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ANALYTICAL CHEMISTRY.

F. P.

TEE AD WELL,

PH.D.,

Profe&or of Analytical Chemistry in the Polytechnic Institute of Zurich.

AUTHORIZED TRANSLATION FROM THE GERMAN
BY

WILLIAM

T.

HALL,

S.B.,

Assistant Professor of Chemistry, Massachusetts Institute of Technology.

VOLUME

II.

QUANTITATIVE ANALYSIS.

THIRD EDITION, REVISED AND ENLARGED
TOTAL ISSUE, EIGHT THOUSAND

NEW YORK:
JOHN WILEY & SOSTS.
LONDON:

CHAPMAN & HALL,

LIMITED.

Copyright, 1904, 1910, 1911,

BY

WILLIAM
First arid

T.

HALL.

Second Editions entered at Stationers'
Hall.

THE SCIENTIFIC PRESS
CRT DRUMMOND AND COMPANY
BROOKLYN,

N! V.

TRANSLATOR'S NOTE.
THIS translation has been made from the second German
but Professor Treadwell has kindly indicated quite a
which he intends to make in the third edition.
Since it has been my aim not so much to prepare an exact literal
translation as to publish a book which will be useful to Englishedition,

number

of changes

speaking students,

I

am

under great obligations to several of

my

That
for suggesting certain other changes.
has
careGravimetric
been
to
the
of
Analysis
proof relating
part
that
Professor
criticised
read
and
Henry Fay,
relating
by
fully
to Volumetric Analysis by Professor F. Jewett Moore, and Profriends

and colleagues

Augustus H. Gill has twice read the chapter on Gas Analysis.
have also received valuable assistance in reading the proof from
Messrs. R. S. Williams, F. R. Kneeland and J. R. Odell, all of the

fessor
I

Massachusetts Institute of Technology. I am indebted to Mr.
A. R. Jackson, of Winthrop, for several drawings.

WILLIAM
1

T. HALL.

HUSETTS INSTITUTE OF TECHNOLOGY,
April, 1904.

In preparing the second edition, the text has been compared
with the fourth German edition, and certain additions have

been made which are not found in the German

text.

W.

T. H.

March, 1910.

The

compared with the fifth German
In the preparation of dilute acids the volume of concentrated acid is always referred to the volume of water added.
Thus sulphuric acid (1:4) signifies one volume of concentrated
acid diluted with four volumes of water.
With solutions of
third edition has been

edition.

solids,

solid

the

first

number

signifies

the weight in grams of the
in cubic centi-

and the second the volume of the solvent

W.

meters.
June, 1911.

T. H.
iii

241336

TABLE OF CONTENTS.

INTRODUCTION.
PAGE

Gravimetric and Volumetric Analysis
Direct and Indirect Analyses

Weighing
Reduction

of

1

2
6
13

Weighing to Vacuo

Testing of Weights

15

and Washing of Precipitates
Drying and Igniting of Precipitates

21

Filtration

18

Evaporation of Liquids
Drying Substances in Currents of Gases
Preparation of the Substance for Analysis

30
33
35
35

Recrystallization

PART

I.

GRAVIMETRIC DETERMINATION OF THE METALS.
V

(ALKALIES).

Potassium ......................................................
Sodium .........................................................
Separation of Potassium from Sodium ........................... 43,
Lithium ........................................................
Determination of Lithium, Potassium, and Sodium ............... .....
Ammonium .....................................................
Magnesium ......................................................
Separation of Magnesium from the Alkalies .........................

38
43
50
53
53
57
65
68

GROUP IV (ALKALINE EARTHS).
Calcium ........................................................
Strontium .......................................................
Barium .........................................................
...........
Separation of Calcium from Magnesium ...............

70
72
74
76

v

TABLE OF CONTENTS.

vi

PAGE

Separation of Strontium from Magnesium
Separation of Barium from Magnesium
Separation of the Alkaline Earths from

One Another

GROUP

79

III.

Aluminium

82
87
100
102
106
107, 147
107

Iron

Titanium

Chromium
Uranium
Separation of Group III from Group
Separation of Iron from Aluminium

78
79

IV

Separation of Iron, Aluminium, and Phosphoric Acid
Separation of Iron from Chromium

Ill

Separation of Aluminium from Chromium
Separation of Iron from Titanium

114

Separation of Aluminium from Titanium
Separation of Uranium from Iron and Aluminium

116

113
114
119

Manganese

120

Nickel

Cobalt

129
138

Zinc

140

Separation of Manganese, Nickel, Cobalt, and Zinc from the Alkaline

Earths

147

Separation of the Bivalent from the Other Metals of the

Ammonium

Sulphide Group
Separation of Zinc from Nickel, Cobalt, and Manganese
Separation of Manganese from Nickel and Cobalt

149
1 56

Separation of Cobalt from Nickel
Separation of Nickel from Zinc

161

Separation of Nickel from Manganese
Separation of Nickel from Iron

165

Removal

167

of Ferric Chloride

165

166

by Ether

GROUP
(a)

161

II.

Sulpho-Bases.

Mercury
Lead
Bismuth

168

Copper

182

Cadmium

189

Separation of the Sulpho-Bases from the Preceding Groups

192

174

179

TABLE OF CONTENTS.

Analysis of Brass
Separation of the Sulpho-Bases from

vii

193

One Another

194

Sulpha-Adds.

(6)

205
218
228

Arsenic

Antimony
Tin
Separation of Arsenic, Antimony, and Tin from
nium Sulphide Group

Members

of the

Ammo235

Separation of Arsenic, Antimony, and Tin from Mercury, Lead, Copper,

Cadmium, and Bismuth
Analysis of Bronzes
Separation of the Sulpho- Acids from

235
236
241
252
257
268
271
272
277
279

One Another

Analysis of Bearing Metal

Gold
Platinum

,

Separation of Gold from Platinum
Analysis of Commercial Platinum

Selenium
Tellurium
Separation of Selenium and Tellurium from the Metals of Groups III,
IV, and

V

Separation of Selenium and Tellurium from Metals of Group II
Separation of Selenium from Tellurium

Molybdenum
Tungsten
Separation of

Molybdenum from Tungsten

Analysis of Wolframite

Analysis of Tungsten Bronzes

.

.

T-

Separation of Tungsten from Tin
Separation of Tungstic Acid from Silica

Vanadium
Separation of
Separation of

Vanadium from Arsenic Acid
Vanadium from Phosphoric Acid
Vanadium from Molybdenum

Separation of
Analysis of Vanadinite

Determination of Vanadium and Chromium in Iron Ores and Rocks.
Determination of Vanadium and Chromium in Pig Iron
Determination of Vanadium, Molybdenum, Chromium, and Nickel in
.

.

.

313

Steel

GROUP
Silver..

279
280
282
284
288
293
296
298
300
302
303
306
307
308
308
310
312

I.

.

317

TABLE OF CONTENTS.

viii

GRAVIMETRIC DETERMINATION OF THE METALLOIDS.
GROUP

I.*

PAGE

Hydrochloric Acid

320
323
324
Chlorine in Organic Compounds
325
329
Hydrobromic Acid
330
Hydriodic Acid
331
Separation of the Halogens from One Another
337
Hydrocyanic Acid
Determination of Hydrocyanic Acid in the Presence of Halogen Hydride 339
339
Sulphocyanic Acid
Determination of Sulphocyanic and Hydrocyanic Acids
342
Determination of Sulphocyanic Acid and Halogen Hydrides
342
342
Hydroferrocyanic Acid
344
Hydroferricyanic Acid
344
Hypochlorous Acid
Analysis of an Insoluble Chloride
Free Chlorine

GROUP

II.

Nitrous Acid

Hydrosulphuric Acid,

344
347

HS
2

Analysis of Tetrahedrite
Acetic Acid

Cyanic Acid
Determination of Cyanic, Hydrocyanic, and Carbonic Acids
Hypophosphorous Acid

GROUP

III.

Sulphurous Acid
Selenous and Tellurous Acids

Phosphorous Acid
Carbonic Acid
Determination of Carbon
Determination of Carbon and Hydrogen in Organic Substances
Dumas Method for Determining Nitrogen
Oxalic Acid
Boric Acid
Molybdic Acid
Tartaric Acid
."

,

Meta- and Pyrophosphoric Acids
lodic Acid
*

For the Division

of

359
371
371
371
372

Acids into Groups

cf.

Vol.

I.

373
374
374
375
398
414
422
427
428
433
433
433
433

TABLE OF CONTENTS.
GROUP

ix

IV.

PAGE

Phosphoric Acid
Determination of Phosphorus and Silicon in Iron and Steel
Separation of Phosphoric Acid from the Metals
Thiosulphuric Acid

GROUP

434
440
448
450

V.

Nitric Acid

451

Chloric Acid

460
462

Perchloric Acid

GROUP

VI.

Sulphuric Acid
Hydrofluoric Acid

471

Separation of Phosphoric and Hydrofluoric Acids
Separation of Fluorine from the Metals

481

464
474

Separation of Fluorine from the Acids

482
483

Hydrofluosilicic Acid

GROUP
Silicic

VII.

Acid

485

Analysis of Silicates

Determination of Zirconium and Sulphur in Rocks
Analysis of Chromite
Determination of Thorium in Monazite
Determination of Water in Silicates.
.

'PART

.

491
505
509
510
512

n.

VOLUMETRIC ANALYSIS.
Measuring Instruments

Normal Volume and Normal Temperature
Calibration of Measuring Flasks
Calibration of Pipettes

Calibration of Burettes

Normal Solutions

I.

Indicators

Alkalimetry
Acidimetry

.

.

.

514
516
522
524
527
530

ACIDIMETRY AND ALKALIMETRY.
538
558
571

X

TABLE OF CONTENTS.
II.

OXIDATION AND REDUCTION METHODS.
PAGE
596
641
644

Permanganate Methods
Potassium Dichromate Methods
lodimetry
Reduction Methods

697

PRECIPITATION ANALYSES.

III.

Determination
Determination
Determination
Determination
Determination
Determination
Determination
Determination
Determination

of Silver
of

Halogens

of

Cyanogen

Acid
Acid
of Phosphoric Acid
of Sulphocyanic

of Sulphuric
of Nickel
of
of

Copper
Lead
.

.

.

PART

702
707
710
712
714
718
720
724
726

III.

GAS ANALYSIS.
The

Collection and Confinement of

Gas Samples

730
743
747
750

Calibrating Gas Measuring Instruments
Purification of

Mercury

Determination of Carbon Dioxide

751

Ethylene
Benzene
Acetylene
Separation of the

Heavy Hydrocarbons

Oxygen
Carbon Monoxide
Hydrogen
Methane
Analysis of Illuminating and Producer Gas
Technical Gas Analysis

Method
Method

of

Hempel

of Winkler-Dennis

Orsat's Apparatus

Bunte's Apparatus
Analysis of Gases which are Absorbed by Water
Nitrous Oxide
Nitric Oxide

.

752
754
756
757
762
770
774
775
786
768
794
797
798
800
800
802

TABLE OF CONTENTS.

XI
PAGE

Nitrogen
Analysis of Gases
Chlorine

by

Titration

Hydrochloric Acid
Sulphur Dioxide
Hydrogen Sulphide

Ethylene
Gas- Volumetric Methods
Determination of Ammonia in Ammonium Salts
Determination of Nitrous and Nitric Acids
Hydrogen Peroxide Methods
Standardization of Permanganate Solutions
Determination of Cerium in Soluble Salts
Silicon Fluoride

Determination of Fluorine
Determination of Vapor in Gas Mixtures

806
808
808
814
815
816
818
822
822
825
826
827
828
828
829
831

APPENDIX.
Gravity of Acids
Specific Gravity of Alkalies
Tension of Aqueous Vapor
Heats of Combustion of Gases
Tables for Calculating Analyses

Logarithms

838
840
842
845
847
849
850
854

INDEX

859

Specific

International Atomic Weights
Table of Chemical Factors

VOLUMETRIC ANALYSIS (Analysis by Volume). from this we can calculate 'the amount of the substance present.QUANTITATIVE ANALYSIS. II. precipitating the barium from the solution by the addition of sulphuric acid and weighing the insoluble barium sulphate formed. THE purpose of a quantitative analysis is to determine the quantity of the constituents present in a compound or in a mixThe methods to be employed depend upon the nature of ture. s = 15-^77- P = weight of. barium in a gm. the amount of barium present may be calcu- lated as follows: BaS0 4 :Ba=p:s. INTRODUCTION. sis we distinguish I. the substances to be determined. for example. pound we have for analysis a sample of barium chloride. . of If we start with a grams of barium chloride and obtain p grams barium sulphate. so that in every case a qualitative In quantitative analyanalysis should precede the quantitative one. The amount of barium present can be determined by dissolving a weighed amount of the chloride in Suppose. of barium chloride. two essentially different methods of procedure : GRAVIMETRIC ANALYSIS (Analysis by Weight). In the case of gravimetric analysis we separate the component to be determined from a solution in t*e form of an insoluble comof known chemical composition. that water. and then determine the weight of this compound.

. a In the case of volumetric analysis the constituents are not weighed. were necessary. this point being reached If t the solution changes to pink. (b) Indirect is Analyses.. in a gms. '. of is then is just color of hydrochloric acid a gms. Suppose that we have a sample of caustic soda which contains some sodium chloride as an impurity and that we desire to know how much caustic soda there is in 100 gms. will first consider A. These are divided into (a) Direct Analyses. it is c. in 100 gms.a -t = per Tj?Tj cent NaOH. NaOH x= We - - 100.= per cent.NaOH. A portion of the substance weighing a gms. we have therefore in this case x= BaSO 4 . customary to express the results in percentages. but they are determined by measuring the amounts of known strength which react with them.3V : It INTRODUCTION. and it a gms. of the mixture. of follows : 5= ~HC1 a '^ == Sms NaOH - in HC1 were used up. some methyl reagents of orange is added and hydrochloric acid of known strength run into the solution from a burette until the alkali when the yellow neutralized.c.c. of the mixture. of the mixture a-t gms. however. GRAVIMETRIC METHODS.-. In the case of a direct analysis the substance to be determined separated from the solution in the form of an insoluble com- pound and weighed. contained of exactly evident that to neutralize the caustic soda contained 1 c. barium. is dissolved in water. is. of which HC1 .

they are simply the quotients of the molecular weights in question.GRAVIMETRIC METHODS. therefore.). suppose that we have a mixture of the chlorides sodium and of potassium and desire to determine the relative amounts of each of the two substances in the mixture. y of the amount of the potassium chloride. two equations with apparently four unquantities. and by n the frao- . - however. For example. a the amount of silver formed from x gms.) is weighed. then chloride We known and XaCl" KC1 x y = a AgCl AgCl a + p = p. dissolved in water. the chlorine precipitated as silver chloride. From these data it is possible to calculate the amount of sodium chloride and of potasr sium chloride that was present in the mixture. The indirect substances are method depends upon the fact that when two or more to undergo the same chemical treatment they ex- made perience a relatively different change of weight. of sodium chloride. but a and /? can be expressed in terms of x y: NaCl:AgCl=z:a AgCl and AgCl . If we let x represent the amount of the sodium chloride. -f have. we If tion AgCl designate by m the fraction we have =a mx+ny=p x+ y ^. For this purpose a portion of the mixture (a gms. are known quantities. of potassium chloride. and the weight of the latter determined (p gms. The determination of barium in 3 barium chloride was an example of a direct analysis. and /? the amount of silver chloride formed from y gms. p.

34 n _AgCI_ T^m T IvCl 4 m i. in order to determine the amount of sodium is only necessary to determine chloride in the original mixture it the values a and p. In the above example in _AgCl_143 _ AT . that an indirect analysis becomes more when the accurate in proportion as the coefficients are small and error in determining a and p is slight. and experiment shows this to Example: be the case.628 and 1...y^^o 74. (a) and consisting of . If these values are substituted in the above equations we obtain s=1.. a is It is clear. therefore.63 . Although this method appears so simple and attractive on paper.52 97.888-p-3. impossible values are often obtained in practice.628-a. 4 and from this we can calculate n-a x= p mn and y = ax or n _JL. so that it is always necessary to be very cautious about using an indirect method.INTRODUCTION. and subtract the first product from the last.46 143. A mixture weighing 0.888 respectively.-<j\j } ift ob.89 . Consequently. The experimental errors which are unavoidable in such an analysis are multiplied by the value of the coefficients.5480 gm. and the error in determining the weight of the silver chloride (p) is multiplied by 1.^i NaCl : 34 4. mn mn All indirect analyses may be calculated by means of this last general equation. then multiply them by the coefficients 3..56 and m n = 0. In the above example the coefficients are relatively small and consequently good results are to be expected. thus in the above case the actual error in the determination of the weight multiplied by 3.

3161 -3.6 Although the above in results are satisfactory. 99. of the true value for the sodium chloride. by weighing the mixture of the chlorides in a platinum crucible.4963 gm.4966 gm. 0. j/ The show calculated values. potassium chloride.GRAVIMETRIC METHODS. but from the values (y) yielded 1.92 per cent. of the true value for the potassium chloride. those of x and y: calculate we can of a and p x= 1. then changing them to sulphates (by treatment with sulphuric acid and evaporating off the excess of the latter) mental error We have and again weighing.0464 Now x + (2) -a mx+ny = p (3) x== m (1) y and n mn . it must be borne was mind that the carried out with chemically pure analysis If this were not so. sodium chloride 5 and 0. is Nad KC1 + x y = a m-n. as is usually the case in prac- the results would be far less accurate.0514 gm.0. tice.3161 gm. substances. = 0.5480 = 0. therefore. potassium chloride (x) of silver chloride (p). The same manner than analysis may be performed in a much more simple as above described.628-0. In this case the actual experislight and excellent results might be expected.0517 gm. sodium chloride. per cent.888-1. 100.

Weighing. In the case of a direct analysis the small unavoidable errors exert a much less influence upon the result. Only in those cases where a an resort to direct method is unknown should one indirect analysis! OPERATIONS. of the potassium chloride present.76 per cent. and the washing.8 per cent.0 per cent. so that the analytical is multiplied enormously in the calculation. 1. The values obtained are. 129. and a horizontal lever with two in order to be serviceable it sensitive. of the sodium chloride present. therefore. 96.p-25. drying. so that a direct determination should always be preferred. of the sodium chloride present. and ignition of precipitates. accurate and . worthless. so much so that error impossible to obtain even approximate values except when the mixture is composed of about equal parts of the two chlorides. 148.181a. The balance. filtration. 6 Substituting the values for m and n in equation (3 we obtain z = 21.9 per cent. of the potassium chloride present. is shown in Fig. Example: In a mixture containing about equal parts of the it is two salts there was found 99.547-.64 per cent.INTRODUCTION.0 per cent. It consists of length. of the potassium chloride present. of the sodium chloride present. It fulfils the first condition (1) The arms arms of equal must be if of the lever are equally long. 100. as used for purposes of quantitative chemical analysis. The principal operations of quantitative analysis are those of weighing. In a mixture containing considerable sodium chloride and potassium chloride there was found (a) x (6) Jiwtib 95. In this case the coefficients are very large.

the heavier the weight added. of the beam. I the length of the balance-arm. and the shorter the distance between the centre of gravity and the point of support. or sensibility. (3) The fulcrum (a knife-edge) and the knife-edges from which the pans are suspended lie in the same plane and are parallel to one another. * a is the angle through which the pointer small weight.g. one milligram. and d the distance between the centre the q weight of gravity and the point of support. therefore. equation 1. The balance is more sensitive the greater the displacement brought about by the addition of of the position of equilibrium a small weight. e. in The is sensitiveness of the balance is greater. The point (2) 7 of support (the fulcrum) lies above the centre of gravity. the longer the beam. may be expressed by the : tan a* q-d which p the weight added. FIG. moves on the addition of the .WEIGHING. The sensitiveness. the lighter the beam.

then (1) Ql=Pl t is established P .. equilibrium takes place when will the statical By moments are equal. On account of unequal warming the arms become of unequal length. with the hand. as the following consideration show. whose weight Q placed upon the left (Fig. the beam is lowered and the balance set in slight motion. balance-pan and equilibrium is (the pointer rests at zero) by putting weights amounting to gms. so that disregard of it this fact may lead to a considerable error. If an object.& INTRODUCTION. The object to be weighed is placed upon the left scale-pan and a pointer is the weights upon the right pan. a If the correct weight gentle draft of air upon one of the pans. and the length of the lever-arm is the perpendicular distance from the axis of revolution (the fulcrum) to the line of action of the force. in the right balance-pan. any inequality it is necessary in the lengths of the arms. when the equilibrium is established. If now the object Q is placed on the right-hand balance-pan and the balance again brought to the state of equilibrium by placing weights upon the left-hand balance-pan. may change during the course of the day. first In order that accurate weighings to make them independent of may be obtained. It is to be noted that usually when the zero-point of the balance (i. 2) is to be ascertained. For convenience in determining the position of the balance. moment is understood the product statical of the force into the length of the lever-arm. the pointer will swing to the same number of scale divisions to the right of the zero that it does to the left. by producing. has been added. In the case of a lever. rests at the zero of a scale on an ivory plate below. fastened to the beam which. which so is with nothing in either scale-pan) coincides with the zero of the scale. which can readily be done. in this case the weights . The cause of the displacement of the zero-point is that the condition for the accuracy of a balance is not fulfilled. the point of the scale at which the pointer rests when the balance is in equilibrium provided that does it scale-pan. when there is nothing in either not the case.e.

For 2. how- (2) I' FIG. sand. established We have. Since. method the object to be weighed (Q) is counterbalanced (tared) by means of shot. The same end obtained by Borda's method of substitution. .. equilibrium has been reached. but to ever. as a result of the first weighing. we obtain by taking the geometric practical purposes. then. etc.. tnerefore. we have will P l gins.WEIGHING. mean of the two values. the object Q is then removed and equilibrium with the tare is again is According to this by placing weights upon the scale-pan. it is accurate to take the arithmetical mean. in which case sufficiently the true weight of the object would be: This method of obtaining the true weight independent of the lengths of the balance-arms is known as that of double weighing. 9 not as a rule amount to P gms. 2. however. If equation 1 is multiplied by equation The true weight is obtained. weights.

3. of the jar in shutting . In order to give the same algebraic sign to all the observed readings it is best to number the divisions on the scale from left to right from to 20 so that the zero-point in case both balance-arms were of equal length would be numbered 10.INTRODUCTION. For this purpose the object placed in the left-hand balance-pan. or extreme positions. method used chiefly in weighing large objects. etc. and recording the turning-points. observing I' FIG. of the pointer on the scale of an uneven number of swings (say five*) and taking the mean of the readings. and by placing weights in the right-hand pan equilibrium is established as nearly as possible is * The first two swings are inaccurate on account the balance-door. For ordinary analytical work the weighing is made by the method of swings. First of all the zero-point of the balance is determined by setting latter is the balance in motion (without any load in either pan). 10 and from the second weighing.. Pl-Tlt from which The it follows. so that they are disregarded. The next thing to be determined is the sensitiveness of the balance for the object to be weighed.

. consequently 19.32 9. therefore 2.WEIGHING.80 = 2.80.52:1 = The 42 = 0. it follows that the object was lighter than the weights in the right-hand pan. then 0.2 in air is mgm.22. and in fact the excess of weights in the pan was sufficient to move the point of rest 10. then the sensitive(i.722 gms.point to gives lie at 10. is added.723 gms.80 = 0. the first point of rest.42 divisions on the scale. In making a weighing one should always accustom himself to note the observations methodically.42: x = 0.32.) ness of the balance will amount to 12.42 of the scale divisions correspond to the weight which must be subtracted from 19.52 of the scale divisions correspond to 1 mgm.17 mgm. was 9. This amount can be calculated from the determination of the sensitive- As the zero-point of the balance ness of the balance as follows: Since 2.7228 * gms. difference (d) between this and the previous point of rest sensitiveness of the balance. in order to obtain the true weight. 1 1 and the point of rest of the pointer on the scale is determined as above. to be at 9.e.22 and the point of rest with a load of 19. the fourth decimal place is increased one... An additional weight of 1 mgm. and the point of rest with a load of 1 mgm. * than As most ^o analytical balances will scarcely detect with certainty less If the is expressed only to the fourth decimal.723 The gms.723 .723 gms. obtained with a load of 19. number in the . true weight of the body or about 0..52 scale divisions.80. mgm. was at 10. the weight fifth decimal place in a calculation amounts to six or more. less to lie at 12.0. or removed if the object was too light before. and the point of rest is again deter*mined.22 9. the Assuming the zero.0002 = 19.. as follows: Assume that a platinum crucible is to be weighed. with a load of 19.

INTRODUCTION. 12 Zero-point. .

in vacuo will be balanced by p gms. and (l-* \ 1 s On and account of the small values of the fractions s sufficient that it accuracy is . weights. it The specific gravity of brass is 8. as in vessels. substance in vacuo . pressure weighs 0. we atomic weight determinations. calibrations of should never be neglected.4. of air at 15 C. In such measuring cases the apparent weight must be reduced to vacuo as follows: 1 c.c. however. but the density of most analytical weights is . in the case of the most accurate work.. The body that weighs po gms.0012 gm. and 760 mm.* The specific gravity of the substance weight = s. The The The in the air. This error is so small that it can be disregarded placement in ordinary analyses.0. the following table of may be used Kohlrausch * Brass has nearer 8. to made in the air with brass are constantly introducing an error due to the disof air. s obtained by simplifying the expression so becomes Po= Instead of making the computation.= /.0 = s'. loss in loss in weight of the substance A is s weight of the brass weights total loss therefore. The weight of the is: pk Po* Po=P + L . . is -^ X s A gms.REDUCHON OF WEIGHING* TO YACUO./& J-t gms. etc. : a density of 8. Reduction of Weighing Since most of our we'ghings are 13 Vacuo.

s .INTRODUCTION. METHOD OF F. REDUCTION OF A WEIGHING MADE WITH BRASS WEIGHTS TO VACUO. KOHLRAUSCH.

* = (20+ 10+ 10'+ .1 gm. .g... 1 mgms. -See also T. 0.. . 0.... 0. Am. s_JE s__ =50 gm. a rider (weighing either 10 or 12 mgms. 10 gm. wt. W. (1900) XXII. pieces obtained by the method of double weighing are compared is with one another.-f-0..) (2) (20+ 10+ 10'+ Left from which 50 Right . + 0..000 mgms. 50 gm. 1' gm. 0.46 mgm.61 mgm...+ 0. Chem. but it is essential that the individual weights represent the corresponding relations to one another. "teitfaden der prakt. Richards. =50 gm.31 + 0.. : agaiijst 20+ 10+ KX+5+2+ 1+ 1'+ 1" found: Left Right (1) 50gm.TESTING OF WEIGHTS. 144. The weights may be tested in the following manner * : The assumption is first made that the sum of the larger weights the weights of the single = 100.. .46 mgm. .) or 50 gm. 2 gm. 2.. yet always be tested. 10' gm.... In most sets of weights the following are found: 50 gm.01 gm. =(20+10+10'+. + 0.. 1. and equal to 100 gms.05 gm.. 20 gm. ) -0.. Kohlrausch. 5 gm. mgm.. \VAuflage. Journ. and ance-arm usually smaller weights weighing 5. 34. p. 0. ) follows: it . now it is Although possible to buy nearly perfect weights.61 mgm. = (20+10+10'+. 1 gm. and it is e. 1" gm. .1' gm. 0.02 gm..01' gm. Soc. 0. Phys.2 gm... Testing of Weights. where the method used at Harvard is described. according as to whether the balis divided into 10 or 12 equal parts between the fulcrum and the point of suspension of the right-hand balance-pan). weight weighs exactly 50 gins.31mgm.. 1. 0. gm. their accuracy should For almost all analytical purposes it matters not whether the 50 gm.5 gm.

4 The sum JA + B+2C+D 5S should equal 0..) 10XlO + A+25+4C. and D may be either positive or negative. !6 The other weights are compared in the same way. obtaining.-5S + = 50 gm.. weight is now compared with the 2+l+l / +l" in exactly the same way. + Amgm.-2S + B + C gm. then = 100 gms.-S =10 gm. which serves as a test for the accuracy of the observations. The sum of the weights to equal 100 gms.-S + D 10' 20 = 20 50 = 50 gm. then we obtain 10-10 gm.+ 2Z>=(50+20 + 10 + If .INTRODUCTION. weight let was assumed . The 5 gm. and . weight. . 50gm.. of the preceding equations A+2B+4C+2D -- c A+2B+4C + S= 10 2D . Ogm. +6 +c same denomination so that they . = (20+10+10'+.)= .) expressed in terms of the 10 gm. each weight is (50+20+10+10'+. for example.B. itself: 10=10- we . +B " +C +D " 10+10' 10 10 * " m which A.C.-S + C 5+2 + l + l' + l"=10 gm. and with the help the 10 gm.+J. with the result that 2 = 1+1' l' * It may be is well to mark =l the weights of the distinguished from one another. " 20 10' = = " (5+2+1+.

000 -S+Z) and 1 = 1000.TESTING OF WEIGHTS.-S 10'=10g. + *A = 20g.o + 26+ 4c+ 2d+ S-D 10 If we let s 10 l l' .-2S + + C 10 =10g. we obtaio = 1000-s = 1000-s+c 2=2000-2s+6+c 5 = 5000-5s+a+6+2c+d In the same way the smaller weights are tested until finally is obtained.1+0. According to the preceding work 5+2+1+1'+!" = 10.-5 + C 50 20 2 + 0. = 50 g. the following correction table TABLE FOR CORRECTIOX OF WEIGHTS.1' .000-3+ Z> consequently 10Xl+a+26+4c+ 2d= 10.

Ostwald. and the greater the excess of the wash water the greater the amount of the precipitate dissolved. raising the mechanical supports so that the beam no longer rests its knife-edges.1 INTRODUCTION.. p. and Washing Filtration How upon of Precipitates. but it is not make difficult to the amount of the dissolved substance When remaining so small as to be negligible. 8 be touched with the -fingers. Amorphous. Die . we consider the precipitate to be completely washed. little absolutely insoluble. 19.e.) is the solution to drain more washing than others varies.. precipitates require due to the fact that the degree of adsorption wissenschaftl. it may out can be no longer detected in the last filtrate. The aim should be not only but to accomplish No precipitate this is with as to remove all of the soluble matter. wash water as possible.* rule. It is clear. however. and nothing should be placed on or removed from the balance-pans without arresting the balance.c. dissolve:! substance remaining on the filter is the amount of so small that it could not be detected by our balance.. and how many times should the large should the filter be precipitate be washed? With regard to the latter question it is evident that the prewashed until the soluble matter is completely be should cipitate removed. so that it is clear that every unnecessary excess of wash water causes harm by removing a fraction of the precipitate. Grundl. In case the must be used for another determination. The amount of wash water to be used depends largely upon the nature of the precipitate itself. gelatinous precipitates always require As a more washing than crystalline. but should The weights should never always be lifted by means of the pincers provided with each set. When should the filtrate' be tested? Let us assume the filtrate * filter The reason why some to hold 10 c. Chem. i. that this point will never be reached because a part of the solution always remains on the filter. (Cf. granular be said that the process of washing must be continued until the substance which is being washed ones. der analyt. it is obvious that the filtrate should not be tested too soon.

Often the washing will be found to have been complete after the fourth washing. of this substance.M/10-(1/10) gm.1/10 2d 3d c. therefore.1 gm.c.1 gm. O. Consequently.1/10. remains There remains after the the 1st 0. until not more than 5/100 mgm. According to the assumption that there was originally 0. the filtrate should be tested qualitatively for the substance to be removed only after the precipitate has been washed four times. gm.1. 2 (l/10)n-lgm.1-9/10. and in many cases it will be found necessary to repeat the operation for from .1.9/10- nth 1st washing. " 0. but as a rule this will not be the case. we have consequently: Removed by nth " " drain off and 1 c. In case n = 4.9/10. After washing n times. " 2d 0.1/10- (1/10).c.1 gm. According to our assumption.1/10 gm.09999 gm. 0. " 2 3d 0. therefore. " 0. the sum of the series is 10 After washing the precipitate four times.c.00001 gm. 0.1-1/10 gm. there remains in the precipitate only 0. or in other words a negligible amount.1-9/10 gm. washing 0. of the solid substance which is to be removed by washto the last drop ing.1-9/10 and the constant factor is 1/10.1. of the impurity has been removed.1. the amount of the solution held back by the precipitate and filter to be 1 c. 19 from the paper.W'ASHING FILTRATION AND OF PRECIPITATES. the amount removed by washing is the sum of the decreasing geometric series of which the first term is 0. of the substance to be removed by washing remains.(l/10) gm. The filter is filled to the upper edge with wash water and allowed to drain to the last drop n times. and to contain 0. 9 behind..

4. 4. 20 In the processes which are described twenty times. be stated how far to carry the washing. b. how should a precipitate be washed with the least possible amount of wash water? According to the above consideration it is necessary to wash every precipitate at least four times. in which case the filter should be entirely filled each time. 4. and even in this case the filter should not be so completely filled as in Fig.INTRODUCTION. in one of the inexcusable ana- . It is better to have the Fig. FIG. edge of the paper. about 5 mm. about as much as room is left for the is shown wash water. and it is evident that the size of the filterpaper will influence the amount of wash water used. filter filled in order that sufficient The use of too large filters is lytical errors. Now with regard to the second point. The precipitate should never reach the upper of the precipitate and not tered. ten it to will usually The size of the filter used should be regulated entirely by the amount at all by the amount of the liquid to be filThe mistake should not be made. of using too small a filter. should be made as small as possible. a. should remain free. The filter. irrespective as to whether there is little or much liquid to filter. however. therefore.

tear off the superfluous paper. In order to accomplish is either weighed cipitate * Wet by this. left) and the dry precipitate is carefully shaken into the crucible. in the case of precipitates of reduced by the burning paper. weight. cm.g. (Fig. stretch it over the ground top of the funnel. Quant. Chem. 6. in which the precipitate is separated from the the filter burnt by itself. This method. etc. is used in those cases when the ignited substance will be e.* placed in a drying-closet (preferably one that is heated by steam) and dried at 100 C. the still always adhere to paper and these must be weighed. Before a precipitate can be weighed it must be absolutely dry.. . When per- this fectly dry. it is permissible to neglect the weight of the ash from the filter itself. 6). silver chloride. Fresenius. The cover thus formed continues to adhere after drying.THE DRYING AND BURNING OF PRECIPITATES. purpose the funnel containing the filter is carefully covered with a piece of filter-paper. lead sulphate. Those precipitates which do not undergo a change of weight on ignition are treated as follows: (a) THE PRECIPITATE IS IGNITED DRY. With an unknown paper it is necessary to determine tfye v/eight of the ash by a separate experiment and then correct t By chloric the weight of the precipitate obtained. a weighed crucible is placed upon a piece of glazed paper of about 20 sq. the ash added to the main part of the precipitate and the mixture then ignited to constant filter. bismuth oxide. itself and weighed with the filter is burnt and the ash obtained or mixed with the main part of the pre- it.f common cut filter. In order to perform this operation it is first necessary that the For filter and precipitate should be completely dried at 100 C. Any small particles of the precipitate which may have fallen into the crucible with the upon the glazed paper are brushed Small particles of the precipitate will aid of a feather (Fig. Analysis. removing it from the paper as completely as possible by gentle rubbing with a platinum spatula. The Drying and Igniting 21 of Precipitates. a and then gently using filter-paper which has been carefully washed with hydroand hydrofluoric acids.

the wire is supported (as indicated in Fig.) The ash is then added to the contents of the . the gas-flame is applied repeatedly until it is no longer possible to make the particles glow any more. beginning at 6.INTRODUCTION. so that the portion of from the precipitate is on the outside. and then it is further folded as indicated by ft and 7. 5 to a narrow strip. precipitate Bunsen as follows The filter is folded together so that posed by the precipitate occupies the position indicated in the shaded part of Fig. (Too strong ignition should be avoided. 5.of is still : Fig. The flame is at once taken away and the paper allowed to burn quietly. a. 22 The combustion of the filter. The paper is then rolled between the b FIG. 6. If carbonized particles still remain. fingers as indicated by d. to which small particles of the best accomplished by the method proadhere. cork in the opening of a porcelain plate and the filter is ignited by means of the gas-flame. 6) by means of a the filter which is free FIG. The roll is now enveloped with a previously ignited heavy platinum wire.

The only danger in this method is that in burning the filter the ash is heated too hot. the temperature being gradually increased until the temperature prescribed of ignition for the given precipThe flame itate is reached.THE DRYING AND BURNING OF PRECIPITATES. is at . filter cannot be burnt. lead sulphate. is still sufficient to protect the wire and prevent the reduced metal from coming in contact with it is not heated strongly enough to melt the metal. The placed on the crucible. is finally removed. however. The metal replaced. what reduced these metals are difficultly volatile. yielding an ash which. only of the anion (chlorine in the case of silver chloride and SO 4 in the case of lead sulphate). but not glowing. there will be no loss of the metal. which is heated at first with a smaU flame. In such cases the previously dried . or of sulphuric acid (in the case of lead sulphate) are added. but a definite temperature and weighed. . 7). however. If. although its weight is inappreciable. and while still warm. so that some of the reduced metal melts and alloys with the platinum wire. is placed in a desiccator (Fig. the allowed ble to cruci- cool some- what. it provided Many precipitates (Mg(XH )AsO4 K 2 PtCl 6 etc.) are changed much by this treatment that it would be impossible to obtain 4 so it. of nitric acid to dissolve it. After cooling (at least three quarters of an hour for porcelain crucibles and 20 minutes for platinum ones) the crucible and its contents are weighed. This loss may be readily moistened with a few drops a few drops of hydrochloric acid (in in the crucible is the case of a silver chloride precipitate). and after evaporating off the excess of the acid the crucible is weighed. Many precipitates (silver chloride. there is always some paper free from precipitate between the precipitate and the platinum wire. the filter-paper is rolled up as was directed. crucible cover is by gentle shaking and the final use of the feather. correct results.) are someto metal by the above treatment. As. etc.

9. The heating and weighing is repeated once more in exactly the same way until two consecutive weighings do not differ by more than 0. By In order to dry the filter. The upper plate has two holes bored in it through which thermometer and thermo-regulator are placed. and the latter in a desiccator filled with calcium chloride (Fig. The bottom plate rests upon a heavy iron wire so that it does not come directly in contact with the bottom of the closet. 7). 8a) upon a watch-glass and near an open weighing beaker. 24 afterwards the precipitate and temperature and weighed filter same are again dried at the again. 8a is fitted with six removable porcewhich prevent any oxide falling from the metallic closet walls lain plates upon the substance to be dried. it is possible to clean them without The only part of the apparatus that wears out is the bottom. and this is fastened by placing an asbestos ring between aa P K A and K. crucible. page 25) of a cru- The crucible is after drying at then the precipitate which is again dried and temperature. provided the pre- filtered is weighed. tion These require and can be regulated to almost any desired temperature. difficulty. 86) and of the upper through the opening closet wall. Several forms of electric ovens are also in use. rendering it impure. It is then covered. removed from the desiccator. little atten- . with the help of the thermo-regulator T for \ to 1 hour. * placed in a drying-closet (Fig. weighed a Fig. it is '. The precipitate is now collected upon the filter and after drying the filter in the funnel at 100 C. asbestos filter. As the plates can be easily taken out. The same plished result by the use This consists cible with with an scribed into is much more simply and of the (as is shown in perforated bottom.INTRODUCTION. allowed to stand in the air near the balance for 20 minutes and. so that it is best to have the closet so that it may be renewed from time to time without taking the apparatus to pieces.0002-3 gm. This upper plate is fastened to the top of the closet as follows: A glass rod provided with a broad rim rr and bulging out at aa is pushed up of the porcelain plate (Fig. the accurately accom- Gooch Crucible. the temperature is brought to the desired point and kept there. then weighed. means of tongs the filter is quickly placed in the weighing beaker. the filter and its contents are removed from the funnel and dried in exactly the same way as before. where it is kept for exactly 1 hour. off The * The drying-closet shown in Fig.

a 25 .THE DRYING AND BURNING OF PRECIPITATES. FIG.

The liquid crucible is is now dried at the and afterwards * Too great a suction should not be employed during the filtration. After drying. long-fibred.INTRODUCTION. The mass is collected in a funnel with a platinum cone. Preparation of Asbestos Filters. funnel. and them the order in to see poured into a small beaker. For the preparation of a Gooch filter. (Fig. Water must now be passed through the crucible until no asbestos fibres run through. the asbestos may be ignited. stretched over a funnel is 10) and the crucible T is placed in the opening. 10. for proper temperature . soft asbestos is cut into pieces J cm.* but in many cases it filters more rapidly than paper without it. is poured produce a placed upon is and some more into poured is without thickness. long. this layer the of sides the layer of 1 to 2 crucible rubber the by the touching the that so enough suspended of the emul- the crucible. 9. use of these crucibles permits such accurate and rapid work that worth while to describe the method of using them more in it is detail. Usually such a filter is prepared and used with a gentle suction. but for most purposes this is not only unnecessary but disadvantageous. digested with concentrated hydrochloric acid upon the Some and water bath for an hour. a small flock of tlie material a that emulsion thin a is A piece of thin rubber tubing formed. A good sample of asbestos will then be separated into very small fibres. and washed with water. or upon a filter-plate. shaken with water in is so flask. The funnel should be la~g? Enough of through the emulsion sion is to crucible mm. a small P) filter-plate (Fig. FIG.

If it is desired to ignite a precipitate contained in a Gooch crucible. asbestos filter. Soc. Chem. Chem. O. 456. the upper part can be carefully removed and the crucible again used.* in which the filtering medium a modification of consists of a porous spongy platinum. The last reference gives a table of suitable solvents for removing ignited *C. as soon as this has reached a certain tension the air is forced between the rubber and the sides of the crucible. the possibility of employing too much suction is avoided. By having the crucible suspended free by the rubber. Gooch crucible which permits rapid and accurate work. . 101. Swett. 11) within a larger porcelain crucible and heated at first gently and finally more strongly. For many purposes it is prefer- able to use instead of the Gooch crucible a glass tube with an. precipitates from the Munroe crucible. Munroe. and when necessary it can even be heated over the blast-lamp. comes too crucible can be used for a large number of determinathe amount of the precipitate in the crucible be- large. ibid. The felt is prepared by igniting a carefully-dried layer of ammonium felt of is the chloroplatinate. weight I fibres is run through) and the crucible is again dried and weighed. for. which has been poured over the bottom' of a platinum Gooch crucible in the form of an alcoholic sludge while in that case the precipitate or even the asbestos itself will be so compressed that the nitration will be prolonged and the washing made more difficult. 2.THE DRYING AND BURNING OF PRECIPITATES. D W. so that we have the effect of a safety-valve to a certain extent. filtration. Am. also 928. the crucible is ready for the after which. E. if the weight is constant. The so-called Munroe crucible. This is particularly desirable when it is neces- sary to heat the precipitate in a gas-stream. it is placed (as shown in Fig.. Chem. News.. 241. 31. when about half a liter of water is once more through the crucible (in order to be sure that no asbestos weighed. Snelling. 58. The same When tions. See J. J. and O. 27 The drying and weighing is repeated until a constant obtained. Anal. 31.

the crucible slowly lowered into a moderfelt ately concentrated solution of alcohol. (6) THE PRECIPITATE IS undergo change on coming IGNITED WET. Fig. 12. especially in the case of FIG. Those precipitates which do not suffer any permanent change by the action of the products of combustion of the filter may be The precipitate is allowed to drain as much as possible and while still moist the filter and precipitate are placed in a platinum crucible. is igniting the crucible and its washed with very convenient for contents. the felt should be saturated again with chloroplatinic acid. those precipitates which are likely to in contact with a reducing flame. the paper being pressed down against the ignited wet. . 12. The use of an ammonium chloride.INTRODUCTION. The can be shaped to the crucible during the ignition and subsequently burnished lightly with a glass rod of suitable form. dried and ignited. electric furnace. 28 the crucible held against several layers of is filter paper. In case imperfections develop.

13. so that a hot crucible should never be placed in contact with iron wire. the filter. and finally burns it.* with the cover inclined against the upper edge of the crucible and resting on the triangle. 13. flame is * In Fig. . after which it can be heated over the blast-lamp if necessary. the outer triangle is heavy iron wire. but platinum alloys with iron. carbonizes. then scorches. the inner triangle is platinum wire. 29 The crucible is placed in an inclined position triangle (Fig. which quickly dries sides of the crucible. Triangles of fused silica or of nickel-chromium alloy are suitable. 13). upon a FIG. The then slowly moved backwards under the crucible until finally the crucible is subjected to the whole heat of the burner. The flame of the burner is directed against the cover.THE DRYING AND BURNING OF PRECIPITATES.

15. the hood is directly connected with the chimney it often happens that on a windy day a considerable amount of dust falls into the hood. FIG.INTRODUCTION.means of a porcewith hard rubber) which lain fork fastened to the iron rod (covered is attached to the water-bath. as shown in Fig. order to prevent anything from falling into the evaporating-dish it is well to cover it with an evaporation-funnel. In case the laboratory is provided with a glass -covered hood with a good draft the use of the funnel is unnecessary. suspended above the dish by. however. . The funnel is FIG. 14. If. 14. In Liquids are usually evaporated upon the water-bath. THE EVAPORATION OFLIQUIDS.

16a). of a truncated brass cone turned back at the base (Fig. sand. often causing a slight loss of the substance. in which there is a small gas-flame (not shown into the the illustration). platinum-brass cone. use is made FIG. 16). furthermore there is often "bumpDuring evaporation of " " creeping .THE EVAPORATION OF LIQUIDS. FIG. 16a. aa. tbove the inner edge of the lower glass plate. dust. Fig. 15. porcelain rings should be used. The hood is provided with a glass roof. many substances have the property over the edge of the crucible or dish. and about 15 cm. in diameter and about 5 cm. in In the evaporation of* liquids crucibles or dishes. about 15 cm. etc. the crucible placed within the cone (Fig. In case the crucible is smaller than the ring.. 31 In order to prevent this. Any. leading directly chimney K. Between the two plates there proit clay pipe R. the falls on the water-bath in weighed platinum should not come in platinum contact with copper or glass rings. below there is a second glass plate bb which does not quite touch the inner wall of the hood but is about 3 cm. and lined with thin platinum foil. 16. none c$n get into the hood. Water-bath with porcelain ring. from the chimney upon the plate bb . This is suspended in the ring and. As a rule. and crucible. the author has made use of the following contrivance which has worked very satisfactorily for some years. away from it 'iroughout its whole length.

17. The first two windings of the metallic spiral come into close con- tact with the sides of the crucible above the liquid. at the most not more than two-thirds liquid. the determination of boric acid according to the method of Gooch). Both of these phenomena can be readily prevented as follows: The crucible. the crucible is either heated cautiously over the free flame (continually moving it back and forth) or else the crucible prepared in some such way is placed in an air-bath. . etc. When steam is through passed upper part warmed of the the the spiral crucible is so that there is no and furthermore by spattering. ing. while the remaining windings should not touch the crucible. 18. In this way it is all is FIG. 6=asbestos plate. the whole of the evaporation "creeping" of the substance avoided. a = asbestos ring. . possible to evaporate off alcohol rapidly without boiling the liquid. the keeping upper edge hot during first.INTRODUCTION. In case it is desired to evaporate high-boiling liquids.. FIG. such as sulphuric acid. 18. which can be as is represented by Fig. with 17). \." so that in some cases the entire contents are thrown out of the crucible (cf. is placed in the cylindrical tin or brass spiral filled kk (Fig. amyl alcohol.

The substance contained in a small "boat" is placed in a glass tube and the latter in one of the copper tubes. An oil-bath provided with a number of copper tubes (Fig. In case it is desired to evaporate off a liquid in a flask and to . 19. Substances may be dried at a high temperature in a current of number of different ways. In order to heat a crucible in a current of carbon dioxide. Dry carbon doxide is conducted through the stem of the pipe. FIG. 20).DRYING SUBSTANCES IN CURRENTS OF GASES. B=tube wittt thermometer for measuring the temperature of the gas-stream. it). and the oven can be heated to any is desired temperature. The crucible K placed in the glass pipe R and the pipe and copper cylinder are covered with watch-glasses. 19) may be used. use can be made of Paul's drying oven (Fig. The gas is now air or of carbonic acid in a passed through one or more of the empty tubes (so as to warm and then through the tube containing the substance. 33 Drying Substances in Currents of Gases.

INTRODUCTION. The solution is placed in the open Erlenmeyer flask evaporated as far as possible over the free flame. 20. 34 ignite the residue at a given somewhat temperature it is necessary to proceed as follows: FIG. FIG. The K and flask is . 216. 21a. ft b FIG.

Ten or fifteen grams of the commercial salt are dissolved in the least possible amount of hot water (it is best to use not quite . For our work we are concerned chiefly with scientific analyses and the first substances to be analyzed are easily crystallized from water. 35 then placed in a metal beaker suspended in an oil-bath (Fig. but must be analyzed air-dry. very difficult to give general rules for the preparation of substances for analysis. Fig. the purity of a commercial sample should never be taken for granted. one in which it in different cases. however. 216 shows the separate parts of the apparatus. Although is it is sounds so simple this it is often one of the most difficult conditions Many substances are hygroscopic and absorb moisture from the air. Many commercial salts are prepared extremely pure and could be analyzed directly. the purpose being to determine the cost or selling price of an article or to control its manufacture. PREPARATION OF THE SUBSTANCE FOR ANALYSIS. Many substances containing water of crystallization cannot even be dried in a desiccator. ride. we obtain them after they have stood for some time in the air and after they have been handled somewhat. provided the substance itself undergoes no change by this treatment. The substance should be purified by Recrystallization. In such a case the sample should represent as far as possible the average composition of the product. which can be removed by heating the substance or by simply allowing it to stand in a desiccator over calcium chlo- to fulfil. Consequently in case it is desired to test the accuracy of an analytical process. In all cases it is necessary to determine whether the substance to be analyzed possesses a constant weight.. 2 la). for it is necessary to proceed differently For a scientific analysis (i. in most cases.PREPARATION OF THE SUBSTANCE FOR ANALYSIS. It is desired to determine the atomic composition of a substance) necessary to choose pure material for the analysis. and dry air is sucked through the spiral copper tube kk as shown in the illustration.e. so that they are not so pure as when freshly prepared. the substance must be analyzed as it is. For technical analyses.

placed upon a dry glass plate. 22. as they usually contain more enclosed mother-liquor than do the smaller crystals. 36 enough water to completely dissolve the substance) and the hot solution is rapidly poured through a plaited filter contained in a This funnel the stem of which has been broken off (Fig. by filtered off qualitatively by means of some suitable reaction. the same process of recrystallization must be repeated until the presence of no impurity can be detected.INTRODUCTION. In case it is not quite pure. . of a crystalline powder. covered with another sheet of the same and allowed to stand for twelve hours at the ordinary temperature. serves to remove all dust or other insoluble impurity.* the which is by pouring through a funnel provided with a perforated cone. By means of the rapid salt is obtained in the form cooling and constant stirring. by placing the dish in a larger one containing cold FIG. The filtrate is received with constant stirring in an evaporating-dish and is rapidly cooled water. covered with another watch-glass and allowed to stand for several hours more. but they are not desirable. One or two grams of the substance are then weighed upon a tared watch-glass. If the substance shows no change in weight it is ready for still * Large crystals would be obtained by allowing the solution to cool slowly. 22). The pure but still moist substance is placed upon a layer of several thicknesses of clean filter-paper. The mother-liquor is removed as much as possible platinum of means The purity of the substance is then tested suction.

