may be confused with the orange-yellow color produced by arsine.The stain produced by phosphine may be differentiated from that given by arsine by means of moistening it with 6Nammonium hydroxide.Astain caused by arsine becomes dark when so treated,but a stain produced by phosphine does not materially change in color.
Chloride in Reagents
STANDARD CHLORIDE SOLUTION
Dissolve 165.0mg of dried sodium chloride in water to make 1000.0mL.This solution contains the equivalent of 0.10mg of chlorine (Cl)in each mL.
PROCEDURE
Neutralize,if alkaline,a solution of the quantity of the reagent indicated in the test in 25mLof water,or a solution prepared as directed in the test,with nitric acid,litmus paper being used as the indicator,and add 3mLmore of nitric acid.Filter the solution,if necessary,through a filter paper previously washed with water until the paper is free from chloride,and add 1mLof silver nitrate TS.Mix,and allow to stand for 5minutes protected from direct sunlight.Compare the turbidity,if any,with that produced in a control made with the same quantities of the same reagents as in the final test and a volume of Standard Chloride Solutionequivalent to the quantity of chloride (Cl)permitted by the test.Adjust the two solutions with water to the same volume before adding the silver nitrate TS,and compare the turbidities.
In testing barium salts,neutralize,if alkaline,the solution containing the reagent,with nitric acid,and add only 3drops more of nitric acid.Conduct the remainder of the test as described previously.
In testing salts giving colored solutions,dissolve 2g of the reagent in 25mLof water,and add 3mLof nitric acid.Filter the solution,if necessary,through a filter paper previously washed with water,and divide the filtrate into two equal portions.Treat one portion with 1mLof silver nitrate TS,allow to stand for 10minutes,and,if any turbidity is produced,filter it through a washed filter paper until clear,and use the filtrate as a blank.Treat the other portion with 1mLof silver nitrate TS,mix,and allow to stand for 5minutes protected from direct sunlight.Compare the turbidity with that produced in the blank by the addition of a volume of Standard Chloride Solutionequivalent to the quantity of chloride (Cl)permitted in the test,both solutions being adjusted with water to the same volume.
Flame Photometry for Reagents
The use of flame photometric procedures to determine traces of calcium,potassium,sodium,and strontium is called for in some of the reagent specifications.The suitability of such determinations depends upon the use of adequate apparatus,and several instruments of suitable selectivity are available.The preferred type of flame photometer is one that has a red-sensitive phototube,a multiplier phototube,a monochromator,an adjustable slit-width control,a selector switch,and a sensitivity control.Other types of photometers may be used,provided the operator has proved that the instrument will determine accurately the amount of impurities permitted in the reagent to be tested.
The flame photometric procedures depend upon the use of semi-internal standards,and thus require both a Sample Solutionand a Control Solution.For the Sample Solution,a specified weight of specimen is dissolved and diluted to a definite volume.For the Control Solution,the same amount of specimen is dissolved,the limiting amounts of the suspected impurities are added,and the solution is then diluted to the same definite volume as the Sample Solution.The flame photometer is set as directed in the general procedures and then adjusted to give an emission reading as near 100%transmittance as is possible with the Control Solutionat the wavelength specified for the particular impurity concerned.With the instrument settings left unchanged,the emission from the Sample Solutionis read at the same wavelength and at a specified background wavelength.The background reading is then used to correct the observed emission of the Sample Solutionfor the emission due to the specimen and the solvent.The specimen being tested contains less than the specified limit of impurity if the difference between the observed background and total emissions for the Sample Solutionis less than the difference between the observed emissions for the Control Solutionand the Sample Solutionat the wavelength designated for the particular impurity.
CALCIUM IN REAGENTS
Standard Calcium Solution
Dissolve 250mg of calcium carbonate in a mixture of 20mLof water and 5mLof diluted hydrochloric acid,and when solution is complete,dilute with water to 1liter.This solution contains 0.10mg of calcium (Ca)per mL.
Procedure
Use the Sample Solutionand the Control Solutionprepared as directed in the individual test procedure.