37 Otherwise it must be dried in the air until it no longer analysis. Deliquescent substances not be allowed to remain exposed to the air for be quickly dried upon a porous very long. .PREPARATION OF THE SUBSTANCE FOR ANALYSIS. Such substances must as as soon possible to a flask provided with a plate and transferred Further rules for the preparaclosely fitting ground-glass stopper. shows a change in weight. It is not permissible to dry the substance in a desiccator except in those cases in which the substance not lose water of crystallization. will of course should tion of the substance for analysis will be given under the special cases.

the phosphoric acid may bo precipitated as basic ferric phosphate Ed. SODIUM.S0 i. finally. 38 . POTASSIUM. LITHIUM. may chloride (see silicate analysis). if it is present as chromate the may be reduced to chromic ions by evaporation with hydrochloric acid and alcohol and then precipitated by ammonia p. First of all the solution bath * in a Under platinum dish (or is if most cases evaporated to dryness on the waternecessary a thin porcelain dish this lu:uling will may be given in every case the symbols of the compounds suitable for the determination of the element in question. POTASSIUM. Forms:* KC1. The Determination as THIS compound when 4 . . METALS OF GROUP V. AND MAGNESIUM Chloride. if it is present as the phosphate. K. K. In almost all of these cases it is a question of separating the potassium chloride from the aqueous solution and in of separating it from ammonium chloride as well. II).PtCl 6 and KC104 . GRAVIMETRIC DETERMINATION OF THE METALS (CATIONS). CrO 4 ions and filtered off. or in case the salt to be analyzed be changed to the chloride by evaporation with hydrochloric it is the potassium is present in the form of its sulpha to it be transformed to the chloride by precipitation with barium If acid. K. or. may Wt. is 39. GRAVIMETRIC ANALYSIS. I.10. A. AMMONIUM. At.PART I. 328. (Vol. chosen for the determination of potassium already present as such.

any ammonium chloride upon a platinum it is removed by careful heating. taking the precaution of stirring the liquid frequently with a heavy platinum wire. . this is effected by cover- ing the dish with a watch-glass and drying in the hot closet for The covered dish is then placed an hour or two at 130. in order to hasten the evaporation of the In spite of long-continued heating and conenclosed water. ble. again covered and allowed to remain in the drying-closet for one to two hours at 130-150 C.50 C.1. the same. as soon as the salt begins parate out. triangle and cautiously heated over a free in the hand and imparting to it a fanning burner the flame. it is to be always understood that a constant weight is to be obtained. 39 be substituted). tinual stirring. when the crucible is allowed to cool in a desiccator and is weighed. the contents of the crucible evaporated to dryness on the water-bath. and it is then placed upon another clean watch-glass. the salt in the dish is brought into solution by rotating this water in the dish and the almost ever-present carbon particles (from the carbonization of pyridine bases usually present to a slight extent in the ammonia and ammonium chloride) are filtered off through a small filter into a weighed platinum cruci- A few drops of HC1 are added.DETERMINATION OF POTASSIUM AS CHLORIDE. After this the crucible is again heated for a few moments over the free flame so that the bottom of the crucible becomes a dark red (the cover of the crucible must not be lifted during this and The procis again weighed. operation) Is obtained. however. it is Therefore. it is not possible to completely expel all of the water enclosed within the crystals. and once more heated over the free flame until all decrepitation has ceased. The dish is kept covered as long as a decrepitating sound can be heard. care being taken not to heat the potassium chloride too strongly on account of its volatility. holding motion. The cover is then taken off. Any potassium chloride remaining on the cover is then washed into the dish by means of a little water. The dish is then heated again over the constantly moving flame until the vapors of ammonium chloride on cease to be given off. a constant until weight repeatod In the case of every analytical operation the heating and weighing must always be repeated until two consecutive weights are . allowed to cool. whenever the terms "heated" (or "ignited ") and "weighed" are used in this book.

Cr(OH) 3 separates out during the evaporation.c.00 of potassium in a gm. and p the weight of potassium chloride obtained. After the washing is found to be complete. covered with a watchis and warmed upon the water-bath until the solution becomes a pure emerald-green. (cf.10 p 74. and the residue of glass potassium chloride is weighed. little it . About 2 c. If. K. of concentrated HC1 and 200 c.56:39.c porcelain evaporating-dish. 40 This method is capable of yielding exact results.c. of the filtrate evaporated upon the cover of a platinum crucible leaves no residue. 33) in a current of dry air. the amount of potassium present in the potassium bichromate may be calculated as follows : KC1:K =p:s 74. of concentrated HC1 and 5 c. of alcohol. the filtrate is evaporated to dryness as previously described.c.GRAVIMETRIC ANALYSIS. on p. Any solution which may have spattered up on the cover-glass is washed into the dish by means of a stream of water from the wash-bottle and the solution is then evaporated to dryness. by The salt is therefore purified. as described recrystallizing three times from water. treated with 10 c. it must be redissolved in water and added to the rest of the filtrate.* the ammonium chloride expelled. heating on the waterbath with constant stirring and finally drying to constant weight in an oil-bath at 130 C.56 * Frequently a must be filtered off 'I** <*nt. placing the moist crystals in an evaporating-dish.c. 35.10 = p:s 39 10 = weight s=='p 74. placed in a 300-c. Example: Determination of Potassium in Potassium Bichromate. Commercial potassium bichromate usually contains potassium sulphate as impurity.c. however. on making this test a residue remains. of water are now added. If a is the amount of potassium bichromate taken. The dry substance then weighed upon a tared watch-glass. p. of bichromate and in percentage X= 100X39. and washed free from the solution. the liquid is heated to boiling and precipitated with the least possible excess of ammonia. filtered and washed with hot water until 1 c.

Since the sulphate of potassium is much less volatile than the chloride. About 200 * The 300-c.c. the form of the chloride. causing a lively evolution of SO 2 gas. as described into a 300-c.c. c. SO 2 begins to slacken. it is Example: Determination About 0. of of the purified when it is necessary to separate preferable to have the potassium in Potassium in Potassium Bichromate. accelerated When by the evolution of the gentle wanning. it is advisible to choose this method in case no other metal is On present. According to the above method results are obtained which are slightly lower than the theoIt is but this should not amount to more than 0. Determination of Potassium as Potassium Sulphate. saturated. of which the mean is taken as the true value. under c. porcelain evapora ting-dish. it can be . aqueous solution of sulphur 1. The dish is covered with a watch-glass and warmed on the water-bath until there is no further evolution of gas perceptible. or be readily changed to sulphate by evaporation with sulphuric acid. and concentrated sulphuric acid is a drop-funnel. 41 customary to cany out the analysis in duplicate and to be satisfied only when two closely agreeing results are obtained. treated with 20 of a freshly prepared.c. 2. This method chosen when the potassium is already present when it is in such a form that it can is in solution as the sulphate. when the cover-glass removed and the solution evaporated almost to dryness. of double-normal sulphuric acid.15 per and the two "check" determinations should not differ by more than 0. of water are now added and the chromium is precipitated from the boiling solution by means of the slightest possible excess of ammonia.c.5 gm. retical value. dioxide* and 5 c. it is most frequently used for determining the amount of potassium in combination with organic acids. potassium from sodium. be prepared as follows: Into a sodium bisulphite slowly added from of a saturated solution are placed.c. from one another.c.DETERMINATION OF POTASSIUM AS POTASSIUM SULPHATE. the other hand. The precipitate is filtered off and washed is rinsed off. which is kept cool by placing it in a larger vessel filled with cold water. 1 per cent. solution of sulphur dioxide Erlenmeyer flask about 150 may c. and dried salt is weighed. This gas is passed first into a small wash-bottle containing water and then into another flask of distilled water. cent.

as this proced- preferable to add a little of which the excess of sul- it is . is under it is comboth nitrate. Thick. 29). K. white fumes of sulphuric acid are soon evolved.20 = p:s 78.27: 78. the residue is dissolved in as little water as possible and transferred to a weighed platinum crucible. in a desiccator 2 the weight of substance taken and p the weight of the obtained. 42 until it can be pletely free shown by the from the solution.20 ~ p 17427 = per cent. is placed in a large platinum crucible. the process being repeated until a constant weight is obtained. A piece of ammonium carbonate the siz? of a pea is placed in the crucible (see below). which is again heated and weighed.20 x= and 100X78. ignition into K SO 2 4 with loss of ure involves a slight loss of potassium solid ammonium carbonate. finally heating it to a dull red until no more vapors are given of off. and then weighed. moistened with a little concentrated sulphuric acid. and heated over the free flame exactly as in the case of igniting a moist precipitate a weighed sample (p. containing potasevaporated in a platinum dish to dry- test applied 1 that The ness. After being evaporated on the water-bath to dryness the bottom of the crucible is heated by means of a free flame to dull redness The crucible is allowed to cool until SO 3 vapors cease to come off. In order to determine the amount of potassium in organic salts. by means SO S but . as soon as these begin to diminish in quantity the flame is gradually brought toward the base of the crucible.GRAVIMETRIC ANALYSIS.20 78. sium and ammonium salts. the ammonium sulphate is removed by gentle ignition (the salt melts and gases are evolved). placing the crucible in an inclined position and directing the flame against the cover of the crucible. then the percentage of potassium in the potassium a If K SO 4 is bichromate may be calculated as follows : K2 SO4 :K2 =p:s 174. KjSO^ and by stronger The mass remaining in the crucible now consists The latter compound can be converted 2 2 7 KSO .

weight of sodium chloride originThe sodium. is soluble. sodium chloride is insoluble in absolute alcohol. is converted into and can be driven 43 ammonium sulphate. A. It may be mentioned. the corresponding deducted from the weight of the combined chlorides. as otherwise the is K PtCl 2 6 obtained will be contaminated with sodium chloride and too high a value will be found for the amount of potassium present. then dissolved and the potassium precipitated out either as exception of From the weight of the prechloroplatinate or as perchlorate. the comThe mixture is bined weight of which being first ascertained.SEPARATION OF POTASSIUM FROM SODIUM. and the same precautions which were discussed under potassium hold in the case of sodium. phuric acid volatile 3. which is readily a much lower temperature. At. Separation of Potassium from Sodium. SODIUM. Wt. so that it absolutely necessary to convert both the potassium and the sodium to the form of their chloroplatinates. K PtCl 2 6 is K PtClg. In order to separate the sodium and potassium they should both be present as chlorides. first consider the determination of sodium itself and after- wards the separation of the two metals. On the other whereas the corresponding sodium salt hand. however.00. off at Determination of Potassium as K>PtCl 3 and as These determinations are only employed when it is KC1O 4. which value is this gives the ence. is determined by differally present. Na. is determined in the form of its chloride and of its sulphate. Separation of the Potassium as Principle. calculated. that NaCl and Na^SC^ are more difficultly fusible and much less volatile than the corresponding potassium compounds. Sodium. 23. therefore. solution should contain salts of no other metals with the The ammonium salts. 2 practically insoluble in absolute alcohol. therefore. Transformation of the Chlorides into Chloroplati- . Procedure: 1. like potassium. will. amount of potassium chloride can be cipitate. necessary We to effect a separation of potassium from sodium.

Pt. p. . The the precipitate which still adheres to it (and likewise any precipitate adhering to the dish in which the original precipitation took place) is dissolved off weighed platinum dish or * by means of a little hot water into a The precipitate is evaporated crucible. 1893. and the precipitate is dried in the hot closet at greater part of the precipitate is then placed a clean watch-glass.GRAVIMETRIC ANALYSIS. and pletely drain 80-90C. the filter is replaced in the funnel. and from this the sodium of chloroplatinic acid necessary to convert the chloride into chloroplatinate can be calculated : 2NaCl:Pt=p:z x= <P Pt = weight Since our reagent (Vol. is repeated until the alcohol up into a fine spatula. ==C C ' ' H PtC1 2 e we have re(luired - solution of the two chlorides in water (contained in a platinum or porcelain evaporating-dish) is treated with a few The tenths more than the calculated number of cubic centimeters of H2 PtCl6 and is then evaporated almost to dryness on the water-bath at as low a temperature as possible (the water should not boil). After cooling. Pt of in H PtCl 2 6 required. upon off. Dupre". the residue is treated with a few c. 236) contains 10 per cent. etc. 44 nates. of absolute alcohol (best methyl alcohol *) after which the solid mass is broken . Inaugural Dissertation. The assumption made rides consisted entirely of p amount is that the weight of the two chlochloride. and the treatment of the residue with alcohol together with the breaking up into powder.c.. powder by means of a stirring-rod or a platinum then decanted through a filter moistened with alcohol. The liquid is runs through the filter completely colorless and the salt remaining assumes a pure. gold-yellow color without any orange-colored partiThe precipitate is then cles being present (Na2 PtCl6 + 6H 2 0) carefully transferred to the filter. the alcohol is allowed to com* . Halle. I.

The calculation of the amount of potassium chloride corresponding to the weight of the precipitate is performed as follows: The weight p of the potassium chloroplatinate is multiplied by this and 0.3056 gives at once the weight of the potassium chloride. H off and a mixture of platinum and potassium chloride will remain behind. anal. Ind.. that correct results are obtained calculations. Modification of Chloroplatinate Method. Halle. perhaps according to the following equation: H 2 PtCl 6 + H 2 O^HC1 + H 2PtCl 5 OH. p. It is dried at 160 C. 799.he chloroplatinic acid is decomposed slightly on evaporation. Bestimmung der Kali urns 1888. 1. "Die als Kali umplatinchlorid. Dupre. Z. and weighed.3056 is used instead of the true factor (0. J. Chem.. Chem. chlorine. and Ber. If (p gm. 6.. Remark. 412. .* more besides a little and in fact." Inaugural Dissert.3056 is used in the relative amounts. Fresenius. oxygen hydrogen. Dittmar and McArthur. but fortunately if the work is always done in the same way these compounds are always formed in the same Innumerable determinations have shown if the factor 0. Also W. when HC1 and O will be given 2 . The coefficient 0.3068). 234.SODIUM: MODIFICATION OF THE CHLOROPLATINATE METHOD. K Instead of weighing the PtCl 6 the dry precipitate may be 2 heated in a stream of hydrogen. and to it is now added the precipitate from the watch-glass. By this hydrolysis a mixture of the potassium salts (K2 PtCl 6 + KHPtCl 5 OH) is obtained. We must assume that . Soc.) made the amount of hydrochloric acid evolved is determined this the calculation of the potassium chloride and from according to the following equation. K PtCl + 4H = 4HC1+ Pt + 2KC1 2 6 4HCl:2KCl=p:s KC1 *Cf. 1893. because the potassium chloroplatinate precipitate It condoes not exactly correspond to the formula 2 PtCl 6 . 1882. 45 to dryness on the water-bath at as low a temperature as possible.. K which are not given off as water at a temperature of 160 C. Ref. tains. Also F.

while the amount of potassium chloride found in the aqueous solution corresponds to the amount of potassium chloride originally present. Inasmuch as the precipitate of potassium chloroplatinate possesses a constant composition it is possible to determine experi- mentally by working with pure materials the exact ratio which exists between (a) the amount of hydrochloric acid evolved. 3. then the amount of potassium chloride calculated from the weight p of the platinum Pi:2KCl=p:x 2KC1 ~' again gives a result which is too low.) and the amount calculated according to the equation in the dish chloride is of potassium (Pt+2KCl):2KCl=p:a? 2KC1 ~Pt+2KCl' P too low a result will be obtained. the weight of is the potassium chloride which goes into solution (by evaporating the solution and weighing the residue) is determined. (c) the weight of platinum remaining undissolved water and the amount of potassium chloride originally present. If the mixture of platinum and potassium chloride remaining is weighed (p gm. According to Dupre. the weight of the platinum remaining undissolved and. on the one hand. (6) the mixture of potassium chloride and of platinum remaining after the ignition.76142 the true amount of potassium chloride will be obtained. if the amount of platinum determined according to 3 is multiplied by the factor 0.GRAVIMETRIC ANALYSIS. Finally. 45 the result will be too low because less HC1 is evolved than corre- sponds to the above equation. 2. on the other hand. if the mixture of platinum and potassium chloride treated with water and. after treatment of the residue with .

and through an opening in the cover hydroilluminating-gas) f is passed and the crucible is heated.* This method does not require that the sodium and potassium be present as chlorides. each time crushing the mass with the rod. If considerable sodium or potassium is present. . * Z. p. cf. is removed by washing six times with ether. Then the supernatant liquid is poured through a platinum Gooch crucible and the precipitate washed by decantation with alcohol.. anal. in the determination of copper as cuprous sulphide. The solution containing about 0. Somewhat more than Procedure. It depends upon the precipitation shall potassium chloroplatinate in the presence of ether-alcohol. and the solution evaporated on the water-bath until its volume does not appear to diminish perceptibly. stance is enough chloroplatinic acid to precipitate the potassium is added. The covered casserole is next allowed to stand for half an hour.MODIFICATION OF THE CHLOROPLATINATE METHOD.c. cheesy consistency but eventually becomes hard and crystalline. 1900. 47 As an example of the modified chloroplatinate method we have the Neubauer-Finkener Method. of water and carefully crushed with the end of a flattened stirring-rod.. the alcohol the latter crucible gen (or at first very gently. by volume) are added in portions of 10 c. washing out the soluble salts.PtCl 6 Xa 2 SO 4 etc. and weighing the residual platiof igniting . f As After five Chem. of subpoured into a large porcelain casserole and treated with a few drops of hydrochloric acid. of alcohol (93-96 per cent. an unnecessarily long heating is to be avoided. the mass toward the end assumes a soft. num. then at least 30 c. rubbing the precipitate from time to time. the rod. The is covered. 485. After cooling the mass is moistened with about 1 c.5 gm. to avoid losses by decreptitation. and by sucking air rapidly through the crucible.c. .c. After each addition of alcohol the crystals are forcibly crushed with As soon as the filtrate passes colorless through the filter the precipitate is transferred to the crucible with alcohol.) in 'hydrogen. 161. the precipitate (K.

anal. If hydrochloric acid were used instead of nitric acid in the above treatment. is filled vrith 5 per cent.. 45.4811. platinum from which the corresponding obtained by multiplying by 0. Dittmar and McArthur (Z. then allowed to It is cool. Chem. nitric acid (not HC1). the is K by using the factor 0. Chem. much magne- .GRAVIMETRIC ANA LYSIS.7614 holds in the case of chlorides.. and hot water is sucked through the crucible for fifteen times to remove the soluble salts comTo remove calcium sulphate.7612 must be used in the presence of sulphates.f or of 2 little fresh acid. The contents are next moistened with cold water. 767) state that the factor 0. and Dupre" found that the factor 0. % crucible should be placed the flame does not of the Gooch come upon a piece of platinum foil so that directly in contact with the perforation in the bottom crucible. Similarly. the platinum would subsequently run through the filter in * The a colloidal condition.7611 applies in the presence of sium. 28.7612. Z. t According to Neubauer the coefficient 0. 315 (1906). from time to time the crucible salts.* and this temperature is maintained for at least twenty minutes. anal. allowed to act for about half an hour. % Kling and Engels. or other difficultly soluble pletely. which is replacing with a dry and weigh amount of KC1 Then wash with hot water. 48 minutes the flame of the burner is turned a little higher so that the bottom of the crucible just shows a faint redness in the center.

potassium. calcium. as indicated in Fig. As the residue often contains small bell-jar. The precipitated salt is washed three times by decantation with 95 per cent alcohol.c. After standing five minutes 5 c. some sodium. amounts other chloroplatinates.c. transferred to the funnel. which has been concentrated as much as possible. magnesium. it should be purified as precipitate is allowed to dry in the air.c. and possibly calcium.DETERMINATION OF SMALL AMOUNTS OF POTASSIUM. dried by suction and then washed three times more with alcohol. The solution is evaporated to dryness on the water-bath if possible (or if sulphuric acid is present the last traces of the free acid are removed by means of the free flame). Hydrochloric acid gas is conducted into the solution.c. and the liquid is evaporated It is then treated with 20 c. for every decigram of the salt mixture 3 c. and sulphuric acid. The precipitate thus obtained contains all of the potassium in the presence of some sodium chloride and possibly sodium sulphate. 93 funnel provided with a platinum filtercone. of absolute alcohol. Determination of Small Amounts of Potassium in 49 the Pres- ence of Considerable Sodium. The solution may contain sodium. In the solution there remains all of the potassium. of ether are added. the precipitated sodium chloride is allowed to settle and the solution poured through a Fio. etc. follows : of The and the above operation is repeated. It is washed with a mixture of ether and alcohol until the liquid runs through . To every 100 c. of double-normal hydrochloric acid are added with more than enough chloroplatinic acid to precipitate all of the potassium. of water are now added. the mixture is allowed to stand half an hour under a and then filtered. it is dissolved in a little hot water.and magnesium in the form of their chlorides or sulphates. 23. and well stirred. a few drops of chloroplatinic acid are added. of the solution 2 c. and should not dip into the liquid).c. until it has become saturated with the gas (the lower end of the delivery-tube should be enlarged. to a paste. the residue is weighed.

The above method serves excellently for the estimation of small amounts of potassium in mineral waters. 2 The mixture ignited until the 2 6 thoroughly dried on the water-bath and gently mercury is all volatilized .c. gives the amount of potassium chloride.. anal. By means of this treatment the potassium chloroplatinate is completely decomposed with separation of platinum: K a PtCl + 4Hg = 2KC1+ 2Hg Cl + Pt 2 e 2 or K PtCl + 2Hg = 2KC1+ 2HgCl + Pt. in 20 c.7612. after weighing. its ash is added to the main portion of the platinum in the crucible which is now ignited.* constantly stirring with a glass rod. dried. and cautiously ignited. and weighed. Z. The filter is ignited in a platinum spiral. . ^This separation depends the Perchlorate upon the insolubility solubility of sodium perchlorate potassium perchlorate and the of in 97 per cent alcohol. The weight obtained p multiplied by 0. 233. at the decantation.GRAVIMETRIC ANALYSIS. and the residual solution aqueous metal is washed with hot water. Chem. until the liquid appears perfectly colorless. treated with 1J * Sonnstadt. 1891. gives the corresponding amount of potassium. the platinum is changed is same time to a denser form. The procedure is as follows The chlorides of the two metals : (sulphates must not be present on account of the insolubility of sodium sulphate in alcohol) are dissolved. 501.. and digested on the water-bath with a few drops of chemically pure mercury. f. S3 the filter completely colorless. the is decanted through a filter. angew. Schlossing-Wense. 36. Separation of Potassium from Sodium by Method. which can be readily washed by After cooling. and 1892.f Principle. Chem. of hot water. t Z. 691.3994. moistened with hot water. or multiplied by 0. the mass is treated with water. after which the precipitate is dried.

and. not to break the crystals of potassium perchlorate into too fine a powder as the up After allowlatter would readily pass through the asbestos filter. mean Chem.24. method. remove phosphoric From Preparation of Perchloric Acid According to Kreider.c.c. to added.04. alcohol to which 0. and the solution is evaporated with One c.11. alcohol containing no free perchloric acid will dissolve 0. the volatilization is replaced from time to time. Fitzenkam obtained in three experiments. but. in case this acid is present. .0158 g. * 100 c.c. it is removed by precipitation with barium chloiide. it is advisable to allow the potassium perchlorate to stand for some time with an excess of perchloric acid before treating it with alcohol.* It is important. KC1O whereas 4 100 c.13 per cent. removed by gentle warming The which a little perchloric acid has been added.c.gen begins This temperature is maintained until the to be evolved slowly.SEPARATION OF POTASSIUM FROM SODIUM. IX.c. anorg.2 per cent. of this alcohol dissolve about 5 mg.of 97 per cent. 342. 100. mass is treated with about 20 c. KC10 (W. of commercial sodium chlorate (NaClO 3 ) are placed in a round-bottomed flask and gradually heated until 0x3. the residue is washed again with the wash-alcohol. of stirring until fumes of perchloric acid are given off. 100.c. ture ing the precipitate to settle the alcohol is decanted off through a Gooch crucible. 4 T Using this J Z. in order to avoid the employment latter. dried at 130 C.f of c. washed with 50-75 of 97 per cent. 97. by weight of perchloric acid has been added and the mixoff. and weighed. It is not necessary to acid.% 100-300 gms. of the potassium chloride taken. the precipitate is transferred by mean^ a rubber "policeman" to a Gooch crucible. much times as of the perchlorate solution stirring to a syrupy consistency.. of hot water. and the excess residue is of the latter is dissolved in 10 the wash-alcohol of is an excess of the c. when tion a little is is vigorously stirred. 100. In case sulphuric acid was originally present. R. alcohol. The perchloric acid lost by After cooling.2 per cent. A little 51 and evaporated with is added and hot water the liquid evaporated with constant stirring until all of the hydrochloric acid is expelled and heavy fumes of perchloric acid are given more water is poured over the residue and the soluagain evaporated with stirring. however. Wense). 100.

Inasmuch as commercial sodium chlorate is often impure. and treated as previously described. In order to ascertain the approximate aiAount of . The distilled alcoholic solution. for For this purpose a small amount of the solution is potassium. hydrochloric tallize out. the melt is dissolved in water.2 gm. alcohol. and the process repeated until a little of the alcoholic solution ly no when evaporated to dryness leaves absolute- residue. the melt obtained by heating the sodium chlorate as above deis treated with HC1 and evaporated to dryness in order to scribed decompose any sodium chlorate remaining. 52 mass becomes solid (requiring 1^-2 hours). it is necessary to test the perchloric acid. with evaporated acid etc. of of sodium chloride) is poured in small amounts acids the presence and crucible the residue is washed once or twice a Gooch through in a tall beaker with of by decantation with concentrated hydrochloric acid.c. . NaClO 3 ) and filtered. After cooling. dissolves 0. is from a spacious flask untiJ the perchlorate begins to crys- when it is poured rapidly into an evaporating-dish. The residue is finely powdered and treated with 97 per cent.c. as it should be. of a potassium perchlorate solution prepared accordabove directions gave A residue of 0. and the evaporated to dryness (the liquid being constantly stirred from the time crystals begin to separate out). which will dissolve it readily in the absence If potassium is found to be present. to dryness. which has been prepared. The dry mass is broken up with a stirring-rod and then treated solution is an excess of concentrated hydrochloric acid.0369 gm. alcohol (1 c. The nitrate evaporated on the water-bath until the hydrochloric acid is completely expelled and heavy white fumes of perchloric acid are is evolved. of potassium perchlorate. evaporated on the water-bath to dryness and the residue is treated with 97 per cent. which i? now free from potassium. One c. sodium chloride separates out after a few minwhich by means now contains perchloric and hydrochloric The solution (it utes. which to the ing was completely soluble in 97 per cent alcohol. sufficient hydrochloric acid is added to decompose any chlorate remaining.GRAVIMETRIC ANALYSIS. whereby the chlorate is almost completely changed to perchlorate and chloride.

Potassium. .chloride tube.c. is placed in a desiccator which is provided with a calcium. filtered through a Gooch crucible. the platinum crucible.94- Forms: Li 2 SO 4 and LiCl.DETERMINATION OF LITHIUM. 22 [N. Since lithium chloride to weigh it is a very hygroscopic salt. evaporated to dryness. the potassium is determined in one portion as K^PtC^. latter which is "Determination Lithium. which on gentle ignition (even without the addition of ammonium carbonate) is changed to difficultly volatile Li2 SO4 . 177. out of contact with moist air. that on evaporating a lithium salt with concentrated sulphuric acid the acid salt. of Sodium in the After determining the weight of the combined chlorides. It should be mentioned. alcohol.66 gm. POTASSIUM. At. the former is quickly placed within the then stoppered.c. then dried and weighed. AND SODIUM- 53 acid contained in the solution. of Arts and Sciences. 6. and in a second portion the lithium methods is determined according to one of the following : (a) Gooch' s Method* Anhydrous LiCl is soluble in anhydrous amyl Principle alcohol (15 parts of amyl alcohol dissolve in the cold 1 part of LiCl. treated with an excess of 97 per cent. LiCl) while KC1 and NaCl are * Proceedings of the Am Acad. and Presence of One Another. and is placed a weighing beaker with ground glass After both crucible and beaker have assumed the tem- beside the crucible stopper. The is precipitate LITHIUM. it is necessary To accomplish this. Wt. dissolve 0. formed. It is allowed to stand for 20 minutes in the balance case and then weighed. LiHSO 4 is . Li. The salt is then placed in the crucible and the above process repeated. 14]. 3. and washed until the filtrate shows no turbidity on being treated with silver nitrate solution. 1 c. however. The determination of lithium in the form of the above salts is carried out in practically the same way as in the case of potassium. after being gently ignited. or 10 c. perature of the room. should be treated with an excess of KC1.

2 gm. has been boiled. of the filtrate (exclusive of the alcohol used in washing the residue) in case only sodium chloride is present. however.GRAVIMETRIC ANALYSIS. and the latter compound is insoluble in all In order to bring this completely into solution. the water evaporates more quickly and without bumping. platinum crucible.* As soon as the water has been boiled off. far as possible. LiCl.) are asbestos plate and cautiously heated. 5-6 c. If air is drawn through the liquid during the boiling. The aqueous solution at the bottom of the beaker soon begins to boil and the water vapor escapes through the upper layer of amyl alcohol.c. the flask should be fitted with a cork stopper through which two tubes pass. should be deducted for every 10 c. and 0. the clear amyl alcohol solution is treated with 2-3 drops of concentrated hydrochloric acid. The filtrate is evaporated to dryness and the residue is dissolved in a little water after the addition of some dilute sulphuric acid The solution is filtered from the carbonaceous residue into a weighed while still is of . warm through a small asbestos filter. . Erlenmeyer flask. some LiOH is formed by hydrolysis.c. The crust which sodium and potassium chlorides and is remains composed which washed with hot amyl alcohol. after having been concentrated as and which should not contain more than 0. The lithium sulphate thus obtained always contains small amounts of potassium and sodium sulphates in case these metals were present.000 of KC1= 1:24. the chlorides of sodium and potassium separate out. placed in a 50 (boiling point 132 c.00092 if both sodium and potassium chlorides are present * To prevent loss by bumping at this point. so that from the weight obtained. or 0. is The solution. During the evaporation of the aquecus LiCl solution. of amyl alcohol added and the flask is placed upon an C.00051 if only potassium chloride is present. evaporated as far as possible on the waterbath.000). boiled two or three minutes and filtered amyl alcohol. it is 0. the excess of sulphuric acid is removed by gentle heating over a flame (the crucible being held in an inclined position) and then weighed. 54 difficultly soluble in this liquid (solubility of NaC'J =1 : 30. while the greater part of the lithium chloride is to be found in the alcoholic solution. Procedure.c.00041 gm.

then the residue obtained after filtering and washing with amyl alcohol is dissolved in a little water and the above treatment is repeated.k made of Jena is evaporated to dry- and provided with a 21a) During the evapo- glass groun< glass. two-way stopper (p. in the author's opinion it all other methods for the determination of to be preferred to lithium. POTASSIUM. I due has become dry the flask is placed in an oil-bath and heated an hour at 140-150 C. Anhydrous lithium chloride is soluble in a mixture Principle. transferred to a weighed . 55 10-20 mgm. and. the lithium being determined in the comIf salt bined nitrates. This method is very accurate. . which has been saturated with hydrochloric acid gas and thereupon diluted with an equal volume of absolute ether. tents are allowed to cool with the hydrochloric acid still passing through the flask. ration a current of dry air is passed into the flask through the long As soon as the resitube a and out through the short tube b. whereas the chlorides of sodium and potassium are practically insoluble therein. and the residue A few is washed three times by decantation with ether-alcohol. The ether-alcohol extract is care- evaporated to dryness in a water-bath containing lukewarm water. of equal parts alcohol and ether which has been saturated with hydrochloric acid gas. more cubic centimeters of ether-alcohol are added to the contents of the flask and it is again allowed to stand for 12 hours the liquid is then poured off and the residue is washed with ether-alcohol until a trace of the residue tested in the spectroscope shows the for half . 34. during which time dry hydroThe flask and its conchloric acid gas is passed through the flask.DETERMINATION OF LITHIUM. is (b) Rammelsberg's Method. of lithium chloride were present in the original mixture. Fig. the residue is dissolved (after the addition of a little dilute full}' sulphuric acid) in as little water as possible. AND SODIUM. . The flask is tightly stoppered and allowed to stand with frequent shaking for 12 hours. wet with the ether-alcohol mixture. complete absence of lithium. Procedure. after which the residue is treated with a few cubic centimeters of absolute alcohol. The solution is then poured through a filter. in The solution of the chlorides a small na_.

Chem. Chem.. 16. 563. the same. 29.* The solution is evaporated as far as possible on the water-bath. By the evaporation and fusion of the lithium chloride there is formed some lithium hydroxide which is changed by the carbonic acid of the air to carbonate.) Indirect Determination of Lithium The method is and Potassium. The results obtained by this method are satisfactory. claims that the Li 3 P0 4 always contains some sodium. Rammelsberg. p. Chem. then cautiously over the free flame. 56 platinum crucible and treated with sufficient sulphuric acid to transform the lithium chloride present completely into sulphate. Pharm. 98. In the presence of considerable sodium and potasadvisable to remove the greater part of these by with hydrochloric acid gas (cf. Walter method is accurate but tedious. anal.GRAVIMETRIC ANALYSIS.) and Sodium. 18. J Z. Z. anal. after being Example for practice: Lepidolite analysis. (See p.. and Merling. . after which it is gently ignited and the residue Remark. Carnot. 209. 3. is ignited and weighed. 49). filtering is precipitation through asbestos and washing the precipitate with concentrated hydrochloric acid until the residue no longer gives the lithium spectrum.J to Mayer the lithium Li 3 PO 4 is precipitated in the presence of NaOH as washed with ammonia water. Rammelsberg evaporates the chlorides in the water-bath. Indirect Determination of Lithium (See Index. sium salts it of lithium sulphate is weighed. . According to Carnot the lithium is separated as the fluoride and claims that this then transformed to the sulphate. 193. Lithium carbonate is insoluble in ether-alcohol so that the extraction with ether-alcohol is not complete. A great many experiments tried in the author's laboratory have led to the same conclusion. t Ann. The Analyst. however. which.. The mixture of the two chlorides is weighed and the chlorine determined either gravimetrically or volumetrically. Asides the above methods for the separation of lithium from sodium and potassium there are two other methods to be menAccording tioned. Mayer f and that of A. so that the method is inaccurate. 332. that of W. * The above-described method has been modified by the author. heats the residue till it melts and then after cooling extracts with ether-alcohol.

The ammonium is present in cations and anions. In this case the be evaporated to dryness and the residue of ammochloride weighed. a little hydrochloric acid solution the dissociation the loss is for the is reduced to a minimum. aqueous solution the XH C1 undergoes 4 simply: NH C1<=NH. evaporated on the water-bath to dryness. is added to the most part prevented so that The ammonium chloride must be dried in a covered crucible as otherwise a small amount of the * In cold.* 3 on the other hand. : chloride in aqueous solution. or the ammonium chloroplatinate can be ignited and the residue of platinum weighed. on account of the 4 C1 being partly decomposed according to the r NH equation into XH If. 4 . solution contains only 1.AMMONIUM. solution. NH. 18.04. AMMONIUM NH 4. and 4 evaporating the aqueous solution some the amount lost increases in proportion to the amount of w ater used and the temperature at which the evaporation takes place.+C1'. 1. The. both of which are volatile. together with other and Cl ions. Pt. (a) The aqueous Determination as solution NH C1. Forms: NHg. and the covered crucible is dried to constant weight in a drying-oven. 4 electrolytic dissociation .C1. Good results are obtained. 4 treated with concentrated is HC1 and evaporated to a small volume on the water-bath at as low a temperature as possible. but they are always too low. and HC1. On (or NH C1 is driven off. (NH4 ) 2 PtCl We have two cases to distinguish The ammonium is present as 2. Wt. or the ammonium can be precipitated as solution nium XH fl may (NH 4) 2PtCl 6 and the precipitate weighed. 57 Mol. the solution is transferred to a platinum crucible one of porcelain).

it In aqueous solution it undergoes only electrolytic dissociation so that the above salt loses no (NH 4 ) during the evaporation of its aqueous solution. suffers heating )2 no dissociation. dried at 130 C. paper is .9.. (c) Determination as Platinum.2) for the amount of is used. 58 salt will be but lost. first to prevent loss.GRAVIMETRIC ANALYSIS. The precipitate must be heated gradually at It is best ignited according to the directions of Rose. If the old value for the atomic weight of platinum is used in this determination the results obtained will be . the ignition must take place in a large porcelain crucible which is provided with a close-fitting cover. then pX 0. the amount of ammonium chloride originally to dryness. it is Determination as (NH 4 ) 2 PtCl 8 . of platinum (Pt= 195. it can be decomposed by ignition* and the weight of the platinum remaining determined. as was explained in the ammonium case of potassium. amount which (6) On amount this is small in comparison with the possible to lose during the evaporation. up to 130 C. ( (196. (NH4 PtCl 6 to 130 C. The aqueous solution ammonium of chloride.2400 =NH C1 PX 0. and filter are placed in the crucible with the filter-paper on The precipitate top. is treated with an excess of chloroplatinic acid and a little hydrochloric acid and evaporated at as low a temperature as possible The residue is taken up in absolute alcohol and through a Gooch crucible. filtered present can be correctly calculated by using the old atomic weight If the new value for the atomic weight of platinum: Pt= 196. too high a value will be obtained present. and weighed. the crucible is covered and heated over a very small flame until the completely charred without allowing the vapor to escape visibly from the crucible. therefore.08095 = NH 4 pX 0.07643 = NH3 4 .9) *As ammonium chloroplatinate decrepitates strongly on being heated. From this weight. If the weight of the (NH 4 )2 PtCl 6 = p. The crucible is then strongly ignited with free access of air until the charred filter is completely consumed. Instead of weighing the (NH 4 ) 2 PtCl as such. therefore. the salt is unchanged.

9. while if the new value (195. (a) (NaOH The solution is distilled Ca(OH) 2 |). Accordt MgO is frequently recommended for expelling the ammonia.AMMONIUM PRESENT WITH OTHER CATIONS.c. Procedure.17364 = X 4 .8 per cent too high. pX 0. About be analyzed is placed dissolved in 200 c.4 per cent too low. Erlenmeyer flask it is * In analyzing chloroplatinates of organic bases (by weighing the platinum) correct results may be obtained by using for the atomic weight of platinum the value 196. and in case the .18391 =XH 4 pX0. a few drops of litmus solution are added. 59 about 0. this base is absolutely unsuited for this purpose. of Neunkirch. 24.c. Correct results can be obtained by multiplying the weight of platinum (p) by the following factors: pX 0. in the 400-500 c.54527 = XH C1. of water. FIG. the results will be about 0. 1 of the substance to gm.2)* is used. The Ammonium is Present Together with Other Cations and Anions in Solution or in Solid Form. K. . chloric acid the after the addition of a strong base is absorbed in hydro- ammonia evolved and the resulting solution is analyzed according to 1. ing to a private communication from Herrn Bormann. 2.

60 solution reacts acid. if the receiver contains a measured amount of standardized acid and the excess mined is deter- after the distillation by titrating with alkali (cf Alkalimetry) .c. Part III. of 2 N. all the ammo* nia will be found in the receiver and can be determined according to 1 (a) or 1 be carried out (6). by pouring water into it. hydrochloric acid.c. one cubic centimeter at a time. . the above methods are not suited. case the procedure is the same as was described in Vol.c. f Cf. Gas Analysis. (In the case of mineral waters it is necessary to add more than one drop of the soda solution. of the Nessler solution and the yellow color produced is compared with the colors produced in the same way from a series of tubes contain- known amounts ing * of ammonia. however. In order to make sure that no ammonia escapes from the receiver it is well to connect it with a small Peligot tube containing 5 c. after which ten c.GRAVIMETRIC ANALYSIS. and marking with a pencil the level of the liquid on the glass. After 100 c.c. 46.c.c. of it is carefully distilled into the receiver F. It is also possible to make an accurate determination of the amount .f amounts of ammonia occur in drinking-water. graduated Nessler tubes (in the fourth one there is Nesslerized. sodium hydroxide solution (which has been previously boiled to expel traces of ammonia) is slowly added at T with constant shaking until the solution changes to blue. which already contains 20 c c. of 2 N. as In this I. usually no The 50 ammonia c.* The liquid is then heated to boiling and 100 c. of ammonia present by measuring the volume Ammonium. to be detected) and of distillate is mixed with 2 these are c. When a standard is found of The separately funnel T should be roughly calibrated before setting up the apparatus. more of the caustic soda solution are added. The determination can preferably the latter.c. Colorimetric Determination of For the determination of such small of the gas. the amount necessary is determined by adding litmus to a definite volume of the water and then adding the soda solution until the litmus changes to blue. much more quickly.) The distillate is received in 50 c. p. hydrochloric acid and some distilled water. of the liquid have distilled over.

) would give too intense a color with the Nessler In such a case only 50 c. this solution 1 c.c. of ammonia The solution now contains (NH3 ) per cubic centimeter.c.c. which would render a colorimetric determinaIn this case 10 c. of Nessler solution and mixed.c. water should be taken for the analysis and this should be diluted to 500 c. of the water to be tested are placed in a narrow cylinder (which is provided with a ground-glass stopper). of the solution. Na^CXDj (calcined) are dissolved in 600 c. a smaller portion should be taken for the analysis than in ordinary cases (500 c. contains considerable ammonia. p. Of XH If 3 . note.c. of sodium carbonate solution often fails to prevent a turbidity on adding the Nessler reagent. liter. I. are dissolved in 1 liter of water free from ammonia (cf foot.c. 2 c. tion impossible. of a boiled BaCl 2 solution (120 gms. of it are taken and diluted to 1 this. 47). Vol. In order to ascertain how much of the water F to take for the analysis. J In the case of mineral waters rich in magnesium sulphate.c. The ammonium standards is chloride solution necessary for preparing the prepared as follows : 3. of pure distilled water and the H with the sodium carbonate solution.c.141. contains 0.COLORIMETRJC DETERMINATION OF AMMONIUM.) as otherwise the first distillate (50 c. then the 61 two solutions contain the same amount of ammonia. or cipitate the calcium * NH C1-XH = 53.e. is too strong for most purposes. of a strongly alkaline sodium carbonate solution f are added to pre- which may be present.141 * gms. About 100 c. 4 3 NaOH and 50 gms. the addition of -he 10 c. treated with pipetted liquid 2 c.c.03 =3. into a 50 Nessler tube. I If a strong yellow color.c. the mixture is vioallowed and to settle.c. same shade the as the solution tested. of ammonium chloride which has been dried at 100 C. 2 O) should be added before treating the water t 50 gms. with water free from ammonia and then distilled.50 -17. solution boiled until the volume is only 500 c. From the clear supernatant shaken lently are off c.c.O in 500 c.c. 1 mgm. however. the following experiment should be made. so that 10 c. BaCl 2 + 2H.01 water the to be analyzed mgm.c. .

5. then only 50 c.0 c. diluted to 50 of the Nessler reagent .c. of the standard ammonium treated with 2 them ).an be readily distilled off.c. methods were sought for the transformation into ammonia of the nitrogen originally present in some other form. KjeldahPs Method for Determining Nitrogen. These are also treated with and by matching the colors obtained in the test with those obtained from known amounts of ammonia the amount present in the water can be easily estimated. etc.0. from which the ammonia ?. etc.c.0. . on the other hand. tion. water of containing 0.GRAVIMETRIC ANALYSIS. of Inasmuch as it ammonia present very accu- rately. there is not more than a faint coloration apparent.c. Beside c. amount coal. of the Nessler reagent.5. of the water should be taken for analysis. This is readily brought about by the method of Kjeldahl and its modifications.c. The methods which have been described thus far are suitable only for the determination of nitrogen when it is in solution in the form ot NH 4 It ions. of the distillate are placed over a sheet of white paper. 3. is obtained. 2. 25. it must more sensitive by the addition of mercuric chloride solumade be chloride solution 2 c. the diameter of the bulb less oughly mixed. NH 3 if this is not the case. then 500 c. of great importance to be it is present other than as an when protein. By up and down twice the liquid becomes thor- the end being only slightly moving it is in Fig. For the Nesslerization.. the three cylinders each containing 50 c.c. For mixing the liquid in the cylinders a stirrer such as is shown this stirrer convenient to employ on than that of the cylinder. c. The Nessler reagent should give a distinct coloration with 500 c. however. 1.c. potassium permanganate. able to determine nitrogen ammonium compound is (in possible to determine the is. mercuric oxide. are placed a series of similar cylinders containing respectively 0.).0.005 mgm. and by the employment of volumetric methods.5. very quickly. the organic matter is destroyed and the nitrogen is completely changed to ammonium and held as ammonium sulphate. and mixed.c. If. 1. 62 even a precipitate. must be taken for the determination. 2. By the oxidation of nitrogenous organic substances with concentrated sulphuric acid.

The heating is continued until the solution becomes clear and completely colorless. however. but in no case should the flame touch the flask above the part occupied by the liquid. as no mercury is added. of sulphuric acid is determined by titration with Ztg. usually complete in two or three hours. In the presence of iron compounds. thoroughly moistened by the sulphuric acid before the heating. f The flask is then heated in an iron dish glass. Gladding uses a mixture of HjSO. commercial potassium sulphide to the liter) to completely precipitate the mercury and cause the liquid to appear black (25 c. its contents gently boil. the liquid is sometimes slightly yellow.) and As soon as a noticeable denser tube. covered with asbestos until nitrogenous matter. and KHSO 4 which usually works very well. Erlen- flask containing a known volume of normal sulphuric acid water to cover the lower end of the con- (10-20 c. are placed in a 500-600-c. of water. of the potassium sulphide solution are usually sufficient). of the liquid have distilled over. the sides of the flask are washed down and the solution is After it is thoroughly cool. 9.c.c. A few grains of powdered zinc are then added and the flask is quickly connected with the distilsufficient ling apparatus. howThe decomposition ever. made of difficultly fusible potash Procedure for From and to it are added 20 c. .c. meyer The distilling-tube dips into a 250-300-c.c. sufficient begins to come over. diluted with about 250 c. The liquid is then allowed to cool. it is first heated for half a minute over a very small flame and then over a larger one. is 80 c. are quickly added potassium sulphide solution (40 gms. . After 100 c. Then.c. the subsequent addition of N t is unnecessary. especially in In order to avoid a loss of the case of mealy substances. and of caustic soda solution.c. of sulphuric acid (3 volumes of con^ centrated acid mixed with 2 volumes of fuming sulphuric acid) ani" a few drops of mercury. 502. It is imporsubstance should be sure that the be to tant.c.c. flask. free from nitrate. of the substance to be analyzed Modification*). it is amount of water vapor no longer necessary to have the condenser tube dip into the sulphuric acid solution in the receiver..KJELDAHLS METHOD FOR DETERMINING NITROGEN 63 Kjeldahl's Nitrogen Determination (W&farth's 1 to 2 gms. the receiver is removed and the excess * Chem.

of phenol dissolved in enough concentrated sulphuric acid of 66 Be. After chloroplatinic the with substance this for mixture four the heating hours. of phenolsulphonic acid (50 gms. oxides. nitrogen. of zinc dust and 5 drops of acid are added and the mixture heated. 64 one-tenth normal sodium hydroxide solution. acid to get .c. of potassium nitrate (or the corresponding 20 c. using methyl orange as an indicator. liquid to becomes c. In standardizing the acid and alkali. anal.4Q1X*. nitrogen.c.= If the nitrogen the form is is per cent. 27. originally present to a considerable extent in of nitrates. the volume of the solution and the method of titrating must be the same as during the analysis proper. *In the titration and then it is best to add the alkali until the solution turns a change to a pale pink. or cyanides. finish by adding enough f Z. colorless and is ready to be distilled with the caustic soda solution. 92. of concentrated of another nitrate) are treated with sulphuric acid and 2. then this by the ammonia evolved from nitrogen may present number t of cubic centimeters of corresponds to tX 0. and the percentage of nitrogen in the substance = 1. the amount of be the be calculated as follows: Let normal sulphuric acid neutralized a gms. * From the amount of sulphuric acid used. Chem. yellow.5 c.5 gm. Jodlbauerrf From amount 0.01401 gms.GRAVIMETRIC ANALYSIS.c.. make 100 of solution) 2-3 gms. of the substance. In such cases it is best to use the modification proposed by M.2-0. the above modification of Kjeldahl's method will not serve to change all of the nitrogen into ammonia.

(c) Determination as Magnesium Pyrophosphate.DETERMINATION OF MAGNESIUM. A weighed amount of the substance is placed in a platinum crucible and treated with * the mixture is a slight excess of concentrated sulphuric acid. and after cooling in a desiccator. MAGNESIUM. as the free sulphuric acid is anhydrous magnesium sulphate (6) is hygroscopic. MgO. most important of all the methods for the determinamagnesium. from the alkalies.+ The procedure in a covered crucible. Mercuric chloride and the excess first of mercuric oxide are volatilized.e.32. (Translator. Forms: (a) MgS0 4 . the tion of : with an alkali orthophosphate solution in the presence of ammonium chloride and ammonia. nitrate or salt of an organic acid.. Determination as MgO. as far as on the water-bath possible.) In this way magnesium is often separated . and the excess of evaporated . as carbonate. and then only in case the magnesium is present in a form that can be readily changed to the oxide by ignition i. removed by cautiously heating the crucible. Wt. consists simply of at first carefully heating finally with the full heat of the Teclu and burner in a half-covered crucible. 24. Mg. is weighed as quickly as possible. f Magnesium chloride can be changed to the oxide by ignition with mercuric oxide hi a porcelain evaporating-dish. Finally the dry mass is heated just to redness in a covered crucible. At. is always applicable and depends upon the following principles If the solution of a magnesium salt is treated This. Mg. the magnesium is completely precipitated H * Substances which react violently with concentrated SO 4 should be 2 treated with water. over a free flame. This method for the determination of magnesium can always be employed when the magnesium is combined with an acid which can be volatilized by heating with sulphuiic acid and when no other metal besides ammonium is present.O Determination as 65 MgS0 4 7 - . This method is seldom used in practice. and dilute sulphuric acid added little by little.P. held in an inclined position.

less is monomagnesium formed. 1896. however. In this case more or phosphate. ammonia.. then stirring in one-third of the solution volume of 10 per cent. so that nearly correct results are then obtained. 20. Formerly it was a common practice to precipitate magnesium ammonium phosphate in the cold. ammonia. 439. This method. On the other hand. and precipitating by the addition of one-third volume of 10 per cent. anorg. angew. See also Gooch and Austin. 121. adding a few drops of sodium phosphate solution. Mg3(PO 4 )2. . the temperature of the blast-lamp will eventually lead to volatilization of some phosphorus pentoxide. ammonia. 66 as to magnesium ammonium phosphate. sodium phosphate to the slightly acid solution of the magnesium salt. however. contaminates the precipitate.. washing with 2.GRAVIMETRIC ANALYSIS. filtering after four or five hours. and the results are too high. Chem. This com- magnesium metaphosphate on gentle ignition. Chem. dissolving the precipitate in a little dilute hydrochloric acid. When only a little of the meta- present. particularly when the phos- phate solution is added slowly. * Z. the results are too high if the precipitation takes place in neutral or slightly ammoniacal solution in the presence of considerable ammonium ammonium pound is salts.5 per cent. The latter is the case when the precipitation takes place in strongly ammoniacal solutions containing but little ammonium salts. gives too high results. phosphate is 2Mg(P0 3) 2 = Mg2P 2 7 + P2 Neubauer recommends adding an excess of 5. Neubauer* showed. which by magnesium pyrophosphate ignition is changed : 2MgNH PO = 2NH + H O+ Mg P O 4 4 3 2 2 2 7 . that this sometimes leads to high results while at other times the results are low. Z. changed to Mg(NH 4) 4 (P04)2. Tribasic magnesium phosphate.

f Method The Mg 67 of B. Chem. containing magnesium in the presence of salts. the solution allowed to cool and filtered through a Munroe crucible after volume standing for several hours. the Mg2P 2 C>7 is weighed: 2MgNH 4 P0 4 = 2NH 3 + H 2 O + Mg 2 P 2 From the weight of the latter. Schmitz. 9. 278. t Am. 1906. but.g.88 per cent. 9. gradually After coolincreasing the heat until the precipitate is white.5 per cent. ibid. ammonia. . ammonia is at once added. cf. by the method instead of B.95. Sci. ing. anal. 1906. Correct results can be obtained or of W. 5. Jorgensen.97. 114. cause the formation of a coarsely crystalline precipitate which is easy to filter. (3). 512. of cent.DETERMINATION OF MAGNESIUM.* Gibbs. the amount of 7. Schmitz. * Z. p. The precipitate is washed with 2. and 9. 7 The precipitate can be filtered upon an ordinary filter. but in all cases the ignition must be gradual or it is almost impossible to obtain perfectly white pyrophosphate.. Ammonium salts do no harm when the precipitation takes place in hot on the contrary. e. acid solution. in MgSO 4 7H 2 O . J solution. magnesium can be calculated as follows: Mg2 P 2 = weight of magnesium. % is heated to boiling and then treated with an ex- ammonium cess of sodium or ammonium phosphate. dried and ignited very slowly. One-third the solution's of 10 per cent. J.98 per 9. Mg.

ammonia. in solution is thrown down almost is completely. 68 Method The of W. ammonia 10 per cent. The methods of Gibbs and of Schmitz serve to separate magnesium from the alkalies in those cases where the determination of magnesium alone If it is desired to is desired. salt containing ammonium solution of magnesium salts is treated at the boiling tem- NaHNH 4 PO 4 perature with a normal solution of microcosmic salt. then more very gently at strongly until the mass is snow white. 2 O. is phosphate: M HP04 + NH 3 = M SNH 4 P0 4 At the same time the magnesium remaining . and the precipitate washed three times by decan- tation with 2. finally transferred to the washed completely with 2. not too concentrated. The dried precipitate is transferred as com- filter. the filterpaper burned in a platinum wire spiral.GRAVIMETRIC ANALYSIS. ammonia and dried the hot closet. until no further precipitation takes place. while stirring the hot solution. Almost fH 90 per cent. the supernatant' liquid filtered off. Separation of Magnesium from The crucible is cooled the Alkalies. in pletely as possible to a weighed platinum crucible. neutral.5 per cent. and the ash added to the main portion of the precipitate. The covered crucible is heated first until the ammonia is all dried off. Gibbs. MgHPO 4 : NaHNH 4 P0 4 + MgCl 2 = NaCl + NH 4C1 + MgHPO 4 about one-third volume of added whereby the amorphous pretransformed into crystalline magnesium ammonium Then. cipitate is . in a desiccator and weighed. of the magnesium present is at once thrown down as amorphous magnesium hydrogen phosphate. After standing two or three hours.5 per cent. determine magnesium and the alkalies in one .

A mixture of 180 c. 58. water. absolute alcohol ammonium The is saturated with commercial is shaken with the powdered carbonate. anorg. are evaporated to dryness and the determined as described on page 43 et seq. dried. and after several hours carbonate. the residue taken up in a little The combined filtrates water. liquid vigorously stirred for a few minutes and allowed to stand for at least half an hour. *Z.c. however. the solution evaporated to dryness. the magnesium may be precipitated as magnesium hydroxide. however. as crystalline magnesium ammonium carbonate. Even in this description of this method see Silicate Analysis. . concentrated ammonia... J For the detailed and the alkalies determined in the filtrate. 482 (1858). solved in hydrochloric acid. and the precipitation repeated. liquid is removed by filtration. alcohol and then with an excess of the The ammonium carbonate re- agent.DETERMINATION OF MAGNESIUM. and the same sample. whereupon it is filtered is through a Gooch or Munroe crucible. is treated with an equal volume of absolute the excess of the latter Procedure. from a solution free from ammonium salts. alkali If. 104. by the addition of barium hydroxide The barium is then removed by ammonium carbonate solution. page 65. 800 c. preferably in the form of chlorides. Ann. If considerable alkali is present the precipitate always conIn such cases the precipitate is distains a small quantity of it. ignited and weighed as MgO. Preparation of the Precipitant.c. footnote to t Pogg. it is best to use the 69 Gooch and Eddy * modifications of the Schaffgotsche Methodf The method is based upon the fact that magnesium can* be precipitated quantitatively. The precipitate is washed with the precipitant. and 900 c.c. Chem. by means of an alcoholic solution of ammonium carbonate. MgC03 -(XH 4 ) 2CO 3 -6H 2 O. it is desired to separate magnesium from the alkalies in order that the latter may be determined. 427 (1908). The neutral solution containing only magnesium and the alkalies (lithium must not be present). the use of the Schaffgotsche method of separating magnesium from the alkalies is more satisfactory. % Cf. case.

09. 40. It should be heated cautiously at first in order that the too rapid evolution of carbonic in a oxide will not cause loss. Richards found that the precipitate was appreciably soluble in pure water but practically insoluble in a dilute solution of ammonium oxalate (Z. which besides magnesium and the alkalies should contain no other metal. when a little more ammonium oxalate solution is added to make sure that the precipitation has been complete. in the desiccator shown in Fig. Finally the whole precipitate is transferred to the cipitate filter is and washed with hot water containing ammonium oxalate from chloride. 28. METALS OF GROUP IV. CaC0 3 CaSO 4 c. It is allowed to stand four hours. f three times. CALCIUM. near an open weighing-beaker and allowed to remain there for one hour. For the determination of calcium as CaO. the air enters the desiccator. the pre- covered with boiling water containing ammonium to settle. CaO. Forms: CaO. The neutral or slightly ammoniacal solution. Determination as Calcium Oxide (Lime). the precipitation should be carried out as described on page 76. 70 . heated to boiling. anorg. During the cooling. . The crucible while still quite warm is placed. through the U tube. . it is best precipitated as the oxalate and converted to the oxide by strong ignition. Procedure. Chem. 7. . I. STRONTIUM. 85 (1901)).. After the filter is burnt the crucible is covered and strongly heated at first over the Teclu burner and finally over the blast-lamp for twenty minutes. Wt. At.* is treated with ammonium chloride. The precipitate is warmed in the hot until free closet until nearly dry. t T.GRAVIMETRIC ANALYSIS. CALCIUM. BARIUM. when the clear liquid is poured through a filter. filtered. and the operation repeated allowed oxalate. Ca. when it is placed together with the filter platinum crucible and ignited wet. After standing some time. the precipitate becomes coarsely crystalline and settles to the bottom of the beaker. W. whose outer half is filled with * If magnesium is present. and precipitated by the addition of a boiling solution of ammonium oxalate.

The above directions when carefully followed usually enable one to obtain a constant weight on the second ignition. a weighed platinum crucible. sulphate loses SO 3 . This method is chiefly used for the analysis of calcium salts For this purpose the calcium salt is ignited in of organic acids. Calcium oxalate is almost insoluble in water and acetic acid in the presence of ammonium oxalate. in a dry condition and free from carbonic acid gas. after which it stand for half an hour in the is weighed. The crucible is again heated over the blast-lamp for ten minutes and is cooled in exactly the same way and weighed. 11. The solution is then boiled for fifteen minutes to expel all carbon dioxide. neutralized carefully with ammonia. of water. in weight. Should the weight not be found constant. On heating for one hour over the blast lamp it lost 0. quickly covered and allowed to air near the balance. Fig. it lost 0. beaker and moistened with 20 c. The crucible is now placed in the weighing-beaker. 27).2052 gm. Calcite: 0.) . CaSO 4 remained unchanged in weight after heating for one hour to dark redness.0051 gm. and precipitated with ammonium oxalate as above described. By strong ignition. the process must be repeated. of hot water. diluted with 150-200 c. Example. the calcium oxalate forms very fine crystals. after which the crucible is covered with a watch-glass.0004 gm. CaS0 4 . calcium and weighed.5 gm. it then settles very slowly and passes readily through the filter. p. but on heating with the full flame of a Teclu burner. Determination of Calcium as Sulphate. carefully treated with dilute sulphuric acid and warmed upon the water-bath until there is no longer any evolution of carbon dioxide. but readily soluble in mineral acids. The beaker is covered with a watch-glass. concentrated hydrochloric acid is added drop by drop. and the liquid is finally heated until all is dissolved. Remark.c.c.* * 0. 71 soda-lime and whose inner half contains calcium chloride.DETERMINATION OF CALCIUM AS SULPHATE. If both solutions are not boiling hot during the precipitation. 2.c. (J. The excess of sulphuric acid is then carefully driven off by inclining the crucible and heating over the free flame (or The residue is gently ignited in an air-bath) (cf. Weber. The under side of the watch-glass is carefully washed and the liquid evaporated as far as possible on the bath. of the finely powdered material which has been dried at 100 is placed in a 300-c.

dried. alcohol. to which a little sulphuric acid has been added. Wt. is allowed to stand twelve hours. gently ignited 3. 72 Calcium may also be precipitated as calcium sulphate. filtered and washed. and finally with pure alcohol until the wash water no longer gives the sulphuric acid reaction. It is then filtered off. SrC0 3 SrO. washed with 70 per cent. a of excess dilute slight sulphuric acid is added and as much alcohol as there is volume of solution. back to carbonate. alcohol. if the oxalate ignited gently. The filtered gently ignited and weighed as carbonate. The precipitate is . and the ash added to the main part of the precipitate in a platinum crucible. the mixture Procedure. SrS0 4 .GRAVIMETRIC ANALYSIS. treated with an excess of dilute sulphuric acid. Only Determination of Calcium as Carbonate. Sr. however. To the neutral solution containing strontium. and the mixture is allowed to stand 12 hours. The which should contain as little free acid as possible. as the sulphate . Consequently it is advisable in all cases to precipitate the calcium as oxalate and weigh it as the oxide. evaporate to dryness on the water-bath. In the presence of considerable ammonium chloride the precipitation of calcium by means of ammonium carbonate is not quite complete. 87. it can be weighed as the carbonate. This is done in order to change small amounts of calcium oxide. the filter burned in a platinum spiral. whereas the precipitation with ammonium oxalate always is.62. Forms: SrS0 4 The determination At. necessary to moisten the residue with a is solution. . is the most accurate. in rare cases ammonium is After weighing it ammonium is CaC03 . calcium precipitated as carbonate by carbonate in the presence of ammonia. is solution. four volumes of alcohol are added. separated from the filter as completely as possible. After stirring well. is STRONTIUM. which may have been little carbonate formed during the burning of the filter-paper. at first with 50 per cent. and again ignite gently. and washed precipitate and weighed. Determination of Strontium as Sulphate.

73 dried and ignited as described under the determination of cium as sulphate. strontium sulphate considerably acid. and changed by ignition to the oxide as described under calcium.DETERMINATION OF STRONTIUM AS OXI^E OR CARBONATE. is less so that the water should not contain very much sulphuric acid. SrSC>4. or alkali chloride. it should be removed by evaporating the solution to dryness and dissolving the residue in water. strontium. precipitated as carbonate. nium nitrate increase its solubility. Solubility of Strontium Carbonate in Water according to Fresenius. ammonium chloride and ammo- less soluble. magnesium and alkali salts are present together. dilute hydrochloric or nitric acid.000 parts of water containing sulphuric acid dissolves 1 part The precipitate is soluble in concentrated sulphuric acid. although it is usually unnecessary to heat with additional ammonium carbonate. It is advisable to treat the precipitate as described under calcium. or as Carbonate. 18. The strontium is Strontium carbonate is decomposed by heat more difficultly than calcium carbonate and the determination as carbonate is very satisfactory.045 parts of water dissolve at ordinary temperatures of SrG0 3 1 part . Determination of Strontium as Oxide. the calcium . SrO. cal~ Solubility of Strontium Sulphate according to Fresenius. described. In water containing ammonium carbonate the salt is much on the other hand. or in some cases as oxalate. In cold. The sulphate soluble in water containing sulphuric acid: 12. SrC0 3 . In case calcium. The strontium is then precipitated as above If. considerable free acid is present. . 6895 parts of water at the ordinary temperature (17-20) dis1 part of SrSO 4 9638 parts of boiling water dissolve 1 part SrS0 4 solve . therefore. soluble. as in minerals and in mineral waters. more magnesium is and also in solutions containing acetic chloride.

the solution is then poured through a filter. I. The . Of. gr. Wt. 000 parts of water . is readily changed back to sulphate. of water to which a few drops of sulphuric acid have been added. r ^ Solubility of Strontium Oxalate in Water.GRAVIMETRIC ANALYSIS.065). but the latter. dilute sulphuric acid. The precipitate is transferred to the filter and washed with hot water until the wash water ceases to give the sulphuric acid reaction. on being gently ignited in an inclined crucible. 137. The procedure for the determination of barium as carbonate is the same as was described under calcium.. pp. and the precipitate is washed four times with 50 c. slightly acid with hydrochloric acid. At. is heated to boiling and precipitated by the addition of an excess of hot. and weighed without previous heating over the blast-lamp. Determination of Barium as Chromate. Remark. Determination as Barium Sulphate. The neutral solution of the barium salt is diluted to about 200 treated with 4-6 drops of acetic acid (sp. solution. 74 and strontium are both precipitated as oxalates and transformed by ignition into the oxides. heated to boiling. ignited wet in a platinum crucible. Forms: BaS04 BaCr0 4 . 1. so that there is no loss to be feared. By the combustion of the filter-paper there is usually a partial reduction of the barium sulphate to sulphide. It is then dried somewhat. Solubility of Barium Sulphate in Water.37. precipitated with a slight excess of ammonium chromate c.c.000 parts of water at ordinary temperatures dissolve 1 part of SrC 2 O 4 + 2 i 2 Ha The solubility is very much less in water containing ammonium oxalate. Ba. BARIUM.c. BaC03 . and . until the color becomes yellow). 79. 2. (prepared by adding mate free ammonia to a solution of ammonium bichro- from sulphate. dissolve 1 part of BaS0 4 344. 78. 12. It is allowed to stand on the water-bath until the precipitate has settled.

p. Chem. and R. precipitate is filtered off through a Gooch micible and washed with hot water until 20 drops of the filtrate give scarcely any reddish-brown* coloration with a neutral solution allowed to cool. " (I JL chromic acid solution dissolve 1 part BaCrO4 . whereby it appears slightly greenish.DETERMINATION OF BARIUM AS CHROMATE.5 per cent. BaCrO 4 acetate solution (at .813 " " (( (I " " -lf\ i\J 10 15) dissolve ammonium nitrate solution (at 14) dissolve ammonium acetate solution (at 15) dissolve ammonium nitrate solution .000 boiling water dissolve 1 part BaCrO 4 .381] 1 part BaCrO4 BaCrO4 part part BaCrO 4 3. 1890.. anal. the chromic oxide is changed back to chromate. 1 ammonium .5 per cent. The solubility of barium chromate. 1 . when the precipitate appears a homogeneous yellow throughout.* Solubility of Barium Chromale. 45. containing neutral amraonium salts. p. 27).618 IQOft .555 parts of a 1. p.988 parts of 0.5 per cent. between the two crucibles (cf. 22.i/oU 5 1. By long-continued ignition in an open crucible.152 parts of a 0. 1890. By the additions of small amounts of neutral ammonium chromate the solubility becomes lessened to nearly zero. t P. Schweizer.75 per cent. 23. Fresenius. ibid.670 parts of 1 2.-f BaOO4 86. acetic acid solution dissolve " " " " " " (I tl " " tl tl (I (f 1 part " 1 BaCrO4 II -I .. after is which the crucible is fastened to a larger porcelain crucible by means of an asbestos ring. so that there remains a space of about \ cm.957 parts of water at ordinary temperatures dissolve 1 part " " 23. -The precipitate of silver nitrate. 414. * Oftentimes small amounts of the precipitate are reduced to chromic oxide by traces of organic matter. increases considerably with increasing concentrations of either acetic or chromic acids the solubility is affected to a much less degree by solutions . . Z. 418. dried in the hot closet. " " a 0. 49. dissolve 1 part . therefore. 75 The. per cent. and the open crucible is ignited over the free flame until the precipitate becomes a bright yellow.

quantity of magnesium oxalate occluded is dependent upon the concentration of the undissociated magnesium oxalate in solution. mag- nesium oxalate complex is much more soluble owing to the formation of salts. The work of T. whereas magnesium oxalate is fairly soluble. The separation depends upon the different solubilities two oxalates. and high results are obtained for calcium. moreover. dissolve 1 part of MgC2 O 4 -2H 2 O. . Chem. anorg. 76 SEPARATION OP THE ALKALINE EARTHS FROM MAGNESIUM AND FROM THE ALKALIES.. 28. Concentrating the solution and increasing the amount of oxalate ions in solution by the addition of considerable ammo- nium oxalate.GRAVIMETRIC ANALYSIS. Richards * has that the shown. and upon the time in which the calcium oxalate is in contact with the solution. W. Consequently anything that prevents the dissociation of magnesium oxalate will tend to increase the amount of occlusion and thereby increase the result of the calcium determination. 1500 parts of cold water. Calcium oxalate is practically insoluble of the in hot water. or 1300 parts of boiling water. Separation of Calcium from Magnesium (and Alkalies). however. 71 (1901). some magnesium oxalate is occluded by the calcium oxalate precipitate even when the solution is by no means saturated with magnesium oxalate. The dissociation of this compound is favored by the presence of hydrogen ions and by dilution. I. compensated according to In such cases the error Fresenius. both tend to repress the dissociation of the magnesium oxalate. however. In an excess of the precipitant. by is dissolving usually the pre- cipitate in hydrochloric acid and repeating the precipitation with ammonia and ammonium oxalate. mag* Z. If calcium is precipitated as oxalate from a dilute solution in the presence of magnesium. A considerable excess of ammonium oxalate is necessary in the quantitative precipitation of calcium and. Anything that will cause the ionization of the magnesium oxalate serves to reduce the amount of error.

1- an almost equal amount of also true that in this it is not advisable to way. so that repeat the precipitation when made magnesium (0. gm. ammonium oxalate until the filtrate gives no test for chloride after acidifying a sample with nitric acid. and wash with hot.. of oxalic acid. therefore. After the neutralization add a considerable excess of hot ammonium oxalate solution. Dilute the solution with hot water so that the Procedure. containing hydrochloric acid to lessen the Introduce a little methyl orange into the boiling solution. *^ . ciated and this is oxalate. and add ammonia until a yellow coloraThe ammonia should not be added all at tion is produced. to prevent the dissociation of the ammonium oxalate as much as possible. a sufficient volume of boiling oxalic acid solution. but in small quantities from time to time so that about half an hour is consumed in the operation. salt. filter.6 gm. and heated to boiling. once. and the brought about by neutral- is Soc. G. 917 (1909).ALTERNATE METHOD.. magnesium is present in a concentration of not over fiftieth normal. of ammonium chloride are added and 1 complete precipitation of the calcium * J. of calcium and magnesium oxides is brought to a volume of 300 c. taining not more than 0. one per cent. Although this precipitate contains a little 0. To precipitate the calcium. Chem.5 gms. and add a considerable quantity of ammonium chloride. Am. 77 nesium oxalate forms readily soluble complex ammonium salts with undisso- desirable.2 per cent. 3.) it magnesium passes is into the filtrate. allow to stand four hours but not longer on account of the fact that the occlusion increases with the length of time. 31. W. Alternate Method. Blasdale * has studied the separation of calcium from different amounts of magnesium and succeeded in getting excellent The acid solution conresults by a somewhat simpler method. It is accomplished by the addition of another ammonium preferably the chloride. three or four equivalents of dissociation of the oxalic acid. add if it is not already present.c.

after the removal of the ammonium salts by ignition. strontium occurs in relatively small amounts amounts in the presence of large amounts of calcium and varying of magnesium. sulphuric acid filtrate and alcohol are added. solution is slowly neutralized as before and allowed to stand ten minutes. of separating calcium and strontium from magnesium. oxalates effected The by the separation is and strontium as containing magnesium may also contain traces of strontium.) pyrophosphate. Separation of Strontium from Magnesium. large filtrate addition of of ammonium salts are present it is preferable to evaporate to dryness in a platinum or porcelain dish. off and the magnesium determined as (Pages 66-69. is consisting of strontium and weighed as the pyrophosphate. precipitation The acid is added to combine with all the calcium present.GRAVIMETRIC ANALYSIS. however. precipitated as magnesium p. and to expel the ammonium salts by gentle ignition. the First only enough oxalic effected in two stages. the magnesium on as described is is filtered off allowed to stand From this filtrate ammonium phosphate and weighed. or barium sulphate. considerably is than ten times as much magnesium as calcium. the residue is dissolved in hydrochloric acid. This separation finds practical application in the analysis of almost all mineral waters and of minerals containing strontium. to dry the residue at 110-130 for an hour or longer. the soluWith more tion made alkaline and allowed to stand for an hour. In the amounts the magnesium can be precipitated by the ammonia and sodium phosphate. so that it is a question. If. 70 and 73. is precipitate more magnesium than calcium is present. Then the balance of the oxalic acid is added. If izing with 1 per cent. 66. In all of these cases. . Any resulting precipitate. 78 ammonia added during five minutes. diluted with water. The residue is taken up in a little warm hydorchloric acid. hence. The allowed to stand for an hour before filtering. first. a little carbon residue filtered II. a double precitation is desirable. This precipitation of the calcium as described on pp. and the solution for twelve hours. however.

The magnesium cipitated as oxalates. In case 79 Separation of Barium from Magnesium. and the barium precipithe solution tated by the addition of boiling. is now added. the temperature of. meanwhile passing a stream of dry. In most cases. Separation of the Alkaline Earths from One Another. heated to boiling. which dissolves calcium nitrate alone. p. however. ether-alcohol. The magnesium is precipitated from the filtrate as magnesium . and calcium from the magnesium is involved. hi an oil-bath. and again allowed to stand twelve hours. and the strontium is determined in the filtrate as sulphate. p. and maintained at this temperature for bath still passing the current of warm air through After the cooling. as described under lithium. the flask. the barium is precipitated as chromate. For this purpose the three alkaline earths are pre- and any barium or strontium remaining in precipitated as described under II. PROCEDURE. The mixture of the dry nitrates is treated with Principle. a separation of barium. . it is desired to separate only barium from magnesium. and allowed to stand An equal volume with frequent shaking for one to two hours. flask. dilute sulphuric acid (cf. It is then filtered through a filter moist- of ether ened with ether-alcohol and washed with ether-alcohol until a few drops of the nitrate evaporated on platinum-foil leave no residue. (which must be free from nitric acid) is acidified with hydrochloric acid. strontium. The three metals are assumed to be present together in solution The solution is evaporated in a nitrates. corked up. the is filtrate is determined hi the final filtrate. warm air through the When all the water is evaporated. in the form of their small Erlenmeyer flask. one to two hours. (a) Separation of Calcium from Strontium and Barium accord- ing to Rose-Stromeyer-Fresenius. the flask closed. the dry residue is treated with ten tunes its weight of absolute alcohol. shaken. 74).SEPARATION OF BARIUM FROM MAGNESIUM AND STRONTIUM. The residue is taken up hi water. III.ammonium phosphate in the usual way. is raised to 140 C. 55. IV.

) the above separation is complete. A solution ammonium of acetate (1 c. In case only a small amount of calcium is present (not more than about 0. it is then washed with pure hot is water until the last washing gives only a slight reddish-brown * Z. the residue of strontium and after ignition Remark. 4. 29. Requirements. 1. solution of the solu- solution is ammonium (free from sulphate) until the color of the solution becomes yellow. gr. is The and barium water and for each gram of salt residue. With large amounts of calcium. consisting of strontium dissolved in a little mixture the solution is diluted until the concentration corresponds to 300 c. barium nitrates almost always contains some calcium.c. is dissolved in water. treated with six drops of acetic acid and about 10 c.GRAVIMETRIC ANALYSIS. bichromate 2.1 (NH 4 ) 2 OO4 of gm. containing 0. of ammonium chromate solution (this should be an excess over the theoretical amount necessary) and allowed to stand one hour. This separation finds application in the analysis of most mineral waters.c. Chem. The precipitate of barium chrornate washed by decantation with water containing ammonium chromate until the wash water no longer gives a precipitate with ammonia and ammonium carbonate. of the salt).c. Acetic acid of sp.31 gm. 1. ammonia to the a (1 c. 8o The filtrate is evaporated to dryness in a lukewarm water-bath. precipitated as the oxalate. tion should c(Jntain prepared by adding solution of 0.5 gm.. * A 1. Nitric acid of sp. anal. Procedure. heated to boiling. nitrates. In this case the aqueous solution is again evaporated to dryness in the same way as before and the treatment with alcohol and ether re- The calcium is then determined in the combined filtrates. (b) Barium from Strontium according Separation of to Fresenius. . The solution should be left acid rather than alkaline.065.20. the calcium nitrate and is weighed as the oxide. peated. gr. 427 (1890). of The salt).. 3.c.

. is washed once with hot water. Experiments performed in this laboratory* completely confirm the results obtained by Fresenius. 99. while any precipitate remaining on the filter is dissolved in a little warm dilute nitric acid and washed into the dish.4. 99. heated to boiling. the residue* is treated in the dish poured through with hot water.77. 100. (H. that reason they will not be discussed in this book.6. 99. In the opinion of the author.6.84. 99.9. 100. . which always contains some chromate. 100. all other methods for factory. * The results of seven chromate obtained: experiments gave (a) for for the percentage of barium 99.3 per cent. 72. treated with nitric acid to the precipitate so 5 c. 99. dissolved in hydrochloric acid. 100.3. 99. ignited gently in an airand weighed as BaCrO 4 The filtrate is treated with 1 c.c. a Gooch crucible. 100. on the filter still contains a little strontium. The results obtained according to this method are very satis- silver nitrate.c.. are necessary). 81 The precipitate It is carefully washed coloration with neutral silver nitrate solution.c. and finally with enough ammonium chromate to cause the disappearance of the odor of acetic acid from the solution (usually about After standing one hour the liquid is 10 c. of ammonium acetate solution.73.) 99. added little by little. The precipitate...c. according to p.47. mean. p.7. nitric acid.9. 75). mean. (6) for strontium sulphate. of nitric acid warming (about being usually necessary).c. back into the vessel in which the precipitation took place. the separation of the alkaline earths give incorrect results.9. bath (cf. 100. and the strontium determined as sulphate.f6.SEPARATION OF BARIUM FROM STRONTIUM. then filtered and washed with cold water until the filtrate gives only a slight opalescence with neutral The precipitate is dried.75 per cent. finally adding enough that it dissolves completely on 2 c. The solution is then diluted to 200 c. Schmidt. Remark. and the strontium precipitated as carbonate by the addition of ammonia and ammonium carbonate. 99. concentrated somewhat. allowed to cool.

TITANIUM. but without applying suction. . that aluminium hydroxide exists in a soluble form (hydrosol) and in an insoluble form (hydro. IRON. and this leads to high results in the case of all preripitatee formed by adding ammonia to an acid solution. which * The ammonia should be When it has been kept for freshly distilled. At. AND MANGANESE. 82 METALS OF GROUP in. the ammonia invariably contains silica. COBALT. heated to boiling in a platinum or porcelain vessel. It must not be forgotten. The precipitate is allowed to settle. and a slight excess of ammonia * is added. In order to determine aluminium in this form. NICKEL. ALUMINIUM. or by remaining in a hot solution containing only a small amount of dissolved salts. ammonium salts become acid on long boiling (due to the escape of ammonia) there is danger of the aluminium hydroxide being redissolved Furthermore. or ammonium ammonium nitrate. TITANIUM.GRAVIMETRIC ANALYSIS. ALUMINIUM. Wt. ZINC. however. Form: A1 2 3 27. URANIUM. Since. and further that the hydrosol is not completely changed by To accomplish this the presence of boiling into insoluble hydrogel. any length of time in glass bottles. the metal is precipitated as its hydroxide and converted to its oxide by ignition of the precipitate. CHROMIUM. A. gel) . IRON. it is true that the hydrogel . or is anything but aluminium that treated with considerable is precipitated by ammonia) chloride.1. CHROMIUM. Al. however. after which the clear solution is poured through a filter rests on a platinum cone. . salts in solution (preferably ammonium salts) is also necessary. gradually changes over into hydrosol by standing in a solution containing only a small amount of dissolved salts. AND URANIUM. DIVISION OF THE SESQUIOXIDES. From these facts the following procedure is derived: The solution containing the aluminium (but no phosphoric acid. ALUMINIUM.

anal. however. the mineral acid that is set hydrolysis of an aluminium salt. By the method of Chancel and in the two following methods these difficulties are overcome. 3. Al .. 83 The precipitate is washed three times by decantation with hot water to which a drop of ammonia and a little ammonium nitrate has been added. In the first place the precipitate always contains more or less basic aluminium sulphate. free in the 2A1C1 3 + 6H 2 CM2 Al (OH) 3 + 6HG1. rend.DETERMINATION OF ALUMINIUM. 6HG1 + 3Xa 2 S 2 Procedure. and finally transferred to the filter. cooled in a desiccator and weighed. is tedious and a very large quantity of the wash liquid is required. 46. possible to wash out by means the sulphate all of a solution of ammonia and ammonium nitrate. to be sure. The precipitate is now washed as quickly as possible with the hot wash liquid (so that the precipitate is thoroughly churned up each time) until the filtrate ceases to give a test for chlorine. Chem. The 3 = GNaCl 4. Another disadvantage arises from the fact that the filtration takes place very slowly. even when the precipitate contains basic sulphate. The precipitate is then dried as completely as possible by the application of suction and ignited wet in a platinum crucible.* In the determination of aluminium in a sample of alum by precipitation with ammonia. there are a number of difficulties to overcome.3H 2 + 3S0 + 3S. It is. Z. Determination of Aluminium by the Method of Chancel. gm.1 * Compt. by salts of weak acids. The principle of this and the following methods consists in neutralizing.. After the precipitate and ash have become white. In the Ghancel method the mineral acid is neutralized by sodium thiosulphate. 2 dilute. the weak acid is removed finally by boiling or neutralization. 391. the operation. on account of the slimy nature of aluminium hydroxide. The process is repeated until a constant weight is obtained. neutral solution (about 0. the covered crucible is heated over the blast-lamp for about ten minutes. and it requires long ignition to expel the last traces of sulphuric anhydride. 987.

If now the iodine in the solution is made to react with sodium thiosulphate and the mixture is heated on the water bath for half an hour. the solution will retain traces of .f The aqueous solution of the aluminium salt. 548.GRAVIMETRIC ANALYSIS. 84 in 200 c.. the final neutralization with ammonia. Procedure. and ignited in a porcelain crucible. t Ber. Ferric iron is reduced to ferrous salt by the sodium thiosulphate and is not precipitated.c. which on account always shows an acid reaction. Remark. should not be carried out or a little iron will cipitation with come down. of A1(OH) 3 is much denser than that produced by direct pre- ammonia and is very easy to filter and wash. +3HOH=*A1(OH). of hydrolysis A1C1. as prescribed in the above directions. Determination of Aluminium by the Method of Alfred Stock. however. This mixture in the presence of acid is decomis posed in accordance with the equation KI0 3 + SKI + 6HC1 = 3H 2 + 6KC1 + 3I 2 . 1900. the precipitate collects in such a condition that filtered it can be quickly and washed. away The precipitate of A1(OH) 3 and S is filtered off. present sodium hydroxide is added until a slight permanent precipitate is obtained which is redissolved by means of a determined should * If the addition of aluminium. and the boiling is continued a little longer.) is boiled until is treated with an excess of sodium thiosulphate and * traces of S0 2 are expelled. +3HC1. whereby the equilibrium which existed in the hydrolysis of the aluminium salt is disturbed and the first reaction continues to take place until all the aluminum is precipitated. washed with hot Such a precipitate water. The solution in which the aluminum is to be if more acid is very slightly acid. Enough ammonia all then added so that the odor is barely perceptible after blowing the vapors. treated in the cold with a mixture of potassium iodide and potassium iodate. This method is often employed for separating aluminium from iron. In this case. be ammonia is omitted.

f first . aluminium precipitated in a form that can be as easily filtered as that of the last methods. ignited and weighed as A1 2 O3. more of sodium thiosulphate are added and the solution heated half an hour on the water bath..DETERMINATION OF ALUMINIUM. Chem. in the presence of organic substances such as tartaric acid. Chem. . potassium iodide solution and a saturated potassium iodate solution (about 7 per cent.. sugar. The pure white precipitate settles out well. If the solution so that the precipitate * J. the phosphate of aluminum is It is obvious that the method cannot be employed precipitated. is acid. enough ammonia is added formed dissolves only slowly on Am. The presence of calcium. 2 . which prevent the precipitation of aluminium hydroxide. but if phosphoric acid is contained in the solution. 877. 434 (1897). One or two c. citric acid. 1909. 85 few drops of hydrochloric acid. chroPrinciple.. Schirm. nium until no more fumes are evolved. magnesium and boric acid does not interfere with the above determination. washed with hot water. etc. 19. Wynkoop * of E. Ztg. sodium thiosulphate solution and a little of the potassium iodide and iodate mixture is added in order to make sure that enough was added in the first place.GXaCl + 6HXO 2 6HXO = 3H O +3XO +3X0 2 2 Procedure. KIOs) are added. nitrite hydroxide is 2 A1C1. + 6HOH<=2 Al (OH) 3 + 6HC1 6HC1 + 6XaX0 2 . and can be filtered through a filter with relatively wide pores.f If a neutral solution of aluminium (iron. Remark. After about five minutes the solution is decolorized by the addition of a 20 per cent. Soc. Thereupon equal volumes of a 25 per cent. . Determination of Aluminium by and the Method of G. or titanium) is boiled with an excess of sodium or ammo- mium.c.

ignited wet in a platinum crucible. In the case of organic salts of organic acids. and weighed as stirring. even after long the presence boiling. washed with (about 20 minutes). and boiled until no more fumes of nitrous oxides are evolved The precipitate is filtered. the solution contains only aluminium in the form of its chlo- can be determined by evaporating the solution in a platinum crucible on the water-bath with the addition of a little sulphuric acid.c. hot water. nitrate. the oxide by strong ignition over the blast -lamp. sulphate before using . and the by drop analysis If is finished as above. of In such a case. * Sometimes the reagent contains a cipitated with ammonium little barium which should be preit in an analysis. the excess of the latter being finally removed by cautious heating over the free flame in an inclined The residue of aluminium sulphate is then changed to crucible. solution of pure ammonium then added. In ammonium salts. after the vapors of nitrogen peroxide are no longer visible. or sulphate. allowed to settle while the beaker is on the water-bath. nitrite* is A1Amore than 1 per cent. of these are hydrolyzed enough so that the solution remains acid and the precipitation of the aluminium is incomplete Remark. 86 An excess of a 6 per cent.GRAVIMETRIC ANALYSIS. it readily obtained by careful ignition of the salt in a platinum crucible. ammonia is added drop The precipitate is until the odor is barely perceptible. the oxide is ride. the solution diluted to 250 c.

Determination as Fe 2 This 3 . . centrated hydrochloric acid on the water-bath. f num and crucible over crucible finally in the half-covered the Bunsen burner. and Metallic Iron. Precipitation with Ammonium Nitrite. not advisable to heat the covered crucible over the blast on account The magnetism of such a precipitate danger of forming some Fe 3 O 4 can be shown by placing a magnet outside the platinum crucible and moving it slowly up and down. Jena beaker * and pre- is in a porcelain dish or by means of a slight excess of ammonia. Fe 2 3. should be freshly distilled or the results will be high. Forms: Ferric Oxide. By (a) the form chiefly used for the gravimetric determination The solution containing the ferric salt in the presence of is of iron. The For this purpose a wash-bottle such as is shown in Fig. J it is of the . J ferric oxide obtained varies in The its appearance according to the temperature to which it has been heated. soluble in dilute hydrochloric acid.IRON. high results are invariably obtained in ordinary glass vessels. but can be readily dissolved by digesting with con- FIG. Gently ignited ferric oxide is reddish brown. IRON.85. 55. ammonium chloride heated to about 70 C. At. precipitation of Fe(OH) 3 from neutral solutions of ferric (6) The By salts takes place as described for * Too ammonia aluminium. 26 is useful. blowing through the long arm of the U-tube (which is provided with a Bunsen valve) and placing the thumb over the short arm a continuous stream of water is maintained which can be stopped at any time by removing f By the thumb. Wt. whereas when strongly ignited it has almost the appearance Both forms are difficultly of graphite. The precipitate is washed by decantation with hot water and finally with a cipitated strong stream of hot water from the washIt is ignited gradually in a platibottle. p. Precipitation with Ammonia. Fe. 85. 26.

so that book. t Ferric oxide after having been powdered and ignited is so hygroscopic that the porcelain boat should be placed within a weighing-beaker with ground-glass top immediately after removing it from the desiccator. Liebig's Ann. After cooling in the stream of hydrogen. Serie. * powdered and weighed f substance contained in a is introduced into a tube of difficultly fusible glass boat porcelain in a stream of dry hydrogen until no more redness to heated and on the cool front end of the tube and the water condense of drops contents of the boat appear gray and not black. Iron may be determined by electrolysis. Phys. the following method is accurate and rapid. it is very important to heat the oxide to bright *Rivot. titanium dioxide.. from which the amount of iron can be calculoss in lated: 2Fe '-3CTPRemark. the boat and its contents are again weighed after remaining some time in a desiccator. Chem. and then weighed. volatile acid. it will not be discussed in this In the case of the analysis of oxide iron ores or of mixtures of considerable iron oxide with comparatively little alumina. 88 If the iron is in solution either as the ferrous or ferric salt of a be readily converted into ferric oxide ration with sulphuric acid and ignition of the residue. 30. Ann. 3. but this method offers no advantages over the gravimetric method just described or the following volumetric process. means of In attempting to reduce ferric oxide to iron by hydrogen. 188 (1850). By this means The finely the ferric oxide is reduced to metallic iron: Fe 2 O 3 + 3H 2 = 3H 2 + 2Fe. . 211 (185). by evapo- Determination as Metallic Iron. 78.. it can 2.GRAVIMETRIC ANALYSIS. The weight p represents the amount of oxygen originally combined with the iron. or silica.

f It is still more accurate to dissolve the metallic iron produced in dilute sulphuric acid out of contact permanganate 3. are not reduced under the plete on account of some of the ferric oxide being enclosed within the particles of foreign oxide. a potassium permanganate solution of slowly added to the solution of a ferrous salt. according to Margueritte. but in such cases black. the iron no longer pyrophoric. f A table is . pyrophoric iron is formed and the latter cannot be exposed to the air and weighed without becoming heating to a bright red heat. Volumetric Determination of Iron. anorg. etc. 393 (1903). it should be used with caution and only when the ferric oxide greatly predominates in a mixture of oxides. 244. strength is * Z. however. of in the stream hydrogen. de chim. Principle of the Method. 89 At a dull red heat. metal. Otherwise the reduction of the iron is incom- Although this is ing oxides of aluminium. the oxide is to be sure reduced to redness. given. and the correspondchromium. This has been proved by the of Daniel and Leberle * and by Treadwell and Wegelin. 34. J Ann.J Although the volumetric methods are discussed in the second part of this book. same conditions. in the German edition of this book. [3]. with the amount present volumetrically by the work air and determining titrating with potassium solution. which is subsequently replaced by be carbon dioxide. 18 (1846). Ferrous salts are oxidized by potassium permanganate hi acid solution to ferric salts: If. p.VOLUMETRIC DETERMINATION OF IRON. method extremely simple. is oxidation.. therefore. safely weighed in the air without fear of By oxidized. if allowed to cool becomes gray. showing the results of twelve experiments. titanium and zircon. et de phys. and can.. this determination is so important and is so often used to test the purity of the iron oxide produced by a gravimetric analysis that it seems proper to discuss it at this place. known it will Chem.

Chem. After this time all of the oxidizable matter in the water will have been completely destroyed.). 2 2 2KMnO 7 2 4 so that from two molecules of permanganate five atoms of oxygen = 10 atoms of hydrogen) are available. is In most cases a TV normal solution of potassium permanganate i. dissolve it in a liter of water. for the distilled water in which the perman- dissolved almost always contains traces of organic matter ganate oxidizable by the permanganate. and Walker.161 gms. Morse. p. whereby the end-point of the reaction is determined.61 4 - 4 5 10 5 oxygen =1 gm.2 gms. thus: ( 2KMnO-^ = KMn0 = 158. Preparation and Standardization of the Permanganate Solution. 401. Jour. the next it. gm. drop of the permanganate will impart a permanent pink color to the solution. * Cf. of hydrogen).1-3. and allow it to stand eight to fourteen days* before using it. yet on the following day its value would be different. gram-atom of hydrogen (1.-atom KMnO = i 4 gm. Potassium permanganate in acid solution reacts according oxidize TV of a to the equation K O. Although it is possible to purchase very pure potassium permanganate. necessary to take -V of a gram-molecule of potassium permanganate (3.-atom of of hydrogen. Hopkins..) for a liter of TV normal solu- Consequently it is tion.e. The solution is filtered through an asbestos filter and then standardized. for although we might in this way obtain the correct strength of solution. Consequently we weigh out is on a watch-glass approximately the right amount of permanganate 3.GRAVIMETRIC ANALYSIS. Mn O =K O-f 2MnO+5O. Am.008 gm. it is not advisable to take the trouble of weighing out just this amount of the substance and dissolving it in exactly the right amount of water. .03 =31. one which contains in one liter enough oxygen to suitable. 18 (1896). po be decolorized as long as there remains ferrous salt to react with As soon as all of the ferrous salt has been oxidized.

91 Standardization of the Potassium Permanganate Solution. as will be discussed in detail under volumetric analysis. then 1 c. In this case we are concerned with the determination of iron only.VOLUMETRIC DETERMINATION OF IRON. so that the most natural way for us to standardize the solution will An accurately weighed porin dilute dissolved tion of iron sulphuric acid out of contact with solution is added from a the air and permanganate glass-stoppered solution remains the burette until pink for one-half minute after be by means of chemically pure iron. represents the titration value of the solution. about only 0. chief It is difficulty difficult to in the procuring of a prepare iron which is exactly lies Moreover. pure.1 per cent.c.283 gm. cannot be determined satisfactorily by means of a gravimetric analysis because the analytical errors are greater than is usually supposed. oxide great care must be taken or some of it will be reduced to magnetite as can be shown by a magnet held outside the crucible. such as is hydroxide precipitate is bulky so that it is customary to take 0.0003 gm. =a gm. of wire for analysis which yields approximately. in igniting a precipitate of hydrated ferric time. It is possible to standardize the solution by a number of different methods.003 gm. cipitate and filter . ordinarily used for standardization. the purity of a sample of iron wire. moreover. in the final ferric weight corresponds to 0. The precipitate of ferric hydroxide. or when the reagents used have been in contact with glass for some This leads to high results and the error may amount to 0. The 100 per cent.2 gm. Again. often contains silica and alumina when the analysis is carried out in glass beakers. iron.* *The carbon from the filter-paper causes the reduction when the preare heated together and too much heat is used at the start. Heatingthe covered crucible over the blast lamp also converts Fe 2 O 3 into Fe 3 O 4 . of Fe 2 3 so that an error of 0. The value Remarks. of iron in the sample. The suitable standard. If for the oxidation of a grams of iron t cubic centimeters of the permanganate solution were necessary. is thoroughly stirring or shaking.

recommended that permanganate should be standardized against one of four substances (1) Pure oxalic acid. with an accuracy if is any carbon. most satisfactory method is to determine the impurities present.. silicon or sulphur present. 1907). A.7 per cent. 195 (1904). Lehrbuch der chem.GRAVIMETRIC ANALYSIS. however. by difficult to carry out a perfect gravimetric estimation of iron The sufficient for standardization purposes. carbon. : The barium hydroxide which is in turn is standardized against hydrochloric acid.. in his report to the Sixth these errors cannot be large. and on igniting is danger of losing a little ferric chloride On account of these sources of error it is such a precipitate there volatilization. against sodium carbonate. Chem. phosphorus. as usually the case. so that a sample of iron may show against permanganate an apparent iron value oxidizable wire of from 100 to 101 per cent. to standardize potassium permanganate against pure electrolytic iron and in the author's laboratory this has been found to be very satisfactory. the precipitate often contains some the addition by magnetite to change chloride it is back to which it is ferric hard to remove by washing. f See also Z. Lunge. in spite of the fact that it contains only 99. of pure iron. G. . 92 When thus once formed it is practically impossible oxide by further heating or by treating the precipitate with concentrated nitric acid. although when the electrolysis is properly carried out. the exact value of which has been determined by titration against standard barium hydroxide solution.-analyt. of ammonia.) * Mohr-Classen. etc. which may exert some effect upon the titration. Angew. 17. International Congress of Applied Chemists f (Rome. (See titrated Acidimetry. There is a possibility. therefore. of such electrolytic iron containing occluded hydrogen. This leads to low When thrown down from hydrochloric acid solutions results. Titriermethode (1896). Classen * has proposed. compounds may be left in solution which are there is by potassium permanganate. but even although this may give the correct percentage of iron.

(See Acidimetry. Some commercial ferrous chloride is dissolved in water and a hydrochloric acid. The contact with the air (passing * For the generation of carbon dioxide. .bottle A is filled with permanganate solution. and the tower C contains pumice soaked with copper sulphate solution. oxide thus obtained is dried. and the solution neutralized by the careful addition of sodium hydroxide. 149). chlorate and hydrochloric acid. oxalate. and filtered. 88. 27. ignited. the solution is saturated with hydrogen sulphide. above which is a plug of cotton. only the wash. the excess of chlorine boiled off.PREPARATION OF ELECTROLYTIC IRON. The well-washed precipitate is dissolved in hot. After boiling off the excess of hydrogen little sulphide. dilute hydrochloric acid and freed from barium by a double The hydrated ferric precipitation of the iron with ammonia. . the exact value of which is known by a comparison with oxalic acid (standardized as above). The iron is then precipitated by the barium carbonate method (see p. The metallic iron is dissolved in the calculated amount of dilute sulphuric acid out of C02 through the solution*). 93 Pure iron wire. The potassium permanganate and copper sulphate both serve to remove H 2 S from the CO2 in Fig. (2) (3) Sodium (4) Hydrogen peroxide by the Nitrometer Method. an apparatus similar to that shown 30 is used. the ferrous chloride is oxidized by means of potassium FIG. and reduced to metal in a stream of hydrogen as described on p.) Preparation of Electrolytic Iron.

27) are prepared taking two pieces of platinum-foil about 25 sq. iron.35 gm. also necessary to provide a solution of am- monium oxalate.c. fastening a piece of fairly heavy platinum wire to each. saturated at the room temperature. 28. For the electrolysis. In addition it is contain about c. free flame. surface and K by FIG. to them over the it is hang them upon a heavy platinum wire which convenient is itself placed . 94 solution is then diluted with water until 20 0. cm. they are bent so that they will conveniently pass through the neck The electrodes are cleaned by boiling in conof a liter-flask. two electrodes (Fig.GRAVIMETRIC ANALYSIS. centrated hydrochloric acid and finally igniting To accomplish the latter purpose.

7 ampere. leaving them suspended from a.17 gm. of the iron solution (about 0. of the ammonium oxalate solution are now 10). the plate are fastened two corks which serve to support the two heavy platinum wires a and b. At the end of this time there will be firmly attached to each of the cathodes about 0.c. steel-gray deposit. 29).* After the ignition the electrodes are allowed to cool in a desiccator and weighed accurately by the method of swings (cf. About 350 c. Through the two side holes are passed from below the bent platinum wires of the (L FIG. The circuit is broken. while through middle hole the end of the spiral anode passes and is the suspended from the cross-wire b. and the solution is electrolyzed for from one and one-half to two hours at about 60 with a current of 0.5-0. of a bright. 28). beaker and 20 c. and wire b with the positive pole of a battery. The beaker is covered with a At the ends of glass plate containing three holes (Fig.PREPARATION OF ELECTROLYTIC IRON. The wire a is now connected with the negative. p. . cathodes K. one of the electrodes is removed. placed in a 400-c. 29. and the circuit again closed.35 gm.c. they are then heated over the non-luminous flame of the Teclu burner (Fig.c. 95 on an iron ring. Fe) are added. The electrode which has been removed is * The electrodes must be above the inner flame mantle.15-0.

apparatus. and then washed with a bottom edge touched with liberal quantity of absolute alcohol that has been distilled over lime. One of the weighed electrodes.GRAVIMETRIC ANALYSIS. and titrated with permanganate solution added from a glass-stoppered burette. the permanganate is added drop by drop and the flask is constantly rotated to insure thorough mix- When the soluing of the permanganate with the ferrous solution. after which it is dried in the hot closet until the ether has evaporated (this takes The lower edge is about half a minute). 30) are placed 500 c. permanent for half a minute. removed from the flame. on which the iron has been deposited. is thrown into the flask containing the sulphuric acid the flask is immediately closed and gently heated on the water-bath. but amount that it can safely be disregarded. of water and 50 c. The iron dissolves very quickly. the a piece of filter-paper to remove the greater part of the adhering water. ond electrode precisely the is It is then placed in a desiccator. or better to boiling. still passing carbon dioxide through the . In the liter-flask (Fig. so that there of the ferrous salt. The sec- now removed from same treatment. then washed with ether which has been distilled over potash. again touched with filter-paper. the circuit and subjected to After the electrodes have been in the desiccator for fifteen minutes they are weighed. of chemically pure concentrated sulphuric acid. it is so . taken out. The contents of the flask are heated to boiling. and allowed to cool in an atmosphere of carbon dioxide. placed in cold water. meanwhile passing a stream of carbon dioxide through the liquid. the * Sometimes a minute trace of carbon remains undissolved.c.* b. tion possesses a slight pink color.c. small in t See under Volumetric Analysis. leaving no residue. 96 at once plunged into a beaker of distilled water. The flask is then closed at After noting the burette reading. While the solution is being electrolyzed the solvent for the iron K should be prepared. After the latter has boiled vigorously for ten minutes the flask is closed at b. placed in cold water. In this manner a solution of sulphuric acid is obtained comis no danger of its oxidizing any pletely free from air.

" " 4 Fe with " " =0. Schudl obtained the following values by using three methods: 1 c.c. is FIG. and after the burette has drained a second A blank test is made with another portion of taken. end-point reading IRON. 30.c. The results obtained by this procedure are excellent. of water and 50 c. = 0. iodine. 1 c.c. by titrating against a solution of the same wire. After the strength of the permanganate solution has been accurately determined by the above method the apparent iron When this is value of a sample of iron wire may be determined. Thus Dr.PREPARATION OF ELECTROLYTIC 97 is reached. 500 c. known it is possible to determine accurately the strength of a new permanganate solution. dioxide). oxalic acid." " electrolytic iron.005470 g. subtracted from the total number is necessary to impart This amount should be of cubic centimeters of the per- manganate solution used in titrating the iron.c.005485 g. KMnO = 0. Ic.005468 g. .c. sulphuric acid solution (boiled free from in a stream of carbon same way and allowed to cool to see how much permanganate air in the this pink color in the absence of iron. or of the same solution at a future date.

The following results of determinations made with great care by W.c.GRAVIMETRIC ANALYSIS. A. The apparent purity. cone. no longer leaves a gray mark on the paper. This is dissolved. therefore.15-0. 601. Angew. The author recommends the standardization against elec- and compares the value obtained with that found with iron wire. Then trolytic iron the apparent iron value of the wire will be * Still better known for future recommended by Contat and improved by Gockel (Z.c. the work all being done on the same day. and if the latter were to be used in the computation the permanganate solution would be found a little too strong. The purity of the sample of commercial iron wire was found in three titrations to be 99. iron. making a spiral.005600 gm. is greater than the actual purity. The wire is wound round a dry glass rod.. water + 5 c.0 and 99. 1898. as otherwise hydrocarbons or other reducing substances remain in solution so that too ganate is used much perman- . Chem.93. 100.2 gm. 601. f is the use of the glass valve as Ztg. and there is no overpressure on the outside. and is then titrated with permanganate which has been standardized against electrolytic iron or sodium The apparent iron value of the wire is then calculated. Christie in the author's laboratory illustrate the process : The permanganate solution was standardized against iron wire and it was found that 1 c. When the boiling is stopped. in a is weighed out. The wire is cleaned by rubbing with a piece of emery paper until It is then passed through filter-paper until perfectly bright. p. 98 Determination of the Apparent Iron Value of Iron Wire. iron value should be determined.. K.c. The actual purity of the wire was determined to be 99. . sodium bicarbonate is sucked back 620). * and contains 55 c.. and a portion of 0. flask which is fitted with a Bunsen valve it is it H the of dilute sulphuric acid (50 c. Every time a new supply of iron wire is obtained its apparent oxalate.c.94 per cent. 2 SO 4 ) solution is boiled f a few minutes after the iron has all dissolved. It is allowed to cool. the average of which is 99. 298) The boiling of the solution is necessary.7 per cent.92 per cent. into the solution. 1899. Cf. as described on p. = 0. (Chem.