Set the slit-width control of a suitable flame photometer at 0.03mm,and set the selector switch at 0.1.Adjust the instrument to give the maximum emission with the Control Solutionat the 422.7-nm calcium line,and record the transmittance.Without changing any of the instrument settings,record the transmittance for the emission of the Sample Solutionat 422.7nm.Change the monochromator to the wavelength specified in the individual test procedure,and record the background transmittance for the background emission of the Sample Solution:the difference between the transmittances for the Sample Solutionat 422.7nm and at the background wavelength is not greater than the difference between transmittances observed at 422.7nm for the Sample Solutionand the Control Solution.
POTASSIUM IN REAGENTS
Standard Potassium Solution
Dissolve 191mg of potassium chloride in a few mLof water,and dilute with water to 1liter.Dilute a portion of this solution with water in the ratio of 1to 10to obtain a concentration of 0.01mg of potassium (K)per mL.
Procedure
Use the Sample Solutionand the Control Solutionprepared as directed in the individual test procedure.[NOTEIn testing calcium salts,use an oxyhydrogen burner.]
Set the slit-width control of a suitable flame photometer equipped with a red-sensitive detector at 0.1mm,unless otherwise directed,and set the selector switch at 0.1.Adjust the instrument to give the maximum emission with the Control Solutionat the 766.5-nm potassium line,and record the transmittance.Without changing any of the instrument settings,record the transmittance for the emission of the Sample Solutionat 766.5nm.Change the monochromator to 750nm,and record the background transmittance for the background emission of the Sample Solution:the difference between the transmittances for the Sample Solutionat 766.5nm and 750nm is not greater than the difference between transmittances observed at 766.5nm for the Sample Solutionand the Control Solution.
SODIUM IN REAGENTS
Standard Sodium Solution
Dissolve 254mg of sodium chloride in a few mLof water,and dilute with water to 1liter.Dilute a portion of this solution with water in the ratio of 1to 10to obtain a concentration of 0.01mg of sodium (Na)per mL.
Procedure
Use the Sample Solutionand the Control Solutionprepared as directed in the individual test procedure.
Set the slit-width control of a suitable flame photometer at 0.01mm,and set the selector switch at 0.1.Adjust the instrument to give the maximum emission with the Control Solutionat the 589-nm sodium line,and record the transmittance.Without changing any of the instrument settings,record the transmittance for the emission of the Sample Solutionat 589nm.Change the monochromator to 580nm,and record the background transmittance for the background emission of the Sample Solution:the difference between the transmittances for the Sample Solutionat 589and 580nm is not greater than the difference between transmittances observed at 589nm for the Sample Solutionand the Control Solution.
STRONTIUM IN REAGENTS
Standard Strontium Solution
Dissolve 242mg of strontium nitrate in a few mLof water,and dilute with water to 1liter.Dilute a portion of this solution with water in the ratio of 1to 10to obtain a concentration of 0.01mg of strontium (Sr)per mL.
Procedure
Use the Sample Solutionand the Control Solutionprepared as directed in the individual test procedure.
Set the slit-width control of a suitable flame photometer at 0.03mm,and set the selector switch at 0.1.Adjust the instrument to give the maximum emission with the Control Solutionat the 460.7-nm strontium line,and record the transmittance.Without changing any of the instrument settings,record the transmittance for the emission of the Sample Solutionat 460.7nm.Change the monochromator to the wavelength specified in the individual test procedure,and record the background transmittance for the background emission of the Sample Solution:the difference between the transmittances for the Sample Solutionat 460.7nm and at the background wavelength is not greater than the difference between transmittances observed at 460.7nm for the Sample Solutionand the Control Solution.
Heavy Metals in Reagents
STANDARD LEAD SOLUTION
Use Standard Lead Solution(see Heavy Metals á231ñ).Each mLof this solution contains the equivalent of 0.01mg of Pb.
PROCEDURE
Unless otherwise directed,test for heavy metals as follows:
(a)If the heavy metals limit is 0.0005%(5ppm),dissolve 6.0g of the specimen in water to make 42mL.
(b)If the heavy metals limit is 0.001%(10ppm)or more,or in the event of limited solubility,use 4g,and dissolve in water to make 40mL,warming,if necessary,to aid solution.