If t c. p. necessary To effect the reduction of a ferric sulphate solution we can to apply this first proceed as follows The solution is placed in a 200-c. of iron. e. method to the analysis of ferric compounds. flask. From what has already been said. it is to reduce them completely. Besides hydrogen sulphide..c. in the case of hydrochloric acid too high results will be obtained . present entirely in it is necessary for the iron to be the ferrous condition. The use of these substances will be discussed in the portion of this book devoted to Volumetric Analysis. tion is then allowed to cool in an atmosphere of carbon dioxide and titrated exactly as in the standardization of the solution of permanganate. zinc. The titration of a solution by means of potassium permanganate takes place preferably in a sulphuric acid solution. therefore. of the permanganate corresponds to a gm. Analysis of Ferric Compounds according to the Method of Margueritte.g. it is evident that in order to determine the amount of iron present in a solution by titration with potassium permanganate. On the other hand.c. acidified with one-tenth its volume of pure. of permanganate were necessary to completely oxidize the solution and 1 c. then the titrated solution evidently contains a t gm. iron. Remark. sulphurous acid. it will See Volumetric Analysis. 597. it must be admitted that the standardization against sodium oxalate is full as accurate and is easier to carry standardizations and out. the flask is closed with a stopper provided with two tubes through : which gas can enter and leave the flask.c. is The now passed through boiling is continued the solution until the The soluexcess of hydrogen sulphide is completely removed. of . In order. a great many other substances can be used to reduce the ferric salt. stannous chloride. 99 be necessary to standardize against electrolytic iron only when a new supply of iron is purchased. the contents of the flask are heated to boiling and hydrogen sulphide is passed through the solution until it is and carbon dioxide perfectly colorless.ANALYSIS OF FERRIC COMPOUNDS. concentrated sulphuric acid.

2593. . but as in the case of method is preferable. from which it ignition into Ti0 2 In is these all changed by . Furthermore. p. the yellow color increases with the of titanium present and is not altered by an excess of amount On the other hand. is determined as its if only small amounts are to be determined. phosphoric acid is added to the colored * If.* (Suitable for small amounts . The two former methods are preferable separation of titanium from aluminium. of iron does not affect the reaction. Titanium. since they also give The presence of small amounts colorations with hydrogen peroxide. cases it is precipitated as titanic acid. (a) Determination as Titanium Dioxide. many rocks and iron ores.1. finally. chromic.) This determination depends upon the fact that acid solutions of titanium sulphate are colored intensely yellow when treated with hydrogen peroxide. Determination of Titanium Colorimetrically A. Method See of of titanium. when present in large amounts. and molybdic acids must not be present. The titanium is precipitated from solution either by means of ammonia. or by boiling a solution strongly acid with acetic acid and containing considerable ammonium acetate. 100 (due to the fact that the permanganate oxidizes some of the acid). but large amounts of iron cause trouble on account of the color of the iron solution. however. TiO 2 . by boiling the slightly acid solution of the sulphate. 48. the colorimetric dioxide. unless the oxidation takes place in a dilute solution in the presence of a large excess of manganous TITANIUM. Weller. 15. . Wt. ferric solution it becomes Berichte. vanadic. At. inaccurate results are obtained in the presence of hydrofluoric acid (Hillebrand) consequently it is not permissible to use hydrogen peroxide for this hydrogen peroxide. determination which has been prepared from barium peroxide by means of hydrofluosilicic acid. sulphate. Ti. (6) to the third. See Volumetric Analysis. or.GRAVIMETRIC ANALYSIS.

finally dissolving in a little concentrated sulphuric acid and diluting with 5 per cent.c.c. Am. 481 (1907). On extracting with water. Chem.00005 gm.. sodium pertitanate goes into solution and The filtered solution is acidified with ferric oxide is left behind. H. Jr. The determination proper is carried out in the same TiO2 . which is added until 5 per cent. of solution give a distinctly visible yellow coloration. of 3 per cent. The reaction is so delicate that 0. 60.6000 gm. only suitable for the estimation of small amounts of titanium. of free acid is iron * The hydrogen peroxide solution is prepared shortly before using dissolving commercial potassium percarbonate in dilute sulphuric acid.2 gm. at least 5 per cent..DETERMINATION OF TITANIUM. hydrogen perThe color of the solution oxide * (free from hydrofluoric acid) the standards. 29.c. f J. filled up to the mark with water and each treated with 2 c. of TiO 2 present as sulphate in 50 c. According to J. One cubic centimeter of this solution corresponds to 0. Soc. way described on p. of TiO 2 ). by .002 gm. IOI and from such a solution the determination of titanium no The solution in which the titanium is to be offers difficulty. decolorized. For this determination a standard solution of titanium sulphate This can be prepared by taking 0. each containing a known amount of the standard titantium solution. sulphuric acid. sulphuric acid to 100 c. with This method is is in question compared . 50 c.f titanium in the pr3sence of may be determined after fusing the finely powdered substance with two or three times as much sodium peroxide. of porequired. of the solution which has been brought to a definite and accurately measured volume is placed in a Xessler tube beside a series of other tubes. of sulphuric acid. as the shades of strongly colored solutions cannot be compared accurately.c. expelling the excess of acid by gentle ignition. must contain determined an excess does not influence the reaction. This is treated in a platinum crucible several times with a little water lized and concentrated sulphuric acid. Walton. tassium titanic fluoride which has been several times recrystal- is and gently ignited (corresponding to 0. under the colorimetric determination of as am- monium.

Barium Chromate. At.1. the filtrate is then colored pink. . and ignited wet in a platinum crucible. and the chromium is all precipitated. From the filtrate the chromium is determined as barium chromate in acetic acid solu- tion as described below. . Chromic Compounds. (a) 3 . Cr 2 O3. by of a slightest possible excess of ammonia * in the presence If the it chromium Ammonia is ammonium salts (or better still. as described under Phosphoric Acid. The melt is dissolved in water. too high on account of the formation of small amounts of alkali chromate even though the entire opera- The alkali comes from the can be shown that the ignited product contains a little chromate. Cr. 102 The present. present in solution as chromic compound be precipitated exactly as described under aluminium. reagents. It of silver chromate. color of the solution is known weight of obtained by fusing a CHROMIUM. whereby sodium chromate and sodium phosphate are obtained. being thereto the The results obtained are always oxide. Forms: Chromic Oxide. and the phosphoric acid precipitated by means of ammonia and magnesia mixture. 1. as the aqueous extraction always possesses a slight yellow color and gives with silver nitrate a red precipitate tion takes place in platinum vessels. 52. By Precipitation with can means or Ammonium Sulphide. In this case the dried precipitate is fused in a platinum crucible with sodium carbonate and potassium nitrate. acidified with nitric acid. Wt. by the addition of prepared ammonium sulphide solution to the boiling soluThe precipitated Cr(OH) 3 is washed with dilute ammonium of considerable freshly tion) . BaCr04 .GRAVIMETRIC ANALYSIS. * An excess of ammonia prevents the complete precipitation of tne chromium hydroxide. If phosphoric acid is present. changed nitrate solution by a few tenths of a per cent. In such cases tlio filtrate must be boiled until the excess of ammonia is expelled. Cr2 then compared with that Ti0 2 with Na2 O 2 etc. Determination as Chromic Oxide. it will be found in the precipitate.

. 83). By Precipitation with hydrox- preferably through a hot water precipitate is ignited wet in a Ammonium Nitrite. 1909. flocculent precipitate of chromic and is filtered The under slight suction. ammonia is added drop by drop until the odor ammonia barely persists in the solution. treated with a little more iodide and iodate and then again with a few c. aluminium. and heated half an hour on The the water-bath. 1287) iron. % If the solution of the chromic salt is acid. According to Scholler J E. By Potassium with Precipitation 103 Iodide lodate Solution.. until a faint permanent turbidity is obtained. 1909. KOH and Schrauth precipitated (ibid. f If the solution is strongly acid. p. 2. washed with hot water. it is neutralized by the addition of pure solution drop by drop.c. free is Chromates. This precipitate is dissolved by the addition of a few drops of hydrochloric acid and then an excess of 6 per cent. Chem. and weighed as Cr 2 O 3 of free is . The precipitate allowed to settle while the beaker remains on the water-bath. Cf. Schirm. and zinc can be . 877. 1901. (&) If the chromium chromate. ide settles quickly.CHROMIUM. 111. p. filter 3. chromium. contained in a porcelain treated with a mixture of potassium iodide and iodate. dish. Method of Stock and Massaciu* The determination is The slightly (cf. of sodium thiosulphate. decolorized after a few minutes by means of sodium thiosulphate solution. and is finally filtered off. platinum crucible. ignited wet in a platinum crucible. ammonium nitrite solution is added and the liquid boiled until all nitrous fumes have been expelled. but in order to throw down the last traces. is aluminium carried out as in the case of acid f solution. by means of aniline.. * Ber. present in solution in the form of an alkali from chloride and large amounts of sulphuric acid. it is neutralized with ammonia until a slight permanent precipitate is obtained. By this means practically all of the chromium will have been precipitated. 467. Ztg.

dried and separated from the filter as completely as possible. This excellent method for the determination of chromium If unfortunately permits only a very limited application. weighing the residue as Cr2 3 The purity of the mercurous nitrate must be tested before using 5 gms. it. on ignition the it latter is changed to OO 2 3 . be deter- just as accurately. or one weakly acid with acetic treated at the boiling temperature with a solution of barium acetate added drop by drop. gently at first and finally strongly. in a platinum crucible under a hood with a good draft. therefore.* and * If the barium acetate solution is after standing for added too quickly some some of it time. or it much more conveniently. will be . and mined by precipitating as may Barium Chromate. the solution contains any considerable amount of chloride. The filter is burned in a platinum spiral and ignited with the main portion of the precipitate. it is necessary to determine chromium present as chromate in a solution containing chloride. the precipitate is filtered verted into the neutral salt quickly. fiery red. is The neutral solution. On heating to mercurous chromate. is formed. Hg2 CrO 4 This red salt settles very the precipitation is complete the solution above the precipitate will be colorless. although volatile on ignition. acid. The neutral or weakly acid solution is treated with a solution of pure mercurous nitrate whereby brown. (4Hg 2 O 3CrO 3 ). . afterwards off. a becomes the beautiful. if washed thoroughly with water containing a little mercurous nitrate. Procedure. precipitate . If. basic Procedure.GRAVIMETRIC ANALYSIS. After cooling. two other methods are at our disposal. being conboiling. The chromate may be reduced by boiling with sulphurous acid chloric acid and (or by evaporating with concentrated hydro- alcohol) and analyzed according to (a). mercurous chloride will be precipitated with the mercurous chromate. and . which. renders the precipitate too bulky and the method inaccurate. which is weighed after gentle ignition. 104 may be determined very accurately by precipitation with mercurous nitrate solution as mercurous chromate. of the salt should leave no residue after being ignited.

as otherwise the filter will soon get stopped up solution will filter extremely slowly). purified present as chromate may be very accurately detervolumetric methods. page 27) and heated. The precipitate is and the washed with dilute alcohol and dried in the hot closet. so that too high results will be . at first gently. The latter gradually takes on oxygen from the air during the long-continued heating of the open crucible. when it is cooled in a desiccator and weighed. is filtered 105 through a Gooch crucible (without using very strong suction. The crucible is suspended in a larger one of porcelain by means of an asbestos ring (cf. If a grams of chroma te were taken for analysis. and the barium chromate precipitate weighed p grams. so that the green color gradually disappears.BARIUM CHROM ATE. the barium chromate. carried down with obtained. then the amount of chromium present may be calculated as follows: BaCrO 4 Cr=p : : s Cr ~BaCrO/ P ' and 100 Cr for practice: Potassium bichromate.) of chromic acid to chromic oxide. traces of alcohol. After five minutes the cover is removed and the heating is continued until the precipitate appears a uniform yellow throughout. etc. as will be shown under Volumetric Chromium mined by Analysis. and finally over the full flame of a good Bunsen burner. Sometimes the precipitate appears green on the sides of the crucible owing to a slight reduction (by means of dust. dried Example and K Cr O 2 2 7. as described on pages 33 and 35.

78. best in a closed und the most a brown powder. the 3 dirty green or black. or over the blastlamp. * Ann. U. in a current of hydrogen. 2 O) in or chloric H H Hillebrand). U 8. U.GRAVIMETRIC ANA LYSIS. but soluble in concentrated also soluble in nitric acid.f the of UO 3 8 is completely dissolved with the formation uranous and uranyl sulphate: U UO 3 8 + 4H S0 = 2U0 2 4 2 (S0 4 ) +U (SO 4 ) 2 f 4H2 O. O 8 appears According to the temperature of ignition.. tube. By heating with dilute sulphuric acid (1 vol. the error is. for a long time (W. 238. Ch. is Ph. Geol. a closed tube at 150-175 C. p. 232 (1886). t Bull. advantage of in the volumetric determination of uranium (which is 8 3 (6) Determination as UO 2. in nitric acid it dissolves gradually. This . until a constant weight is obtained This whereby it is quantitatively changed to UO 2 accurate method for the determination of uranium. insoluble in dilute acids. d. is heated over a good Teclu burner. however. UO 3 8 and U0 Determination as 2. wt. S. Survey. 3 almost always precipitated by means of ammonia uranate and changed to U 3O 8 by gentle ignition in a platinum crucible with free access of air. The ignited precipitate. 287. Uranium as is ammonium so small that for ordinary purposes it can be neglected. According to Zimmerman * this transformation is only complete when the precipitate is ignited in a stream of oxygen.5. . 106 URANIUM. obtained in exactly the same way as before. also readily soluble in dilute sulphuric acid in the These two last facts are taken presence of potassium bichromate. The UO 2 thus obtained is hydrochloric and sulphuric sulphuric oxide is acid after long heating. F. cone. and is difficultly soluble in dilute hydro- U sulphuric acids. p. Forms: (a) At. 90. 2 SO4 + 6 vol..

t acid. Chromium. The precipitate contains the iron as hydroxide. ' . diluted with hot water. filtrate from the by acidifying with precipitated as hydroxide nitric acid and then adding ammonia. and weighed as Fe^ hydrogen sulphide is passed into the solution until it is saturated. and Uranium from Calcium.SEPARATION OF IRON FROM ALUMINIUM. and filtered. while the solution contains the aluminium as aluminate. and the sulphide It is then of iron is allowed to settle in a closed Erlenmeyer flask. the aluminium.A1 2 O 3 )). Barium. after filtration. and Magne- Separation sium.* dissolved in For the iron hydrochloric determination the precipitate is with ammonia. in hydrochloric acid and to reprecipitate with ammonium sulphide. reprecipitated The aluminium is (see page 83). The acid solution is treated with tartaric acid (three parts (2) of tartaric acid for each part of the mixed oxides (Fe^^. 107 of Iron. chromium. Titanium. some of it is almost always present in the precipitate. It contains the iron and uranium as sulphides. as slight an excess as possible of ammonia is added. boiled. Instead of using ammonium sulphide. Separation of Iron from Aluminium. so that it flask nium sulphide then necessary to dissolve the precipitate. After standing overnight the precipitate is filtered off and washed with water containing ammonium sulphide. very hard to wash the be dissolved in hydrochloric acid KOH precipitate free from alkali so that the precipitate should not be weighed. The solution containing the above substances in the presence ammonium chloride is placed in an Erlenmeyer of considerable and treated with a slight excess of freshly prepared ammofree from sulphate and carbonate. the iron must then be in the ferric condition. (1) The solution is treated in a porcelain dish with pure potassium hydroxide solution until strongly alkaline. dried. * If the precipitate and again t It first is is large. as hydroxides. the separation can be is accomplished satisfactorily with ammonia. Aluminium. and titanium In case large amounts of magnesium are present. it should precipitated with KOH. Strontium.

for each 0. with on page ammonium oxidize with monia. it is (3) The neutral the nitrates) is solution of the chlorides or sulphates (not treated with sodium carbonate until a slight permanent precipitate is formed. the SO 2 boiled described iron acid. and the aluminium precipitated from the solution by the addition of ammonia. The solution is diluted to about 250 c. which is ignited gently until all the sulphur has been expelled and then more strongly off. over the blast or a Teclu burner until the weight is constant.2NaCl + Na 3 is 2 S 4 O 6 + 2FeCl 2 . 87. still filter. The residue is gently ignited in a platinum dish in order to destroy the tartaric acid. the filtrate may be acidified with hydrochloric acid. oxidized with a little potassium chlorate or nitric acid. the solu- and precipitated by ammonia acid. the filter burned in a platinum spiral and the ash added to the crucible. and the solution S0 2 has disappeared. transferred as completely as possible to a porcelain crucible. dissolved in hydrochloric acid. tion oxidized with nitric acid It is sulphide. washed with water containing ammonium sulphide.1 or 0.c. after which dissolved in dilute nitric acid. nitric off. dried. To determine the iron. reduced to ferrous salt boiled until every trace of tion the ferric salt 2Na2 S 2 is 3 and the aluminium By this opera- : + 2FeCl . and precipitated as ferric hydroxide by the addition of ammonia. of the metals present.GRAVIMETRIC ANALYSIS. + 3H 2 O + 3Na 2 S 2 O 3 = 6NaGl + 3SO 2 + 3S + 2 Al (OH) 3 . 108 filtered. the sulphur filtered off. the carbon filtered off. precipitated as the hydroxide: 2 A1C1. which is dissolved by the addition of a few drops of hydrochloric acid. an excess of sodium thiosulphate solution is added. The aluminium is determined in the nitrate by evaporating to dryness with the addition of a little sodium carbonate and potassium nitrate. as to precipitate the dissolve in hydrochloric better and then precipitate with am- .2 gm. The precipitate of aluminium hydroxide and sulphur is filtered washed with hot water.

ignited in a platinum crucible. Chem. Z. and the melt is dissolved by warming gently. on the other hand. the solution is heated and saturated with hydrogen sulphide. Vol. The iron is then titrated with potassium permanganate solution The aluminium is determined by differas described on page 99. and which can be detected by the produced by ammonia. The mixture is then digested with concentrated hydrochloric acid to which a little water has been added (10HC1:1H 2 O) in a covered crucible until the iron is com- If ferric oxide predominates. The reduction of the ferric salt to ferrous salt by means of hydrogen sulphide possesses great advantages over the reduction by means of zinc. filtered.. and furthermore zinc serves to reduce the titanic acid is * E. the If. The crucible together with its cover is placed in a beaker. as is frequently pletely dissolved. K 2 S 2 O7 (cf.. water and a little sulphuric acid are added. Both (4) of the metals are precipitated 109 with ammonia. a relatively large amount of alumina is present (as is usually the case with silicates). I).HF works better. small amount of platinum is always dissolved by this treatment. For the determination of iron in silicates the above process is most suitable (Hilleis r brand). the precipitate very slowly and in many cases only incom- color of the precipitate then dissolves pletely. 815.SEPARATION OF IRON FROM ALUMINIUM. The solution to boiling a flask and carbon dioxide is then it until the excess of filtered into is passed through hydrogen sulphide completely removed. dried. The contents of the flask are then cooled by placing the flask in cold w ater. A After removing the crucible and its cover. . washed. and passing a current of air through the solution in order to keep the liquid in motion. angew. for in the former case no foreign element is introduced. and the weight of the combined oxides determined. the carbon dioxide still passing through the flask. from the weight of the combined oxides. The platinum not attached and the solution is effected more readily. Deussen finds that fusion with KF. is effected in one or two hours. In the latter case the ignited oxides are brought into solution by fusing with 12-15 times as much potassium pyrosulphate. ence. 1905. solution the case.* The decomposition of the oxides is usually complete in 2-4 hours.

no GRAVIMETRIC ANALYSIS. The latter method is to be recommended for the determination The reduction watch-glass. is almost always present in rocks. * If titanium is present.c. as is usually titration. the solution is treated with a few cubic centimeters of dilute sulphuric acid. free from iron. but the results of small is are not quite so reliable: The solution from which the iron and aluminium are to be.g. the case. After cooling. + Pt + 2HC1= The chloroplatinic acid is H PtCl 2 -f 4FeCl2 . f Platinum solution is perceptibly attacked by long digestion with ferric chloride : 4FeCl. as the case in the analysis of mineral waters. so that too high an iron value will be ob- that by tained.. and the solution is titrated with potassium permanganate solution. determined is volume (e. The with the excess of zinc into a flask already filled with carbon dioxide. while in the other the iron is determined by If the solution contains hydrochloric acid. If the iron is all is by treating the oxides with hydroevaporated to dryness and the residue dissolved chloric acid.) and two by means of a pipette (usually 100 diluted to a definite aliquot portions are taken c. filtered.* slight residue of platinum f is is filtered off amounts of iron in the presence of still less aluminium. the product is dissolved in water and the ferric sulphate reduced to ferrous sulphate by introducing a piece of zinc. and then heated over the free flame until fumes of sulphuric acid are evolved.). the iron is first precipitated with ammonia. The following procedure leads to the same end. . into the crucible and covering the latter with a complete in 20-30 minutes. reduced to platinum by the action of zinc. evaporated on the water-bath as far as possible. the solution is reduced by means of hydrogen sulphide. and this will be again oxidized the permanganate. 250 c. In one portion the weight of the combined oxides of iron and aluminium is determined by precipitation with ammonia and ignition of the precipitate.c. The residue is washed with water that has been boiled.

as phosphates of these metals. Vol. In the first case the determination of all three constituents must be undertaken in the same portion. under Iron).* is Separation of Iron. and phosphoric acid.f platinum crucible in a and weighed: Fe2O 3 + A1 2 O 3 + P 2 O5 = A. Anal. Aluminium. The solution is first treated with ammonia whereby the iron. ALUMINIUM. in The solution washed. The solution contains large amounts of these substances. to which a little ammonium carbonate has been added. the melt is extracted with water. is consisting of four parts anhydrous * It is necessary to get rid of the hydrochloric acid on account of its action upon potassium permanganate (cf. we will describe its determination in the presence of iron and aluminium because this highly important separation is necessary in the analysis of almost all minerals containing iron and aluminium as well as in the analysis of many mineral waters. and Phosphoric Acid. the filtrate is evaporated with hydrochloric acid on the water-bath to dryness. Although the determination of phosphoric acid has not yet been considered. while the residue contains all of the iron and aluminium and considerable silica. as otherwise errors would be introduced on account of the small amounts to be determined. aluminium. 2. alu- minium and phosphoric acid The precipitate is ignited are precipitated. The product then fused with six times its weight of a mixture sodium carbonate and one part pure silica. 1. and dissolved in dilute sulphuric acid.. The solution contains only a small amount (a few centigrams or less) of iron. t The phosphoric acid is usually present in such small amounts that the iron and aluminium are more than sufficient to effect the precipitation of all the phosphoric acid. Two cases are to be distinguished: 1. on the addition of ammonia. The filtrate contains all of the phosphoric acid and a very little silicic acid. For the determination of the phosphoric acid. then reduced and titrated as previously described.SEPARATION OF IRON. and filtered. PHOSPHORIC ACID. . The mixture is heated over the blast-lamp.

For the determination of the iron. or iodimetricaily with titanous chloride may (cf. and then over a free flame until fumes of sulphuric anhydride are evolved.H2 GRAVIMETRIC ANALYSIS. . 109. 699. be titrated directly 681). p. the ferric salt (cf. evaporated on the water-bath as far as possible. in the second the phosphoric acid is determined by the molybdate method and in the third the iron is determined 2. aluminium. obtained after treating the product of the fusion with water and ammonium carbonate. after removing the excess of hydrogen sulphide. in order to remove the silica. After cooling. calculated (=B): Mg P 2 2 7 :P 2 5 =p:B. and phosphoric acid. the insoluble residue. water is added and after digesting on the water-bath for a long time the silica is filtered the solution reduced by means of hydrogen sulphide (cf. taken up in a little phosphate is changed to magnesium pyrophosphate by ignition and from its weight p the amount of phosphoric anhydride. it is divided into three aliquot por" A " is determined by precipitation tions and in one the value of with ammonia. 4). filtered. P 2 O 5 is . p. In case the solution contains large amounts of iron. in which the iron is determined volumetrically and the aluminium by difference.* From the the iron amount of permanganate used. the amount of ferric oxide (C) can be calculated. and the phosphoric acid precipitated in the filtrate by the addition of ammonia and "magnesia mixture. the residue is moistened with hydro- water. sub. off. and. with dilute sulphuric acid. the weight of the A1 2 O 3 is ascertained : A-(B+C)=A1 2 3 . and by deducting this amount from the weight of the combined oxides. is digested with hydrochloric acid in a small porcelain crucible The solution is treated until the iron oxide is completely dissolved." The precipitate of magnesium ammonium chloric acid. p. by titration. * Instead of reducing the iron. By subtracting B from A the combined weight of the iron and aluminium oxides is obtained. . is titrated with permanganate solution.

If the latter is present. warmed on the water-bath and chlorine gas is conducted through the liquid. or bromine water is added. it is the melt is extracted with water. The insoluble the solution residue from the aqueous extraction of the fusion hydrochloric acid. and the iron deter- desired to precipitate the chromium as mercurous chromate. hydroxide The Procedure. is ammonia and the chromium determined as In the case of a precipitate containing iron and chromic oxides. If it is is dissolved in with ammonia. The chromium 1. The The solution is filtrate is carefully acidified chromium precipitated by the addition barium acetate. If the chromate is barium chro- to be determined as mate. hydroxide has asthe oxidation When performed by chlorine gas. 0. of the mixed oxides will be completely oxidized in fifteen to twenty minutes. fused with sodium carbonate and a little potassium chlorate. which should be placed in an Erlenmeyer flask of Jena glass provided with a ground-glass stopper and tubes by which gas may enter and leave treated with potassium hydroxide solution until strongly alkaline. the precipitate containing the iron and chromic oxides is fused with sodium carbonate and potassium nitrate. in hydrochloric acid.5 gm. diluted with water with acetic and acid. the filtered. is by means of and the insoluble ferric oxidized in alkaline solution chlorine or bromine to a soluble chromate is filtered off. solution of the chlorides. 104.SEPARATION OF IRON FROM CHROMIUM. until the flask. the melt . and the precipitate of barium chromate is The ferric hydroxide is dissolved treated as described on p. the chromate is reduced by evaporating with hydrochloric acid and alcohol. it becomes distinctly yellow and the sumed is is its ferric characteristic reddish-brown color. the solution of chromic chloride thus obtained precipitated with chromic oxide. the solution must contain no sulphuric acid. 113 Separation of Iron from Chromium. precipitated mined as ferric oxide. Remark. and the chromium is determined in by precipitating with barium acetate. reprecipitated with ammonia and weighed of as ferric oxide.

H4 GRA VIMETRIC ANALYSIS. the chromium is already present as chromate. 2. while the chromic oxide is unchanged. 104. for the ferric oxide is so enveloped in chromic oxide that it is not even approximately re- duced even when heated over the blast-lamp. the is at once precipitated with ammonia as hydroxide. it is made oxidized by strongly alkaline The solution is then acidified with and the aluminium precipitated by ammonia as hydroxIn the absence of sulphuric acid ide. present as chromic in a solution bromine salt. Separation of If the means chromium of chlorine or is Aluminium from Chromium. being weighed as the oxide. aluminium Separation of Iron from Titanium. the chromate is with potassium hydroxide. and weighed as the oxide If. If sulphuric acid is present. but it is more often necessary to determine It is frequently necessary to determine in a precipitate t : J . as described on p. seems from This method. simple. The iron could then be determined by the loss of weight. 2. Iron may be separated from chromium by precipitating the former with ammonium sulphide from a solution containing sufficient ammonium tartrate to prevent the precipitation of the is the same as was described under The separation chromium. however. 3. the solution neutralized with nitric acid and precipitated with mercurous nitrate solution. p. It has been proposed to analyze the mixture of ferric and chromic oxides by strongly igniting them in a stream of hydrogen whereby the ferric oxide is reduced to metallic iron. although theoretically very experiments carried out in the author's laboratory to be absolutely inadequate. sub. extracted with water. aluminium. precipitated with ammonia. both iron and titanium produced by ammonia consisting of a mixture of these two oxides alone. nitric acid. reduced to chromic salt again by the action of concentrated hydrochloric acid and alcohol. p. the chromium may be determined in the nitrate as barium chromate (cf. 104). 107.

The solution thus obtained is diluted to a definite volume. aluminium. sulphur. one being used for the determination of titanium and the other for the determination of iron. obtained. For the iron determination. all of which are precipitated by ammonia in the analysis of rocks. and weighed as carbon dioxide . and the solution is hastened by keeping the liquid in motion by means of a current of air passed through it. and 5 gms. For the separation of titanium from iron in the absence of alumina. when it is cooled in an atmosphere of carbon dioxide and then titrated with permanganate. The filtrate is heated to boiling and is passed through the solution until the excess of hydrogen sulphide is completely removed. saturated with hydrogen sulphide in the cold. The solution from the pyrosulphate fusion. the melt is dissolved in cold water containing sulphuric acid. 115 titanium in the presence of iron. ignited wet in a platinum crucible. heated to boiling. and the precipitate of platinum sulphide. . washed with water containing hydrogen sulphide. Carbon dioxide is conducted through the solution. obtained is If considerable iron likely to is present. and washed thoroughly with hot water. In this way a precipitate free from is iron is 2. TiO 2 . the titanic oxide thus It is brought into solution contain iron. For the titanium determination. and phosphoric acid. the following methods are suitable 1. the other part of the solution is treated with sodium carbonate solution until a slight precipitate is formed this is dissolved in as little sulphuric acid as possible. footnote tD pa~e ICO. it is heated to boiling. again by fusing with potassium pyrosulphate and the precipitation repeated exactly as before. Remark. The precipitate produced by ammonia is ignited and then : fused with 15-20 times as much of previously dehydrated potassium pyrosulphate over a small flame until completely attacked. . and after being thoroughly mixed is divided into two portions. the acid solution is saturated with hydrogen sulphide in the cold. in this case after being * Cf. filtered hot. and a little titanium is filtered off into a flask filled with carbon dioxide.SEPARATION OF IRON FROM TITANIUM. of sodium acetate which has been neutralized with acetic acid* are added. After cooling. The Chancel-Stromayer method is also satisfactory.

During the filtration. pp. howtated. heated to boiling.GRAyiMETRIC ANALYSIS.c. however. in which case a considerable amount of titanic acid remains in solution. and the precipitate of sulphur and platinum sulphide (the latter from the platinum crucible in which the fusion with pyrosulphate was the filtrate is acidified * Chemical News. II 6 neutralized with sodium carbonate. while the aluminium The sulphide of iron is filtered titanium remain in solution. iron the metatitanic acid obtained by this method is also contamthe inated with iron. . so that ever. is treated with an excess of sodium thiosulphate. and off. so that the method of Gooch will be described for this more general case. It has been proposed to effect this separation by diluting to a considerable volume the slightly acid solution of the melt obtained by the potassium pyrosulphate fusion and boiling for some time. for alumina is presolution. Aluminium from Titanium. however. the amount of aluminium present is large (as is usual in rock analysis). thereby precipitating the titanium and leaving the aluminium in This method. and then made slightly ammoniacal. is useless. In practice it is almost always necessary to separate the titanium not from aluminium alone. 52. is saturated with hydrogen sulphide gas. cipitated with the metatitanic acid unless the solution contains enough acid to prevent this hydrolysis.* it consists of boiling a two elements containing considerable free acetic acid and alkali acetate by this means all of the titanium and none of the aluminium is precipitated. titanium being incomplete. the precipitate will contain some aluminium. with sulphuric acid. 55 and 68. and boiled for In this way me ta titanic acid and sulphur are precipiiron while remains in solution. If. In the presence of considerable first method is preferable. so that the separation Separation of must be repeated. diluted to about 400-500 c. the divided sulphur passes through the filter. By this means all of the iron is precipitated as ferrous sulphide. but from iron and aluminium. The best separation is that of Gooch. finely some time. In no case is there danger of the precipitation of the solution of the . The solution obtained by dissolving the pyrosulphate melt cold water is treated with three times as much in tartaric acid as the weight of the oxides. so that the separation must be repeated.

p. 117 The filtrate is boiled to expel the last traces and the tartaric acid is destroyed by adding hydrogen sulphide much as times 2^ potassium permanganate as the amount of tartaric acid present.* transferred to the filter. for usually the the precipitate amount of titanium present and wash quickly. cone. tThe sodium metatitanate is hydrolized and forms a taining a much higher percentage of TiO2 . of H H :1 vol. after which a slight excess of ammonia is added and then 7-10 c. the precipitate is filtered off. dried. The dried precipitate is burner for from Bunsen fifteen to twenty minutes over a ignited and then weighed.c. then with water. and the filtrate is decanted through a filter.c. *Schleicher <fc of very small Schiill's filter-paper Xo.c. and treated with 5 gm. practical example of this determination. allowing to stand until settled.9 c. is usually free from aluminium. acetic acid. of solution. washed with 7 per cent. acetic acid and finally with hot water. For the determination is so small that the precipitates filter amounts of titanium. The precipitate is filtered off by means of a small filter. the contents of the crucible are dissolved in 1. the precipitate is allowed to settle. so that it is again fused with sodium carbonate and the melt again treated This time etc. The melt (nade) is filtered off. exactly as described above. but the process should be repeated until a constant weight is obtained.. leaving sodium metatitanatef and some alumina undissolved. it is advisable to use the colorimetric method proposed by Weller Under the analysis of silicates will be discussed a (cf. cooling.SEPARATION OF ALUMINIUM FROM TITANIUM. 589 is satisfactory for this purpose. of glacial acetic acid for each 100 c. This precipitate usually contains aluminium. so that it is fused with three times as much sodium carbonate.c. of (colored green by the manganese) is leached with cold water. The solution is boiled for one minute. sulphuric acid (1 vol. and weighed. ignited. precipitate con- . The precipitate contains manganese and aluminium. washed with 7 per cent. is ignited in a platinum After crucible. and fused again with a little sodium carbonate. with sulphuric acid. 100). sodium acetate and one-tenth of its volume After boiling one minute and of glacial acetic acid. 2 SO 4 2 O) diluted to about 150-200 c. This analysis does not require much time. Sulphurous acid is then added until the precipitated manganese dioxide is redissolved.

solution of the ferric oxide and sodium titanate in hydrochloric acid. Chem. gr. sulphates and aluminates. and the mixture heated carefully until finally no more sulphuric acid fumes are evolved. Am. Soc. Isham. the beaker being rinsed * J. The residue in the and washed with hot water.) The hydrochloric acid washings from the platinum crucible are transferred to the beaker and the whole heated on the hot plate until solution is complete and the total volume reduced to 15 to 20 c.c..c.n8 GRAVIMETRIC ANALYSIS. evaporation to dryness and fusion with sodium carbonate and a little potassium fluoric nitrate (which converts the iron and titanium to insoluble ferric oxide and sodium acid titanate) extraction with hot water to remove the soluble phosphates. with hydrochloric 957 (1910). and any adhering particles of ferric oxide and sodium titanate are dissolved in hot hydrochloric treated with a little acid (sp. 1.1). of hydrofluoric acid. and 1 c. and heated until the melt is disintegrated. of 0. 1. 32. This solution is saved. Ferric oxide and sodium titanate are left insoluble in hot water. is water. accurate and not long. M. The solution is then cooled. gr. reduction of slight traces of iron with sulphurous acid. The crucible and cover are cooled. The sample Procedure. acid . washed. placed in a beaker. The crucible is removed. L. precipitation of the titanic acid by boiling in acetic acid solution. this stage of the analysis until after the treatment with ether. filtration and ignition to titanium oxide (or the titanium The method is may be determined colorimetrically) . Barnebey and R. and transferred to a separabeaker is filtered tory funnel. covered with hot water. Five or 10 grams of sodium carbonate and a little potassium nitrate are added and the mixture fused at least thirty minutes. 5 to 10 drops of sulphuric acid. weighed into a platinum crucible. extraction of ferric chloride with ether. Determination of Titanium in Rutile and Iron Ores. The filter is perforated and the residue carefully washed into a clean beaker with (No water is to be added from hydrochloric acid (sp.1).* This method is based on the volatilization of the silica Method by hydro- acid in the presence of sulphuric acid.

1) and the washings are added to the aqueous solution. iron and aluminium.1).c. which has been saturated with concentrated hydrochloric acid solution. gr. the stop-cock opened. c. 119 (sp. gr. The precipitated titanic acid cent. a rubber stopper is inserted in the top. containing considerable quantities salts. The cooled solution is diluted to about 100 c. ferrous salt oxidized to ferric salt by the addition of potassium UO2(CO3) 3 (XHJ 4 its . the funnel placed in an upright position and allowed to stand ten minutes.c. portions of hydrochloric acid (sp. finally filtered ammonium and washed with water sulphide. allowed to stand for in a closed flask. and nearly neutralized with ammonia. is heated to expel the dissolved ether. ignited Separation of The of is washed with 7 per filtered off. slightly acid solution. An equal volume 01 ether.1) are added. acetate are now added and the solution boiled for fifteen minutes. The stop-cock is then closed. 1. the solution acid. . 20 c. and the solution evaporated until fumes of sulphuric anhydride are evolved. in the filtrate is found all and the aluminium uranium as of the The precipitate is dissolved in hydrochloric freed from hydrogen sulphide by boiling. when the aqueous layer is drawn off into a second separatory The ether is rinsed twice by shaking well with 5 to 10 funnel. if solution containing all the titanium in the presany. The aqueous ence of little.DETERMINATION OF TITANIUM IN RUTILE AND IRON ORES. of sulphuric acid (1. 1. One or two grams of ammonium bisulphite are added and the solution heated on the hot Ten to 15 grams of ammonium plate for half an hour. iron as sulphide The precipitate contains the as hydroxide. Uranium from Iron and Aluminium. The treatment with ether repeated two or three times until the last portion of ether fails to show any greenish tinge due to the presence of dissolved is ferric chloride. is treated with an excess of ammonium car- ammonium bonate and then with some time containing ammonium sulphide. the funnel is inverted. and weighed as Ti0 2 .c. is added to the solution in the funnel. and the whole thoroughly shaken. acetic acid.

93. as ammonium uranate. NICKEL.GRAVIMETRIC ANALYSIS. of reducing . At. and weighed as UaOg. u. result obtained may repeatedly in a current of be verified by heating the residue hydrogen in a Rose crucible (see Copper Determination) until a constant weight is obtained. MnS0 4 MnS. p. After the sulphuric acid has been removed. MnSO 4 4. metric ally (see Volumetric Analysis). The walls of the smaller crucible p. should be separated from those of the larger one by about 1 cm. or of manganous manganite. with 2 per cent. (1898). precipitated. 27) serves for the air-bath. % f. Forms: Determination as i. Experiments performed by Schudel in the author's laboratory This method. 11. SO 2) or of pure hydrogen peroxide. Pharm. p. ZINC. ignited. d. 17. 54. agent (best anorg. Wt. 120 chlorate. evaporated as far as possible on the water-bath. . after which the excess of acid is removed by heating in an air-bath. 328. The filtrate containing the uranium is evaporated almost to dryness. is dissolved in as slight an excess of sulphuric acidt as possible in a porcelain crucible. MANGANESE. 198. ammonium washed precipitate nitrate solution to which a little ammonia has been added. The oxide obtained by the ignition of the carbonate. first proposed by Volhard. t and has been found strictly accurate. COBALT. Mn. Mn 2 P 2 O 7 Manganous Sulphate. The manganous manganite (Mn 3 O 4 ) requires the presence t Zeit. MANGANESE. DIVISION OF THE MONOXIDES. 264. Chem. Mn 3 . acidified with hydrochloric acid. B. the two crucibles * Ann. and the iron and aluminium determined by one of the methods described on pages 107-109. weighing as The purity of the precipitate may also be tested volu2 U0 . Chem. dried.. . sulphide. tested completely confirm Gooch's results. boiled. A porcelain crucible provided with an asbestos ring (see Fig.* has recently been by Gooch and Austin. and the uranium ammonia. by the addition The is The of filtered off. Procedure.

121 are covered and heated to redness over a good Bunsen burner. is filtered off. p.. allowed to cool in a desiccator and weighed. the precipitation is not always contains small amounts of quite quantitative. whereby the manganous car- bonate is completely decomposed hydrolytically into carbonic acid and manganous hydroxide. p. Chem. the precipitate will always contain After the alkali carbonate that cannot be removed by washing.*the precipitation is best accomplished ammonium carbonate. Mn3O< according to 2. therefore. the small amount . and the latter in contact with the air The residue obtained changes to brown manganic oxide. For this purpose the neutral solution (which may contain other ammonium salts) is treated with a slight excess of ammonium carbonate. washed with hot water.SEPARATION OF MANGANESE AS CARBONATE. Tamm. According to H. Remark. . 11 (1872). t Ch. and Zeit. 425. f. become clear. the remove to this. because no other metal that is precipitated by alkali carbonates can be simultaneously present. and by means of the beaker containing the solution is allowed to remain in a lukewarm water-bath until the precipitate has settled and the upper liquid has The ignited. The method. anal. alkali the carbonate can be precipitate has been ignited. News. however. warmed gently. is only suitable for the determination of manganese in solutions of pure manganese salts containing nothing else except alkali and ammonium salts. If either easily extracted by water. 26 (1872). the amount of manganese present may be calculated as follows: MnSO4 :Mn=p:rc ~ Mn Separation of Manganese as Carbonate. and weighed either as sulphate according to 1 or as precipitate dried. (a) This method for the separation of the manganese permits only a limited application. sodium or potassium carbonate is used to precipitate the manganese. 37. Mn 2 O 3 after the evaporation is treated with water. it is necessary to evapomanganese. From the weight of the manganous sulphate. Furthermore. In order filtrate rate the aqueous solution to dryness.

The solution is placed in an Erlenmeyer flask of Jena glass and about 5 gm. strontium. the flesh-colored precipitate will have settled. and a nium sulphide slight excess of freshly-prepared.c. or. is The clear upper liquid carefully decanted through a filter. solution of is washed three times by decannitrate to which has ammonium ammonium The precipitate is then sulphide. and allowed After this time to stand twenty-four hours. when the flame is increased * Schleicher & Schull's filter-paper No. barium. and washed with dilute ammonium sulphide water until 20 drops of the filtrate evaporated to dryness on a crucible-cover leave no residue. The uncovered crucible is heated over a small flame until the greater part of the sulphur has been burned off. and the ash crucible. been added 1 c. of ammonium chloride or ammonium nitrate are added. is If the precipitate is at all bulky. solution contains only small amounts of the alkaline earths or magnesium. better. besides manganese. corked.* taking pains not to disturb the precipitate and to keep the filter filled with liquid all the time. the manganese sulphide must be precipitated in the cold in the presence of considerable ammonium salts. ignited. In case the solution reacts acid. large amounts This method : of the alkaline earths or (/?) The magnesium.GRAVIMETRIC ANALYSIS. (a) In case large amounts of the alkaline earths or magnesium are present. it tation with a 5 per cent. . colorless solution added. still longer. The flask is ammo- now nearly filled with cold distilled water that has been boiled. (b) Separation of Manganese as Sulphide. 590 can be used to advantage. and magnesium. the filter-paper added to the main portion of the precipitate in the crucible. Now for the first time the filter As much of the preis allowed to drain completely and is dried. 122 of brown manganese compound filtered off. ammonia is added until it is slightly alkaline. and added to the main part of the precipitate. is employed when it is necessary to separate manfrom calcium. ganese We will distinguish between two different cases (a) The solution contains. of transferred to the filter cipitate as possible is transferred to a small thin-walled porcelain is burned in a platinum spiral.

sub. Mn O The heating is 4 (cf. p. 125. to evaporate the solution to dryness in order to remove all hydrogen sulphide. the reaction MnCl 2 + Br 2 + 2H 2 O<=MnO 2 + 2HC1 + 2HBr does not take place unless the halogen acids are neutralized as as they are formed. washed precipitate of manganous sulphide in dilute hydrochloric acid. The precipitate is allowed to settle for some minutes and is then filtered and washed with water containprecipitate the : ing a is the little same (c) If ammonium sulphide. (See p. a dilute solution of a bromine water and manganous salt is treated with boiled. on account of some manganous sulphate In this case it is advisable to dissolve the of getting a too high result not being decomposed.2 gm. such as sodium plished by even when the solution contains free acetic acid.) small amounts of alkaline earths are present. p. is in the quadrivalent . Manganous sulphide is readily changed to Mn3 O 4 if the amount of sulphide is comparaIn case more than 0. which acetate. 152) the mancan be precipitated quantitatively by boiling with an ganese excess of bromine water. (/?) In case only the following procedure can be used The neutral solution is heated to boiling.SEPARATION OF MANGANESE AS MANGANESE DIOXIDE. or the manganous sulphide can be weighed as such. as described under (a). 125. to dissolve the residue in a little water and to manganese as carbonate according to 1. 3). although most of the manganese . Thus obtained after the removal of iron and all in is aluminium b'y a basic acetate separation (cf. From this point the procedure Separation of Manganese as Manganese Dioxide. 3 repeated until a constant weight is obtained. and weighed as cooled. The oxide does not correspond exactly to Mn0 2. This neutralization can be accomof the means salt of a weak acid. is present there is danger tively small. fast is scarcely ionized at such as in a solution the presence of its alkali salt. and the crucible is finally 123 heated over the flame of a Teclu burner. an excess of ammonia and some ammonium sulphide is added and the boiling is continued until the manganous sulphide has become a dirty green.

Some chemists and weigh as Mn 3 4 but it is more accurate to dissolve the precipitate in a mixture of HC1 and H 2 S0 8 and to it settle. but these reagents have no especial advan- phosphate. the precipitation of the manganese can be effected. H 2 MnO 3 and some manganous manganite.) Chlorine.GRAVIMETRIC ANALYSIS. may be used instead of bromine. because the sodium acetate serves rather to neutralize the acid set free by the following reaction: 2NH C1 + 3Br = N + 2HC1 + 6HBr. + 3Br9 = 6HBr + N. it seems fair to assume Upon that the reaction goes through the following stages: MnCl 2 + 2NH 4 OH<=Mn (OH) 2 + 2NH 4C1. The MnO 2 acts as the anhydride of metamanganous acid. is filtered ignite this precipitate precipitate the manganese finally as manganese ammonium (See 4.* When flocks. 126. In that case present ammonia or considerable solution of nitrogen. and. precipitation with bromine and ammonia is not so satiswith bromine alone in the presence of acetic acid and as factory sodium acetate and in the absence of ammonia or ammonium The salt. the precipitation of the manganese does not take place by the above procedure. when of bromine is added the solution may become acid an excess enough to dissolve the precipitated manganese: 2NH. etc... p. 2 4 2 the addition of ammonia. the boiling the precipitate has collected together in large discontinued and the precipitate allowed to is and washed with hot water. In this case. tages. When the solution of the manganous salt contains ammonium salts. however. . moreover. hypochlorites. MnMnO 3 or Mn 2 O 3 is contained in the pre* . 124 condition. . hydrogen peroxide. because when ammonia used up in oxidizing the there is is much of the bromine is ammonium salt. cipitate.

57. but even then it is not possible to obtain a precipitate altogether free from these If the other metals are present only in small amounts. the manganese has been precipitated. . by this method are sufficiently accurate. Z.. when ammonium salts are present sure that the solution is ammoniacal at the end of the operation. at the oxides of manganese are slowly but quantitatively changed into 3 . as well as those compounds which are converted into oxide on ignition (manganous salts of volatile organic and inorganic acids. placed in a Rose crucible (of unglazed porcelain). Determination of Manganese as Inasmuch as all the oxides of manganese. This method of precipitating manganese from solutions possesses disadvantages which make it useless in many cases. It is make to 12$ necessary. 104 (1908). the filter is burned in a platinum spiral. the solution contains calcium. Some pure sulphur which has been crystallized from CS 2 is added. 530 Mn O 2 R. anorg. is weighed as MnS.DETERMINATION OF MANGANESE. Determination of Manganese as Sulphide. The manganese as sulphide in the presence of other always satisfactory and should be used in almost all cases. After the excess of sulphur has and been burned. If. this case the precipitate must be dissolved in hydrochloric acid and the precipitation repeated several times. results obtained precipitation of metals is 2. J. manIn ganites of these metals are precipitated with the manganese. therefore. with the ex* ception of the halogen salts). as described on p. zinc. as sulphide. Meyer and K. Retgers. besides manganese.. etc. Chem. it * Cf. the precipitate is separated from the filter as completely as possible. after which the crucible and its contents are heated in a current of hydrogen by means of a Bunsen burner exactly as described under the Determination of Copper as Sulphide. ignited temperatures 1100. and the ash If 122 added to the main portion of the precipitate. the metals. the crucible is cooled in a stream distilled off of hydrogen and the precipitate 3. are converted into Mn 3 O 4 on being in the at between 940 and air.

methods described under 1 and 2.GRAVIMETRIC ANALYSIS. 7.1027 gm. . by precipitating as sulphide and weighing as such. XVII (1898). Chem. Chem. until a slight excess is present. Mn. J Am. GibbsJ and The slightly acid solution. quite is if manganese is nearly as accurate as the the ignition of the precipitate takes place in an electric furnace at about 1000.. containing an amount of manganese corresponding to not over 0. is sulphide) entirely surrounded manganous manganite.c. anal. Chem. This excellent method was recommended by subsequently studied by Gooch and Austin. Z. Determination of Manganese as Manganese Pyrophosphate. the amount of its From is obtained with- contents are cooled in the weight p of the manganese can be calculated according to the equation 3Mn 4. 268. or by the oxidation flame of a Teclu burner. the crucible and a desiccator and then weighed. 18. Mn. 46. Mn2P2O7. 0.. W. 5 to 10 c. The solution is heated *Zeit. ammonium chloride. oxide.f After the ignition.1029 gm. J. 126 follows that this method for the determination of It generally applicable. anorg. 216. Z. Science.. Weitnauer are given. 101 (1868). whereby a moderately high heat out too much free access of air. and by changing the sulphate to Mn 3 O 4 0. but very good results are obtained if. accuracy of the three methods just described for the determination of manganese. Mn.1025 gm. * the porcelain crucible (containing the carbonate. He obtained after making six determinations by each method the following mean values: 50 c. 339 (1898). of a pure manganese sulphate solution treated with ammonium carbonate and changing the precipitate to sulphate f illustrate the gave 0. as recommended by Gooch. and no other metals except alkalies.c. To f. of a cold saturated solution of sodium phosphate. is treated with 20 gm. the following results obtained by H. anorg. Mn2 P2 7. . p. drop by drop.5 gm. and ammonia.

c. gr. 2 c. measuring-flask. If the solutions are colored exactly the same shade. If more than 1.5 gm. of this solution contains 0. 1 c. After thoroughly mixing.2) are added. treated with KMnO 4 . Exactly 0. 0. the warm. the results are The method depends upon the oxidation unreliable.c. of lead peroxide is added. Manganese can be determined very accurately by volumetric methods (see Volumetric Analysis). in nitrate solution. After flame is standing some time. the mixture shaken and then heated for two minutes to boiling.c. Small amounts of manganese may be determined by the colorimetric method. 127 to boiling and kept at this temperature for three or four minutes. when the is removed.c. ignited. 500 A standard solution of potassium permanganate prepared by dissolving 0. The acid which the mark with water. solution.5 per cent. is first c. 1. 10 c.c. of nitric acid (sp. is heated to boiling to effect complete solution. 5. 1. then the amounts of manganese which they contain are the same.05 mgm.072 gm.2 gm.2) in a 100-c. of manganese is present. gr. of the manganese permanganic acid.COLOR/METRIC DETERMINATION OF MANGANESE. After cooling. Colorimetric Determination of Manganese. of water. after solution is allowed to cool and diluted up to the c. or until the precipitate assumes a silky. violet-colored solution is filtered through a small asbestos filter* into a glass-stoppered test-tube * The asbestos must have been previously and finally washed with water. dried. accurately and quickly This is chiefly used for the estimation of the manganese present in iron arid steel. of the crystallized salt in Procedure. bringing the solution to a definite volume and comparing its color with another solution containing to a known amount of manganese. of manganese. and the liquid is heated until it begins to boil. of the iron or steel is dissolved in 15-20 of nitric acid (sp. crystalline appearance. the precipitate crucible. washed with cold is filtered through a Gooch or Munroe ammonium and ignited within a larger crucible or The results are excellent. an electric furnace.c. of the liquid are brought by means of a pipette into a small beaker.