For the control,transfer 7mLof the solution from (a)to a color-comparison tube,and add a volume of Standard Lead Solutionequivalent to the amount of lead permitted in 4g of the reagent.Dilute with water to 35mL,and add diluted acetic acid,or ammonia TS,until the pHis about 3.5,determined potentiometrically,then dilute with water to 40mL,and mix.Transfer the remaining 35mLof the solution from (a)to a color-comparison tube closely matching that used for the control,and add diluted acetic acid,or ammonia TS,until the pHis about 3.5,determined potentiometrically,then dilute with water to 40mL,and mix.Then to each tube add 10mLof hydrogen sulfide TS,mix,and compare the colors by viewing through the color-comparison tube downward against a white surface.The color in the test specimen is not darker than that of the control.
If the solution of the reagent is prepared as in (b),use for the control 10mLof the solution,and add to it a volume of Standard Lead Solutionequivalent to the amount of lead permitted in 2g of the reagent.Dilute the remaining 30mLof solution (b)with water to 35mL,and proceed as directed in the preceding paragraph,beginning with add diluted acetic acid,or ammonia TS,in the second sentence.
If the reagent to be tested for heavy metals is a salt of an aliphatic organic acid,substitute 1Nhydrochloric acid for the diluted acetic acid specified in the foregoing method.
Insoluble Matter in Reagents
Dissolve the quantity of reagent specified in the test in 100mLof water,heat to boiling unless otherwise directed,in a covered beaker,and warm on a steam bath for 1hour.Filter the hot solution through a tared sintered-glass crucible of fine porosity.Wash the beaker and the filter thoroughly with hot water,dry at 105,cool in a desiccator,and weigh.
Loss on Drying for Reagents
Determine as directed under Loss on Drying á731ñ.
Nitrate in Reagents
STANDARD NITRATE SOLUTION
Dissolve 163mg of potassium nitrate in water,add water to make 100mL,and dilute 10mLof this solution with water to 1liter,to obtain a solution containing the equivalent of 0.01mg of NO3per mL.
BRUCINE SULFATE SOLUTION
Dissolve 600mg of brucine sulfate in 600mLof nitrate-free,dilute sulfuric acid (2in 3)that previously has been cooled to room temperature,and dilute with the acid to 1liter.[NOTEPrepare the nitrate-free sulfuric acid by adding 4parts of sulfuric acid to 1part of water,heating the solution to dense fumes of sulfur trioxide,and cooling.Repeat the dilution and heating three or four times.]
SAMPLE SOLUTION
To the weight of sample specified in the individual reagent specification,dissolved in the designated volume of water,add Brucine Sulfate Solutionto make 50mL.
CONTROL SOLUTION
To a volume of Standard Nitrate Solutionequivalent to the weight of nitrate (NO3)specified in the individual reagent specification,add the weight of sample specified in the individual reagent specification and then add Brucine Sulfate Solutionto make 50mL.
BLANK SOLUTION
Use 50mLof Brucine Sulfate Solution.
PROCEDURE
Heat the Sample Solution,Control Solution,and Blank Solutionin a boiling water bath for 10minutes,then cool rapidly in an ice bath to room temperature.Adjust a suitable spectrophotometer to zero absorbance at 410nm with the Blank Solution.Determine the absorbance of the Sample Solution,note the result,and adjust the instrument to zero absorbance with the Sample Solution.Determine the absorbance of the Control Solution:the absorbance reading for the Sample Solutiondoes not exceed that for the Control Solution.
Nitrogen Compounds in Reagents
PROCEDURE
Unless otherwise directed,test for nitrogen compounds as follows:Dissolve the specified quantity of test specimen in 60mLof ammonia-free water in a Kjeldahl flask connected through a spray trap to a condenser,the end of which dips below the surface of 10mLof 0.1Nhydrochloric acid.Add 10mLof freshly boiled sodium hydroxide solution (1in 10)and 500mg of aluminum wire,in small pieces,to the Kjeldahl flask,and allow to stand for 1hour,protected from loss of,and exposure to,ammonia.Distil 35mL,and dilute the distillate with water to 50mL.Add 2mLof freshly boiled sodium hydroxide solution (1in 10),mix,add 2mLof alkaline mercuric-potassium iodide TS,and again mix:the color produced is not darker than that of a control containing the amount of added N(as ammonium chloride)specified in the individual test procedure.