Rather more accurate results are obtained if. 76 (1904). from acid with nitric or sulphuric acid. this is carefully diluted Assuming that 1 c. E. is Mn. instead of using a standard solution obtained from potassium permanganate. 239 (1904).02 gm.c.GRAVIMETRIC ANALYSIS. 128 about 20 cm. by the addition of alkali persulphates. and treated Marshall * and H. f is precipitated as manganous acid. Walters. and graduated in cubic centimeters. then as the concentrations of the two liquids are directly proportional to their heights. of the percentage of manganese present = 7=er cent. a fresh standard being prepared for each analysis. so that the is contained in 0. the tube is stoppered and shaken until the solution is thoroughly mixed. Into a filter is second tube of the same meters. 83.c.c. the oxidation goes farther and Although manganese solutions slightly *Chem. The height of the liquid in each tube is then carefully read. c.c. with water until the two liquids have exactly the same shade when viewed horizontally. of the standard solution were placed and diluted to T c. high. . The washed with as little water as possible.. 84. of the other solution. and also graduated in cubic centi- of the standard manganese solution. T:t = _ OM mgm. An even better colorimetric method has been devised by M. a sample of steel is used containing a known amount of manganese in exactly the same way as the sample to be analyzed. News. t Ibid. and is placed 1-5 size. in order to obtain the same in the cylinder shade produced by t c.::r 1 O05_mgm : This amount of manganese iron.

was recom- mended by L. . Chem. 144 (1905). NiC 8 H 14N 4 4 . and Of this solution 10 c. 20. angew. and the color is compared with a standard solution containing a known amount of permanganic acid.. 834 (1907). water).DETERMINATION OF NICKEL AS NICKEL GLYOXIME permanganic acid is formed within a short tune nch as silver nitrate. Or better a solution t Z. gr. 38. Chem. Ni(C 4 H 7 N 2 O 2 ) 2 . the bubbles of gas arising become more numerous and remain at the top for a few seconds. Nickel.38 gm. 1. Thereupon 10 c. AgXOa in a liter of c. O. the it to furnish a tative estimation of nickel either * of a steel of known manganese content. 20. mixed. After adding 2. ibid.2 Procedure. 58. are added. At. Ni. Ibid. of silver nitrate solution (1. and of cold nitric acid (sp. flask gm.. CH -CXOH-CXOH-CH 3 3..2). in a liter of water) the test-tube is sulphate to 90 and allowed to remain there until at 80 in water placed graduated test-tube. is present. J Z. are placed in glass-stoppered. 2Mn(XO 3 2 + 5 (XH 4 ) ) if a catalytic agent O 8 + 8H 2 O = 5 (NH 4 2 SO 4 + 5H 2 SO 4 + 4HNO 3 + 2HMn0 4 2S2 ) 0. and Nickel Oxide. of ammonium persolution (200 gm. the solution made up to exactly 100 c.c. .68. i. 1793 (1906). Kraut J for detecting the presence of traces of nickel in ashes. dissolved in 20 129 of steel is placed in a 100-c.c.* NICKEL. Ber. anorg.. acid enough to prevent the precipitation of iron by ammonia.c. Dimethyl glyoxime. Brunck and others have also studied the reaction and found most rapid and accurate method for the quantiby itself or in the presence of If the solution contains tartaric cobalt. Determination as Nickel Glyoxime.5 c.c.. Tschugaeff f as a reagent for nickel and used by K.c.c. NiO. Forms: Nickel Dimethyl Glyoxime. Ni. 1844 (1907). 2520 (1905). zinc and manganese. 19. 46. Wt. The solution is then cooled by placing the tube in cold water.

but an excess of ammonia tends to prevent the formation of the precipitate. however. When thrown down soluble. Dimethyl glyoxime. a red. crystalline precipitate of nickel dimethyl glyoxime is formed. so that not the solution smells slightly. the precipitate is filtered into a Gooch or Munroe crucible. The precipitate is distinctly soluble in absolute alcohol. The neutral or slightly acid* solution is diluted more than 0. neutral solution of a nickel salt is treated with an alcoholic solution dimethyl glyoxime. of 2(CH 3 ) 2 C 2 (NOH) 2 = (CH 3) 2C 2 (NO) 2 Ni. (CH 3 ) 2 C 2 (NOH) 2 Nickel dim3thyl glyoxime. heated nearly to boiling and treated with somewhat more than the theoretical amount of an alcoholic 1 per cent. if the mineral acid is neutralized by ammonia or if sodium acetate is added. When a dilute. The salt is soluble in mineral acids so that precipitation is incomplete because of the acid set free in the reaction.1 gm. but only traces dissolve in 50 per cent. The It nickel salt of dimethyl glyoxime is red and crystalline..31 per cent. etc. then the reagent is added. whereby the mineral acid is replaced by acetic acid in which the precipitate is prac- Large quantities of ammonium salts or of alkali acetate do no harm. the solution is nearly neutralized with caustic potash. * If strongly acid. of cobalt is present in 100 c.c. as the precipitate is soluble in alcohol. contains no water of crystallization and sublimes at 250 without decomposition. solution of dimethyl glyoxime. alcohol. and in more dilute alcohol it is even leas tically insoluble. 130 nickel in a sample of nickel steel can be determined accurately within two hours and without the removal of any other metal. washed with hot water and dried at 110 to 120 for 45 minutes. much to free ammonia the in the cold or in the presence of precipitate is very voluminous and hard filter. t The volume of the alcoholic solution should in no case be more than half that of the nickel solution. f Ammonia is then cautiously added until Procedure.GRAVIMETRIC ANALYSIS. It becomes quantitative. While still hot. . It contains 20. Ni.

178. Chem.% Fig. the gain in weight represents the quantity of nickel. Fig. anal. Fresenius and Bergmann. as well as for all other electrolytic determinations. about 2 cm. against the cold wax. * Xickel sulphate or chloride (but not the nitrate) an ammoniacal solution of The nickel end of the is and on to be is is dissolved in ammonium sulphate and electrolyzed. acid solutions the deposition is not quantitative. and accuracy this method for the determination of nickel. 19.. and from here to the decomposition cell finally back to the battery. anal. and the ends fastened to binding posts. Requirements and Procedure. 334 (1864). These cavities are filled with mercury and the switch finished with copper wire. Q. which is provided with the binding posts MM. * Z. 32. Z. the apparatus shown in Fig. a deposited upon weighed cathode and. deep. making little cavities at aa'Wce' by pressing a test-tube. p. then through the ohm known resistance W (a resistance most convenient to use f). 36. The current is led first through the variable resistance TT.DETERMINATION OF NICKEL AS METAL BY ELECTROLYSIS. Cf. 131 Determination of Nickel as Metal by Electrolysis. 31 may be used. .. 3. 320 (1880). From strongly acid solutions nickel is not deposited upon From slightly stationary electrodes by a current of 1-3 amperes. The resistance t The resistance w'=lQ can be made from nickelin wire. B represents a storage-battery. Cf. (a) Method of Gibbs. of the wire is measured with the aid of the Wheat stone bridge and a length cut off corresponding to one ohm. at the electrolysis. after cooling. 2. one can be prepared by taking the cover of a pasteboard box. and then. so the voltmeter V is connected with the by throwing the switch decomposition that c is connected with 6 and c' with 6'. + If a commutating switch is not available. From ammoniacal account of its solutions nickel simplicity recommended strongly is readily deposited. If at any time it is desired to measure the voltage between the of 1 is electrodes of the cell. The binding posts of the cell. For this. which is filled with hot water. This wire is wound round a wooden block Chem. fining it with melted paraffin.

132 GRAVIMETRIC ANALYSIS. FIG. . 31.

arranged so that the current may be taken from different MM. 32. then A. FIG. 31. Ohm's Since. the known resistance can be ao that the voltmeter will show ten times the actual current. the Strength of current = - - Electromotive force ^ -. and the voltmeter V serves as measuring instrument for all the analyses that It is points along are in progress. By easily the voltmeter means of the SS with the different it is cells.DETERMINATION OF NICKEL AS METAL BY ELECTROLYSIS. the electromotive force in volts. then if the strength of the current is expressed in amperes. made TF'= 10 Q . is obtained by placing the switch in the opposite position with a united to 6 and a' to &'. and it is thus possible to carry out a number of electrolytic determinations at the same time. possible to connect While a measure- * With weaker currents. 32. as shown in Figs. we have In case W= 1 ohm. and the resistance in ohms. 133 strength of the current.-E. according to law. on the other hand. Resistance . and the voltmeter (amperes) will show directly the strength of the current * .

(See Fig. . In the gauze electrode to use a platinum dish as cathode. The electrodes FIG. bottom of the beaker and the top of should be nearly covered by solution. all other switches must be cut circuit. 33). The decomposition cell consists of a glass beaker in which is as a wire cathode placed gauze electrode (first recommended by Cl. as it is desirable some cases must always reach to the recommended by Classen. Winkler) and as anode a platinum spiral. 36.) The electrodes are usually connected with two electrode stands on which metal arms are attached to an upright glass rod To prevent serious loss of electrolyte by spattering. 33. (Fig. 134 ment out of is being made at any cell.GRAVIMETRIC ANALYSIS. p. 178.

and spoil the analysis. the author bends the ends of the electrodes to a right angle and connects them with an electrode stand designed arms as shown in Fig. 34. of the electrode support and in some cases the liquids thus condensed dissolve some brass and the resulting solution may drop into the beaker.DETERMINATION OF NICKEL AS METAL BY ELECTROLYSIS. the rods are fastened to the ring . as when much gas is evolved a little of the liquid is still carried off mechanically. This is not entirely satisfactory. To prevent this misfortune. e. as the case may be. has the disadvantage that when the electrolysis is carried out in a hot solution. 34. and r through a piece of ebonite. condense on the brass FIG. acid or ammoniacal vapors. 135 the beaker is covered with two halves of a watch-glass. This method of fastening the electrodes. This electrode holder consists of two brass rods insulated from one another by means of an intervening layer of mica. moreover.

the electrode on being Page 131.5-1. This treatment last traces of nickel. and the bottoms washed immediately with water. at the room temperature with a current of 0. the beaker can be covered tightly by means of a whole watch-glass. of ammonium sulphate and 30-40 c. . For every 0. add enough nitric acid (1:1) to wet all the nickel. and the upper parts of the electrodes are washed thoroughly with water from a washThe electrodes are then raised entirely out of the solution bottle. The Electrolysis of Nickel. cooling in a desiccator. present as sulphate or chloride. The deposited metal adheres firmly to the electrode.8-3. of concentrated ammonia are added. the watch-glass is removed.c. * 5-10 gm. but not as nitrate.25-0. The electrolysis after three hours. and heat for at least fifteen minutes. After after which it is dried by holding it high above a gas flame. is If this * absolutely necessary to remove the is not done. but there is absolutely no danger of contamination from the outside. The current is then turned off and the cathode rinsed with absolute alcohol. and possesses almost the color of platinum. is bright. nickel.GRAVIMETRIC ANALYSIS. and the solution diluted with This solution is electrolyzed distilled water to a volume of 150 c. the electrode holder is raised so that only the bottoms of the electrodes remain in the liquid. only about one hour is necessary for the deposition. as can be shown fairly satisfactorily a little is finished by adding water and allowing the current to pass through the solution twenty minutes longer.5 amperes and an electrode potential of 2. the determination is If the solution is kept at a temperature of from finished.30 gm. and not only are losses by spattering avoided. 136 The openings to hold the wires are cut wedge-shaped.c. To clean the cathode.3 volts. As soon as the electrotysis is finished. so that any shape of wire can be inserted. it is weighed. place it in a small beaker. 50-60 C. Since the ends of the electrodes leave the beaker in a horizontal direction. If at the end of this time for fifteen or no nickel has deposited upon the electrode surface which was wet for the first time by the last dilution.

W. and soon afterward the red crystals of nickel salt be precipitated. Minister. The nickel not deposited by an electrolysis may be estimated accurately by shaking the solution thoroughly and comparing will the color produced by the addition of dimethyl glyoxime with that produced with a dilute nickel solution containing a known quantity of nickel. the analysis then method for depositing nickel comes out too low. the ammonia is almost wholly neutralized with hydrochloric acid and a few cubic centimeters are added of glyoxime nickel is in alcohol. it will per cent. Remark. The nickel solution is heated in a porcelain dish with bromine water and an excess of pure potassium hydroxide.THE ELECTROLYSIS OF NICKEL. The discolored electrolytic electrode. present. The presence of too little tion of black is deposited upon the cathode. washed by decantation . * A. 1907. Naturally such a colorimetric test can be used only with very small quantities of nickel. Zurich. because the cathode slowly gains in weight even after all the nickel has been deposited from the solution. ammonia often results in the forma- Xi(OH) 3 at the anode. 1909. Xi(OH) 3 The precipitate is filtered off. Treadwell. whereby the nickel is precipitated as brownish-black nickelic hydroxide. at least. The anode is attacked. 137 ignited becomes discolored. D. solution of dimethyl than a tenth of a milligram of take several minutes for a yellow coloration When 1 less to appear. Classen's ammonium oxalate apparently cannot be recommended. gives too from a solution of * and high results Determination as Nickelous Oxide. sertation. and it is then very difficult to clean the electrode by repeated treatment with acid followed by ignition. determination. Dis- . 3. The electrolysis of nickel from an ammoniacal solution should not be continued for too long a time. causing platinum to go into solution. To make has been deposited from the electrolyzed solution. can be used for another sure that all the nickel however. Dissertation. Windelschmidt. which partially.

Ni(OH) 2 is not so easily filtered and washed as Ni(OH) 3 These two methods are more tedious to carry out and the results are not as accurate as in the case of the first two methods described and will probably not be used much in the future. D. filtered through a small filter. A. it has been proposed to preas . 58. washed with hot water. Forms: Co. loc. At. Treadwell. and. COBALT. Cf. t H. 138 with hot water. cipitate nickel as the sulphide. II.. the dry residue moistened with concentrated hydrochloric acid and then with hot water. By treating the ignited mass with hot water. ignited as NiO.97. the electrolytic method. and the filter together with the residue ignited wet in a platinum The weight of this silica. . loc. and weigh it as the oxide by ignition in air. It is possible to precipitate nickel quantitatively Ni(OH) 2 by means of caustic potash alone and the precipitate This method is open to the same is changed to NiO by ignition. 6 (1906). e. SiO 2 subtracted from the crucible. loc. . . . tit. i.. furthermore. dried. The grayish-green oxide thus obtained always contains small quantities of silicic acid and alkali. Co. evaporated completely to dryness.f The method is good but hardly comparable with the dimethyl glyoxime method. after burning the filter. former weight of NiO + Si0 2 gives good results. Windelschmidt. A. objections as the above and. Cormimboef. or the volumetric titration with potassium cyanide. cit. Windelschmidt. Besides the methods described. Determination as Metal. chim. i. appl. The most accurate method for the estimation of cobalt is by and the details of the process are precisely the same as have been given under nickel. the greater part of the alkali can be removed. The Drying and again igniting gives the weight of NiO + SiO 2 oxide is treated in a porcelain crucible with hydrochloric acid. Wt. from a strongly ammoniacal electrolysis * Cf. and W.* and weighed whereby the results are too high.GRAVIMETRIC ANALYSIS. CoS0 4 . tit. (a) By Electrolysis. Ann. Remark.

At the end of the deterthe electrodes have been removed. By Reduction (6) The cobalt solution ing-dish. No. Schleicher & Schiill's giving a turbid filtrate on washing. and then the residue is ignited After weighing. heated to boiling in a porcelain evaporatprecipitated as black cobaltic hydroxide is The preand ignited. evaporated to dryness. the entire mination. of the Oxide in a is and the cobalt Stream of Hydrogen. solution containing ammonium (preferably the former) more ammonia than salts of cobalt. rather than somewhat longer. has the tendency of If. hydroxide by caustic potash alone. filter-paper through. and the small residue of silicic acid filtered off. in a stream of hydrogen and weighed as metal. the metal is dissolved in hydrochloric acid. in 139 and the sulphate or chloride is customary to use a little It the determination of nickel. because cobalt has a greater tendency to deposit as black Co(OH) 3 at the anode. however. The results obtained by this method are usually a and Go 3 little higher than by * Cobaltic hydroxide. .DETERMINATION OF COBALT AS METAL. The duration of the electrolysis is the same as with nickel.* potash and bromine water. After cooling it is treated with water in order to remove the small amount of alkali which is always present. the dry mass moistened with hydrochloric acid. after solution is tested for cobalt by adding ammonium sulphide or potassium sulphocarbonate. by the addition cipitate is of caustic filtered off. electrolysis. so that they are not suited for 4 the quantitative determination of cobalt. ^he oxides of cobalt when ignited in air yield a mixture of CoO in varying proportions. Remark. but the resulting precipitate The is not so easy to filter and wash as the cobaltic hydroxide. precipitation by means of sodium carbonate is not so satisfactory. dried. due is ignited and its weight subtracted from that obtained after the Cobalt may also be precipitated as cobaltous ignition in hydrogen. then treated with This resiwater. 589 (blue band) is used. unlike nickelic hydroxide. none of the precipitate passes .

2 or 3 gins. Austin. The cold acid|| solution of the zinc salt is treated with ammonia. f M. To the hot solution. Determination as Zinc Wt. Ztg. the precipitate is washed immediately with hot water.. Losekann and T. 1909. first recommended by H. The method is the same as was described under Manganese (p.) The first forms is amorphous.c. ZnS. in a platinum or porcelain dish. 1886. 24. Z. 729. Care is necessary at this point. until it is left barely acid. but it soon that into precipitate changes ammonium phosphate. (If the diammonium phosphate contains some monoammonium phosphate. 148. Z. Chem. Procedure. the salt should be dissolved in cold water and dilute ammonia added until the solution just becomes pink with phenolphthalein. . Dakin.37. * has been studied and improved by G. 39. 273 (1900). J and especially H. 2282.GRAVIMETRIC ANALYSIS. ZINC. Ammonium Phosphate or Zinc Pyrophosphate. Chem. solution 1f until free from chlorides 1899. Sci. Z. After the heating has continued for about fifteen minutes. anal.. Chem. of ammonium chloride are added analysis carried out. The transformation takes place more rapidly in proportion to the quantity of ammonium salts present. I 4o Determination as Sulphate. ^ According to Voigt. ten times as much ammonium phos- phate is added as there is zinc present. Meyer. This excellent method. Zn. 22. Zn.. washed with hot. 212 (1900).. * ammonium phosphate f Chem. anorg. the dish is removed from the water-bath and after fine crystals of zinc being allowed to settle for a short time the precipitate is filtered through a Gooch or Munroe crucible. 65. angew. is neutral. J Am. News. It is then diluted with water to a volume of 150 c. || If the solution and then the . J. D. At. ZnNH P0 4 4. 2. Zn 2 P 2 O 7 ZnO. 104). Forms: i. and heated on the waterbath. 1 per cent.. Chem. Tamm. as zinc ammonium phosphate is soluble both in acids and ammonia.

The crucible is heated until its weight is constant. The determination as pyrophosphate is to be recommended when the zinc solution contains a very large quantity of ammonium salts because it requires long washing to remove these and this renders the results a little low. alcohol. it may be dissolved in a few drops of hydrochloric acid. If such an oven is not at hand. and heated a few minutes on the water-bath before filtering. in which case the dried zinc ammonium phosphate is heated very slowly in an electric oven to 900-1000. containing ammonium salts as well. Remark. Zn. for an hour and weighed as ZnNH 4 PO 4 which dried at 110-120 . Zn 2 P 2 O7. Zn 2 P 2 O7 contains 42. the precipitate of ammonium phosphate and aluminium phosphate the zinc ammonium phosphate being soluble The is in magnesium filtered off. then with 50 per cent. the Gooch or Munroe crucible is placed in a larger platinum crucible and heated over the gas flame. Zn. contains 36. as when magnesium or aluminium The soluis present.. the solution immediately neutralized with ammonia. If some of the precipitate should treated as described above. In some cases.DETERMINATION OF etc. 141 then twice with cold water. the procedure of K. After standing some time.90 per cent. the precipitate may be weighed as the pyrophosphate. the ammonium salts are volatilized and it is not necessary to remove them by washing. . When the precipitate is weighed as pyrophosphate. is treated with an excess of ammonia and then with ammonium phosphate. received in a platinum or porcelain dish and is heated on the water-bath until all the free ammonia has been filtrate is expelled. Voigt is followed.64 per cent. ammonia. ZINC. The temperature is gradually raised until finally the full heat of the Teclu burner or of the blast lamp is reached. whereby zinc ammonium phosphate separates out It is quantitatively in the form of the crystalline precipitate. adhere firmly to the sides of the dish. Or. tion of the zinc salt.

The chloride weighed plati- dryness on the water-bath. 2. and changing of Volhard as described below. whereby mercuric chloride and zinc oxide are curic oxide *. and evaporated to dryness on the water-bath. large amounts. acetate. nitrate. and quantitatively changed when present in relatively in the case of the sulphate. Enough mercuric oxide should be used so that the residue obtained after the evaporation is noticeably yellow. according to Volhard. contained in a is platinum dish. washed by decantation with water until free from chloride. and the residue of zinc oxide is weighed. and kept suspended in water in a bottle with a wide neck. in case the 'zinc is present as sulphate. ignition. at first gently and finally strongly. evaporating to to oxide by the method ing as such. say 5-10 gin. is treated with a large excess of pure yellow mersuspended in water. however. or to dissolve the sulphide on the filter in sulphate It may is dilute hydrochloric acid. advisable. and oxalate of zinc are readily to zinc oxide by ignition in the air. The process is as follows: The neutral solution of the chloride. both mercuric chloride and oxide being volatile. 142 Determination as Zinc Oxide. receiving the solution in a num dish.GRAVIMETRIC ANALYSIS. The dry mass is ignited under a hood with a good draft (on account of the mercury vapors being poisonous). The results are excellent. should leave no weighable residue after is chloride with pure caustic potash. and weigh- readily changed to oxide. to precipitate it from the aqueous solution as sulphide and weigh it as such according to 3. . both of which are white substances. formed.. Small amounts of the be changed to oxide by igniting over the blast-lamp. ZnCl 2 + HgO = ZnO + HgCl 2 . the transformation into oxide is difficult. The carbonate. * The mercuric oxide prepared by precipitating a solution of mercuric The precipitate is allowed to settle. A considerable amount of the mercuric oxide. by gentle ignition with pure mercuric oxide.

Two phenolphthalem solution are then added and enough part of the zinc drops of is sodium carbonate solution this way which by to impart a distinct pink color. over a Teclu burner and weighed f after cooling in a desiccator. or when it is necessary to separate zinc from alkaline earths.* is filtered 20 drops cipitate from the of the filtrate is The precipitate and washed with hot water until leave no residue on evaporation. when it is heated to boiling. alkalies or metals of this group. f If the solution contains sulphate. not the case if the hot solution is at once precipitated is the addition of an excess of sodium carbonate. besides zinc. and lain crucible. . or from solutions containing free acetic. or sulphocyanic acids. Zinc sulphide may be precipitated from ammoniacal solutions. at first gently and finally strongly. barely acid solution free from ammonium The sodium carbonate is added until the zinc solution salts. which may In the presence of sulphates. the greater part transferred to a weighed porceburned by itself in a platinum spiral. the filter the ash added to the main part of the precipitate in the crucible. therefore. Determination as Sulphide. advisable to precipitate the zinc as sulphide and determine it as such according to 3. the precipitate produced by sodium carbonate always contains more or less basic zinc sulphate. it is easily lead to high results. which is ignited. 143 If the solution contains. This determination is chosen when the zinc is present in a solution containing ammonium salts. The pre- hot solution dried. 3. also alkalies. formic. whereby the greater precipitated as granular zinc carbonate.DETERMINATION OF ZINC AS SULPHIDE. *In may the solution is amounts of ammonium salts are present there Sodium carbonate should then be added until slightly alkaline and the solution boiled until all the ammonia case considerable be no precipitation. becomes turbid. is expelled. citric. the zinc be precipitated as carbonate and changed to oxide upon can ignition. In a precipitate of zinc carbonate is obtained free from alkali. The precipitation of the zinc carbonate should take place in a porcelain dish and the sodium carbonate solution should be added drop by drop to the cold.

of ammonium acethiocyanate) and 2 c. the clear upper liquid is poured through a Schleicher & SchiilPs filter No. ZnS:Zn=p:s Zn . in case again. ammonium thiocyanate) slight excess of freshly prepared ammonium sulphide.GRAVIMETRIC ANALYSIS. and the turbid upper liquid is poured through the filter.c. 590. followed turbing the precipitate. of ammonium by a are added. stoppered and allowed to stand twelve to twenty. it comes through turbid The decantation it is poured through repeated three times. shaken. 5 gms. The precipitate is is now mixed with the aid of a platinum wire. the filter burned by itself and the ash added to the main portion of the precipitate. after transferred to the filter and washed comis which the precipitate is pletely with the above solution. covered with a layer of sulphur and heated.c. taking pains to keep the of the wash filter full liquid during the entire operation. better. after which for every 100 c. finally washing with water containing ammonium sulphide only. Without dis- 5 gms.c. few drops of ammonia. of ammonium sulphide solution. The 125) in a current of hydroallowed to cool in the stream of Manganese (page crucible is finally hydrogen and from the weight of the zinc sulphide the weight of zinc present is calculated. The slightly acid solution is placed in an Erlenmeyer flask and treated with sodium carbonate solution until a permanent This is dissolved by the addition of a precipitate is obtained. The precipitate then dried. of the solution acetate (or. 144 (a) Precipitation of ZnS from Ammoniacal Solutions. The precipitate is covered with a solution containing in every 100 c.four hours. transferred as completely as possible to a weighed Rose crucible. the flask is nearly filled with boiled water. taking care to receive the filtrate in a tate (or ammonium fresh beaker the filter . allowed to settle. as described under gen. with one-third as much pure sulphur.

From complex the solution of potassium or sodium zincate. In the presence of acid. . zinc is not deposited by an electric current of 0.. After gen precipitate has settled completely. or from the it is easy to deposit the zinc quan- alkali zinc cyanides. 2 to 4 per cei\t. Elektrochem. 11. zinc sulphide shows less tendency to form colloidal solutions when it is thrown down from a slightly acid solution than when it is precipitated from alkaline solutions. of zinc amount The is original substance. to 25 c. titatively. acetic acid 4. the sulphide.* solution of zinc sulphate (chlorides and nitrates should is treated with a drop of phenolphthalein and with be absent) sodium hydroxide solution until a permanent coloration is obtained. the Then 20 * Z. which has been nearly neutralized with ammonia. treated ammonium with .ELECTROLYTIC DETERMINATION OF and a if is the per cent.5 to 1 ampere. (a) The Method of F. ammonium chloride or sulphate and a little or sodium acetate and is then saturated with hydro- solution. of normal caustic soda solution are added. When thoroughly washed It is to be noted that the it is treated as described above. 401 (1905). and the prehas been which cipitate saturated with hydrogen sulphide. the supernatant solution. although it may be deposited even then by stronger currents. Spitzer.c. H5 then the is rc= (b) of the ZINC. washed with is poured through a filter. 100 Zn Precipitation of ZnS from Acid Solutions. Electrolytic Determination of Zinc.

To make sure that all the zinc was deposited. J. ~ f zinc is If too little caustic soda is present. then the electrodes are taken entirely out of the solution and rinsed with water. and weighed. When deposited way. this reason the above directions should be followed closely. Am. Soc. If. with a current of 0.* gain in weight zinc To clean the electrodes. The experiments have been repeated in the author's laboratory by Janini. then the deposition of the was complete the first time. If at the end of half an hour the is not over 0.1014 about 0. the cathode washed with absolute alcohol.8 to 1 ampere and 3 to 4 volts electrode potential.c. the electrodes are present. and electrolyzed. ammonium salt. in this electrodes are cleaned and the solution electrolyzed for thirty minutes longer. who obtained as an average from fourteen determinations with 50 c. slight increase in weight will be obtained in A every case because the anode is attacked slightly by the alkaline solution so that the cathode slowly continues to gain in weight from deposited platinum. the value 0. 146 solution is diluted to 150-200 c. Spear. chlorides or nitrates >r * Ellwood B. raised nearly out of the bath. The current is then turned off.GRAVIMETRIC ANALYSIS. 530:(1910). and It is not necessary to cover the platinum gauze with a ignited. dried above a cooled in a desiccator. gm. The results are always a little high.3 gm. it is desired to analyze a solution containing an T . they are boiled thoroughly with hydrochloric acid (1:2) washed well with distilled water. therefore. Chem. thin coating of copper or of silver.5 gm. a spongy deposit obtained which does not adhere well to the electrode.c. the flarilfe. moreover.1008 gm. as can be shown by testing with sodium sulphide. it must be boiled with caustic soda until all the ammonia has been expelled. Remark. of zinc was Without breaking the current.. In the presence of ammonia the determination is not successful. of a zinc sulphate solution. zinc forms a bluish-gray layer that adheres firmly to the electrode. Zn instead of 0. provided not more than 0.6 per cent. At the end of three hours the electrolysis is finished.'a difference of . as has been recommended when a platinum dish is used as the cathode. the upper portions are washed quickly with water. using a plat- inum gauze cathode. Zn. 32.

c. If only a small amount of alkaline-earth metals are present and case it is not t Luckow. I (ISSQ).. The Potassium Cyanide Method. usual manner. COBALT. The separation depends upon the insolubility of the sulphides and the solubility of the sulphides of of the metals of this group the alkaline earths.5 ampere. anal. Other methods for the electrolytic estimation given in A. . Classen's book Quantitative Analysis by account of the current heating the solution. electrolyzed with a current of 0. Z. * (6) A drop of phenolphthalein is added to the solution of zinc sulphate. FROM ALKALINE EARTHS. heated over the free flame until dense vapors of sulphuric acid The solution is then diluted and analyzed in the are expelled. 147 are present they must be removed by evaporation with sulphuric The solution is evaporated on the water-bath and finally acid. and solution results.SEPARA TION OF MANGANESE. At first the electrode potential is about 5. 19. but it falls during the analysis on The two or three hours. of zinc are Electrolysis. and allowed to stand twelve hours. and then potassium cyanide solution until a clear This is diluted to a volume of 150-200 c. The flask is then almost completely filled with boiled water. AND ZINC FROM THE ALKALINE EARTHS.8 volts. corked. contained treated with ammonium chloride (hi already present) and freshly -prepared colorless ammonium sulphide solution is added drop by drop until no further precipitation takes place and the liquid has a distinct odor of ammonium sulphide. The precipitate is filtered and washed as described in tne Determination of Zinc (p. The neutral Procedure. is electrolysis finished in SEPARATION OF MANGANESE.. Chern. in an Erlenmeyer flask. 144). caustic soda solution until a permanent pink coloration is obtained. NICKEL. is solution of the chlorides. ETC.

I). the solution is evaporated to dryness. dissolved in hot water. treated with a little concentrated hydrochloric acid. which is now covered with a watch-glass. treated with dilute hydrochloric acid. dried. separation is usually complete after one precipitain the tion. p. metals The ammonium sulphide solution used in the above be free from ammonium carbonate. 148 ammonium sulphide solution is entirely free from ammonium the carbonate. and again evaporated to dryness in order to change to chloride any nitrate that may have been formed. and the slight residue of sulphur filtered off. it is treatment. barium. Vol. dissolved in hydrochloric acid. a too great excess of ammonium sulphide must be carefully avoided. and heated to boiling after the evolution of hydrogen sulphide has ceased. A very little concentrated nitric acid is now added and the mixture warmed completely dissolved. however. however. As. .GRAVIMETRIC ANALYSIS. which. in case barium is present. and passing hydrogen sulphide into the solution. filtered off 156 et seq). transferred as completely as possible to a porcelain crucible. must separation ammonia contains this salt. 76 et seq. The dry mass is moistened until the precipitate is with a few drops of concentrated hydrochloric acid. always contains a small amount of barium sulphate. and examined as described on p. the filter-paper burned in a platinum spiral and the ash added to the main part of the precipitate in the crucible. The and combined with the main precipifiltrate containing the alkaline-earth is freed from ammonium salts by evaporating to dryness. washed with hot water. as otherwise the nickel sulphide In all cases. strontium. For this purpose the washed precipitate is or dried. the should be tested for nickel by acidifying with acetic filtrate heating to boiling. will pass through the filter (cf. and is therefore in a porcelain crucible. In case nickel is present. the magnesium the sulphide precipitate will always be more or less contaminated with these substances. If a slight black precipitate is produced by this acid. ignited and weighed. so that the precipitation must be repeated. tate (cf. in order to remove all of the hydrogen sulphide. The nitrate is then precipitated exactly as before by the addition of ammonium sulphide. it must be freed from all commercial Remark. presence of considerable calcium.

By warming the water-bath the ammonia is now distilled over into the flask containing the boiled water. of ammonia contained in a liter flask that is connected with a condenser. it . of freshly slaked lime are added to 500 c.c. is prepared suitable SEPARATION OF THE BIVALENT FROM THE OTHER METALS OF THE AMMONIUM SULPHIDE GROUP. and this is connected with the delivery-tube. This method depends upon the fact that ferric. aluminium and chromic salts (as well as titanic and uranyl salts) are preci* The distillation of ammonia also serves to free it from silica. flask containing the ammonia is then placed on the waterbath in such a position that the condenser-tube is inclined slightly upward. meanwhile passing through the water a current of air that has been freed all traces of carbon dioxide by passing through concentrated from caustic potash solution soda-lime. through which the air previously passed into the flask of boiling water. This separation is often designated as that of the protoxides from the sesquioxides. The condenser is closed by means of a tube concentrated containing soda-lime. * About 10 gms. which always contains when kept in glass bottles for any length of time. 400 c. in the The Barium Carbonate Method. a solution of ammonium sulphide for the above-described separation. Preparation of Ammonia Free from Carbonate. carbonate before being used for the preparation of 149 ammonium sulphide solution. and the contents of the flask are allowed After this. By saturating a part of this ammonia with hydrogen The sulphide.c. by which it is completely absorbed. this designation is not applicable case of titanium and uranyl derivatives. The water and then through a tower is filled with allowed to cool in this air-stream.PREPARATION OF AMMONIA FREE FROM CARBONATE. from 300to stand for a day with frequent shaking. of water are placed in a flask and boiled.

f The barium carbonate must be free from alkali carbonate. /// QTT // / . cold zinc. but not the sulphates. and the total set free .GRAVIMETRIC ANALYSIS. will precipitate the bivalent metals when sulphates : ZnSO 4 + BaCO 3 = ZnCO 3 -f BaSO4 . e. 2FeCl 3 + 6HOH + 3BaC0 3 =3BaCl 2 +2Fe(OH) 3 + The CO metals are not subject to this hythe in cold. which is then redissolved by the addition of a few drops of dilute hydrochloric acid. permanent turbidity is produced. Sodium carbonate Procedure. cobalt. !5 pitated in the nickel. in an Erlenmeyer flask until a slight. solution is added drop by drop to the slightly acid solution of the chlorides or nitrates. the equilibrium is disturbed and the hydrolysis goes further droxide is insoluble hy- until finally the formed: Fe (OH) C1 2 + 2HOH = 2HC1 + Fe(OH) 3 The barium carbonate. by barium carbonate. The trivalent metals are strongly decomposed hydrolytically: (HCl) Free acid and a basic +Fe(OH)Cl 2 formed by salt are . consequently they are not precipitated by drolysis the addition of barium carbonate. the composition of the latter depending upon the quantity of the water and the temperature.. then. and ferrous salts are not. On warming.* of the metals. this hydrolysis. to neutralize the acid reaction is expressed by the following equation: . If the free acid is removed by the addition of barium carbonate. The solution is diluted and treated with pure barium carbonate f (suspended in water) until after thoroughly shaking an excess of the * Barium carbonate are present. they are hydrolyzed to an appreciable extent and are then precipitated salts of the bivalent by barium carbonate. however. . while manganese. serves only by the hydrolysis.g.

The precipitate is dissolved in dilute hydrochloric acid. the precipitate produced by barium carbonate contains small amounts of nickel and cobalt. 100 c. chromium remore to and (titanium uranium) are separated from the barium * by double with ammonium sulphide as described on p. particularly when considerable iron is pres- ent. titanium.THE BARIUM CARBONATE METHOD. The barium sulphate is filtered off and the monoxides are separated from one another as described on p. The filtrate contains the bivalent metals and barium chloride. The above separation of the sesquioxides from the protoxides is not absolutely certain in the presence of nickel and cobalt. latter 151 remains on the bottom of the flask. 156. aluminium. so that the author prefers the above procedure. aluminium. by double precipitation of the other metals with ammonium sulphide.The flask is closed to stand for several hours with frequent shaking. Remark. chromium (titanium and uranium) are separated from one another as described on pp. The and allowed clear liquid is then decanted off. the residue treated with cold water and again decanted. . by adding ammonium chloride to the solution (3-5 gms. t Or. however. after which the precipitate is transferred to the filter and completely washed with cold water. 147. etc.c. The precipitate of barium sulphate always contains small amounts of the heavy metals. 107-120. of solution) before precipitating with barium for each carbonate. aluminium. In this case. and uranium in the presence of the excess of barium carbonate. The filtrate from the barium carbonate precipitation is freed from barium by the addition of sulphuric acidf to the boiling solution after it has been made acid with hydrochloric acid. chromium. better. aluminium. and the iron. boiled the carbon dioxide. precipitation The iron. The precipitate contains all of the iron. the separation * Most authorities is then satisfactory. This difficulty can be overcome. This decantation is repeated three times. . recommend precipitating the barium first with sul- phuric acid and then separating the iron.

AND ZINC. dilute solutions much more readily than the acetates of the bivalent From the metals. which tends to stop the reaction. When the iron solution is ready.GRAVIMETRIC ANALYSIS. as a rule. Hydrated manganese dioxide is more insoluble than manganous hydroxide. is treated with sodium carbonate solution in the cold until a slight permanent opalescence is obtained. through a filter. Then. tinued the iron solution for one minute. gm. Meanwhile a boiling.c. is added. water. Fe (C 2 H 3 it is 2) 3 equation + 2HOH<r>2HC 2 H 3 evident that acid set free is due to the solvent action of free hydrogen ions. and that remaining on .5 to 2 flask. lent results. COBALT. but gives excel- slightly acid solution of the chlorides. which is then redissolved by the addition of a few drops of dilute hydrochloric acid. con- tained in a small beaker. settle fluted washing three times by decantation with boiling water containing ammonium or sodium acetate. is sodium acetate. This classic method depends upon the fact that ferric. the bulk of the precipitate rinsed into a porcelain dish. some manganese is likely to be precipitated. of acetate and 300 to 400 c. so that it is advisable to dissolve the precipitate and repeat the precipitation.2 gm. of iron or aluminium. The is somewhat manganese tedious. 1. dilute solution of sodium or ammonium acetate is prepared in a large round -bottomed containing for each 0. Mn(OH ).1 to 0. kept low by the addition of hydrogen however. Basic Acetate Method. the precipitate allowed to and filtered immediately while the liquid is hot. aluminium and titanium acetates are hydrolyzed in hot. NICKEL. and then the boiling is conflame removed (the precipitate the becomes slimy on long boiling). ALUMINIUM. 352 SEPARATION OF IRON. Procedure. AND TITANIUM (BUT NOT CHROMIUM AND URANIUM) FROM MANGANESE. and hence long 2 boiling in the air tends increase the quantity of to The method precipitated. The concentration ions. the lamp is taken away from beneath the flask. of 2 + Fe (OH) 2 C 2 H 3 - 2. The filter together with the precipitate is spread upon a glass plate.

and then Chem. of iron present.c.SEPARATION OF IRON FROM MANGANESE. The solution is is evaporated to dryness on the water-bath. It is especially suited for the separation of iron and titanium from the protoxides. (a) O.. This procedure requires practice. is The filtered and washed precipitate is dissolved in hydrochloric acid and the iron separated from aluminium according to page 107. in order to prevent the precipitation of hydrated manganese dioxide.* The acid solution. so that they should be dissolved in a little water and the solution made bare'y * t acid before adding it to the iron solution. Chem. and zinc precipitated by ammonium sulphide as described on p. cobalt the separation is usually less satisfactory with aluminium. of concentrated hydrochloric acid. W. 147. heated. 1904. I.35 gm. If it is merely a case of the Separation of Iron from Manganese.1 gm. Funk. of potassium chloride or 0. stirring. Brunck's Method.2 gm. nickel. of iron present.1 diluted with boiling water is for each 0. . of water and to the resulting solution there is added gm.5 gm. the barium carbonate separation is to be preferred.3 gm. 45. until boiling begins. By this time practically all the mineral acid is expelled. the following modifications of the basic acetate process give satisfactory separations with only a single precipitation. 156. The residual salts are dissolved in 10 to 20 c. the filter dissolved 153 alternately treating with concentrated by and hot water. treated with 0. and heated five or ten minutes longer. anal. with constant sodium acetate for each 0. containing not more than 0.. The combined filtrates containing the protoxides are acidified with 10-20 c.c. the residue pressed with a glass rod. ammonium chloride for each 0. Ztg. 513. so that in case considerable amounts of the latter are present. The sodium acetate crystals often contain a little sodium carbonate.c. of The solution 500 c. of iron. The resulting solution is hydrochloric to dryness on the water-bath and the basic evaporated nearly acid acetate precipitation repeated exactly as before.26 gm. dissolved in a little water. evaporated almost to dryness. f to a volume of 400 to it is 1. of iron present. the manganese. 181 (1906). and analyzed according to p. Z. Remark. Cf.

c.c. Then c. dried. 3 c. 50 10 c. The decanted through a fluted filter and the precipitate washed with hot water. the residue dissolved in a little water and the manganese. J Commercial ammonium acetate has the symbol 4C 2 3O2 2 3 O2 .c.c. of concentrated hydrochloric acid before adding it to the filtrate from the basic acetate precipitation. of hot water and heated until it begins to boil. is carefully ammonium car- c. anal. the dilute reagent being added until the precipitate produced will not At this point.3 gm. nickel. Chem. while stirring constantly.c. of 2N. and 10 c.c. If none of it is on hand.c. the mixture must be faintly acid. acetic acid are used for the precipitation of the iron. containing not more than of iron and having a volume of not over 100 neutralized.. 2N.GRAVIMETRIC ANALYSIS. The precipitate is dissolved in as the flame solution little hydrochloric ammonia. dissolve within one or two minutes of stirring. and (6) The Method of A.c.. otherwise manganese is likely to be precipitated when the two filtrates are mixed. from the basic acetate precipitation. of the commercial 20 salt in 1 liter of water) { are added and the boiling continued for * The ammoniacal filtrate from the Fe(OH) 3 precipitate is acidified with 5 c. acetic acid.c.c. t Z. of the first solution and diluting to 1 liter. .* is acidified with filtrates hydrochloric acid. the neutralization is finished with an ammonium carbonate solution. by adding 0. of ammonium acetate solution (60 gm. solution ammonia are mixed with NH H HC H 2N. cobalt zinc precipitated with ammonium sulphide according to the directions on page 147. evaporated nearly to dry ness.c. or better the from both precipitations. and separated according to page 156. or burette. The is is filtrate combined acid filtered. as possible. the iron precipitated by and ignited as described on page 87. which is prepared by taking 50 c. of double normal acetic acid are added. bonate solution (200 gm. of the commercial salt in 1 liter of water) from a pipette. 42. 500 c.f slightly acid solution. c.-f-5 c. When the precipitate that is first produced begins to dissolve very slowly. 508 (1903). 154 removed and the precipitate allowed to settle. c. Of this solution 2N. and the solution The solution is diluted stirred until the precipitate disappears. Mittasch. acetic acid are added to dissolve the precipitate produced by ammonium carbonate. when with 400 the greater part of the iron will have been precipitated.

This method. Procedure. NICKEL. then with warm water containing ammonia. washed to allowed cool. and then the becomes acetate which after the mixture is warmed alkali of solution succinate. applicable for the separation of large quantities from small quantities of manganese. the ferric succinate is changed to ferric hydroxide which is dried and weighed as ferric reddish-brown coloration is added is formed. while manganese. until the color oxide after ignition in a porcelain crucible. filtered. The small quantity vessel in of precipitate adhering to the sides of the which the precipitation took place is dissolved in a few drops of hydrochloric acid. until 20 drops of the filtrate leave no residue when evaporated to dryness on platinum. By means of the washing with ammonia. etc. iron is In case the solution contains free acid and all the it is neutralized with ammonia until a hi the ferric form. etc... Both niters are now dried. Sodium Succinate Method. a minute longer. when sodium or ammonium a deep brown. is based of iron upon the fact that ferric iron is quantitatively precipitated from neutral solutions as light-brown ferric succinate by the addition of neutral alkali succinate solution. burned and the iron weighed as Fe 2 O r SEPARATION OF IROH AND ALUMINIUM FROM MANGANESE. COBALT. The bivalent metals in the filtrate are best precipitated by the addition of ammonium sulphide and analyzed as follows: . nickel. and washed with hot water until free from chlorides. remain in solution. 107. If aluminium is present. the ignited residue is further analyzed as described on p. nickel.SEPARATION OF IRON AND ALUMINIUM FROM MANGANESE. AND ZINC. and at first with cold water. gently. the iron precipitated by ammonia and the ferric hydroxide filtered off through a separate filter. it is filtered off 155 Without waiting for the precipitate to settle.

has of which one is soluble and the other insoluble. Every increase . of [B] or [C] causes. as the solution is already saturated an increase of with A } this will produce precipitation of the substance. If the concentrations of the ions [B] and [C]. aqueous solution according to this scheme: is decomposed in A<=B+C. stance A. never been isolated. which if exceeded causes a supersaturation of the solution.C].GRAVIMETRIC A NA LYSIS. . a few r Solubility Product.* w ords with regard to the most recent explanation of the process that takes place in the solution of electrolytes. Cobalt. and consequently precipitation. and Manganese. 156 SEPARATION OF THE BIVALENT METALS OF THE AMMONIUM SULPHIDE GROUP FROM ONE ANOTHER. . and. [A]. Separation of Zinc from Nickel. therefore. All methods for this separation rest upon the slight solubility of zinc sulphide and the ready solubility of the remaining sulphides At this point it may be well to say in their state of formation. and that B and C are designated by portion by [A]. The soluble form. This product [B. is called the * Nickel and cobalt sulphides when once formed are insoluble in dilute These substances probably exist in two allotropic modifications. acids. it where a precipitate is produced the solution is saturated with the substance and (according to Ostwald) in follows that in every case the case of difficultly soluble substances the dissolved portion is The binary subpractically completely dissociated electrolytically. Inasmuch as no substance is absolutely insoluble in water. then of the undissociated according to the mass-action law the following relation holds for any given temperature: . consisting of the elements B and C. = constant.

g. however. there is an increase in the concentration of the hydrogen ions: /SH* ZnCl2 + 2HSH = Zn< The precipitation complete. so that sulphur ions disappear from the solution slight and the solubility product of zinc sulphide is no longer reached: ZnS + 2HC1 = H 2S + ZnCl2 . If we. then. desire to precipitate zinc by means of hydrogen sulphide from a neutral solution of an inorganic compound. If. * is.. the positive into ions. + 2HC1. therefore. This practically completely dissociated On adding acid to the solution. but as the amount of zinc sulphide formed increases. therefore. According to the above theory. in any solution IN ACIDS. dissolves more of the solid zinc sulphide and the above reaction again takes place and this process is repeated The soluuntil all of the zinc sulphide is brought into solution. the zinc is indeed precipitated.EXPLANATION OF THE SOLUTION OF SULPHIDES solubility product. is proportional to its solubility product and to the concentration of the hydrogen ions. therefore. . the i57 solubility with respect product is already not is and the to the substance A. liquid. then the solution is saturated Explanation of the Solution of Sulphides in Acids. then solubility product if the solid substance. if The Zn(SH) 2 . the solution of a sulphide On salt is treating the dissolved until the solubility product is (e. the following consideration shows us how this may be accomplished: If hydrogen sulphide is conducted into a solution containing zinc combined with a mineral acid. incomplete. reached. a part of the zinc sulphide) in acid almost inappreciable amount is is reached. ions unite with the negative sulphur ions to form neutral hydrogen hydrogen sulphide. . It can be made therefore. avoid this increase in the concentra- we can is at once decomposed into ZnS and HjS. conceived to take place as follows: solid sulphide with water. a action solvent the liquid exerts upon reached. which being a very weak acid is only dissociated to a extent. The bility of a sulphide in acid.

Method Smith and Brunner. Chem. The weakly certain. allowed to stand is gen sulphide dilute solution of solution is overnight. some nickel or cobalt sulphide may be precipitated (shown by the gray color of the zinc precipitate). so that the solution will contain fewer hydrogen ions. filtered.GRAVIMETRIC ANALYSIS. and washed with hydrogen sulphide water which contains in every 100 c. Inasmuch Remark. which is redissolved by the addition of a few drops of very dilute hydrochloric acid.. p. 1910. 26. Zimmerman. Procedure. especially when considerable nickel and little zinc are present. The addition of hydrochloric acid is in all cases necessary.c. j Ann. then for every 80 c. 5. and it is The zinc according to the as the exact amount is then determined methods described of acid to be set free impossible to tell exactly how herein lies the chief difficulty. one which is only slightly dissociated. Zentr. is necessary. 1895. This can take place by replacing the mineral acid formed by a weaker acid. 226. 199. (1879) p. 2 gms. the zinc will not be completely precipitated.c. o: 15.e.f of The hydrochloric acid solution of the four metals with sodium carbonate until a permanent precipitate is is treated is redissolved by the addition of a few drops of very formed. 3. If not enough acetate is alkali acetate is added. which Into this almost neutral solution hydrodilute hydrochloric acid. * Concerning the equilibrium conditions in the precipitation of sulphides by hydrogen sulphide. d. see Bruner and Zawadzki. The following separation Method Procedure. of ammonium salt (either the chloride. either as oxide or sulphide on pp.c. more is of Cl. drops of double-normal hydrochloric acid. is unknown. 204 (1880).. Phann. i. or sulphocyanate). because otherwise nickel sulphide will be precipitated with the zinc sulphide. then a few drops of a -very sodium or ammonium acetate are added and the saturated with hydrogen sulphide. 142 and 143. of the solution 10. Chem.* The following methods depend upon this principle. u. Centrabl. . 158 tion of the hydrogen ions. passed for five minutes. t Chem. sulphate. much If alkali acetate too much alkali added. J acid solution is treated with sodium carbonate solution until a permanent precipitate is formed. or at the most and 10 c.

and is saturated with hydrogen sulphide. for sulphocyanic acid is not. will * There are at the start but few zinc ions in the solution. At first the solution becomes only slightly turbid. Remark. (see Vol. constantly becoming denser. after which the heated to about 70 C. cobalt. I) is slightly dissociated. . [Zn(CNS)J(NH) 2^Zn and the zinc thiocyanate is converted into insoluble sulphide by the action When the zinc begins to precipitate as sulphide. Vol. the separation of zinc succeed equally well if the ammonium sul- nickel. After the solution has become sat- urated with hydrogen sulphide. like carnallite of the general formula [R(CNS) 4](NH 4 ) 2 . By the action of hydrogen sulphide phide is produced both in the hydrogel ammonium hydrogel.* but after some time pure white zinc sulphide is thrown down in clouds. of hydrogen sulphide.. 159 ammonium solution is sulphocyanate (1:5) solution are added. ZIMMERMAN.METHOD OF CL. Ammonium sulphocyanate probably simply "salts out" the zinc sulphide (cf. From by means the filtrate nickel. after which the precipitate is and washed. What is the part played by the ammonium sulphocyanate in this determination? Certainly it cannot act the same as the ammonium acetate in the Smith-Brunner method. The four metals are present for the most part in the form of complex thiocyanates The zinc salt. filtered and separated according to the following methods. as described in the method of Smith an. the equilibrium is disturbed and eventually all the zinc becomes precipitated. and manganese are precipitated of ammonium sulphide. I). etc. the beaker is covered and allowed to stand in a moderately warm place until the precipitate has settled and the upper liquid is clear. from upon the zinc salt. but a very strong one.d filtered Brunner. zinc suland hydrosol forms and the sulphocyanate changes the latter into the insoluble If this explanation is correct. and the dissociation of strong acids is only slightly influenced by the addi- tion of their neutral salts. a weak acid. almost as strong as hydrochloric acid itself. like acetic acid.

oxides present amounting to about J per cent. the warm solution is sulphate (referred to the saturated at 50 C. of of liquid) ammonium and the solution hydrogen sulphide. i6o phocyanate phate. zinc to the liter and a solution of nickel sulphate containing 5. with is allowed to stand until the pure white precipitate of zinc sulphide has settled out and is then treated exactly as described under the Method of Zimmerman. The neutral solution f containing the nickel and zinc either in the form of sulphate or chloride (the sum of the Procedure.890 gms. containing 5. H.* The results obtained showed this to be possible.320 gms.^ Experiments were performed by G. In the following experiments a zinc sulphate solution Results. is That replaced by ammonium chloride or ammonium sulis the case is shown by the following method. Kramers in order to determine whether the separation of zinc from nickel and cobalt could be accomplished in weakly acid solutions by hydrogen sulphide after the addition of any ammonium salt of a strong acid. this "Salting-out Method. of the weight of the solution) is treated with 8-10 drops of double-normal hydrochloric acid total and about 2 per amount cent. .GRAVIMETRIC ANALYSIS. nickel to the liter were used.

warmed. strongly acidified with acetic acid. and in the other the two elements are deposited electrolytically as described on page 136. 1848. Separation of Cobalt from Nickel. It is then made slightly acid with acetic acid. heated to saturated with hydrogen sulphide. the quantity of nickel. Z. . the solution should be concentrated and colorless ammonium sulphide added.c. from a barely ammoniacal solution or from a slightly acid solution containing sodium acetate. and washed with hot water. The manganese is in the filtrate. 1907. Remark..* This method is probably the quickest and most accurate for the estimation of nickel in the presence of cobalt. If only a little of the substance is available..SEPARATION OF MANGANESE FROM NICKEL AND COBALT. the original solution is divided into two portions. In order to remove these metals. For the determination of both nickel and cobalt.. filtered. of ammonium acetate are added. the solution is diluted to 100-200 c. 161 Separation of Manganese from Nickel and Cobalt. the filtrate is again tested in the same way and the process repeated until no further precipitation is produced. is not precipitated. The filtrate often contains small amounts of nickel and cobalt. In case a precipitate of nickel or cobalt sulphides is formed by this treatment. and filtered. with larger quantities of cobalt two or three times as much of the dimethyl glyoxime reagent is added and the precipitation is accomplished exactly as described on page 129. and the cobalt found by difference. In one portion the nickel is determined as outlined above. If the quantity of cobalt present does not exceed Procedure. Cobalt. It depends upon the fact that nickel is quantitatively precipitated by means of dimethyl glyoxime. angew. Brunck. the procedure is exactly the same as when nickel alone is present. The solution of the chlorides or sulphates is treated with an excess of sodium carbonate. and cobalt are in the precipitate. and for each gram of nickel or cobalt present 5 gms. (a) Method of Tschugaeff-Brunck. under these conditions. the two metals are deposited * O. and the nickel 70-80 C. Chem.

c. At the end of time the precipitation is almost always complete. the residue transferred to the filter and washed with a 10 per cent. the whole solution is and again allowed to stand. results. angew. half of the solution's volume of 50 per cent.* Brunck's Modification.. the weighed deposit dissolved in nitric acid (the electrodes must be completely immersed in the acid and the solution boiled for at least 20 minutes). the mixture is stirred is dissolved in as little glacial acetic and allowed to stand twenty-four hours. of water. W. and heated on the water-bath until no more brown vapors are evolved. Fischer. adding to it a little more potassium nitrite solution.c. then If at all the end of an hour the cobalt has been formed. The clear liquid is poured through a filter. by removing a little of the undiluted solution with a pipette. and the nickel deteras described above.c. show test glyoxime As much of the precipitate as possible after washing four times. of is now transferred to a small porcelain dish. treated with If a precipitate more potassium is nitrite the filtrate on being acidified with acetic a 1 per cent.^ The solution containing an excess of acid is evaporated to dryness in a porcelain dish and the residue treated with one or two drops of dilute hydrochloric acid and 5 to 10 c. solution of dimethyl no This is usually the case will for nickel. Pure caustic potash until the reaction is solution is then barely alkaline. % Z. of acid and boiled with 1 c.1 62 GRAVIMETRIC ANALYSIS. 545 (1847). Ann. and 10 drops more of acetic acid. cautiously acidified with sulphuric acid. * Pogg. (6) The Potassium Nitrite Method of N. It should be tested. well this and allowing to stand a no further precipitation little longer. Chem. which is covered with a watch-glass.. together by electrolysis. 1847.. potassium acetate precipitated. potassium nitrite solution is added. The method can be recommended mined strongly. solution until 1 c. added drop by drop The resulting precipitate acid as possible. 71. however. 1907. the resulting solution concentrated to a small volume. .

128. according to p. . as described on p. of the process method. as described on p. . dilute sulphuric acid through the filter and this acid is added to the main solution of the cobalt.) (c) Liebig's Potassium Cyanide This method Method. Vol. 139 (6). * Ann. Care must be until no more nickelic hydroxide is precipitated. 98 per cent. After evaporating as far as possible on the water-bath. and alkaline-earth metals are precipitated with the cobalt. washed. and the nickel then precipitated as black nickelic hydroxide by caustic potash and bromine water. 163 The small quantity of precipitate remaining on the filter is dissolved by pouring hot. I.ietermined according to p.) The neutral solution. (Cf. This method gives reliable results provided the In the latter case the nickel solution is free from alkaline earths. is treated with an excess of purest nickel. taken that the solution remains strongly alkaline until the end Procedure. 87. I. Chem. the solution is evapo. 137'. If it is not convenient to carry out an electrolysis. upon this point depends the success of this excellent When the precipitation is complete. (Cf. d. the cobalt determined electrolytically. * based upon the different behavior of the complex cyanogen compounds of both metals towards bromine or is chlorine in alkaline solution. the nitrite precipitate is dissolved in hydrochloric acid and the cobalt . potassium cyanide and 5 gm. The cobalt remains in the filtrate as potassium cobalticyanide. 138. 65. Pharm. after which bromine water is added.. the solution is' diluted with cold water and the nickel determined as oxide. 137. of pure potassium hydroxide. The nitrate containing the nickel can be treated with hydrochloric acid until the nitric acid is completely decomposed. cobalt. the residue is dissolved in water and are evolved. u. with constant stirring. Remark. 244. Vol. \ After the addition ot dilute sulphuric acid. filtered. which may contain only and the alkalies. and weighed as the oxide.SEPARATION OF COBALT FROM NICKEL. the heating is continued on an air-bath until dense vapors of sulphuric acid After cooling.

to dissolve the nickel oxide in sulphuric acid and determine it electrolytically according to p. 137. filtered. whereas potassium cyanide. is better. a little concentrated sulphuric acid is added. white ceased : 2K Co(CN) + 12H SO + 12H O = 6 3 2 4 2 2CoS0 4 + 3K S0 4 + llCO+C0 2 +6(NH 4) 2 SO 4 + SO 3 2 The cold. . mercuric oxide. then treated with a suspension of mercuric oxide in water and heated for a long time. or as the salt of dimethyl glyoxime. and the excess of dried. The under containing potassium cobalticyanide and mercuric treated with sulphuric acid exactly as described and the cobalt determined as metal. is unaffected is cobalti' : Procedure. preferably by filtrate cyanide is (6) electrolysis. The decomposition is complete after one or two hours. 129. which is pure potassium cyanide is added then heated on the water-bath for at least one hour in order to change the potassium cobaltoThe solution is cyanide to potassium cobalticyanide (cf Vol. like almost all is taken of the fact that potassium other complex cyanogen compounds. or. with frequent stirring. 136. good draft. dissolved in water and the cobalt deposited electrolytically. upon the waterbath. A slight excess of to the neutral solution. I) . 1 64 rated as far as possible on the water-bath. The solution is diluted somewhat with hot water. blue mass is . dried and determined as metal according to p. decomposed by mercuric oxide. (d) In this method advantage nickelocyanide. however. the cobalt may be precipitated by the addition of bromine water and potassium hydroxide. and the preconsisting of nickelous hydroxide cipitate. according to p. and the residue is heated over a free flame fumes are evolved and the effervescence has until dense. Liebig's Mercuric Oxide Method.GRAVIMETRIC ANALYSIS. ignited under a hood with a the residue of nickel oxide weighed as described is filtered off. on the contrary. . and It on p. 139.

and enough no slightly ammoniacal. Separation of Nickel from Zinc. and have obtained excellent results. heated to boiling and the nickel precipitated with an alcoholic 1 per dimethyl glyoxime solution exactly as outlined on p. Separation of Nickel from Manganese. 165 and found satisfactory the method seems to have no advantages over the above-described procedures. sodium acetate is added and the analysis continued according to p. a very voluminous precipitate is formed which. 1907. can be filtered * Berichte. If the alkali acetate is added before the dimethyl glyoxime. precipitate will be ammonium chloride has been added. Method of Tschugaeff- Brunck. after the precipitate has formed. I. In the filtrate. dimethyl glyoxime solution and then. When considerable zinc is present it is necessary to add more dimethyl glyoxime to precipitate the nickel. The it sufficient then just acidified with hydrochloric acid. angew. present solution is is neutralized carefully with ammonia. The solution is ammonia to make formed solution if is treated with Method of Tschugaeff-Brunck. t Z. the barely acid treated with 1 per cent. Chem. it is cent. 129. p. Ibid. 669. . 34.. The analysis is carried out exactly as described above with the only difference that the final precipitation takes place in an The greater part of any mineral acid acetic acid solution.. 1849. Vol. 145). best to precipitate the zinc as sulphide by acidifying with acetic acid and saturating the hot solution with hydrogen sulphide (cf. p. 129. 2050.* but of Ilinsky it ZINC. 18. Recently Rosenheirn and Huldschinsky f have applied VogePs qualitative test for cobalt (cf.SEPARATION OF NICKEL FROM The author has also tested and Knorre. to be sure. 137) to the quantitative separation of this metal from nickel.J ammonium chloride. Remark. t Ibid.

is dissolved in 10 c. from the nickel dimethyl glyoxime precipitation. iron has been removed by a basic acetate separation and nickel and manganese are to be determined in the nitrate. * O. and the solution diluted to a silica at this volume of 300 tartaric acid c. enough nitric acid is added to completely oxidize the iron.c. Stahl und Eisen. and if there is any separation of point some hydrofluoric acid is added. * The sample. Determination of Nickel in Steel. 66 with suction. of a 1 per cent. acid with hydrochloric acid. is nearly boiling the solution is alcoholic solution of dimethyl glyoxime. more tartaric acid if added The solution. Two or three gms. 125.. Thus when possible it is best to add the sodium acetate after the dimethyl glyoxime.c. 129. 331.1 GRAVIMETRIC ANALYSIS. leaving the solution so that The precipitate is filtered through it barely smells of this reagent. but even then the nitration is tedious. Brunck. 28. to heated and treated with 30 c. If the iron is present in the ferrous condition it is oxidized Then from 1 to 3 gm. of concentrated hydrochloric acid. the precipitation must take place in a In the nitrate solution already containing sodium acetate. is It is then carefully tested to see whether enough present to prevent any precipitation of iron when -made alkaline with ammonia. . of tartaric acid are introduced. acid are added and the solution made slightly ammoniacal in by order to find out whether enough tartaric acid has been added After making barely (the solution must remain perfectly clear).c. and the analysis continued according to p.5 gm. the acid just neutralized with ammonia. Separation of Nickel from Iron. on the other hand. the nickel is precipitated with dimethyl glyoxime. weighing about 0. the manganese with ammonium sulphide and determined as is precipitated described on p. which is left slightly acid. When. of tartaric boiling with nitric acid. The acid is finally very carefully neutralized with ammonia. being necessary.

method the nickel in a sample of steel By mined within about two hours. gr. dried at 110-120 for 45 minutes and weighed as Ni(C 4 H 7 N 2 O 2 ) 2 . because the cobalt is usually determined with the nickel. which does not dissolve in the ether. The results are this -can be deter- accurate. sp.1. is more soluble in ether than in this acid is often taken advantage of in the determination of metals such as nickel. but lower than is often obtained in practice. chromium and nickel in steel. vanadium and chromium in samples of steel. lying principle is the iodine between water same as that governing the distribution of and carbon disulphide (see pp. An example will be given of such a process in the footnote).) . The fact that ferric chloride dissolved in hydrochloric acid. Blair method for estimating vanadium. molybdenum. copper. 167 a Gooch or Munroe crucible.REMOVAL OF FERRIC CHLORIDE BY ETHER. 658 and 659. Removal of Ferric Chloride by Ether. which is not the case in this method. Method of Rothe. It has also been used for the determination of sulphur in steel after oxidation to The undersulphuric acid. (See p. 1. 313. washed with hot water.

GERMANIUM. saturated with hydrogen sulphide in the cold. and weighed. Forms: HgS. Hg. by the decomposition of organic mercury compounds by the method of Carius. MERCURY. of the c. CADMIUM. washed with 105-110 C. applicable. because considerthe evaporating able amounts of mercuric chloride are thereby volatilized with salts). BISMUTH. COPPER. yielded in separate = 88. in other words.c. The solution containing no oxidizing substances (FeCl 3 O. Thus 50 containing 0. TIN (PLATINUM. 2. however. LEAD. MERCURY. salt.0. Unfortunately. and 0. of nitric acid and evaporated on the water-bath five times almost to dryness.c. 200. SULPHO-BASES. LEAD. mercuric sulphide = 82. dried at Remark. the precipitate allowed to settle. 68 METALS OF GROUP II. Hg Cl 2 Wt. for in most cases the solution to be analyzed contains by the solution of impure mercuric strong nitric acid (obtained sulphide in aqua regia.39 per In such a case the cent. . or by the oxidation of mercurous not possible to expel the excess of nitric acid by solution with hydrochloric acid. MERCURY. Determination as Sulphide. with the addition each time of 50 c. much HNO3 etc. it is not always cold water. of a mercuric chloride solution treated with 10 c. ARSENIC.c. TELLURIUM.56 . (a) By Precipitation with Hydrogen Sulphide.5235 gm. ANTIMONY. MOLYBDENUM. It is the escaping steam. and Hg. A. filtered through a Gooch crucible. AND VANADIUM).3972 gm. concentrated hydrochloric experiments 0. BISMUTH. SELENIUM. mercuric sulphide per cent..1 GRAVIMETRIC ANALYSIS.) and the mercury entirely as mercuric salt is . TUNGSTEN. COPPER. following procedure suggested by Volhard should be used: acid. a loss of 11-17 per cent. CADMIUM. This method affords excellent results and should be used whenever possible.3695 gm. GOLD. or. At.

aus der quantitative!! chemischem . solution now Ammonium Hg< o contains the mernitrate is then added and the solution boiled until the ammonia is almost entirely expelled. nitrate. f G. completely washed with water and then three The crucible is now placed upon a glass times with alcohol. p. solution (free from Ag. the sulphur Na 2SO 3 + S = Na S 2O 3 2 is changed to sodium . 35) . (b) By Precipitation with Ammonium 169 Sulphide. and the precipitate is allowed to settle. 28.t * By boiling with thiosulphate. Uebungsbeispiele Analyse. A1 2 O 3 and SiO 2 ) is then added. mercuric sulphide. meanwhile . still better A way of cent. rotating the solution until the dark liquid begins to lighten. dried at 110C. analyzing pure mercuric and obtained as a mean of chloride with the addition of nitric acid. tripod in a beaker containing some carbon bisulphide (Fig.* H.85 per cent. sulpho-salt. Rauschenbach tested this method. free sulphur from the precipitate In this case the consists of extracting with carbon bisulphide. Vortmann. By means of the boiling with ammonium. two experiments 73. Hg instead removing of the theoretical value. is filtered through a Gooch crucible.and it should weighed. 1899. The acid solution of the mercuric salt is almost neutralized with pure sodium carbonate and is treated with a slight excess of Pure sodium hydroxide freshly-prepared ammonium sulphide. together with the sulphur. Vienna.80 per 73. In case the precipitate contains free sulphur. poured through a Gooch crucible.. which it will do much more quickly than if it were produced by hydrogen sulphide directly. The The clear liquid is precipitate is then transferred to the crucible. sodium sulphite. when it is heated to boiling and more sodium hydroxide is added until the liquid cury as is The perfectly clear. and the washed decantation with hot water until the by precipitate wash water no longer reacts with silver nitrate solution. be boiled with a little sodium sulphite before filtering. the sulpho-salt decomposed according to is this equation: Hg(SNa) 2 + 2NH 4 N0 3 = 2NaNO3 + (NH^S + HgS.DETERMINATION OF MERCURY AS SULPHIDE.

Rauschenbach analyzed pure mercuric by this method and obtained as a chloride mean Hg of eight experiments 73. 170 the beaker is covered with supported over a vessel filled with hot water and a round-bottomed flask con- taining cold water which serves as a condenser.. instead of the theoretical value. For the analysis of a solution containing a mercurous salt. The ether is driven off by gently warming. diluted considerably with water. the solution boiled until the ammonia is almost entirely expelled. and the mercury precipitated as sulphide by the method of Volhard or the acid solution is treated with pure sodium hydroxide solution to alkaline reaction and then with pure potassium cyanide until the mercuric oxide has dissolved.GRAVIMETRIC ANALYSIS. and finally with water. the precipitate allowed to settle. removed from the precipitate by washing once with alcohol and once with ether. ammonium acetate added. then with hot dilute hydrochloric acid. after standing twelve hours. dried at 105 C. 73. Determination as Mercurous Chloride.84 per cent. filtered. and the precipitate then dried at 110 C. After about an hour the sulphur will be com- The carbon bisulphide is pletely extracted. and weighed. is desired to determine mercury in an organic non-electro- the compound is decomposed by the method of Carius (see Elementary Analysis) by heating in a closed tube with concentrated nitric acid. . After drying at 110 C.17 per cent. instead of 73.. through a Gooch cruciIf the solution contains a merble. the solution is saturated with hydrogen sulphide. filtered. solution is . after which lyte. the precipitate of mercuric sulphide is weighed.79 per cent. the treated with sodium chloride. If it Determination of Mercury in Non-Electrolytes. and in the case of eight further experiments made without JT IG 35> removing the sulphur he obtained 74. and washed first with hot water.85 per cent. and weighed. H.

dried at 105 C. then the other burners are lighted one after another until finally the entire contents of the loosely filled with pure gold-leaf. open at both ends. a glass tube 50 1. suited) is passed through it for half an hour. acid phosphorous The mercury solution (which almost always conProcedure. Almost all mercury compounds are quantitatively decompose on heating with lime according to the equation . finally a layer of lime 30 cm. is taken and in one is placed. long and at the other end of the tube another asbes- tos plug tos plug. and weighed. and is connected by means of rubber tubing with the empty narrower arm of a Peligot tube. The phosphorous to be acid necessary for this method is obtained by the oxidation of phosphorus in moist air or by the decomposition of phosphorus trichloride with water. diluted conan excess of phosphorous acid is added.DETERMINATION OP MERCURY AS METAL reduced. but in spite of this fact the method is recommended. The iodide alone To carry out is not readily acted upon. by means in the presence of hydrochloric acid. After the tube has been filled. Rose. During the whole of the operation illuminating-gas is being passed through the apparatus at the rate of about three bubbles a second. layer of lime is. evaporating the solution to remove the hydrochloric acid and dissolving the residue in water. Remark The results obtained by this method are always about 0. wide. of 171 it is first is treated with hydrochloric acid.'. HgX + CaO = CaX + Hg + O. too low. long and end an asbespure lime. cm. by the method of H.. Determination as Metal. The greater part of the tube mercury collects in the lower empty end of the Peligot tube and . and with water. then an intimate this determination. The other wider end of the Peligot tube is The glass tube is placed in a combustion-furnace and illuminating-gas (carbon dioxide is less The tube is heated. at first where the 30 cm. curie salt. of mixture of a weighed amount of substance with lime. siderably after standing for twelve hours the precipitate is filtered through tains nitric acid) a Gooch crucible. followed by 8 cm. the end nearest this second asbestos plug is drawn out until it is only 4 cm.5 cm. wide.4 per cent. is subjected to gentle ignition.

15 (1880). the mercury may collect at the bottom of the platinum dish used as cathode.GRAVIMETRIC ANALYSIS. anal. The Peligot tube is usually moist. Luckow. 388.). 31.74 per cent. 8.. Although it is easy to obtain good results by this method.. con- ducted through it for some time. 206.. Winteler found in the analysis of pure mercuric chloride 73. f J. Riiderff. 324 (1886). W. or alkaline solutions. 73. 385. 11. 24. Am. the form of The use of silver-plated electrodes is also advised.. when the quantity is small. The dif- ference in weight gives the amount of mercury condensed in the tube. The electrolysis takes place to advantage in solutions slightly acid with nitric acid.. J. Classen and Ludwig. prakt.f Mercury can be determined by the electrolysis The metal is deposited in satisfactorily of acid. which.. G. it is amount of mercury vapor only necessary to aspirate the gas The gain through a calcium-chloride tube filled with gold-leaf. Electrolytic Determination of Mercury. Chem. * First proposed by Erdmann and Marchand. adhere to the electrode. Experiments made attempting to condense the mercury under water invariably gave too low values (about 1-2 per cent. Chem.. Chem. little drops. F. Z. or. for the sulphide method affords just as exact results in In case it is much less time. Vortmann. when larger amounts are present.85 per cent. Ber. 19. Smith and Knerr. angew. 73. in weight of the latter shows the amount of mercury present in the gas. Clarke. 1409 (1878). after which it is weighed. desired to determine the present in a given space. It is then heated gently while air is passed tube. Z. The results obtained by this method * are perfectly satisfactory. neutral. therefore. it can be dispensed with. Chem. 2750 (1891). 73. After cooling the apparatus (in a current of illuminating-gas) the narrow part of the tube is cut off both sides of the condensed mercury and weighed. instead of the theoretical value.81. Ber. dry air is. through it to volatilize the mercury and again weighed. Ber.88. 19. 172 the mercury vapors that are carried further amalgamate with the A small amount of the mercury condenses in the drawn-out gold. . 1894.

without breaking the current. and similarly from not to be used.00133 mm.6-1 ampere the electrolysis is finished at the end of two or three hours. the a metal is washed with water without interrupting the current. During the electrolysis of mercuric chloride J the solution often becomes turbid in consequence of the formation of insoluble mercurous chloride. 7 (1905). hours. how ever. which is not always the case When a dish is use4 as cathode.ELECTROLYTIC DETERMINATION OF MERCURY. it will be finished next morning. and The drying requires several the electrode dried as above and weighed. Drying at 100 and then over sulphuric acid in a desiccator gives rise to low results because the acid absorbs considerable mercury vapor. but with gauze does no harm. elect roly zed provided the amount of mercury does not exceed 1 gm. it is better to use a platinum dish dull. The metal is further dried by touching it with filter paper. amounts to 0. the washing is finished. cf. the tension of mercury vapor is considerable. Revisto tecnica.. As soon as.5-5 volts. then with alcohol* and dried. with a platinum gauze cathode at the ordinary The voltage temperature with a current of 0. communication from A. The current is then turned off.c.c. as the metal r is subsequently deposited on the cathode. If the electrolysis is started at night.10 ampere. and then placing it in a desiccator f over fused potassium hydroxide and a small dish of mercury. 173 The neutral or curous or mercuric salt is slightly acid solution of the merplaced in a beaker. this does no harm. Part It is alkali. diluted with water treated with 2 or 3 c. the water carefully poured off. washed with water. At the end of the electrolysis. the rest of it removed by touching it with filter-paper. under these conditions corresponds to 3. Even at 20 Miolati. the electrode is with gauze electrodes. . the ammeter (or voltmeter used as an ammeter) reaches the zero mark. unpolished inner surface (Classen) because then any mercurous chloride will certainly be reduced to metal.055-0. of concentrated nitric acid. by pouring water into it from a wash-bottle while the solution is being siphoned off. Borelli. % with In the electrolysis of the chloride. to 150 and c. Mercury can also be electrolyzed from a solution in potassium cyanide in the presence of some caustic * It is electrodes usually stated that alcohol it f Private V. In this way correct results are obtained. By using current of 0. Procedure.

At. 174 a solution formed by dissolving mercuric sulphide in 5060 c. Pb.* Determination as Lead Oxide. washed at first with 4 per cent. t The solution at the time of filtering should contain about 5 per cent. If the lead is present as carbonate. The treatment of the nitrate requires care. use an ordinary filter. then with alcohol. LEAD. present in solution in the form of its chloride or placed in a porcelain dish. 207. or element. provided with and ignited over the full flame of a Teclu burner. . of the reducing action of the burning filter.GRAVIMETRIC ANALYSIS. the filter ignited in a platinum If it is desired to washed with alcohol spiral (p. lead sulphate adhering to it is always reduced to lead.c. 22). filtered through a Gooch crucible. and dried at 100 C. an excess of dilute sulphuric the lead it is PbS04 is added t and the mixture evaporated on the water-bath as then over a free flame until dense white fumes of acid are evolved. The dried sulphuric acid. If nitrate. and the ash added By means to the contents of the crucible. nitrate. PbS0 4 Pb0 2 and . 2. the precipitate is finally until the wash liquid no longer gives the sulphuric acid reaction. sodium sulphide solution. of free sulphuric acid. allowed to stand some hours. Forms: PbO. Determination as Lead Sulphate. The great advantage of the electrolytic determination of mercury lies in the fact that good deposits are obtained irrespective of the nature of the acid radical. and afterwards allowed to cool. dried. as much of it as possible is transferred to a weighed porcelain crucible. . Wt. A little sulphuric water is added.1. the mixture stirred. which is combined of concentrated with mercury. ring. because on rapid ignition the mass decrepitates. some of the which must * See Analysis of Vanadinite. precipitate an asbestos is placed in a larger porcelain crucible. or peroxide. acid is far as possible. in rare cases PbCl2 . it is only necessary to ignite a weighed portion in a porcelain crucible over a small flame and weigh the residue. . i. PbO.

DETERMINATION

Of"

LEAD AS LEAD SULPHATE.

I?S

be changed back to sulphate before weighing. For this purpose
the precipitate in the crucible is moistened with dilute nitric acid,
evaporated on the water-bath to dryness, a few drops of concentrated sulphuric acid added and the crucible heated over a free
flame until no more fumes are given off, when it is gently ignited and

weighed.
In case the lead

is originally present as acetate, the solution
treated with an excess of dilute sulphuric acid and twice its
volume of alcohol, filtered after standing some hours, and the

is

precipitate of lead sulphate treated exactly as described above.
In order to determine the amount of lead present in organic

compounds, the substance can be placed in a large porcelain crucible,
treated with an excess of concentrated sulphuric acid, and very
cautiously heated in the covered crucible over a free flame until
the sulphuric acid is completely expelled. The crucible is then
gently ignited, and if the residue is white it is ready to be weighed;

otherwise more sulphuric acid is added and the process repeated
until finally a white residue is obtained.

In case the organic lead compound is soluble in water, it is
preferable to first precipitate the lead by means of hydrogen

For
sulphide and then transform the precipitate into sulphate.
this purpose, as much as possible of the washed and dried precipitate is placed upon a watch glass, the filter and remainder
of the precipitate are heated in a large porcelain crucible, which is
supported in an inclined position, and heated carefully over a
small flame until the filter-paper is completely consumed. The

main part

of the precipitate

is

added to the

crucible,

which

is

then covered with a watch-glass and treated with concentrated
When the
nitric acid at the temperature of the water-bath.
main reaction is over, the treatment with fuming nitric acid is
repeated until the contents of the crucible are pure white in
The watch-glass is then removed, five or ten drops of
dilute sulphuric acid are added, the liquid is evaporated as far
color.

as possible

on the water-bath, the excess

moved by heating on

of sulphuric acid

is

re-

and the lead
Should the precipitate be dark colored

the air-bath

(cf.

Fig. 11, p. 27)

sulphate is weighed.
after the ignition, it is moistened with concentrated sulphuric
acid and the excess of acid again expelled.

GRAVIMETRIC ANALYSIS.

176

If the lend is present in an organic compound \\hich is not
capable of dissociation, the compound should be decomposed in a
closed tube with strong nitric acid according to the method of

Carius (see page 287), finally washing out the contents of the tube,
adding sulphuric acid, and treating the precipitate as above described.

Separation of Lead Sulphate from Barium Sulphate and
Acid.

Silicic

In the analysis of sulphide ores containing lead, it is customary
to dissolve the finely powdered ore in nitric acid, or aqua regia,

and to remove the
phuric acid

come

by evaporation with sulphuric
over the free flame until fumes of sul-

volatile acids

acid, eventually heating

off thickly.

The sulphuric

acid should be diluted

with an equal volume of water before adding

it to the original
After the
solution; usually 5 c.c. of the diluted acid is sufficient.
evaporation the moist residue is allowed to cool, then water is

added and the precipitate filtered and washed with 1 per cent,
The precipitate contains all the lead as sulphate
sulphuric acid.
but often contains silica and barium sulphate (also strontium
sulphate and sometimes calcium sulphate). It is purified by
redissolving the lead in hot ammonium acetate solution (made by
neutralizing acetic acid, sp. gr. 1.04, with ammonia, sp. gr. 0.96,

When the precipand leaving the mixture barely ammoniacal)
amount it is best to wash it into a beaker or flask
and heat it with about 20 c.c. of the ammonium acetate solution
.

itate is large in

enough to dissolve all the lead sulphate), then filter through
filter and wash with hot ammonium acetate solution,
and finally with hot water until the filtrate gives no blackening
with ammonium sulphide. Small amounts of lead sulphate are
The silica and barium sulphate will all
dissolved on the filter.
remain behind.
In order to obtain lead from the acetate solution, it is precipitated as sulphide by hydrogen sulphide, and transformed, after
drying, into sulphate as described on page 175.
(or

the original

Or, the ammonium acetate solution may be treated with 10 c.c.
of 50 per cent, sulphuric acid, the acetic acid removed by evaporation, the residue allowed to cool, diluted with water, and the

ELECTROLYTIC DETERMINATION OF LEAD.

177

Gooch crucible, washed with dilute
in
an
heated
air
bath and weighed.
sulphuric acid,
If the amount of ammonium acetate solution used is not too
large, the lead may be precipitated by adding enough sulphuric
lead sulphate filtered into a

acid to the acetate solution to

make

the solution contain from

5-10 per cent, sulphuric acid. Sometimes the precipitate is not
pure lead sulphate, in which case it should be redissolved in

ammonium

acetate

3. Electrolytic

Many

and the precipitation as sulphate repeated.

Determination of Lead as Peroxide (Pb02 ).

neutral solutions of complex lead salts, a neutral solu-

tion of lead acetate, also alkaline lead solutions yield deposits of
metallic lead on the cathode when subjected to electrolysis; but
is never determined this way; partly because of the roundabout process necessary, and partly on account of the fact that
the deposited lead is oxidized so readily.
If a neutral or slightly
acid (nitric acid) solution of lead nitrate is electrolyzed, the
lead is deposited partly as metal upon the cathode and partly as
brown peroxide on the anode. If, however, the solution contains

lead

sufficient free nitric acid, it is easily possible to deposit the lead

upon the anode as firmly -adhering lead peroxide.
The solution of lead nitrate, containing not morethan 0.5 gm. lead, is placed in a platinum dish whose inner surface is unpolished (as recommended by Classen), 20-30 c.c. of
quantitatively
Procedure.

pure nitric acid, sp. gr. 1.4, are added, the solution is diluted to
150-200 c.c. and electrolyzed in the cold with a weak current of
about 0.5-1 ampere and 2-2.5 volts.
When the electrolysis is
carried out in the cold, all the lead will be deposited as the peroxide
at the end of

two hours and a

or an hour and a half
is

kept at

50-60.

is

If it

half or three hours.

Only an hour

required if the temperature of the cell
is desired to let the electrolysis run over

night, a current of 0.05 ampere is sufficient.
A suitable arrangement of the electrolytic apparatus is shown
in Fig. 36, but the dish should serve as anode and the platinum
spiral

as cathode.

The

resistance

10 m. of nickel wire of about 0.5

board as shown

W

is

made by taking about

mm. diameter,

fastening

it

to a

drawing and connecting the wires in pairs
means
of
a
brass
by
hook, of which only one is shown in the
sketch.
By suitably moving these hooks it is possible to vary
in the

GRAVIMETRIC ANALYSIS.

i 78

the resistance at
in Fig. 31,

will.

132,
convenient but also
trolysis,

p.

which

is

Instead of this arrangement, that shown
be used; such an apparatus is more
At the end of the elecmore expensive.

may

shown by the

fact that dilution with a little

water so as to expose a fresh surface of platinum causes no yellowish-brown coating to appear at the end of half an hour, the
This is accomdish is washed without breaking the current.
while
the
solution
is being
water
plished by introducing distilled
siphoned

It

off.

is

important in this operation to keep the deposit

FIG, 36.
of

lead

peroxide completely covered with liquid.

When

the

no longer reacts acid, or at
being siphoned
least only barely acid, the washing is complete and the circuit can
be broken. The dish is finally washed once more with distilled
water, dried at 180 C., and weighed. The results obtained are
always slightly high on account of the lead peroxide not being
solution that

off

is

completely anhydrous when dried at this temperature, so that it
seems to the author to be advisable to gently ignite the dish
before weighing, thereby readily converting the peroxide into
lead oxide.* The results obtained in the author's laboratory

leave nothing to be desired.
* Cf.

W.

C.

May,

Z. analyt.

Chem.,

14,

347 (1875).

DETERMINATION OF BISMU7H AS BISMUTH OXIDE, ETC.

179

(a) 10 c.c. lead nitrate solution containing 0.0631
lead
deposits of PbO 2 weighing 0.0734, 0.073L 0.0735,
yielded
gm.
0.0733 gm. ; mean 0.07332 corresponding to 0.0635 gm. lead. After

Results.

ignition the lead monoxide formed weighed respectively 0.0679,
0.0678, 0.0679, 0.0681 ; mean 0.0679 gm. corresponding to 0.0630

instead of 0.0631 gm. lead.
(6) 10 c.c. of a lead nitrate solution containing 0.1898 gm.
lead yielded deposits of PbO 2 weighing 0.2202, 0.2200, 0.2203,

0.2202;

mean

0.2202 corresponding to 0.1907 gm. lead.

After

ignition the weights of lead oxide obtained were 0.2042, 0.2046,
0.2043. 0.2044; mean 0.2044, corresponding to 0.1897 gm. Pb

instead of 0.1898 gm.

These experiments were performed by M.

Stoffel.

By employing a stronger current and keeping the
warm during the electrolysis, the deposition is complete

Remark.
solution

in much less time, but according to the author's experience the
results obtained are not so satisfactory.
By rotating one of the

and using a stronger current, the deposition can be made
If a little lead deposits on the
to take place in a short time.
this
is
remedied
cathode,
by stopping the current for a short time,

electrodes

toward the end

of the electrolysis.

Besides the above-mentioned forms, lead is also determined
as the chromate and as the chloride. The latter method is

sometimes used in the analysis

of bearing metal,

cf. p.

252.

BISMUTH, Bi. At. Wt. 208.0.
Forms: Bi 2 3 Bi 2 S 3 Bi.
,

,

I.

Determination as Bismuth Oxide, Bi2

Solid bismuth nitrate or carbonate

is

s

.

readily changed to the

oxide by gentle ignition. When bismuth, however, is present in
solution as the nitrate, it should be first precipitated as the basic

carbonate and this changed by ignition to the oxide.
Procedure. The solution is diluted with water (if a turbidity
ensues it makes no difference) a slight excess of ammonium

carbonate

is

added, and after heating to boiling the precipitate

GRAVIMETRIC ANALYSIS.

i8o
is filtered off.

as Bi 2 O 3

washed with hot water, dried, ignited,* and weighed
from which the bismuth is to be pre-

If the solution

.

H

2 SO 4 etc.),
cipitated contains besides nitric acid other acids (HC1,
the precipitate produced by ammonium carbonate always contains basic salts of these acids which cannot be converted to the
,

oxide by ignition. In this case, which is most frequent in analysis,
the bismuth should be determined according to one of the following methods.

Determination as Sulphide, Bi 2 S 3

2.

The
filtered

.

slightly acid solution is saturated with hydrogen sulphide,
through a Gooch crucible (or a filter that has been dried

at 100 C. and weighed) washed with hydrogen sulphide water,
then with alcohol to remove the water, and afterwards with freshlydistilled carbon bisulphide f to remove any sulphur that may be
,

mixed with the precipitate.
The washing with carbon bisulphide is continued until a few
drops of the filtrate leave no residue on being evaporated to dryThe precipitate is then washed with
ness on a watch-glass.
alcohol to remove the carbon bisulphide and finally with ether,
dried at 100 C., and weighed as Bi 2 S 3
The distillation of the carbon bisulphide should be performed
.

Ordinary commercial carbon bisulphide is placed in
a long-necked, round-bottomed flask, provided with a closely fitThrough the
ting cork (not rubber) stopper which is bored once.

as follows:

hole in the cork

is

placed a glass tube bent twice at right angles,
flask (without using a stopper

whose further end leads into a dry
for this receiver).

one

filled

Two

large beakers are placed upon the table,
C. and the other with cold

with water at about 60-70

If the flask containing the carbon bisulphide is placed
beaker containing the warm water, and the other flask in the
beaker of cold water, the carbon bisulphide will distil rapidly from
one flask to the other. Care must be taken during this operation

water.
in the

* If the
precipitate is large in amount, the greater part is placed on a
watch-glass, the remainder adhering to the filter is dissolved in hot, dilute
nitric acid, the solution evaporated to dryness in a weighed platinum dish,

and the main portion

of the precipitate added.
The dish and its contents
gently but finally over the full flame of a Bunsen burner.
described on p. 169 or on p. 223.

are heated at
t

As

first

DETERMINATION OF BISMUTH AS METAL.
that there

is

181

no lighted gas-burner in the immediate vicinity, for
is danger of the vapors of carbon bisulphide taking

otherwise there
fire.

3.

Determination as Metal.

Method

of

H. Rose.*

The bismuth is first precipitated as basic carbonate as described
1, and the dried precipitate, together with the ash of the filter,
Five times
is placed in a porcelain crucible and ignited gently.
as much of 98 per cent, potassium cyanide is added to the contents of the crucible and the mixture is fused, whereby the oxide
and basic salt are changed to metallic bismuth
under

:

+ 3KCN = 3KCNO + Bi,
2BiOa+4KCN=2KCNO f 2KC1+ (CN),-f Bij.
Bi 2

3

Since bismuth melts at 268 C., but boils at 1600 C., it is possible to perform this operation with a Bunsen flame of about half the

usual height without running, any risk of losing some of the bismuth
by volatilization. The reduction is usually complete at the end of

twenty minutes. After cooling, the melt is treated with water,
which dissolves the salts and leaves the metallic bismuth behind
in the form of a fused metallic globule.
Frequently, however, the
fusion will have loosened some of the glaze of the porcelain crucible,
which will remain behind with the bismuth after the treatment
witii

water.

Consequently the aqueous solution

is

filtered

through

that has been dried at 100 C. and weighed with the empty
crucible.
After washing first with water, then with absolute

a

filter

alcohol

and ether and drying at 100 C., the filter is again placed
and weighed. The gain in weight represents the

in the crucible

amount of metallic bismuth.
Bismuth sulphide can also be reduced by potassium cyanide,
but in this case a longer and stronger heating is necessary.
4.

Determination as Metal.

Method

of

Vanino and Treubert.t

In this method the bismuth is precipitated as metal by means of
formaldehyde in alkaline solution. The slightly acid bismuth solu*
Pogg. Ann., 110, p. 425.
f Berichte, 31 (1898), 1303.

GRAVIMETRIC ANALYSIS.

182

tion

is

treated with formaldehyde and a considerable excess of pure

10 per cent, caustic soda solution and warmed on the water-bath until
the liquid above the precipitate has become perfectly clear more for;

maldehyde and caustic soda solution are then added and the mixture
heated over a free flame,* decanted repeatedly with water to which
a little aldehyde has been added, again boiled, and by pressing with
a glass rod the partly spongy, partly pulverulent precipitate is made
The precipitate is then filtered through a filto collect together.
ter that has been previously dried at 105 C. and weighed, washed

with absolute alcohol, dried at 105 C. and weighed.
Remark. Results obtained in the author's laboratory by this
method were as a rule too high. Thus W. Urech obtained from
pure bismuth nitrate solution, as a mean of four experiments, 100.78
per cent, instead of 100 per cent.
The high results are caused by the difficulty in removing
the last traces of alkali. Absolutely accurate results may be

obtained by dissolving the precipitated bismuth in nitric acid,
precipitating by ammonia and ammonium carbonate and weighing
as the oxide according to (1).
Naturally this roundabout process
would only be chosen when the bismuth solution contained other
acids (HC1,

H SO
2

4,

or

H PO
3

4)

;

the necessity of fusing with potas-

sium cyanide would then be avoided.

COPPER, Cu.

At. Wt. 63.57.

Forms: CuO, Cu^S, Cu, Cu2 (CNS) 2

.

Determination as Copper Oxide, CuO..
solution, which must be free from organic substances and
ammonium salts, is heated to boiling in a porcelain dish and pure
i.

The

is added, drop by drop, until the precipibecomes dark brown and is permanent, while the solution
After the
itself shows an alkaline reaction towards litmus-paper.

caustic potash solution

tate

precipitate has settled, the upper liquid

a

is

carefully poured through

and the precipitate washed by decantation with hot water
the wash water no longer shows an alkaline reaction, when the

filter

until

*
Frequently, particularly on long boiling, the liquid becomes colored
yellow or brown. This has no influence upon the results.

DETERMINATION OF COPPER AS COPPER OXIDE.

183

is transferred to the filter and completely washed.
small
amount of copper oxide adheres to the porcelain
a
Usually
dish so firmly that it can be removed only by vigorous rubbing

precipitate

with a glass rod

covered at the end with a piece of rubber
and
when
the precipitate is removed from the dish
finally
tubing,
some will then remain on the rubber. Consequently it is better to
proceed as follows As much of the precipitate as possible is removed
by a stream of water from the wash-bottle, then two drops of dilute
nitric acid are added, and by inclining the dish and rubbing with
the glass rod, the whole of the precipitate remaining on the dish is
:

moistened with the acid.

Two

drops of the acid are

sufficient,

with

A

small
correct manipulation, to dissolve all of the copper oxide.
fresh filter is prepared and the dish is held in an inclined position,
so that the liquid remains near its lip, the sides are washed once

with hot water and the contents of the dish (which is continually
maintained in this inclined position) are heated to boiling over a
small flame and precipitated by the addition of caustic potash,
drop by drop. (A large excess of alkali is to be avoided on account
*

The whole contents
poured through the small filter and
the dish is immediately washed once with water. The copper oxide
is now all on the filter.
The precipitate is washed with hot water,
both filters are dried, and the most of the precipitate transferred
to a porcelain crucible, the filters ignited in a platinum spiral, and
the ash added to the contents of the crucible. The crucible is covered and ignited, at first gently, and finally with the full heat of the
of its solvent action

upon the

precipitate.)

of the dish are then quickly

Bunsen burner then weighed.
fully,

If the process is carried out carethe results obtained are almost the theoretical values but

as a rule they are a trifle high.
2.

Determination as Cuprous Sulphide,

The solution, which contains for every 100 c.c. about 5 c.c. of
concentrated acid (best sulphuric acid), is heated to boiling and
hydrogen sulphide is introduced until the solution becomes cold.
If the right

amount

was present, the precipitate settles
and the upper liquid appears completely

of acid

quickly in large flocks

*Cf.

VoM.

1

GRAVIMETRIC ANALYSIS.

84

wash liquid is prepared by passing
the
hydrogen sulphide through
long tube of a wash-bottle for one
with a piece of rubber tubing
then
short
tube
the
minute,
closing
and shaking vigorously. As soon as no more bubbles pass through
colorless.

Before

filtering,

the liquid, the water

is

the

saturated this takes about a minute at the
;

most.

A

filter is

the funnel

is

now

placed in a funnel containing a platinum cone,
and the filtration is begun

fitted to a suction-bottle

at first without using suction, taking care that the filter is constantly kept full. When all the precipitate is on the filter, it is

washed with the hydrogen sulphide water containing acetic acid,
The
and, at this point also, the filter must be kept full of liquid.
washing is continued until 1 c.c. of the filtrate shows no test for
mineral acid.*

The

filter

drain completely, and

it

is

is

now

for the first time allowed to

dried as

gentle suction, then completely
closet at 90-100 C.

of

As much

much

as possible by means
in the drying

by heating

of the precipitate as possible

is

now

transferred to a

weighed Rose crucible (of unglazed porcelain), f the filter is
burned in a platinum spiral and the ash allowed to fall at first
upon an unglazed crucible cover, where it is heated gently till it
glows, in order to make sure that it contains no unburned carbonaceous matter; the ash is then added to the main portion
of the precipitate in the crucible.
A little sulphur that has been
recrystallized from carbon bisulphide is added to the contents
of the crucible, the perforated cover is now placed on the crucible
(Pfg. 37), a stream of hydrogen is passed through it (the washbottle shown contains concentrated sulphuric acidt), and the crucible is heated at first over a small flame and finally so that the
* The test for
sulphuric acid is made with barium chloride. To test for
hydrochloric acid, the solution is boiled until the hydrogen sulphide is expelled and is then treated with silver nitrate.
t

A

quartz crucible

is

more

desirable, as the transformation of

CuS

into

Cu2S can then be watched.
% If the hydrogen is prepared from zinc and hydrochloric acid, the gas
should be passed first through water and then through a wash-bottle containing concentrated sulphuric acid.

DETERMINATION OF COPPER AS CUPROUS SULPHIDE.
bottom

185

glows faintly, at which temperature the
changed to cuprous sulphide,

of the crucible

cupric sulphide

is

Too strong heating

When

is

inadvisable according to

Hampe.

*

the excess of sulphur has been driven off (which can be
by removing the cover of the crucible and

readily ascertained

FIG. 37.

no blue flame to be perceptible and no odor of burning
sulphur), the current of hydrogen is increased so that eight
bubbles per second pass through the wash-bottle (at first, not
more than four bubbles per second should have been the
The crucible is allowed to
rate), and the flame is removed.
cool in the current of hydrogen and weighed after remaining
finding

The cuprous sulphide
in the desiccator for fifteen minutes.
should be brownish black or black, and should show no reddishbrown stains (due to Cu or Cu 2 O); this is the case if the current of hydrogen was too slow during the cooling.
In this case
f Z. anal.

Chem

.,

38,

465 (1894).

GRAVIMETRIC ANALYSIS.

l86

a

little

sulphur must be added to the precipitate and the process

repeated.

Remark.

It

ment should

evident that the sulphur used for this experiThis is why

is

leave on ignition no weighable residue.

the sulphur used should be recrystallized from carbon bisulphide.
The reason why it is necessary to keep the funnel filled with
liquid during the filtration and washing of the cupric sulphide is this

:

moist copper sulphide

exposed to the air it is quickly oxidized
and the hydrogen sulphide wash water acts upon the salt formed by
the oxidation, (CuS 2 O 3 CuSOJ and transforms it into colloidal
If

is

,

cupric sulphide, which forms a pseudo-solution, passes through the
filter, .and on coming in contact with the acid filtrate is coagulated.

If,

is not exposed to the air
during
no oxidation and the filtrate remains clear.

however, the precipitate

the filtration there

is

Instead of changing the cupric sulphide into cuprous sulphide,
has been proposed to convert it to oxide by ignition in the
air and weighing the copper in this form.
If, however, the highest

it

degree of accuracy

is

desired, this should not be done, for the

contains some sulphate.
When this
the
should
in a glazed
be
heated
chosen,
cupric sulphide
a
at
first
over
small
so
that
the mass
porcelain crucible,
flame,
does not melt, and the heat gradually increased until finally a
ignited

method

product

always

is

blast-lamp is used and the copper weighed as CuO. The results
are about 0.1 per cent, too high when not more than 0.2 gm. of

Holthof* states that copper oxide absopresent.
from sulphate can be obtained if the precipitate is
ignited wet in an inclined porcelain crucible.

precipitate

is

lutely free

3.

Determination as Cuprous Sulphocyanate, Cu 2 (CNS) 2

Method

The

.

of Rivot.f

solution, slightly acid with sulphuric or hydrochloric acid

(oxidizing agents

must not be present), is treated with an excess
after which ammonium sulphocyanate is

of sulphurous acid,J

* Z. anal.
Chem., 28, 680 (1889).
t Compt. Rend., 38, 868; see also R. G.
26, 230,

and Busse,

Zeit.

f.

van Name,
and 30,

anal. Chem., 17, 53,

Zeit.

f.

anorg. Chem.,

122.

t Instead of sulphurous acid, ammonium bisulphite
latter is prepared by saturating aqueous ammonia with

may
SO
2

.

be used.

The

ELECTROLYTIC DETERMINATION OF COPPER.

187

added drop by drop with constant stirring, whereby at first a
greenish precipitate of cupric and cuprous sulphocyanate is pre
The precipitate
cipitated, which after stirring becomes pure white.
is

allowed to settle completely (this requires several hours) it is
filtered and washed with cold water until the filtrate shows
;

then

cnly a slight reddish coloration

when

ferric

chloride

is

added,

which it is washed several times with 20 per cent, alcohol,
dried at 110-120 C., and weighed.
R. Philipp found by this
method 99.95 per cent, instead of 100 per cent, copper, as a mean
of twelve experiments. The cuprous sulphocyanate can be dried
at a temperature as high as 160 C., but at 180 C. it begins to
decompose. The Munroe crucible can be used to advantage in
cfter

The precipitate permits rapid filtration, and
never obtained. After the determination is
finished, the greater part of the precipitate is shaken out of the
crucible, and the remainder dissolved in hot nitric acid.
this determination.

a turbid

filtrate

is

4. Electrolytic

Determination of Copper.

This most accurate and most convenient of
the determination of copper was
1864.*

first

all

proposed by

methods

for

W. Gibbs

in

Copper may be deposited by means of the electric current
from acid, alkaline, and neutral solutions, but for analytical purposes only the use of acid solutions is of importance.
Procedure. The safest way, according to F. Forster,*

is

to

deposit the copper from a sulphuric acid solution. To the neutral
solution containing the copper in the form of sulphate, 10 c.c.

normal sulphuric acid are added, the solution is diluted to
c.c. and electrolyzed with exactly two volts
and this potential is kept constant
at
the
electrodes
potential
These
conditions are fulfilled by simply
the
during
electrolysis.
of twice

a volume of 100

connecting the electrodes with the poles of a single storage cell.
electrolysis requires at least eight hours if done at the ordi-

The

nary temperature, but by keeping the solution at 70-80, 0.2
gm. of copper is deposited in 60-80 minutes. If, therefore, it
* Z. anal.
Chem.,

3,

334.

1

GRAVIMETRIC ANALYSIS.

88

is

desired to carry on the electrolysis over night, it is done in the
It is very easy to decide when the electrolysis is finished

cold.

by adding a

little

water and noticing whether there

is

any more

copper deposited upon the freshly exposed electrode surface.
The cathode is then washed with water, without breaking the
exactly as was described under the electrolytic determination of nickel (p. 136). Finally/ the cathode is rinsed with alcohol,
dried by holding it high above a flame, cooled in a desiccator,
circuit,

and weighed.
If these directions are followed closely, the

copper

is

never

deposited in a spongy condition. The presence of Ni, Co, Fe,
Zn and Cd does not influence the analysis and the copper may be

separated from these elements by means of such an electrolysis.
If the solution to be analyzed contains copper and some of
the above-mentioned base metals, it is evaporated to dryness,

heated with a

little

sulphuric acid until dense fumes are evolved,

cooled, treated with 10 c.c. of 2 N. sulphuric acid, diluted to 100
c.c. and electrolyzed as described above.
If, however, only copper is present in the solution, it may
The solution
be deposited very nicely in the following manner.
should contain 4-5 c.c. of concentrated nitric acid in 100 c.c. If,
originally, i: contained more nitric acid than this, it is either
evaporated to dryness or neutralized with ammonia, and then the
required quantity of nitric acid added. The solution is heated
to 50-60 and electrolyzed with a current of 1 ampere and electrode potential of 2-2.5 volts. The electrolysis is over at the

end of two hours, when not more than 0.3 gm. of copper is present.
The analysis is finished as above but there is more danger of
traces of copper being dissolved while the electrodes are being
removed.
Remark. The copper may be deposited electrolytic ally much
more rapidly by the use of a rotating electrode or any stirring
arrangement. The use of a gauze cathode has also been recommended. The solution should not be diluted too much, as
spongy deposits are obtained from very dilute solutions unless
a very weak current is used. As a general rule, the more concentrated the copper solution, the stronger the current that can.
be used.

ELECTROLYTIC DETERMINATION OF CADMIUM.

CADMIUM, Cd.

189

At. Wt. 112.4.

Forms: Cd, CdS0 4 CdO.
,

I.