Phosphate in Reagents
STANDARD PHOSPHATE SOLUTION
Dissolve 143.3mg of dried monobasic potassium phosphate,KH2PO4,in water to make 1000.0mL.This solution contains the equivalent of 0.10mg of phosphate (PO4)in each mL.
PHOSPHATE REAGENT A
Dissolve 5g of ammonium molybdate in 1Nsulfuric acid to make 100mL.
PHOSPHATE REAGENT B
Dissolve 200mg of p-methylaminophenol sulfate in 100mLof water,and add 20g of sodium bisulfite.Store this reagent in well-filled,tightly stoppered bottles,and use within one month.
PROCEDURE
[NOTEThe tests with the specimen and the control are made preferably in matched color-comparison tubes.]Dissolve the quantity of the reagent specified in the test,or the residue obtained after the prescribed treatment,in 20mLof water,by warming,if necessary,add 2.5mLof dilute sulfuric acid (1in 7),and dilute with water to 25mL.(If preferable,the test specimen or the residue may be dissolved in 25mLof approximately 0.5Nsulfuric acid.)Then add 1mLeach of Phosphate Reagents Aand B,mix,and allow to stand at room temperature for 2hours.Compare any blue color produced with that produced in a control made with the same quantities of the same reagents as in the test with the specimen,and a volume of Standard Phosphate Solutionequivalent to the quantity of phosphate (PO4)designated in the reagent specifications.
Residue on Ignition in Reagents
PROCEDURE
Unless otherwise directed,determine the residue on ignition as follows:Weigh accurately 1to 2g of the substance to be tested in a suitable crucible that previously has been ignited,cooled,and weighed.Ignite the substance,gently and slowly at first and then at a more rapid rate,until it is thoroughly charred,if organic in nature,or until it is completely volatilized,if inorganic in nature.If the use of sulfuric acid is specified,cool the crucible,add the specified amount of acid,and ignite the crucible gently until fumes no longer are evolved.Then ignite the crucible at 800±25,cool in a suitable desiccator,and weigh.If the use of sulfuric acid is not specified,the crucible need not be cooled but can be ignited directly at 800±25once the charring or volatilization is complete.Continue the ignition until constant weight is attained,unless otherwise specified.
Conduct the ignition in a well-ventilated hood,but protected from air currents,and at as low a temperature as is possible to effect the complete combustion of the carbon.Amuffle furnace may be used,if desired,and its use is recommended for the final ignition at 800±25.
Sulfate in Reagents
STANDARD SULFATE SOLUTION
Dissolve 181.4mg of potassium sulfate (dried at 105for 2hours)in water to make 1000mL.This solution contains the equivalent of 0.10mg of sulfate (SO4)per mL.
PROCEDURE
Method I
Neutralize,if necessary,a solution of the quantity of the reagent or residue indicated in the test in 25mLof water,or a solution prepared as directed in the test,with hydrochloric acid or with ammonia TS,litmus paper being used as the indicator,and add 1mLof 1Nhydrochloric acid.Filter the solution,if necessary,through a filter paper previously washed with water,and add 2mLof barium chloride TS.Mix,allow to stand for 10minutes,and compare the turbidity,if any,with that produced in a control containing the same quantities of the same reagents used in the test and a quantity of Standard Sulfate Solutionequivalent to the quantity of sulfate (SO4)permitted in the test.Adjust the two solutions with water to the same volume before adding the barium chloride TS.
Method II
Heat to boiling the solution,prepared as directed in the individual test procedure,or the filtrate designated in the procedure,and add 5mLof barium chloride TS.Then digest the solution on a steam bath for 2hours,and allow to stand overnight.If any precipitate is formed,filter the solution through paper,wash the residue with hot water,and transfer the paper containing the residue to a tared crucible.Char the paper,without burning,and ignite the crucible and its contents to constant weight.Perform a blank determination concurrently with the test specimen determination,and subtract the weight of residue obtained from that obtained in the test specimen determination to obtain the weight of residue attributable to the sulfate content of the specimen.
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