Electrolytic Determination of

Cadmium.

Of all the methods for the determination of cadmium the electromethod is not only the most convenient, but by far the most
accurate, and of the many methods proposed that of Beilstein and
Jawein* can be recommended. From the experience obtained in the
lytic

author's laboratory the best procedure

as follows:

is

To the

solution

of the sulphate a drop of phenolphthalein is added and then pure
caustic soda solution until a permanent red color is obtained.
so-

A

lution of 98 per cent, potassium cyanide is now added with constant
stirring until the precipitate of cadmium hydroxide produced by the
caustic soda has completely dissolved (an excess of potassium cyanide should be scrupulously avoided), the solution is diluted with
water to 100-150 c.c. and electrolyzed in the cold, using a gauze

cathode, for from five to six hours with a current of 0.5-0.7 ampere
and an electromotive force of 4.8-5 volts; at the end of this time
the current
is

is

increased to from 1-1.2 amperes and the solution
one hour more. If these directions are followed,

electrolyzed for

all of

the

cadmium
as

deposited
white metal.

(if not more than 0.5 gm. is present) will be
a firmly adhering dull deposit of almost silverThe current is then stopped, the liquid is quickly

poured off and the deposited metal washed
then with alcohol and finally with ether;
weighed.

first
it

is

with water,
dried and

Experiments performed by von Girsewald gave

fault-

less results.

After the electrolysis

be tested for cadmium.

hydrogen sulphide.

is

finished, the solution should

For

much cadmium

If

is

always

saturated with
present, a yellow pre-

this purpose, it

is

cipitate
obtained, but if very little, a yellow coloration results.
The latter is due to the formation of colloidal cadmium sulphide,
and the color is so intense that R. Philip estimates the quantity
is

of cadimum not precipitated, by comparing the shade with that
produced in a solution containing a known quantity of cadmium
and the same amounts of potassium cyanide and caustic potash

as in the solution tested.
*

Berichte, 12, 446.

GRAVIMETRIC ANALYSIS.

190

Remark.

If for the electrolysis a current of 0.5

cadmium

not be

ampere were

deposited at the end of twelve
hours; if, however, the current is increased at the end, as above
stated, to 1 ampere, the electrolysis will be surely finished at six
used, the

will

all

To work with the stronger current from the
to seven hours.
beginning is not to be recommended unless a gauze cathode is
used, or one of the electrodes is rotated, for otherwise the metal
is

deposited in a spongy form and on washing some of

it is

likely

to be lost.

A solution containing 0.4568 gm. Cd., 3

gm. KCN,

1

gm.

NaOH,

and diluted to 125 c.c. with water, can be electrolyzed in fifteen
minutes with a current of 5 amperes and 5.5 volts if one of the
electrodes be rotated.*

From

deposited electrolytically,
2.

Next

cadmium can be
but not from strongly acid solutions.

neutral and weakly acid solutions,

Determination as

to the electrolytic

Cadmium

Sulphate,

CdS0 4

.

method, the determination of cadmium
If the cadmium is combined with a

as the sulphate is the best.
volatile acid, the compound

is treated in a weighed porcelain cruwith a slight excess of dilute sulphuric acid, the solution evaporated on the water-bath as far as possible, and finally the excess

cible

is removed by heating in an air-bath (the crucible
placed in a larger crucible that is provided with an asbestos ring).f
The heat is applied at first slowly, and the temperature is raised

of sulphuric acid

is

gradually until finally no more fumes of sulphuric acid are evolved.
The outer crucible can even be heated with the full flame of a Teclu

burner without running any risk of decomposing the cadmium sulAs soon
it is, however, not necessary to heat it so strongly.

phate

;

fumes of sulphuric acid cease to come off, the operation is
ended and the crucible and its contents are weighed after cooling
in a desiccator.
The cadmium sulphate should be pure white
and should dissolve in water to form an absolutely clear solution.
If the cadmium has been precipitated from a solution as the
as the

is placed in a large
with
a
porcelain crucible, covered
watch-glass, and treated with
After the precipitate
on
the
water-bath.
acid
(1:3)
hydrochloric

sulphide, the greater part of the precipitate

*

See Edgar F. Smith's Electro- Analysis,

t Cf. Fig. 11, p. 27.

THE PRECIPITATION OF CADMIUM AS SULPHIDE.

191

has dissolved and the evolution of hydrogen sulphide has ceased,
the lower side of the watch-glass is washed, the crucible is placed
under the funnel, and the precipitate which adhered to the filter-

paper

is

dissolved

by dropping hot hydrochloric

acid (1: 3)

upon

it,

with hot water, evaporating the solution
upon the water-bath, and proceeding as above described.
The results obtained by this method are excellent.

finally

washing the

filter

The Precipitation of Cadmium as Sulphide.
The frequently recommended determination of cadmium as the
sulphide must be rejected; it is useless. It is not possible to precipitate pure cadmium sulphide from acid solutions by means of hydrogen sulphide; the precipitate is always contaminated with a basic
(Cd 2 Cl 2 S-Cd 2 SO 4 S, etc.) whether the precipitation takes place
in cold or hot solutions, whether under atmospheric
pressure or
under increased pressure (in a pressure-flask), and in fact the amount
salt

of basic salt

formed increases with the amount of

Results are obtained as

much

free acid present.

as 5 per cent, too high.

Follenius *

attempted to make the method possible by igniting an aliquot part
of the dried and weighed precipitate in a stream of hydrogen sulIf the sulphide was contaminated with sulphate, he succeeded in changing it all to sulphide and obtained results that were
acceptable.
If, however, chloride was present, a considerable

phide.

part was lost by sublimation, so that the results obtained were too
low.
It is, furthermore, not possible to ignite the cadmium sulphide with sulphur in a current of hydrogen, as was described

under Zinc and Copper, for cadmium sulphide

some

of

it is

is

so volatile that

lost.

On the other

hand, the method of precipitating the cadmium as

sulphide from solutions containing 2-7 c.c. of concentrated sulphuric acid in 100 c.c. is to be recommended, for by this means a
precipitate is obtained which can be readily filtered and which by
solution in hot hydrochloric acid (1:1) and evaporation with sul-

phuric acid can be changed without loss to the sulphate and weighed
as such.
* Zeit.

f.

anal.

Chem., XIII, 422.

GRAVIMETRIC ANALYSIS.

192

3.

Cadmium

Determination as

Cadmium

cadmium

carbonate and

Oxide, CdO.

nitrate can be

changed to

the oxide

by strong ignition.
The cadmium is precipitated from

its

solutions at the boiling

temperature by the addition of a slight excess of potassium carbonate, and after standing for some time on the water-bath, and
when the precipitate has completely settled, it is filtered off, washed
with hot water, and dried. As much of the dried precipitate as
possible is transferred to a watch-glass and set aside for the time
The filter is washed with dilute nitric acid to dissolve
being.
the small amount of the precipitate which still adheres to it and
is received in a weighed porcelain crucible and evaporated to- dryness. The main portion of the precipitate is now
added, and the crucible is at first very gently heated by placing
the open crucible high above a small flame from a Teclu burner/

the solution

until the

whole mass has become a uniform brown throughout-

The temperature
the burner

is

now gradually raised

reached.

until finally the full heat of

important during this operation to
take care that the inner flame-mantle does not touch the crucible, for otherwise reducing gases may enter the crucible and reduce
a part of the oxide to metallic cadmium, which is volatile at this
temperature.* The cadmium oxide is obtained as a brown
powder which is infusible, insoluble in water, but readily soluble
is

in dilute acids, f
Remark. It

is

It

is

not advisable to precipitate the cadmium by

means of sodium carbonate solution, for
to wash the precipitate free from alkali.

in that case it

is difficult

SEPARATION OF THE SULPHO-BASES FROM THE METALS OF
THE PRECEDING GROUPS.
"

Hydrogen sulphide precipitates only the metals of the hydrogen sulphide group" from acid solutions. It is to be noted that
zinc precipitates with this group
* If the

cadmium carbonate

in

an

of

any volatilization.
f The oxide after

electric oven, the

is

if

the solution

filtered into

is

not acid enough;

a Munroe crucible, and ignited

transformation takes place readily without danger

ignition

is

a black, crystalline powder.

-

-

228. until the filtrate gives no precipitate on being sulphide is filtered off. are often is 5-7 c. They should be washed with . the solution is evaporated on the water-bath as far as possible. stirred well. EXAMPLE.c.c. p. p. while the solution if is 193 too acid lead and cadmium incompletely precipitated.c. A suitable concentration of concentrated hydrochloric acid to 100 c. of and any metastannic acid present is allowed to filtered off.c. 100 c. dried.c. of alcohol. 236. Analysis of Brass (Alloy of Copper and Zinc with Small Amounts About is of Lead.ANALYSIS OF BRASS. ether before weighing. of double-normal sulphuric acid and at the end with 5 per cent. from the copper sulphide is evaporated to a small remove completely the excess of hydrogen in order to The borings are usually somewhat greasy. ing to p. 1. 174. concentrated sulphuric acid are added.2. acetic acid. of water and 15 c. and hydrogen is conducted into it until it becomes cold.c. when the copper sulphide w ashed r first with hydrogen sulphide water containing in every 100 c. dissolved in about 50 c. 20 c.c.5 gm. and the lead sulphate determined according to p. The solution is then evaporated to complete dryness. the solution is heated to boiling.c. alloy. treated with barium chloride. as The volume * filtrate The copper is determined. 0. cf water are added. of dissolved in about 20 and Nickel). is To the cold filtrate 3 c. in a 200-c. casserole moistened with a little nitric acid. The filtrate is evaporated until the alcohol is completely removed. After the reaction to begins slacken. Iron. sp.c. the c. washed with hot water. of pure. complete solution is effected by warming on the water-bath. After cooling the residue is treated with 50 c. which is covered with a watch-^lass. accord- Cu 2 S. gr.4-0. in the form of borings. which is saturated with hydrogen sulphide. settle. and then heated tin determined according to r cautiously over a free flame until dense w hite fumes of sulphuric acid are evolved. Cf. of liquid. 183.c. foot-note.* of nitric acid. and the hot water. washed. filtered.c.

it is dissolved in a ammonia is little hydrochloric acid and the precipitation with repeated. p. and filtered. For the determination of nickel. 160. the precipitate filtered off. sure that the precipitate of ferric hydroxide contains no zinc. Rath. This separation is based upon the insolubility of Principle. mercuric sulphide in boiling. Method of Gerhard v. transferred to a porcelain dish and boiled for a considerable length above concentration. The combined with a little filtrates from the ferric hydroxide are acidified C. The solution (containing the mercury entirely in the mercuric form) is precipitated by means of hydrogen sulphide. and the zinc sulphuric acid. and Cadmium. 169). dilute nitric acid (sp. dissolved in a little aqua with water. precipitated by ammonia. filtered from the separated sulphur and lead sulphate and the mercury precipitated according to the method of Volhard. It is.3) and the solubility of the remaining sulphides. I. with ammonium sulphide (cf. 129. Bismuth. filtered ignited in a porcelain crucible p. The residue of mercuric sulphide thus obtained always contains of time with nitric acid of the with a little sulphur. The and washed precipitate is and weighed as ferric oxide (cf. gr. 194 sulphide. the filtrate from the zinc sulphide precipitation is boiled to expel the hydrogen sulphide and the nickel determined as the salt of dimethyl glyoxime according to p. therefore.. washed with hydrogen sulphide water. Copper.GRAVIMETRIC ANALYSIS. then diluted water and washed with water containing nitric acid. heated to about 50 determined as zinc sulphide according to the " salting-out " method described on p. 87). diluted lead sulphate should go into solution with the mercury on treating . Separation of Mercury from Lead. Procedure.2-1. the iron is then oxidized by the addition of bromine In order to make water. 1. and in case considerable lead were present it will also contain lead sulphate. SEPARATION OF THE SULPHO-BASES FROM ONE ANOTHER. If some of the regia.

Principle. (a) Method of Lowe. the filtrate the lead is precipitated according to p. In this is filtered off. it will be converted by the ammonium sulphide and potassium hydroxide into insoluble lead sulphide.^ The separation depends upon the different volatwo bromides. cadmium oxide. and finally with the full flame of a Bunsen burner. in order to make sure that the lead The nitrate is completely dissolved. the solution is filtered. * It is still better to proceed as in the determination of t Praktischer Leitfaden der Gewichtsanalyse. 169. and after standing some time. stirring with a glass rod the evaporation is repeated and the process continued until the addition of the water fails to produce any further turbidity.* at first gently. washed with dilute potassium and the mercury then precipitated as sulphide. case the lead sulphide hydroxide solution. A 3 H O) cold solution of ammonium nitrate now added. as sulphate. Bismuth bromide is fairly readily lead bromide is only difficultly so. of the tility volatile.SEPARATION OF BISMUTH FROM LEAD. p. and after thorough water ency. (1 3 :500 is washed with the dilute ammonium nitrate solution As much of it as possible is transferred to a weighed porcelain crucible and together with the ash of the filter is ignited. while lead nitrate undergoes no such transformation. while the mercury will be in the form of its soluble sulpho-salt. 195 with aqua regia. cipitate the (b) Method of Jannasch. basic salt Bi 2 O 2 NH NO NO OH. precipitate dried. Separation of Bismuth from Lead. as described on p. . 192. is and It is weighed as Bi2 From 3 . It is less satisfactory to prelead as sulphide and weigh it in this form after gentle heating with sulphur in a Rose crucible. 2. 4 2 with frequent stirring. 174. Bismuth nitrate is changed by the action of water Principle. The solution of the two metals in nitric acid is on the water-bath until it reaches a syrupy consistevaporated is added. into an insoluble basic salt. and weighed as such. a sign that the bismuth has been completely converted into the Procedure.

sufficient sulphides are immediately filtered.* after which hydrogen sulphide is introduced. the bulb of the tube is unnecessary .GRAVIMETRIC ANALYSIS. * By the addition of the fuming nitric acid the precipitated sulphide is contaminated with considerable sulphur. made of difficultly-fusible glass. carrying bromine vapors with it. 38. 100 c. and a few drops of fuming nitric acid are added. J For this experiment the bromine used must be absolutely free from chlorine and is prepared as follows: 50-60 c. such a precipitate is more readily decomposed by the action of bromine.c. is passed through the vertical calcium chloride tube filled with pieces of calcite. For other analyses it is better to have the bulb. in order to completely dry it. . The funnel is shaken vigorously. the precipitate is dried at 100 C. in a tightly stoppered separatory funnel. At first a stream of dry carbon dioxide is passed through the is gently heated by means of a small apparatus and the substance The water condensing in the flame. front part of the tube is driven over into by careful heating. in a stream of carbon dioxide. The precipitated ness. 38). 196 Procedure. with a 10 percent. of commercial bromine are treated. The whole of the precipitate is ground fine and transferred without loss to a weighed porcelain boat. it should be replaced by one such as is shown in Fig. after which as much of the precipitate FIG. 38. and the bromine separated from the aqueous alkali solution. potassium bromide solution. is now bromine connected with the The bottle J containing E A apparatus and the stream of carbon dioxide is passed through it.c. the gas. which is then introduced into the decomposition tube R^ (Fig. t In this determination. The solution of the nitrates is evaporated to dryhydrochloric acid to afford a clear solution. as possible is placed in an agate mortar and the ash of the filter added to it. of water. //. After washing two or three times with water it is ready for use.

. whereby more bismuth bromide this is again distilled as is vola- completely as possible into the heated more strongly still. Z. O. 1895. the bromine bottle is removed. the chlorine water. so that they will not be discussed check this. and the bismuth precipitated by the addition of ammonium carbonate and determined as metal as described on p.SEPARATION OF BISMUTH FROM LEAD. until FinaJly the substance is the lead bromide begins to melt. Steen. and the solution is evaporated to remove the hydrochloric acid. water and alcohol are added. latter stant motion) and substance tilized. When no more of the yellow sublimate is formed. which contains dilute nitric acid (1 HN(>3:2 H^O).* all of which are less satisfactory than the two methods just described. To lead bromide is dissolved in freshly-prepared an excess of dilute sulphuric acid is added. 197 then through the concentrated sulphuric acid contained in B. After cooling. K in this book. * Cf. at first on the water-bath and finally over a free flame until dense fumes of sulphuric acid are evolved. is and heated hotter. The stance. evaporated to a small volume. 174. The bromine that escapes from the tube K is passed into alcohol contained in the beaker F. after this through the tube C containing glass beads moistened with D filled with glass sulphuric acid. For the bismuth determination. p. The boat filled with lead bromide is then weighed. the decomposition is shown to be complete receiver. and finally through the tube from this the and bromine wool. 530. the precipitate filtered off and the weight of the lead sulphate determined as described on p. and from the weight of the PbBr2 that of the lead is computed. filtered acid solution contained in E and if necessary from any sulphur. There have been many other methods proposed for the separation of lead and bismuth. and the bromine is removed from the apparatus by passing carbon dioxide through it for some time. Chem. When the apparatus has become cold. angew. 181. dry vapors reach the sub- The is heated over a small flame (kept in conthe yellow bismuth bromide distils off and condenses partly in the narrow part of the tube and partly in the /eceiver E. and the substance is allowed to cool in a stream of carbon dioxide. . the nitric is poured into a beaker.

so it is dissolved in nitric acid and the separation by means of that ammonium carbonate is repeated. and the solution warmed and filtered. 4. completely deposited. For this purpose the acid solution is precipitated by the addition of a slight excess of sodium carbonate. The filtrate containing the copper is evaporated with nitric acid. in order to destroy the cyanide. The residue is. or the sulphuric acid solution trolysis as described on is subjected to elec- p. while the copper is either not deposited at all under these conditions After the lead is is found upon the cathode to some extent. For the copper determination. bismuth can be separated from copper very nicely by means of potassium cyanide. potassium cyanide is added. evaporated to remove the excess of ammonium carbonate. the excess of the acid is neutralized with or . acidified with sulphuric acid. According to Fresenius and Haidlin. according to p. All of the copper is found in the filtrate. being determined as cuprous sulphide according to p. 181. and the copper precipitated by means of hydrogen sulphide. warmed gently. The basic bismuth salt is fused with potassium cyanide and weighed as metal. and filtered. The precipitate of basic bismuth carbonate almost always contains small quantities of copper. 187. therefore. and the copper determined electrolytically according to p. 198 3. The solution is treated with an excess of ammonium carbonate. the bismuth precipitated by means of ammonium carbonate and determined as metal according to p. the two nitrates are combined. dissolved in nitric acid. 187. the copper solution is poured into a second weighed platinum dish. 181. while the precipitate contains bismuth oxide contaminated with alkali. This separation depends upon the fact that the electric current deposits lead quantitatively as Pb(>2 upon the anode from solutions containing a definite amount of nitric acid. 183. Separation of Bismuth from Copper.GRAVIMETRIC ANALYSIS. Separation of Lead from Copper by Means of Electrolysis.

gr. platinum dish (of the form recommended by Classen with the inner surface unpolished) and 15 c. brown coating of lead peroxide. after which the solution is diluted to 150 c. but the remainder will still be in solution. with a current of 1-1. and the washings added After washing the electrodes with water. in case traces of lead remain in solution after the first electrolysis. After 1-1. circuit PbO2 deposit is dried at 180 and weighed. and the solution electrolyzed at 60. while the plate electrode * serves as the anode. it will now be After an hour or two deposited. of concentrated nitric acid are added. 187. trodes are washed without breaking the circuit and the weight of the copper and PbO 2 is determined. 4 c. only small amounts of lead and copper are present. while the copper will separate out upon the dish. The platinum dish now serves as the cathode. The solution in the second dish contains a little lead and some copper. The solution of the two nitrates is placed in a Procedure.5 hours practically all the lead will be deposited upon the anode (dish) in the form of At a firmly adhering. 199 ammonia. and electrolyzed at 50-60 C.5 amperes and an electrode potential of 1. with a current of one ampere all the remaining copper and lead When the electrolysis is complete the elecwill be deposited. the first to this dish.4 volts. and . The is broken and the solution poured as quickly as possible into a second weighed platinum dish. weighed plate electrode should be these conditions the lead will be Under deposited as the peroxide upon the anode. upon it was weighed. the cathode (a plate electrode) a considerable part of the copper will be deposited.c. the electrolysis should take place under the conditions described on If p.c. The copper will now deposit quantitatively upon the cathode. dish with the It is made slightly ammoniacal. cleaned. *The plate electrode with copper then weighed again.351. and the solution again electrolyzed. except in this case a employed as the anode. PbO2 . of nitric acid (sp.38) are added.SEPARATION OF LEAD FROM COPPER.c. 1.

200 5. The copper sulphide is. Experiments performed in the author's laboratory showed that in the form proposed by Hofmann this method cannot be used for the quantitative separation of the two metals on the other hand. d. The copper sulphide thus obtained is easy to filter and wash. and the lead determined as sulphate as described on p. 174. after which the solution is boiled for fifteen The solution is filtered while hot through a with carbon dioxide and the precipitate is washed with boiled. if it is carried out according to the following modifications. but neverthemethod is given in all early text-books without submitting less this any analyses to prove its accuracy. Method of A. . excellent results are obtained.. hot water to the disappearance of the acid reaction. W.) The solution of the nitrates or chlorides is treated with an excess evaporated to remove the nitric or hydrochloric of sulphuric acid. 286. Sufficient sulphuric acid is added to the solution one part of the acid is contained in four The latter is now heated to boiling. W. during the boiling hydrogen sulphide is passed through it for twenty minutes. Hofmann Cadmium. Hofmann* states that copper and cadmium can be sepaby boiling their sulphides with sulphuric rated from one another cadmium sulphide is dissolved while copper Hofmann seems to have tested this acid (1:5) whereby sulphide is unacted upon.GRAVIMETRIC ANALYSIS. Chem. so that the separation must be repeated. acid. Separation of Lead from Copper and (From Bismuth Cadmium. (a) A. always contains small amounts of cadmium. transferred to a porcelain dish by means of a stream of water from * Ann. 115. Separation of Copper from 6. less satisfactorily. und Pharm. it minutes longer. and of the sulphates so that parts of the solution. funnel kept filled however. Procedure. therefore. . separation only qualitatively and not quantitatively.

SEPARATION OF COPPER FROM CADMIUM. 183.5 gm. the dish covered : with a watch-glass and heated on the water-bath until the precipitate is dissolved and until the hydrogen sulphide is all expelled. the precipitated cadmium sulphide after being washed is transferred by means of a spatula to a porcelain dish. the wash-bottle. and the cadmium determined as sulphate according to p. or it is dissolved in nitric acid and the solution electrolyzed as described on p. the dry mass dissolved in a little sulphuric acid. regard to the separated sulphur. finally washing the filter with water. of and the separation by means of hydrogen sulphide is repeated exactly as above described. the mass is washed with as little water as possible into an Erlenmeyer flask. the dry mass treated with sulphuric acid (1:4) and again evaporated on the water-bath as far as possible After this. The pure copper sulphide that is finally obtained is dried and the copper determined as cuprous sulphide as described on p. washed into a weighed porcelain crucible. the excess of sulphuric acid removed by heating in an air-bath. 187. are evaporated as far as possible upon the water-bath. For the cadmium determination. are not destroyed they will cause a partial reduction of the phate. where is it 201 dissolved in nitric acid. of concentrated nitric acid* and The dish After this the contents of the crucible a little more sulphuric acid. without to remove the greater part of the nitric acid. is now placed under the funnel and the cadmium sulphide which remained upon the filter is dissolved by dropping hot hydrochloric acid (1:3) upon it.c. The contents of the dish are evaporated to dryness. of sulphuric acid (1:4) are added.30.c. for every 0. 190. hydrogen sulphide is passed into the cold filtrate. the solution evaporated to dryness. and treated with 1 c. The above method was tested by Oberer in the author's laboratory and the following results obtained: * The nitric acid is added to oxidize the fibres of filter-paper. if these cadmium sul- . hydrochloric acid (1 3) is poured over it. copper about 150-200 c.

202 Amount Taken.GRAVIMETRIC ANALYSIS. .

and it is not advisable to wash the salt out with water. within 12 or 14 hours . The experiments of R. filtered if necessary from separated sulphur. copper is deposited perfectly free from cadmium. a disk electrode. is c. to p.c. as recommended by Neumann.c. it Schull "hardened filter.c. The solution. 203 The cadmium sulphide thus precipitated shows a great tendency of passing through the filter-paper even when a "hardened" filter is used. containing not more than 0. Philipp in the author's laboratory show that a very accurate separation can be made. the residue dissolved in water. It is.SEPARATION OF COPPER PROM CADMIUM. so that it is "salted out. 0. in a platinum dish. of the solution 5-7 c. This time the cadmium easily filtered. of concentrated nitric acid or 10 c.2 gm.2 gm.c.2. and in the morning it is filtered solid is & through a Schleicher tate is washed first chloride solution. nitric treated with 4-5 acid sp. and for every 100 c. The anode. cadmium.gr. according sulphide The is filtrate is The cadmium evaporated with is determined as sulphate nitric acid until the odor of hydrocyanic acid can no longer be detected. is placed so that it only dips into the Under these conditions. and the copper is most conveniently determined according to p. the solution is evaporated to dryness. (d) By Electrolysis. dissolved in hot hydrochloric acid (1:3) from a washbottle. 1. and the cadmium is precipitated by passing hydrogen sulphide into the cold solution. the precipitate allowed to stand overnight. 190. Remark. of liquid a short way. 183 as cuprous sulphide." considerable amount of pure. The results obtained by this method are good. for in this case a turbid filtrate will be obtained. A potassium chloride is stirred into the solution. of concentrated sulphuric acid are added.c. For the cadmium determination this precipitate cannot be used on account of the potassium chloride which adheres to it. and diluted to 150 c. therefore." The precipi- by decantation with concentrated potassium is then transferred to the filter and washed with the same solution. by electrolyzing the nitric acid solution. but considerable time and patience are required.

dried and weighed with the deposited copper. less during the washing. with a current of solution is siphoned off. and the cadmium electrolyzed from on p. there is danger of small amounts of nitric acid.3 volts. and a stronger current.5 amperes and 2.5-2. In analyzing a solution containing a large amount of cadmium and small amount of copper. The separation requires but a few minutes with a rotating anode or cathode.GRAVIMETRIC ANALYSIS. it is best to wash at first with 2 per cent. The solution is treated with sufficient sulphuric acid. 204 by a current of 0. especially when the anode extends well into the This is because the concentration of the acid becomes solution.2 gm.6 volts electrode the cadmium is deposited in about five hours. nitric acid rather than with distilled water.c. Remark. evaporated to expel the . diluted cyanide solution as described cadmium separating out upon the copper during the washing of the deposit.3 ampere and a voltage of 1. If considerably more than 0.9-2. while pure water is poured into the dish without breaking the current the dish is finally rinsed with alcohol. therefore. 1 to 1. . cooled. of the solution. 189. The potential.2-0. Cd is present in 150 c.

anal.) ARSENIC. SELENIUM. 682. Ann. Tin. ETC. 32. 45.. Chem. according to Bunsen.* Modified by Fr. keep the solution cooled by surrounding the flask with ice) until the solution contains at least two parts of concentrated hydrois A chloric acid for each part of water. Chem. which must contain all of the arsenic as arsenic treated with hydrochloric acid little by little (it is best to acid. 265. Thiele.. Monatshefte. d. B.96.DETERMINATION OF ARSENIC AS TR1SULPHIDE. und Pharm. Chem. TUNGSTEN. 74. i. dried at 105 C. very rapid stream of hydrointo this solution is conducted (contained in a large gen sulphide Erlenmeyer flask) until it is saturated with the gas. anal. At.. been previously dried at 105 C. The solution is made strongly acid with hydrochloric acid and the arsenic precipitated in the cold with hydrogen sulphide. d. . 607. 2. PLATINUM. Antimony. Determination as Arsenic Pentasulphide.. The excess of the latter is removed by passing a stream of carbon dioxide through the solution. after which * Ann.. 65. it must be present as arsenious acid or as arsenite. and J. The washed with hot w ater. The solution. VANADIUM. u. I. which is then filtered through a Gooch weight. As. McCay. Chem. Wt.e. of arsenic in this form. TELLURIUM. 192. For the determination in its trivalent state. to constant crucible that has precipitate r is and weighed as As 2 S 3 . A^Sg. t Z. GOLD. 205 THE SULPHO-ACIDS. Pharm. 305. 8. Forms: Determination as Arsenic Trisulphide. MOLYBDENUM. Z. DIVISION OF Arsenic. see also Brunner and Tomicek. 27.

and the precipitate is washed completely the flask is pentasulphide with water.1 gm. on the other hand. 3. per 0. is upon The it * Prepared by dissolving 55 gms. If the method this gives faultless results. The arsenic is then filtered through a Gooch crucible which has been dried at 105 C. and have a volume of not over 100 c. sp. crucible by ammonia filtered some of the original solution from precipitate is then washed with 2. ammonium chloride in 650 c. there is added 7-10 c. ftow. If. ammonia is added to make onethird the volume of the neutralized solution. 0.1 gm. then with hot alcohol (to hasten the subsequent dryAfter drying at 105 C. with 5 c. with constant stirring. The solution.GRAVIMETRIC ANALYSIS. 206 stoppered and allowed to stand two hours. of * and a arsenic. so that on passing hydrogen sulphide into the solution a mixture trisulphide and arsenic pentasulphide will be obtained. It is not necessary to wash it with carbon bisulphide.c. is treated drop by drop. above directions are conscientiously followed. If the solution is not kept cool and the hydro- will chloric acid is added too rapidly.. which must contain all of the arsenic as arsenate.c.c.96. and then enough more of the 10 per cent. of concentrated hydrochloric acid and then. It is drained as squirting a small wash bottle. of arsenic Determination of Arsenic as Magnesium Pyroarsenate.gr. per cent. arsenic. After standing through a Gooch or Monroe The precipitate in the beaker is transferred to the twelve hours the liquid crucible. ammonia is added from a burette until the phenolphthalein imparts a permanent red color to the solution.c. according to Levol. water and diluting this to a volume of one liter with ammonia. under constant stirring. the heat of the reaction suffices to change a part of the arsenic chloride (this compound probably exists in solution) to arsenious chloride and chlorine. the precipitate is weighed as As 2 S4 ing). for each 0.5 until free from chloride. the directions are deviated from in the slightest respect. . the precipitate is likely to contain some arsenic trisulphide. of magnesia mixture drop of phenolphthalein solution. 10 per cent. Remark. whereby low results be obtained. crystallized magnesium chloride and 70 gms. .

however. precipitate nitrate is powder * is added to the which precipitate. after which the precipitate is allowed to cool in a desiccator and The results obtained are excellent. it has. 27). so that the procedure is not to be recommended. Then the temperature is raised to 800 to 900 and kept there for about The 10 minutes. until there is no more ammonia evolved. 11. The precipitate produced by the magnesia mixture has the formula MgNH 4 AsO 4 + 6H 2 O and loses 5J molecules of water at 102 C. at first gently. 2 as follows: [MgNH AsO4 + iH2O] As = p : 4 : x. the from water and at a salt is obtained almost slightly higher temperature The only form in which the magnesium pyroarsenate. It is. gradually increasing the temperature until a light-red glow on the outer crucible is obtained. 207 completely as possible by suction. is then heated. the crucible perforated cover and heated in a current of oxygen.. may it precipitate be provided with .O 7 Remark. should be weighed is as * Instead of using a 105-110 C. A thin layer of ammonium of the bottom of the outer crucible. dried at 100 and heated in an electric oven quite gradually to a temperature of about 400 to 500. weighed as Mg As. been proposed to dry the precipitate at this temperature and to compute the amount of arsenic present is . therefore. Fig. p.DETERMINATION OF ARSENIC AS MAGNESIUM PYROARSENATE. If the precipitate is dried at entirely free begins to decompose. having the bottom of the Gooch crucible [come within about 2-3 mm. ammonium nitrate. the precipitate crucible is then cooled in a desiccator and weighed with the precipitate in the form of M&PAIf an oven electric is not available the crucible with the placed in an air-bath (cf. impossible to obtain a constant weight at this temperature.

Lockemann. 1907. 8. J. Acad. such as are present in wall papers. Dissert. 13. all the organic matter is destroyed by heatthe ing sample in a tube with fuming sulphuric and nitric acids The (see Vol. 44. Chem. 600 parts of water dissolve 1 part of the salt. f to use the much simpler apparatus used for the Gutzeit test. 504 (1905). No. Amer. In 1\ per cent. Arts and Sciences. Z. Chem. Colorimetric Determination of Arsenic. In the resulting liquid is evaporated with sulphurous acid on the waterbath in order to reduce the arsenic acid to arsenious acid and when all the excess of S0 2 has been expelled. 431 (1891). 38. F. I). Proc. (a) Method of Hefti. both of which must be free from arsenic. Zurich. 1 1 mercuric chloride paper.* 1 part of anhydrous magnesium ammonium arsenate dissolves in 24. flask K * Z. and 377. J This method was given in the former editions of this book. 429 and 491.. 137 J . Sanger and O. and much more convenient and that of C.. as it does not keep very Almost equally accurate. may be estimated very accurately by means of the Marsh apparatus. G.208 GRAVIMETRIC ANALYSIS. Sanger. anal.. must be produced freshly with each analysis. angew. 1907. Hefti Black in which the arseniuretted hydrogen is allowed to act upon well. Virgili. comparing the mirror with a series of standards formed with known It is just as accurate. R. Chem. unfortunately. first place.558 parts of ammonia water. Small quantities of arsenic. the solution is poured into the graduated tube T of the apparatus shown in are placed 6-8 gm.fC. F. R. According to J.. quantities of arsenic. II Inaug. Z. is the method of F. ammonia it is almost entirely insoluble. anal. of OT^Tn ~the 100-150 c.c.. according to Levol. 1905. Treadwell and Comment % allow the arseniuretted hydrogen to react with disks containing silver nitrate and compare the Suiting color with a standard which. . Am. Solubility of Magnesium Ammonium Arsenate. Chem. however.

water). and tube is under 0. all or a apparatus. At the end of twenty minutes the experiment is finished. granulated zinc coated with copper* and about 20 c.c.* The for larger quantities ground perfectly flat. t tube I. For quantities D should be 8 upper edge of the of arsenic mm.COLOR/METRIC DETERMINATION OF ARSENIC. At the end of ten minutes all the air should be expelled from the The outlet Z)f is now covered with a piece of mercuric chloride paper and kept in place by a small piece of ground glass.02 mg. By com- paring the color of the spot produced on the mercuric chloride * Cf. FIG. Vol. the upper diameter of the it should be 16 mm. 209 of sul- phuric acid free from arsenic (1 vol. part of the solution in T is allowed to flow into the flask K. 39. According to whether little or much arsenic is present.. acid + 7 vols. . cone.

The disks of mercuric chloride paper are prepared by dipping pure filter paper into a saturated solution of mercuric pieces of and drying them in an oven at a temperature of 60-70. t 0. of C. R. the exact amount of arsenic can be determined. An older standard is not reliable.GRA^ METRIC 210 ANALYSIS.05 cm. paper. Three grams 30 c. = 0. The enlargement of the horizontal tube contains a wad of cotton and at the outer end is a piece of thick filter-paper which has been dipped into mercuric chloride solution and dried. Sanger. quantity of the arsenic solution to be tested is added to the flask. of arsenic-free. 40) which is fitted with a stopper holding a thistle tube and a gas delivery tube. which is then nearly filled with water. pure zinc is placed in the evolution flask (Fig. The spots thus obtained soon lose their color when exposed to moist air. but can be used to estimate the approximate quantity of arsenic and then. At the end is of this time.002 etc.001 mg. with the standard spots. Through the thistle tube poured 15 c. The standard solution of arsenious acid used in preparing the scale should contain 20 mg. The standards are prepared by carrying out a series of experiments with known quantities of arsenic. dilute hydrochloric acid* (1:6) and the hydrogen evolution is allowed to proceed for at least ten minutes to drive out the air from the apparatus. of uniformly granulated. but when dry chloride can be kept in the dark for several days. After a few minutes. of As 2 O 3 in a Then liter. hydrochloric acid is used it is unnecessary to plate the zinc with . As 0. a measured.c. or weighed. the mercuric chloride and at the end of thirty minutes will attain paper begins to color * When copper. =0.c.c. by making two or three standards with known quantities.1 c. the quantity of arsenic present is determined. For smaller amounts nine times' as of arsenic the much water and (6) Method 2 O 3> above solution thus made is diluted with one-tenth as strong.

Some 6N-HC1 is placed in a small test tube. middle drying. . at least to remain there row. followed by a little cotton.COLOR/METRIC DETERMINATION OF 4RSENIC. heated to color holds a little better 60. The upper end of the paper is moistened with a Canada balsam. washed thoroughly in running water. the maximum coloration. The if the strips of paper. 40. See the colored chart at the end of the book. then the strip of paper is shoved in with the colored part at oxide and is 211 is FIG. after being are with moistened strong hydrochloric acid and then colored. the strips of paper dipped in the acid and allowed two minutes. upper row. the strongly influenced strips in a per- recommends preserving the For this purpose a little phosphorus pent- placed in a small test-tube. dried. the color is a little duller. After the See the colored chart. By comparison with quantity of arsenic present is estimated. dried and sealed in tubes as described above. standards. although the freshness disappears after a few weeks. Sanger fectly dry condition. of drop In this way the color can be preserved for several months. after which the tube is closed and sealed. Inasmuch as the color of the standards by moisture. the bottom.

Zentr.GRAVIMETRIC ANALYSIS. 1907. W. 4. Thomson. 19. J. 1295. 183 (1903). T. ammonja solution. 3. Zentr. the strips of colored paper are treated with normal If. Hackford. Memoirs. HgCl 2 paper. Chem. the spot which was originally red turns black. 212 however. Sand and E. Bloxam. is used and is shown in Fig.. 259. Remark. Dissert. 1904. After drying. Thorpe. The wad 12 experiments 5. 1904. S. which is wrapped around the porous cell. zinc Thorpe passes the arsine through a heated tube and produces an arsenic mirror. the following conditions must be prepared as above. Chem. This suspended from the platinum wire that has been fused into the ground-glass stopper of the cathode compartment. As cathode a perforated cone of thin lead foil is used.. 483 (1862). strips uniform as regards the length and the color. it may be formed with the aid of cathodic hydrogen.. Chem. 17 (1904). 3 as they give a * Electrolytic Determination of Arsenic. and colored spot with the (c) PH must not be present. 48. of the spot To make the fulfilled: The evolution flask must be kept the same size and the delivery tubing must be of uniform bore. 1. No. Zurich. The anode consists of platinum foil.. all the tests. t Inaug.. anal. Tootmann. The same quantity of zinc of the same size must be used in 1. Proc. Chem. R. Manch.. After 10 or the same. such strips are kept in small test-tubes over calcium These standards are much more permanent than when chloride. See the colored chart. SbH 2 3 should be renewed. two or three centimeters wide. 1. 41. E. but Hefti f allows the gas to react with mercuric In both cases the apparatus devised by Thorpe chloride paper. Instead of producing the arseniuretted hydrogen by means of and acid. S. Soc. of cotton it H S. . Z. H. bottom row. is * Cf. The volume and concentration of the acid must remain must not get too moist. II. 2.

and about 0. Pure. if this is not the case.) Sanger's method can be used. metric determination. Thorpe recommends bright platinum foil and Hefti uses lead. the arsenic solution is poured directly It must be present as arsenious into the acid of the inner cell. production of mirrors. (See Method 6. from the bottom in the For the coloriformer. Remark. dilute sulphuric acid (1:7) is poured into the earthenware cell and into the glass outer vessel. For the acid and the excess of the latter expelled FIG. higher in the latter. E. .) comparing the spot with a standard scale. As regards the influence of the cathode material. end of twenty minutes and the quantity of arsenic estimated by (See Method a. it must be reduced with sulphurous by heating. and. 213 Procedure. the air must all be expelled by hydrogen before the arsenic solution is added.ELECTROLYTIC DETERMINATION OF ARSENIC. disk of mercuric chloride paper (see Method a) and then the The potential should be about 7 volts and the current about 2 to 3 amperes. the level of the acid should be about 2 or 3 cm. If the apparatus is connected with a horizontal delivery tube.5 cm. acid. The tube C is filled with The outlet at D is covered with a crystallized calcium chloride. The analysis is finished at the circuit is closed. 41.

If arseniuretted passed through a solution of iodine in potassium immediately oxidized to arsenic acid in the cold. reduced with sulphurous acid. To determine arsenic in a mineral water. Determination of Larger Quantities of Arsenic as Arsine. Hefti. iments performed by Hefti in the author's laboratory showed that zinc alloyed with a trace of copper or platinum. Method of F. bright platinum foil and lead did not hold back arsenic when used as the cathode. and low concentration of the solution. In the electrolysis of larger quantities of arsenic it possible. and the concentration of the arsenic solution.c. is titrated with sodium thiosulphate Methods) it is possible to determine the quantity of iodine that has reacted with the arsine. zinc in the presence of chloroplatinic acid and platinum foil with spongy platinum held back a considerable quantity of arsenic. the quantity of arsenic deposited becomes zero and the yield of The estimation of arseniuretted hydrogen is then quantitative. The resulting solution is acidified with sulphuric acid. necessary. of 0. to recover all the arsenic in the was not form of arseniuretted hydrogen. AsH3 + 4H2 O + 4I2 = SHI + H AsO 4 3 . and the analysis continued by one of the above three methods.c. it is easily possible for low results to be obtained. 100 c. and since bright platinum becomes dull with Experuse. If T c.1N" thiosulphate If the excess of iodine (see lodimetric . the latter is hydrogen is it is iodide. The quantity of arsenic deposited as metal depends upon the potential of the electric current at the electrodes..GRAVIMETRIC ANALYSIS. the excess of the latter expelled. some arsenic was deposited upon the cathode in the form of the element arsenic and was not trans- formed into arsine by the further action of the electric current.. best accomplished iodimetrically. but platinum with a rough surface does.lN" iodine were used at the start. in the past. of O. At high potentials.the temperature. 214 Polished platinum does not hold arsenic'back.c. low temperature. or more if are evaporated to a small volume in a procelain dish. on the other hand. and t c.

then the quantity of arsenic or arsenic trioxide. 43 and consists of a wide U-tube capable of holding 120 c. is suspended a platinum plate electrode as anode. 42. The decomposition cell is also shown in Fig.000937 gm. In one arm of the tube (the anode compartment) which remains open during the whole experiment. (T -0X0. a piece of thin parchment paper. 42. made in two halves. taking care that the edges of the parchment paper are by the wire. and the other arm (the cathode compartment) is tightly stoppered with a three-holed rubber stopper. The tube is FIG. of solution.001237 gm. the edges of the bottom being ground so Between these edges is placed that they fit tightly together. tubing holds the two halves of the U-tube together and also the parchment paper in place.DETERMINATION OF ARSENIC AS ARSINE. at the bottom of this tube also covered . As 2 O 3 .c. Through one hole passes a glass tube containing mercury. the extending edges of which A piece of rubber are folded over one side of the tube. This tubing is wired tightly in place. present is (T -0X0. arsenic. The apparatus necessary is shown in Fig. 215 solution were used for the titration.

5 cm. If the pressure there exceeds pressure in the cathode space. The third hole in the stopper carries a tube that leads to the Erlenmeyer flask E which. 43. 2l6 is sealed in and from this a plate electrode of suspended to serve as cathode. of . then it is very easy to overcome the pressure in the absorption vessel without having diminished the pressure in the If ' cathode compartment enough to tear the parchment membrane. in turn. the arsenic solution is placed in the cathode compartment and this is filled to within 3. that of the anode space. the anode compartment is filled to within the top with 10 per cent. Through the second hole in the stopper is passed a gas delivery tube leading to the absorption vessel A. The arsenic solution to be tested must contain all the arsenic in the trivalent condition. 42. Procedure. is connected with the empty flask F. The wire from the negative pole of the battery dips into the mercury. of the top (in other words. a part of the arsenic solution will pass into the anode compartment and will be lost in the analysis. and the latter with the rubber tubing shown in Fig. sulphuric acid. Such an arrangement provides for the regulation of the a platinum wire lead foil is FIG. the level in the 3 cm. In the first place. suction is applied at the extreme end of the absorption apparatus. so that bubble after bubble of air passes through the Erlenmeyer. This tubing leads to the hood.GRAVIMETRIC ANALYSIS.

DETERMINATION OF ARSENIC AS ARSINE. . of a saturated solution of pure XaHCO 3 and the excess of iodine is titrated with O. absorption tube. When all the conditions are maintained satisfactorily. of which only one is shown in Into the first absorption tube is now placed an accurately measured volume of tenth-normal iodine solution. and about 40 c. The U-tube is dilution c.lX iodine. of sodium thiosulphate solution. the tit ration is finished with O. Moreover. . should not exof solution. and its temwater. While the apparatus absorption vessels are being filled. which is not shown in the drawing.lX sodium thiosulphate solution using starch solution as indicator. of As 2 O 3 are present. of the drawing. the electric circuit is closed* and the suction is regulated so that bubble after bubble of air slowly streams through the pressure regulator and into the cathode compartment throughout the whole duration of the electrolysis. after mgm. As2 O 3 this in 50 with acid.c. care is taken that enough ice remains in the cooling bath. the contents of the two absorption tubes (first the iodine and then the thiosulphate solution) are poured into a beaker containing 5 c. something has gone wrong and it is In a normal experiment. If on mixing the contents of the two absorption bulbs the solution is decolorized. 10 c. catch when the analysis is ready to perature should be about Gentle suction is started at the end of the second begin. the arsenic solution should be in the ice-water. 217 about 0. useless to continue the experiment. which eventually If a black turbidity is formed that settles to the disappears. the liquid in the cell should remain perfectly clear. and into the second tube. The purpose of the sodium thiosulphate solution is to any iodine that may escape from the first absorption tube. is finished of the arsine in an hour. when not the evolution more than 50 mgm.5 cm. or at the worst be colored only by a slight brownish turbidity. The current is then stopped. * A current of 2 to 3 amperes and 7 volts is used. lower than on the other cathode compartment is side of the U-tube) the concentration of the arsenic solution in the ceed 80 U-tube. placed in ice-water and the gas delivery tube is connected with two ten-bulb absorption tubes. bottom of the U-tube.c.c.c.

Instead of extracting the melt with water. same result as when the Hefti found 42. arsenic. H 12 per cent. Henz. the solution is slowly heated to * F. Wt. Determination as Trisulphide. 120. solution. ANTIMONY. i. so that it is suitable for a rapid determination of the arsenic present in iron minerals. and Sb. This method can be carried out very easily and gives accurate results in the presence of iron. Forms: Sb 2 S 3 Sb 2 . 37. Z. of and the arsenic is then determined as 2 S0 4 outlined above.2. Chem. with dilute sulphuric acid. whereby all the iron goes into solution. At. of potas- crucible with 6 sium nitrate.. . of sodium carbonate and 1 gm. . without stopping the current of hydrogen sulphide.73 per cent. by the latter. 4. Henz. it may be treated . After this solution has been reduced with sulphurous acid.72 per cent. The mineral analyzed was supposed to contain 42. in the author's opinion. using one-tenth of the solution.67 per cent. * for the determination of antimony is. Sb 2 S 3 Method The best method of F. the analysis of an aliquot part gives the first procedure is followed. anorg.c. the solution is boiled to expel the excess of SO 2 allowed to cool. the following: Hydrogen sulphide is passed for twenty minutes into the cold solution of an antimonite or antimonate. Determination of Arsenic in Mispickel. As by the former process and 42. Sb.2i8 GRAVIMETRIC ANALYSIS. To the filtered solution 200 c. The resulting melt is extracted with hot water and the residue (Fe 2 O 3 NiO) washed with hot sodium carbonate .c. of water saturated S0 2 are added to reduce the arsenic. then. 18 (1903). with sulphuric acid so that the entire solution contains 10 to with . diluted to 500 c. One gram of the finely powdered mineral is fused in a nickel gm.

of hot. until it begins to run out through the By this means all the air has been expelled stop-cock. through the siphon while hydrochloric acid (1:4) is poured in at the top As soon as carbon dioxide begins to be evolved. 386) see Fig. but after all the mineral acid has been removed. The tube R is then closed with a rubber stopper that holds a glass delivery tube. and water is poured through the upper compartment. and R is pushed is placed in the end of the stopper is reached. At first the filtrate runs through perfectly clear. This differs from the ordinary form of the Kipp apparatus only as regards the siphon tube a. but herein lies a distinct advantage. 219 and the gas passed through it for fifteen minutes more. long and 10 cm. and washed on the filter with the same wash liquid until all chloride is removed. the stop-cock is opened. The precipitate is washed four or five times by decantation with 5075 c. The apparatus is charged as follows: First of all. very dilute acetic acid into which hydrogen sulphide has been passed. which is then closed. Henz then proceeds The crucible. To rubber the stopper during the subsequent heating. 45..DETERMINATION OF ANTIMONY AS TRISULPH1DE. the filtrate shows a slightly orange tint. fitted to a drying oven (about 18 cm. pieces of pure marble are placed in the middle compartment. carbon dioxide* and heated for two hours at 100-130. This may be prepared by the use of the Kipp generator as modified by Henz (Chem. covered with asbestos paper). The air-free air is now expelled from the tube by a stream of dry. owing to an unweighable amount of the antimony sulphide passing As soon as this point is reached through in colloidal solution. the tube a of the generator. Ztg. 1902. Fig. as follows: precipitate has been dried as much as tube R. 44. after the F. When the acid has become is closed and the apparatus is ready for use. high. the washing is stopped. after which the now dense precipitate is allowed to settle and filtered through a Gooch crucible which has been heated at 280-300 and boiling weighed. which is held in place by wrapping the tube a with a strip of asbestos into the drying closet until the paper. t In order to obtain accurate results it is neceesary to have the carbon dioxide perfectly free from air. the water is allowed to run out hydrochloric acid. its protect inner surface is provided with a Rose crucible cover. . from the lower parts of the apparatus and it only remains to introduce the To accomplish this.c. which is possible by suction.

and the temperature is raised to 280-300 and kept there for two hours. the transformation of antimony pentasulphide can be accomplished in his drying oven (shown . it is in at the top. as shown in the drawing. 44. * According to Paul (Z. anal. Hereby some sulphur is volatilized and collects in the tube R outside the oven. 540 (1892)). a air little completely expelled from the oven. 31. 45.* The crucible is allowed to cool in the stream of too weak. there no danger of water condensing in the tube. Inasmuch as the tube R extends so far into the drying oven. It removed through the siphon while a fresh supply is poured is no need of taking the apparatus apart during this is obvious that the same apparatus can be employed to there advantage for generating hydrogen or hydrogen sulphide. Chem.. 5 cm. but it is all is expelled as vapor at b. The tube R is now withdrawn FIG. The antimony pentasulphide is also cominto the black modification of the trisulphide by pletely changed this heating. The precipitate is now dry and the from the heating tube. about FIG..220 GRAVIMETRIC A'N'A LYSIS. operation.

c. is treated with concentrated hydrochloric acid. precipitated by hydrogen sulphide from a strongly acid with hydrochloric acid. anal. however. and the hot solution subjected to the action of hydrogen sulphide gas. gradually it becomes heavier and denser. . slightest The The Erlenmeyer flask containing the solution is placed in a dish of boiling water and the water in the latter is kept boiling during the precipitation. fectly true.c. (6) Method When antimony hot solution which is is of Vortmann and Metzel. so that the crucible does not come in contact with any of the sulphur sub- The crucible limate. Chem. in an Erlenmeyer flask. transferred to the balance case. The transformation into the crystalline form is hastened by shaking the flask. and finally black in color. t Z. 20 of this book) by heating to a temperature of 230. At first. adding 24 c. in Paul's drying oven and often some white antimony oxide is noticeable in the crucible. assumes a crystalline form and becomes darker. on withdrawing it. dioxide will rarely show any change in weight. 526 (1905). it becomes redder. A * piece of writing-paper should be rolled up and placed in the tube R. while the precipitate is of a yellowish color.. and can be filtered easily is crystalline. 44. solution.DETERMINATION OF ANTIMONY AS TRISULPHIDE. but towards the end a slow stream is The antimony sulphide as it comes down is yellow at first.* and after standing The black antimony trisulphide is not half an hour is weighed. A further heating in the current of carbon at all hygroscopic. but the transformation takes place more readily at a temperature It is more difficult to replace the air completely with carbon dioxide of 280. is removed with the paper. The shaking. The duration of the This is perin Fig. and washed with water without the tendency to pass into the hydrosol condition. as otherwise some of the precipitate is likely to adhere to the upper portions of the flask and escape the transformation. of the neutral solution. but as the precipitation proceeds. of the concentrated acid to each 100 c. advisable to introduce the hydrogen sulphide first. It is gas quite rapidly at sufficient. It is heated to boiling. should not be too violent. the sulphide eventually becomes grayish black in color. there is no need of shaking the flask but later on it is very desirable to do so. 221 carbon dioxide.

are obtained It therefore. dense. Compt. then with alcohol.. Bunsen.J have shown. Determination as Tetr oxide. 499 (1897) . 34. 316 (1878). Pharm.GRAVIMETRIC ANALYSIS. later abandoned it because his assistant succeeded in volatilizing more than 0. thin-walled. Ibid. purely accidental if exact results such a procedure. anal. 9 (1902). is. however. two sulphide as the solution above the precipitate will become clear.. however. 192. 2. If the pentoxide is ignited in a large porcelain crucible over the blast lamp.. changes into Sb2C>4. rend. it is possible to change the antimony is II pentoxide quantitatively into the tetroxide. 222 whole process amounts to from 30 to 35 minutes. solution is diluted with an equal volume of water. whereby low results are obtained. if. 41. when ignited at a definite temperature. a small. although they did not specify the exact temperature at which the precipitate should be ignited. cit. therefore. which is allowed to flow around the walls of the flask in order to wash down any adhering sulphide.f Brunck. placed boiling water and more hydrogen In or three minutes the solution is introduced. little of the antimony is held in solution by the strong acid and is diluted this is caused to precipitate by the The flask is. the tetroxide loses oxygen and is transformed into the volatile trioxide. based upon the fact that antimony pentoxide. t Ibid. procelain crucible is used. u. once more dissolved hydrogen sulphide. Sb 2 This method 4 (Bunsen). Chem. 106. crystalline precipitate The is obtained which settles well and permits a rapid filtration. Baubignyf disby * Ann..* who first proposed the method. The dilution almost always causes the forma- The reason for this is that a tion of a slight yellow turbidity. In 1897. || If Loc. in the vessel of shaken.1 gm. Finally a of antimony trisulphide heavy. and placed in the drying oven. 3 (1858). 171 (1895).. that under certain Rossing and Henz conditions accurate results can be obtained. It is filtered through a Gooch crucible. Chem. washed with water to remove >the acid. of the precipitate by heating it over the blast lamp. 124. J Z.

1909. Zurich. precipitated from hot solution. 263. complete it is possible to volatilize 0. To oxidize the antimony sulphide. is poured through a small and the filter into treated repeatedly no longer colored brownish filter is with ammonium sulphide until it is red at the edge of the paper. of antimony. where it begins to dry. has work confirmed the of Bauassistant. Chem. of the precipitate in about If these facts are borne in mind..35 gm. f again with alcohol and finally with ether. stirring constantly with a glass rod. the'precipitate becomes white and the greater part of the acid is * Inaug.c.and penta- sulphides. although even then the method is less satisfactory than the determination as trisulphide. Ann. resulting solution porcelain crucible. Procedure.gr. is washed first with hot water. Beckett places the crucible. 1. Dissert. it is possible thirty minutes. afterwards with a mixture of alcohol and carbon disulphide (in order to remove the sulphur). in the crucible is evaporated to dryness and the main part of the precipitate is added. Beckett. afterwards drying the The bulk of the precipitate is separated from the precipitate. under a bell-jar and allows it to stand over night. Dr. the extracThe solution tion of the antimony sulphide is then complete. then with alcohol. 372. und Pharm. filter and placed upon a watch-glass and the filter is placed in a small porcelain dish and boiled with a little of a freshly prepared solution of ammonium sulphide. E. with a dish of fuming nitric acid beside it. covered that antimony pentoxide is 223 converted quantitatively into the tetroxide at a temperature of 750-SOO form the volatile trioxide at a little above 950. a 30 The c. and begins to The author's G. fThiele. or in a mixture of one or the other of the two compounds It is best to proceed as follows: The sulphide with sulphur.DETERMINATION OF ANTIMONY AS TETROXIDE.* 7oO-SOO the At transformation and is at 1000 bigny. . the amount of In the majority of cases it is desired to determine antimony present in a mixture of its tri. The vapors of fuming acid slowly oxidize the precipitate in the crucible and in the morning it is possible to complete the oxidation by means of nitric acid (sp.4) without the reaction being too The crucible is then heated on the water-bath until violent. d. to get accurate results.

f then modified by Luckow. Chem. so that this method cannot be used for its quantitative determination. or antimonate. beaker. which has been gently sand-blasted. does not adhere well to the electrode. and Beckett have all found. or the deposited antimony pass into solution. 2074 (1894). Determination of Antimony as Metal. 27. as Finkener. 1629 (1881). metallic antimony. and the deposit adheres so firmly that The chief condition for it can be dried and weighed without loss. the following method proposed by Parrodi and Mascazzini.c. Antimony may be deposited from acid solutions by means of the electric current. 14. According to the experience in the author's laboratory. more hour the crucible water ammonia concentrated is is to give transferred quickly to a glass-stoppered weighing stand twenty minutes in the balance case. is subjected to electrolysis with a current of 1-1. 408 (1885).5 amperes at 70 for 90 minutes. the success of this operation is the absence of polysulphides. 17. enough an alkaline reaction.. with stirring. 11. 27) until no fumes of sulphuric acid are evolved.. After cooling in a desiccator. gBerichte. 18. containing not more than 0. it is not so accurate as the trisulphide method. expelled. as steel- gray. allowed to The and then weighed. On was first is suitable. Sb in a volume of about 140 c. anal. it the other hand. however.J and afterwards improved by Classen Reiss. 224 A added and. 13 (1880). The conof the crucible are now evaporated to dryness on the watercarefully heated in an air-bath (Fig.3 gm. p. little tents bath. t Ibid. . 18. 587 (1879). 2474 (1884). In case these substances are present the antimony is incompletely deposited and in some cases not at may all. the antimony will be deposited upon a platinum dish.* until a constant weight 3.GRAVIMETRIC ANALYSIS. t Z. the metal. and If a solution of sodium or ammonium sulphoantimonite. 19. Dexter. and then for half an at 800 in an electric oven. on account of being oxidized to sodium * Sb 2 O 4 is hygroscopic and must be weighed in a weighing beaker. is ignition and weighing are repeated obtained.

antimonite by means of the sodium polysulphide which 22$ is formed at the anode during the electrolysis: 2Sb + 3Na 2 S 2 = 2Na 3 SbS 3 . The filtered and washed precipitate. Z. keeping out the air as much as possible.. 828. anorg.DETERMINATION OF ANTIMONY AS METAL. pouring pure either precipitated * A.. t Z. whereby the polysulphide transformed into thiosulphate is : Na 2 S 2 + Na 2 SO 3 = Na 2 S 2 O 3 + Na 2 S. of NaOH solution should give 1218 c. 1. For this reason Lecrenier It is added sodium sulphide to the bath. 363 (1904). When this is accomplished. When the solution ceases to increase in volume (1000 c. Chem. of sodium XaSH solution). Bull. Ber. A.c. 23 [3] 292 (1900). to make use of potassium cyanide for this purpose. necked flask of such a size that the solution just reaches the neck of the flask. Chem.c. necessary.. is dissolved on the filter by not responding sodium sulphide solution (sp. 13.2 gin. after and some time. It is better. Ztg. or sooner is a colored standing pale yellow. 37. Lecrenier. Fischer. Chem.14) over it. Ost and Klapproth f carry out the electrolysis with the aid of a diaphragm to keep the polysulphide away from the cathode. Inhelder prepares the solution of sodium sulphide as follows: 666 gms. Chem. Soc. Henz. angew. In most cases the antimony is first isolated as the sulphide.. Na 2 S 2 + KCN = Na 2 S + KCNS. 1900. anorg. therefore. of purest sodium hydroxide (prepared from sodium) are dissolved in 2 liters One-half is placed in a lon-gof water and the solution divided into halves. 42. corto over 0. Z. 1219 (1889). JCf.gr. 31 (1903). 36. Sb. 2048 (1903). The flask is closed with a two-holed rubber stopper and a rapid current of well-washed hydrogen sulphide is introduced through a glass tube 1 cm... Chem. to prevent the formation of poly* sulphides during the electrolysis. Hollard. wide. prepared . A. { Procedure.S thus original sodium hydroxide solution is added. however. the other half of the The solution of Na. which is by hydrogen sulphide from acid solution or obtained by acidifying an alkaline solution of the thio-salt. F.

To make sure that the deposition is complete. the total not be over 80 phide solution volume is liquid is less than The added.. is diluted until the specific gravity is 1. and the of the liquid in the if c. lightgray deposit. For the antimony determination.. contained 69 per cent.c. washed thoroughly with water. the suspended sulphides are removed by filtration. The cathode is removed.5 pass through the liquid (the voltmeter connected as ammeter points to the zero reading). or in a beaker if a platinum gauze electrode is to be After washing the filter with the sodium sulphide soluused. The results obtained by this method are invariably too high. this. If According to A. 37. t Z. Chem.22. 31 (1903). anorg. the liquid may be transferred quickly to a second dish and electrolyzed for half an hour longer.c. and weighed. water and 2-3 gms. partly in suspension and partly in colloidal solution. NiS.5 to hours of 2-3 volts. The solution keeps indefinitely in a well-stoppered flask. If the sodium sulphide solution is prepared from caustic soda purified by alcohol. tion. Classen formerly recommended that the solution be prepared by boiling a solution of sodium hydroxide which had been saturated with hydrogen sulphide. the error amount- as F.14. Na2S (F. Such a solution after an hour's boiling. Henz f showed in the author's laboratory. . which has a specific gravity of 1. Ag 2 S) is formed after some time. the final solution is colored a deep yellow or brown and it contains more foreign sulphides. a slight precipitate of black metal sulphide (FeS. dried at about 80. on shaking. while water is added until the current ceases to and electrolyzed with a current of 1-1. Wegelin). all the antimony potential will be upon the cathode in the form of a firmly-adhering. a satisfactory solution can be prepared by dissolving the purest grade of commercial Na2 S.GRAVIMETRIC ANALYSIS. NaSH * and 31 per cent. It is heated to 60-70 amperes and electrode 2 After 1. platinum dish should enough more sodium solution is diluted with 60 sul- c. a further precipitate will appear on standing. cooled in a desiccator. then with absolute alcohol. tetragonal crystals of Na 2S + 9H 2 O are deposited. the saturated sodium sulphide solution. the electrolyte is siphoned off. 226 The solution is caught in a weighed platinum dish with unpolished inner surface. of potassium cyanide are added anode until all the cyanide has of the purest stirred with the dissolved and the solution is well mixed. It is seldom that there will be any gain in weight shown by this dish. without breaking the circuit. Classen. while introducing a stream of hydrogen.* Now.

14. Cleaning the Electrodes. 827. Elektrochem. however. the high values are due to the presence of a little sulphur and more oxygen. polished dishes. 257 (1908). According to the work of Scheen. but has been confirmed by a number of other investigators. M. 1910. 227 ing to about 1. If.f F. Karl Mayr also obtained high values no matter whether the electrode surface was bright 1f carefully or dull. the weight of the latter corresponds to the theoretical value. Inhelder. 1901. therefore. 53. in The error in the analysis from the truth will is so constant that values not far be obtained by subtracting 1. of the total antimony present.'! which was suggested by Classen. I J . M. showing that the deposit contained all the anti* mony. 36. 205 (1907). 13. of the weight of antimony deposited electrolytically. using new. the deposit is dissolved alkali polysulphide. Wolff. Chem. Dissert..6 per cent. Forster and Wolff. % and recently by A. Elektrochem. t Z. and again electrolyzed with addition of potassium cyanide. of oxygen. Scheen. J Z. anorg. Inaug. || Tf Z. 1910.. If.. reca bright electrode surface. Zurich. Inaug. Inhelder has repeated the experiments of Scheen. including O. as A.DETERMINATION OF ANTIMONY AS METAL. Forster and Wolff assert that the metal contains from 1 to 1. D. the same weight of antimony is obtained as at first. Ost ** recommends heating with a * Berichte. ** Z. the error is due to enclosed mother-liquor and is greater in proporof free tion as the electrode surface ommends is rough. Zurich. This error of the electrolytic antimony determination was first detected by Henz. the antimony deposit is dissolved and precipitated as the trisulphide. 2348 (1903).5 per cent. or one that is dulled but slightly. angew. Dissert. A. Dormaar.5 to 2 per cent. but has not been able to confirm Scheen's conclusions. Fischer recommends. The error is greater in proportion to the quantity sodium hydroxide present in the electrolyte. According to Dormaar. Forster and O. Chem. but the antimony is not pure. 349 (1907)..

it always contains small amounts of other oxides and must be purified as follows: The After weighing. the precipitate is mixed with six times as much of a mixture consisting of equal parts calcined sodium carbonate and pure sulphur. in contact with the air) has ceased. mixture of equal parts concentrated solution of tartaric by heating with a readily and a saturated nitric acid The antimony acid. tin dioxide thus ob tamed is never pure . (a) The Tin (a) is Present in an Alloy. will also dissolve solution of alkali polysulphide. anal. At. f. 53.. Chem. 17. After burning ash with the nitric acid and drying on the filter. Determination of Tin Dioxide.c. gr. then filtered. . the solution and diluted with 50 c.5). the precipitate and dried. the SnO2 .0. Sn. 1. TIN. Wt. Forms: Sn0 2 Sn. i. at first gently and finally It is weighed as strongly. washed.5 gm. When the evolution of nitric oxide (brown vapors on coming place.c. of water are slowly added and the beaker is then quickly covered with a watchAs the water is mixed with the acid a violent reaction takes glass. is heated to boiling is allowed of boiling water. in the form of borings. over the Teclu burner or blast-lamp. This point is easily recognized by there being no longer any odor * Zeit. c. 3 c. . a beaker with 6 of of I. and this mixture is heated in a covered crucible over a small flame until the excess of sulphur is almost entirely removed.228 GRAVIMETRIC ANALYSIS. Method In case the tin ing to the About method 0. an alloy it may be treated accordBusse* as follows: the alloy. the precipitate is ignited. of nitric acid (sp. to settle completely. Sn02 . Two cases are to be distinguished: The Tin is Present as Metal (in (6) The Tin is Present in Solution. is treated in present in is an Alloy). moistening water-bath.c. 119.

I. etc. dissolved in nitric acid. after which any iron or copper. will original weight of the tin dioxide. dried. the filtrate from the insoluble sulphides can be acidified with acetic acid and the tin precipitated as yellow stannic sulphide. brought into solution. Vol. In this case the residue is filtered. will be quantitatively precipitated as sulphides. If this weight is subtracted from the original amount impure stannic oxide. the insoluble metastannic and washed as in the first method. after it has completely settled. the different metals must be separated according to one of the methods for the separation of the sulpho-bases and the weight of each oxide determined separately and the sum of their weights subtracted from the of be obtained. to which a little sodium sulphide has been added and finally with hydrogen sulphide water. sulphite changes the sodium polysulphide to monosulphide. first with water iron. however. and the fusion repeated ficient. washed. As a rule the amount of insoluble sulphide formed by this treatment is so small that after drying it can be ignited in the air and changed to oxide without introducing any appreciable error. and weighed as such. amount Instead of determining the of impurity present with the tin dioxide. therefore. Method The acid is alloy is II. as described on p. which. whereby the tin goes into solution* as sodium (cf. is treated with sodium sulphite t solution until it becomes only slightly yellow in color. together with some copper and sulphostannate The deep-brown liquid. 233. little hot water. 222). the amount of impurity present with the residue of metastannic acid should be large. until all the tin is t The sodium in which copper and iron sulphides are insoluble. The latter are filtered off and washed.. p. . S0 2 and no of 229 blue flame of burning sulphur evident between the After cooling the melt is treated with a cover and the crucible.DETERMINATION OF TIN AS TIN DIOXIDE. Instead of filtered off * Frequently a single fusion with sodium carbonate and sulphur is insufthis is recognized by obtaining a sandy residue insoluble in water. the weight of pure stannic oxide If. is filtered off and changed by careful ignition into tin dioxide.

covered with about 1 sulphide solution and heated on the water-bath. As soon as no 1 more bubbles of oxygen are evolved. the tin should all be dissolved. these quantities sufficing for 0. sulphide is most the of alkali beaker and dissolved in 10 and c. of pure sodium hydroxide solution and 10-15 c. tartaric acid. filtered. of tin. It is. then a cubic centimeter in excess.c.c. evaporated on the water-bath almost to dryness.c.1 to 0. and the other metals remain undissolved as sulphides. and then treated with 1 c. upon which the metastannic acid was retains some of the precipitate. it is washed into a porcelain evaporating dish. The solution is boiled for about ten minutes to make sure that the oxidation is complete. pure 30 per cent.2 gm. The warm solution is electrolyzed cool directly as described on page 234. of oxalic acid dissolved in a little hot water are cautiously added. then transferred back to the original boiled to expel the hydrogen sulphide. The solution is poured through a small filter and the latter is washed with a little hot water. The filter. however. of hour. Merck) is added until the yellow liquid becomes perfectly colorless. and the dish with its contents is heated for about 45 minutes on the water-bath. For the determination of the tin. of 50 per cent.GRAVIMETRIC ANALYSIS. gm. 230 drying and igniting the precipitate. of concentrated sodium sulphide solution The evaporating dish is covered with (see foot-note. and that the excess of peroxide is decomposed.c. a watch-glass. . the two solutions containing sodium thiostannate are combined. still therefore. hydrogen peroxide (Perhydrol. The two filters are dried. 225).) the solution. (The last traces of precipitate adhering to the filter To are dissolved in a very little sodium sulphide solution. p. ignited in a platinum spiral. whereby all the tinshould pass into solution. they are removed by filtration. the solution is allowed to somewhat and 15 g. second sodium After half an c. laid in a small evaporating dish. the ash treated with concentrated hydrochloric acid and the resulting solution is added to that obtained by the solution of the alloy in nitric acid. filtered off. caustic potash. acidified with acetic acid and The precipitated stannic washed once with water to remove the salts.

and the possible The first total volume of the filtrate should not exceed 150 c.DETERMINATION OF TIN AS TIN DIOXIDE. of borings are dissolved in a small beaker The solution is evaporated and the beaker removed as the on to water-bath.c. The washing is completed by boiling and decanting with a 1 per cent. HNOs.c. 1. determination. off nitric acid. A mixture is prepared of 20 c. 1. The resulting solution of the impurities that were originally present in the metastannic acid. 1. residues of metastannic acid which are pure and the work is not as unpleasant as concentrated acid is employed. The residue of slightly impure metastannic acid is treated under either of the above methods. nitric acid sp. and each successive portion removed from below the funnel before new wash water is added. gr. fully as when the more gm. may be ignited in a porcelain crucible and weighed as SnC>2. more dilute nitric acid for dis- It is possible solving the alloy than was recommended by Busse.c. it is advisable to treat the filters containing the residue from the sodium sulphide treatment with 15 c. sp.c. refiltered if necessary. and 40 c. each time heating to boiling and decanting off the solution through a hardened filter paper. ignited .c. lytic a little .c. water and this is divided into three portions.c.5 c. with 15 0. Method The translator prefers to use a III. Procedure. sp. water) II instead of burning and treating with hydrochloric acid as directed above. of hot dilute nitric acid (7 c. The filters are dried. gr.2. . In case Method as described is chosen. as obtained above by acidifying the sodium thiostannate solution. The residue is treated successively with each portion of the above mixture. is portions of the filtrate are carefully examined for metastannic acid.2 and 8 c. gr.2. The results are usually high and the method is not as accurate as the electroCf page 233 /?. just dryness soon as this stage is reached. is filtered and added to the original nitric acid solution. to obtain. solution of ammonium nitrate. however. 231 The precipitated stannic sulphide. As much of the precipitate as allowed to remain in the original beaker. in this way.

(6) (a) Tin is is It solved left is undis- not safe.* dried. of concentrated ammonia exactly neutralized with nitric acid). more ammonium nitrate solution is added (20 c. to discard the filters. 71). after which the solution is neutralized with ammonia and treated as above described. In this case the tin must be first precipitated as sulphide by means of this hydrogen sulphide (cf. Lowenthal. Remark. 233). amorphous by evaporation on account of the . If the solution contains only tin in the form of stannic salt (chloride or bromide). it "salts out" the precipitate t The excess of acid cannot be removed volatility of stannic chloride. (cf. * The ammonium nitrate prevents the formation of soluble. heated to boiling.c. of concentrated ammonia with nitric acid) is added and the solution is diluted to a volume of 300 c. p. Methyl orange is added to the solution and then stannic ammonia until a yellow solution is obtained f dilute nitric acid is now added. ignited in a porcelain and weighed as Sn02. tin may be precipitated from slightly acid stannic chloride or bromide solutions in the presence of ammonium nitrate. If the solution contains non-volatile organic acids. Ammonium nitrate (obtained by the neutralization of 20 c. until the solution just becomes pink again. the solution must be first oxidized by the addition of bromine water until a permanent yellow color is obtained. p. According to J. the solution is . stannic acid.c. 232 and the ash weighed added to the result The amount thus found is Sn02. Present in Solution. ammonium nitrate. but as stannous salt. Vol. The Solution Contains Tin only. filtered after the precipitate has settled. method cannot be used for the determination of tin.. therefore. washed with hot water containing crucible. If the tin is not in solution as salt. I.c. Remark. Sometimes a little metastannic acid by the treatment with alkaline sulphide. drop by drop. a few drops of methyl orange are added and then ammonia until the pink color of the indicator is changed to yellow.GRAVIMETRIC ANALYSIS. obtained from the sodium thiostannate as solution.

The tin sulphide is at first gently heated in a covered crucible to avoid loss by decrepitation. and the ash of the filter added. 39 (1903). diluted to 300 boiled for c. dried. therefore. the crucible covered and again heated. but although the tin will be quantitatively precipitated. and afterwards in an open crucible until the odor of sulphur dioxide is no longer perceptible. they remain in solution. dried. . according to page 234. Metals of the Preceding or Organic Substances.. transferred as completely as possible to a porcelain crucible. and determining the tin by electrolysis. The precipitate is washed with a solution of ammonium nitrate (or ammonium acetate). some sulphuric acid with great tenacity. anorg. The author recommends. some sodium sulphate will be also thrown down. some time. Henz * in testing this method always obtained This is due to the fact that results which were a little too high. it is difficult to wash the stannic sulphide precipitate free from sodium salts. be obtained. transforming this solution into potassium stannioxalate. Sodium sulphate can be used instead of ammonium nitrate to "salt out" the tin precipitate. * Z. so that high results will of alkaline earths . the solution is allowed to stand until the odor of hydrogen sulphide has In form this case. filtered. after cooling the crucible somewhat a piece of ammonium carbonate the size of a pea is added. (/?) The Solution Contains. The temperature now is raised gradually until finally the full heat of a good Teclu burner is obtained or the cruci- As tin dioxide holds fast to is heated over the blast-lamp. hydrogen sulphide is conducted into the dilute solution until it is saturated with the gas. 233 washed with water containing ammonium nitrate. Remark. repeated until a constant weight is obtained. Chem.. dissolving the well-washed stannic sulphide precipitate in a little sodium sulphide.c. F. ignited. and weighed as SnO 2 This method is employed when the solution contains small amounts . 37. of stannic or almost disappeared and then filtered.DETERMINATION OF TIN AS TIN DIOXIDE. after which it is weighed as Sn02 The heating with the addition of ammonium carbonate is ble . independent of whether the tin is present in the stannous salts. Groups besides Tin.

c. At the end of about six hours all the tin will have been deposited upon a gauze The deposit is washed with water. Anal.* It is necessary.GRAVIMETRIC ANALYSIS. by Electrolysis" and Methoden der analytischen Chemie. reached no more precipitates some stannic It is necessary. deposited. 234 2. Classen's "Quant. is free acid that some oxalic however. dried by holding above a flame. acid. Remark. all exactly as The final solution. 4 + 0= (NH 4 2 C0 3 + C0 2 ) ammonia When as a result of the hydrolysis- this point is The ammonia often . is heated to in of ampere and 3-4 volts potential at the electrodes. from time to time a little solid oxalic acid is added. and finally acidified with oxalic acid. ammonium oxalate is changed by anodic oxidation into ammonium carbonate and carbon dioxide. best accomplished as follows: The thio-salt is decomposed by acidifying with acetic acid. Procedure. which escapes the electrolysis. the deposited sulphide dissolved is in caustic potash solution." his of the potas- (eight to ten " Ausgewahlte . about 150 c. During the process. always present while the solution is undergoing electrolysis. the solution oxidized with hydrogen peroxide. If ammonium oxalate is used in place sium oxalate. 60-70 and electrolyzed with a current described on page 230. (NH 4) 2 C 2 and the solution of tin ammonium is will smell of carbonate. volume. and weighed. then with water. electrolytic deposition of tin from a solution of the ammonium double oxalate gives excellent results. scribed for nickel on page 136. the electrolysis requires more tim * Cf. The results 1 are excellent. and this is best accomplished by adding a little solid oxalic acid from time to time. cooled in a desiccator. In the course of an analysis it is usually necessary This to precipitate the tin from a solution of alkali thiostannate. therefore. The Determination of Tin as Metal. exactly as preelectrode. to avoid letting the bath become ammoniacal.

Antimony. (cf. Cadmium. TIN. or the solid sulpho-salts of the above jnetals. in solution. chief conditions are the presence of enough oxalate and a slightly acid solution. while the remaining metals remain in solution. insoluble in dilute nitric acid. all the alloy nitric acid. tin is left phosphorus and arsenic are thrown down in the insoluble residue as phosphate and arseniate of metastannic acid. 235 the addition of hydroxylamine the duration of the shortened (Engel). while the chlorides of these three metals are those of the remaining metals are only difficultlv so. with the antimony as nearly insoluble antimonic acid. The small . all the tin is If too not precipitated. Separation of Arsenic. antimony.) the metals of this group are in the form of an alloy (arsenic and mercury are seldom met with to any extent). the antimony If and tin are separated from the remaining metals with The on treating behind as metastannic acid. and Bismuth. and Tin from Mercury. they are precipitated by means and the precipitated sulphides after being hydrogen sulphide filtered and washed are treated with alkali sulphide solution. Antimony. much The sulphuric acid is added. arsenic. In the presence of tin. and tin are precipitated as sulphides. but subsequent experiments have shown that it is better to proceed as described above. metals are If the all of If mercury is present. and Tin from the the Ammonium Sulphide Group. to prevent the bath becoming ammoniacal by adding sulphuric acid during the course of the electrolysis. By is electrolysis Henz proposed F. but in the absence of this metal sodium polysulphide works better Vol. ammonium polysulphide should be used. ANTIMONY. From an alloy. AND hours). antimony. readily volatile. Copper. I. Members of The separation is effected by passing hydrogen sulphide into the acid solution of the above metals whereby arsenic. Separation of Arsenic. Lead.SEPARATION OF ARSENIC. and tin may be readily volatilized by heating in a stream of chlorine.

taining all the tin. phorus. beaker glass. of is of the alloy in placed in a beaker.5-1 gm. After this from 20 to 30 c. after which the immediately covered with a watch- When the reaction begins to diminish. iron. until no more fumes are evolved. 1. varying tains aluminium. and weighed after cooling in a desiccator. About 0. dried at about 80 C. where they are condensed and drop upon the borings. A bronze an alloy is of tin and copper in It almost always conproportions. The ether vapors pass through the wide side-arm to the condenser A'.c. it is siphoned back into the flask. sp. of ether are added to the flask and this is heated gently on the water-bath. The separation of tin from the remaining metals of the group can be illustrated by a \ practical example. FIG. when 50 c. The washing with ether is best accomplished in a Soxhlet's fat-extraction apparatus. the precipitate (conthe phosphoric acid. gr. 46. in which case they should be washed with ether that has been distilled over potash. heated to boiling. of nitric acid. besides these metals more or less lead.c. as shown in Fig. * The borings are usually somewhat oily. the form c.c.GRAVIMETRIC ANALYSIS 236 amount of the latter (and the remaining metals of this group) are precipitated by hydrogen sulphide and separated from the copper group by means of alkaline sulphide solution. 46. Procedure.c. of the liquid brown zinc.5.t an d borings c. The borings are placed in the extraction-tube. The tube is then connected with the condenser K. and always small amounts of copper oxide) is allowed to settle completely. will be removed from the borings in from half an hour to an hour. of treated with 6 3 manganese. * and phos- is water are added. As soon as the ether in tfye tube has reached the height All the oil b. where it is again distilled. t See pages 228 and 231. Analysis of Bronzes. . which is filled with ether nearly up to the bend b of the siphon-arm.. is boiling water are added.

The sulphides. viously obtained.ANALYSIS OF BRONZES. In order to obtain the weight of the SnO 2 a separate portion is analyzed according to the method of Oettel as described below for phos- phoric acid. After cooling. In this w ay the weight of the SnO 2 + P2O 5 + In order to obtain the weight of foreign foreign oxide is obtained. 237 washed with hot water. It is evaporated to a small volume in order to expel the hydrogen sulphide. 183. dried. . case the filtrate from the copper sulphide is treated with sodium acetate. the precipitate of lead sulphate and its weight determined as described on p. ignited in a porcelain and weighed.c. 50 c. the zinc in the precipitate.* whereby the iron and aluminium are left behind as hydroxides * If considerable zinc is In this present. acid. and the amount of phosphoric anhydride subtracted from the weight of SnO2 + P2 O 5 .c. 22S. is filtered. and weighed. 174. The oxides obtained by the are dissolved in a ignition of the insoluble sulphides nitric acid (in case Fe 2 O3 is present a also necessary) and the solution of the little hydrochloric acid is nitrates is added to the first filtrate from the impure metastannic To this solution an excess of dilute sulphuric acid is added. converted into oxides by ignition in the By subtracting this weight from that preair. the weight of SnO 2 + P2 O 5 is obtained. it should be separated from iron and aluminium as described on pp. of and it is alcohol are added. from the lead sulphate is is filtered off The filtrate heated to remove the alcohol and the copper precipitated by means of hydrogen sulphide and weighed In the filtrate from the copper sulas Cu 2 S according to p. If manganese is present in the alloy. the above separation is inexact. found. remaining after the solution of the melt in hot water. and the iron and aluminium determined in the filtrate. r crucible. white fumes of sulphuric acid are evolved. saturated with hydrogen sulphide. oxidized by the addition of a few drops of concentrated nitric acid. of water and 20 c. 149 to 155. are filtered off. aluminium. and the iron and aluminium separated from the zinc by means of a double precipitation with ammonia. oxide (chiefly copper oxide) the precipitate is fused with a mixture of sodium carbonate and sulphur as described on p. heated to 60. zinc (also manganese) will be and phide the iron. little evaporated on the water-bath as far as possible and then heated over a free flame until dense.

formed to oxide by heating with mercuric method (cf. in which form * it is by ignition to weighed. By skilfully rotating the crucible during the fusion. and changed pyrophosphate. The filtered off. dissolved in hydrochloric precipitated zinc sulphide acid. After standing for twelve hours. 107. 238 and are separated and determined according to p. the substance is mixed with three times as much solid potassium cyanide. magnesium . and the impure metastannic acid with all the phosphorus is filtered off. dried. After treated with water and filtered. dried. and the contents fused. by passing hydrogen sulphide into the boiling solution. while the phosphoric acid is converted into potassium phos- phate. * phosphorus determination Oettel recommends the folFrom 2-5 of the substance are dissolved. in nitric acid. 19. After cooling. oxide Sn0 2 + 2KCN = 2KCNO -f Sn. Chemiker-Zeitung (1896). ammonia water. and the phosphoric acid precipitated as magnesium ammonium phos- phate by the addition of magnesia mixture. the melt is filtration is greatly facilitated. lowing procedure: as before. is added. and the contents of the crucible ignited. freed from hydrogen sulphide by boiling. it is possible to unite the small particles of molten tin into a larger button whereby the subsequent cooling. and transferred as com- For the The ash of the filter pletely as possible to a porcelain crucible. the crucible covered. p. is The acetic oxide and trans- by Volhard's 142). p. washed with 2J per cent.GRAVIMETRIC ANALYSIS. The filtrate cautiously treated with hydrochloric acid under a good hood and boiled to remove the hydrocyanic acid. the latter is filtered off. evaporated to dryness in a weighed platinum dish. gms. made ammoniacal. zinc is precipitated from the filtrate after acidifying with acid. the stannic is reduced to metal. It is then saturated is with hydrogen sulphide in order to remove traces of copper and The filtrate is tin which almost always remain in the solution.

c. Erlenmeyer flask. After cooling. with a watch-glass. of water are added. 239 Ordinary bronzes may be analyzed very nicely in the following manner: The alloy is treated with nitric acid as described above. and the supernatant liquid should show no blue color. the contents heated nearly to boiling for fifteen minutes. more ammonium sulphide must be added. the precipitated sulphides of copper and lead allowed to settle.90) to redissolve all of the copper hydroxide and to produce a deep blue colored solution. 25 c. which are determined as above. gr. The beaker is covered solved in 20 c. using a dull platinum dish as cathode. Method of Dudley and Pease Modified* One gm. or so dilute that a spongy deposit is obtained.c. both of which are weighed.. and a plate as anode. decanting tion * Dudley and Pease. R. In Determination of Phosphorus. and R. .2 amperes at about 60 and at the end of two and one-half to three hours the electrodes are washed without breaking the circuit. The siphoned aluminium and zinc. made by mixing equal volumes of the concentrated acids just previous to use. Eng. The electrolysis is carried out with a current of 1 to 1. and then just sufficient ammonia (sp. On the anode will be found all the lead as PbO 2 and on the cathode will be found the copper. The phosphorus is determined solution contains the iron. in a special sample.c. If it does. Remark. the chief dangers to be feared are having the solution so acid that the copper is not all precipitated. of the borings are weighed into a small beaker and dis- of aqua-regia. March. thereupon 50 c. The solu- is digested at a temperature near the boiling point for fifteen minutes. of colorless ammonium sulphide are introduced. the metastannic acid removed by filtration and the filtrate electrolyzed. 0. The method just outlined will give exact results when the metastannic acid is purified and the recovered only solution of copper and lead nitrates added to the main solution.DETERMINATION OF PHOSPHORUS. the electrolysis.c. and then filtered into a 300 c. and. Journ. 1894. after solution is complete. This should be enough to precipitate the sulphides.

but it is not necessary to evaporate in case this volume is slightly exceeded. which is heated to boiling.20.2 ampere.c. and stirred occasionally. 0. The electrolysis is usually finished in twelve hours. An excellent method for the analysis of ordinary bronzes consists in dissolving the alloy as described under Tin.c. determining the tin as there described. taking care that all of the precipitate adhering to the walls of the and then poured through the filter. 240 the clear liquid carefully from the precipitate. of ammonium sulphide wash water and allowed to drain completely. Often a little more copper will be found. To the filtrate 10 nesia mixture are added and the solution shaken. solution to run into a No.c. and flask is dissolved. gr. ignited with the usual precautions. When the filter has drained the filter and precipitate is returned to the beaker.c. The total volume should not be over 250 c. gr. ammonia water until free from chlorides. and then treated with ammonia (sp. sp. Method III. gr.c. The solution is allowed to stand in ice water for two hours. the copper being deposited on the cathode and the lead as peroxide on the anode. it is then poured upon another filter. of The mag- flask is placed in ice water and allowed to stand with occasional shaking two hours. washed with 50 c.96 sp.GRAVIMETRIC ANA LYSIS. 3 c. The flask and filter are washed with 10 c. and finally throwing the precipitate upon the filter. especially . for ten minutes. ammonia to three parts water) until for 10 c. with 2J per cent. removed from the flame. 1. The copper and lead are determined in the nitric acid solution by electrolysis with a current of 0. and The precipitate is then filtered and washed stirred occasionally. c..c. of hydrochloric acid (one part nearly free from sulphide. The precipitate of magnesium ammonium phosphate is filtered upon a small filter and washed with ammonia water (one part 0.. to four parts water) are placed in the flask.90= 10 per cent. more of the same acid. NH 3 ) until the latter is present in large excess. 50 c.c. of ammonium sulphide wash water (one part colorless ammonium sulphide to three parts of water) are added. allowing the 1 beaker. HC1. of magnesia mixture are added to the filtrate. weighing as Mg 2 P207. but it is well to clean the electrodes after weighing the deposits and then to test the solution with the current for an hour or so longer to see whether any lead or copper remains in the solution. and the mixture is heated.

warm Concen- solution drop by decomposed and no more chlorine is evolved. (a) Principle. solution of hot dilute pure caustic potash of pure solid caustic alkali are added. zinc remain in solution. Chem.SEPARATION OF ARSENIC FROM ANTIMONY. If a and antimonate and the excess Method slightly acid Bunsen* of solution of an alkali arsenate treated with hydrogen sulphide in the cold of the latter immediately removed by conductis air through the solution. During the 241 electrolysis the concentration of the acid gradually diminishes so that eventually The iron. this takes from The casserole is It is placed one-half to three-quarters of an hour. the antimony is quantitatively precipitated as pentasulphide. in the solution as by dropping a From 3-5 gms. upon it. i.c.! now covered with a perforated watch-glass. porcelain casserole. and the precipitate remaining on the filter is dissolved into the casserole Procedure. The greater part of the precipitate is transferred by means of a spatula to a 200-c. filtered. 305. t If alkaline earths were the only metals present besides the arsenic and antimony. the first precipitation with hydrogen sulphide would be omitted. and then an equal amount of concentrated hydrochloric acid is added and the solution again is * Ann. aluminium. The watch-glass is removed. SEPARATION OF THE SULPHO-ACIDS FROM ONE ANOTHER. 192. while the arsenic remains in solu- ing tion. and the precipitate dissolves to a clear solution. the solution is evaporated to half its volume. By this operation the arsenite and antimonite are oxidized to arsenate and antimonate and a small amount of potassium chlorate trated hydrochloric acid is now added to the drop from a pipette until all the chlorate is formed. the water-bath. Assume the and antimony to be present Both eleand washed ments are precipitated by hydrogen sulphide. . und Pharm. and are determined as above outlined. d.. and all the copper will be thrown down. and chlorine is conducted into upon the solution until all the alkali is decomposed. with water. if the solution was a little too acid. arsenic arsenious and antimonous acids. Arsenic from Antimony.

242 evaporated to half are washed its volume. 180). the solution If contains no very large excess of hydrogen sulphide. washed it is filtered twenty-four hours. the combined filtrates are consomewhat by evaporation. and weighed as For the arsenic determination. the precipitate will always contain trisulphide. however. antimony pentasulphide is to likely The precipitate of of arsenic contain traces pentasulphide so that it is dissolved once more in caustic The precipitate now potash and the above operation repeated. antimony pentasulphide is likely to be changed bisulphide. .c. the above procedure is better. a 280 stream of carthrough a Gooch crucible.GRAVIMETRIC ANALYSIS. a few drops of chlorine water are added and hydrogen sulphide is passed into the warm solution (being kept on the water-bath) for from six to eight hours. and for every decigram or less of the antimony 100 c. and times with pure alcohol. Sb 2 S 3 is reduced to Sb 2 S2 on long-continued treatment vrith CS2 . in dried at C. current of air (filtered through a wad of cotton) is then passed through the solution without delay until the excess of hydrogen sulphide is completely removed. after which it is allowed to cool in a rapid stream of centrated hydrogen sulphide.. The contents of the casserole by means diluted with water of dilute hydrochloric acid into a large beaker. According to Braun. An orange precipitate of antimony A strong pentasulphide is formed at the end of a short time.c. four times with a mix- pure carbon bisulphide and alcohol (cf. p. bon to the trisulphide on treating with carbon bisulphide. It is filtered obtained will be pure antimony pentasulphide. with water. bon dioxide Sb 2 S 3 . to a volume of 600 c. then three times w ith r alcohol.* described as under antimony. a large beaker should be used to contain the solution and it should be covered with a perforated watch-glass. this usually requires about In order to avoid loss during this operation twenty minutes. so that it is safer to dissolve it in ammoniacal hydrogen per* Bunsen weighed the antimony as pentasulphide after washing with carAs. After drying at 110 C. three finally the precipitate is weighed as As 2 S 5 ture of . Remark. After allowing the precipitate to settle for through a Gooch crucible. of freshly prepared hydrogen sulphide water are added.

the portion adhering to the filter is dissolved by hot ammonia into the same beaker. the arsenic antimony solution is diluted solutions are at with twice its volume of this cold solution a rapid the strong hydrochloric acid. HO the solution heated for some time on the water-bath and 2 2 are added. When both C. Neherj This.c. as described on p. for every 0. (6) Method of Fred. stream of hydrogen sulphide is Into passed and one-half hours.. but con- sumes considerable time. of pure 3 per cent. another with the ing potash solution hydrochloric acid (sp.1 gm. anal. previous and cooled by surroundis washed into an Erlenmeyer flask In flask some concentrated flask ice. The flask is stoppered up and allowed The As 2S5 is filtered through a Gooch to stand one to two hours. The method gives very accurate results. depends upon the fact that arsenic is precipitated from a solution strongly acid with hydrochloric acid by a rapid stream of hydrogen sulphide.c. the acid solution method. t Z. 32. of the filtrate after being considerably diluted with water and tested with hydrogen sul- phide shows no precipitation. 206. of AszSj. then boiled ten minutes. and this is warmed until the precipitate has entirely disAfter this. 1. crucible and washed with hydrochloric acid (1 vol. Chem. the best method for the separation of arsenic and antimony. weighing it as Mg2As2C>7. while antimony is not.. in the author's estimation. Starting with a precipitate consisting of the triand antimony. . and * For this purpose as much of the precipitate as possible is placed in a beaker.SEPARATION OF ARSENIC FROM ANTIMONY. con- for one centrated hydrochloric acid) until 1 c. gr. 30-50 c. It is then washed with water. 2 vols. this is dissolved in caustic sulphides of arsenic and oxidized exactly as described under the When free from chlorate. Remark. water. 45. 243 oxide * and then to precipitate the arsenic with magnesia mixture as magnesium ammonium arsenate. Procedure. solved.2) is likewise cooled.

magnesia mixture is added to a solution of an alkali arsenate and antimonate containing tartaric acid. The Sb2S 5 is filtered through a Gooch crucible. however. some arsenic trisulphide will be found The results are scarcely affected. of a precipitate is formed. it is advisable to dissolve the precipitated sulphide nitric acid. For the is . when the merely washed with water and alcohol. The separation is based upon the fact that if Principle. finally is (c) The Tartaric Acid Method. an insufficient amount of tartaric acid is present. acid. dried at 280 C. washed a few times with 2J per cent. only arsenic will be precipitated. After drying at 110 C. foot-note). not cause any turbidity. and reprecipitated by the addi- dissolved in hydrochloric acid. Procedure. slowly with constant stirring (cf. (a) by tartaric acid and an excess ammonia added. more. the precipitate of magnesium ammonium arsenate is filtered off (it usually contains a little basic mag- nesium tartrate). Th& sulphides are oxidized as described under solution in aqueous caustic potash and introduction of The solution thus obtained is made acid. highest degree of accuracy. p. precipitate is weighed with the sulphide of arsenic. tion of an excess of ammonia. magnesia mixture is added warming with To is If tartaric the clear.. however. 206. * If the solution was not cold. the precipitate * weighed as As2Ss. . The filtrate from the arsenic sulphide is diluted largely with water and saturated with hydrogen sulphide. and weighed as magnesium pyroarsenate as described on p. treated with chlorine. the precipitate is After standing for twelve hours washed with 2J per cent. 206. filtered. the clear solution decanted off.GRAVIMETRIC ANALYSIS. in a current of carbon dioxide and weighed. or in fuming mine the arsenic as Mg2 As 2 O 7 as described on page in 206. After standing twelve hours. ammonia. and to deter- ammoniacal hydrogen peroxide. because the free sulphur in the precipitate. the precipitate is This should it shows that In this case dissolved by and the two solutions are mixed. ammonia. If. ammoniacal solution. 244 with hot alcohol. the precipitate is washed with CS 2 it is evident that the results will be too low.

21. p. of potassium bromide . under which conditions antimony chloride is not volatile. Rohmer.. the arsenic and antiare obtained first in the form of the sulphides.c. A. hydrogen bromide may be used which has previously been prepared by treating 1 gm. the alkaline solution may be boiled with hydrogen peroxide or If potassium percarbonate. J Instead of the potassium bromide.5 gms. and the bromine would oxidize the volatilized AsCl 3 and thus interfere with the subsequent determination of the arsenic by pre. 245 Arsenic can also be separated from tin according to the above method. Remark. 1649). as a in the presence of -some reducing rule. f Fischer used a ferrous salt. Ber. or by titration. in Fig. the boiling evolution of oxygen. oxidation. V. 28. solution and oxidized by chlorine. and Friedheim and Michaelis used methyl alcohol of (Ber. been placed solution is transferred. The apparatus shown determination. The process as described is the modification M. trichloride in a current of hot hydrochloric acid of arsenic tility If gas. 1414). because it is then possible for bromine vapors to get into the receiver by means of the air which is first expelled from the apparatus. consists of a large flask of * Z. Stock used hydrogen sulphide (Ber. Chem. A.{ the solution is diluted in the flask with about 200 c. as described under (a). by means of a longto the 500-c. Method of E. anal. in caustic potash Instead of using chlorine. It is not permissible to introduce the bromine into the flask. mony. the distillation must take place agent.c. distilling flask. except that more tartaric acid is necessary to prevent the precipitation of the tin than is the case when an- timony alone is present (d) 255). Fischer* This separation depends upon the ready volaPrinciple. (cf. Piloty and A. t Procedure.SEPARATION OF ARSENIC FROM ANTIMONY. 266. The fuming hydrochloric acid to a volume of from receiver. 33 and 1565 (1901). 34. 47 is used for this In the course of analysis. . in which has 1.. of bromine with sulphurous acid. and these are dissolved. O. cipitation as the trisulphide.. the latter method must be continued is until there used for the is no further The oxidized stemmed funnel. which is usually the case. in order to convert it to hydrogen bromide by introducing sulphur dioxide gas into the flask.. the arsenic is present as arsenic acid. 30.

Then. arsenic was volatilized com- . the contents of the two receivers are each diluted to a volume of about 1250 c. * If there is is any tendency to suck back. 48. 246 1. 800 c. of cold distilled water..c.* meanwhile constantly passing a little sulphur dioxide into the flask. t Rohmer found pletely by one that as distillation.15 gm. A is reduced to about 40 c. the volume of . 205 and weighed dioxide) the solution . The flame is then removed and the T-tube between the two evolution flasks removed in order to prevent liquid from backing up into the wash bottles.)Cl FIG. When the sulphur dioxide has all been expelled (as can be shown by inserting a stopper with delivery tube into the flask so that the escaping vapors can be led into a dilute sulphuric acid solution of decittormal permanganate which will be decolorized by sulphur allowed to cool and the arsenic determined as trisulphide according to the directions on p. for the determination of the arsenic. it is kept surrounded by a current of cold water coming from the condenser and contains at the start.c. with the apparatus all connected as shown in the drawing. and the excess of sulphurous acid is removed by heating to boiling and passing a stream of carbon dioxide through the liquid as is shown in Fig.5-2 liters capacity. until at the end of about forty-five minutes. The adapter tube which connects the condenser with the receiver is rinsed off and the receiver removed. much as 0.c.CH-N(Am. the distilling flask is heated and its contents partially distilled in a current of hydrogen chloride. a little more sulphur dioxide should be introduced. A new receiver is now placed at the end of the apparatus and liquid in a seccond distillation is made in order to make sure that all of the arsenic has been volatilized. t Then. 47.GRAVIMETRIC ANALYSIS.

or 247 it may be titrated with iodine. or it is estimated volumetrically by titration with iodine as described on p. and the iodine solution must be standardized in a solution as dilute as that in which the analysis is made. and the solution titrated with decinormal iodine solution as described on p. when all the SO 2 is expelled. Determination of Arsenic by Titration.* The antimony is determined by treating the contents of the distilling flask with 2 or 3 gms. 688. of tartaric acid. . 688. washing the FIG. expelling the sulphur dioxide as above.DETERMINATION OF ARSENIC BY TITRATION. 48. solution into an Erlenmeyer flask. as As2Sa after treatment with CS 2 (pp. 218. The and treated with a few drops of phenolphthalem potassium hydroxide is introduced until a permanent solution solid is pink color is imparted to the liquid. f The escaping gas will not decolorize a solution of 2-3 c. of sodium bicarbonate are added. f and determining the antimony gravimetrically by precipitating as the trisulphide according to the directions on p. dilute sulphuric acid and one drop of 0. Tho solution is then decolorized by the addition of a few drops of hydrochloric acid. * A blank determination should be made with all the reagents that are to be used.c. KMnO 4. 170. 5 gms.01X. 223).

21. of The analysis arsenic will be driven over in about fifteen minutes.. 248 Determination of Arsenic in Commercial Sulphuric Acid. 124. the acid is kept hot by means of a small flame until all of the arsenic has When been expelled.. p. XLI. however. Chem. Vortmann and Metzl. Chem. is finished as described above. News. of the acid to tilling flask About 30 c. anal. the contents of the distilling flask have been concentrated so that concentrated sulphuric acid remains. so that the tin must be in the stannic form. Z. whereupon 50 to 100 gms. Zeitschr. Henz. 18 (1903). are placed in the dis(Fig. were left open. 47). fiir anal..c. Cf.'W. also Rossing. Z. while stannic salts are not. A.* the funnel is rinsed with concentrated hydrochloric acid. forming an insoluble crystalline stannous oxalate. of concentrated hydrochloric acid and a little potassium bromide. * When the concentrated sulphuric acid runs into the flask. 1. 37. Stan- nous sulphide. Chem. anorg. (a) F. is decomposed by oxalic acid. F. A determined by difference) is introduced fastened by means of rubber tubing to through a funnel that the upper end of the delivery tube which enters the flask. t Chem. or hydrogen bromide. from mony is completely precipitated from a that fact the antimony upon Of solution containing oxalic acid.GRAVIMETRIC ANALYSIS. it often happens that distillation begins to take place and some of the arsenic would be lost if the flask. 44. and the be tested (the weight is is distillation begun. all the present known methods for the separation of antiIt depends tin this is probably the most accurate. On account of the high temperature. Separation of Antimony from Tin. . Vol. 1 gm. 525 (1905). Clarke' s^ Method.

At the end of fifteen minutes the solution is diluted with hot water to a volume of 250 c. After this a rapid stream of hydrogen sulphide is conducted into the boiling solution.e.c. 249 a question of sepa- rating antimony from tin after these metals have been separated from the members of the copper group by means of alkaline polysulphide. at 300 twice by decantation with 1 per cent. tion is cooled somewhat. in order to completely the solution is boiled vigorously for ten minutes. the soluperoxide. At the end of five or ten minutes the solution becomes orange-colored and the antimony begins and from this point the time is taken. filtered off with very dilute acetic acid before bringing it in the crucible. in excess is added and the solution is boiled for a few minutes to change any thiosulphate and to decompose the greater part of the excess As soon as the evolution of oxygen ceases. the beaker covered with a watch-glass.. This causes the evolution of considerable gas (CO 2 -f O 2 ).c. then 1 c. the tin and the antimony are in the form of their soluble sulpho-salts. hydrois gen peroxide added slowly until the yellow solution is com- pletely decolorized. and ten minutes later the current of hydrogen to precipitate.SEPARATION OF ANTIMONY FROM In the majority of cases Procedure. of the mixed metals). i. . pure recrystallized oxalic acid gms. it is TIN. Jena beaker and treated with a solution of 6 gms. The volume of the liquid should amount to from 80 to 100 c. has been heated in a stream of carbon dioxide The precipitate is washed C. containing not more than 0. remove the excess of hydrogen peroxide. of the purest caustic potash (one-third the sum of the weights of tartaric and oxalic acids to be added) and 3 gms.c. and for some time there will be no precipitation. Now. oxalic acid and twice sulphide is is stopped. To this mixture 30 per cent. at the end of another fifteen minutes the flame is removed. The solution of the sulpho-salts. of the two metals. of tartaric acid (ten times the maximum weight of the two metals). for at least one hour. but only a white turbidity formed. before weighing and after drying.c.. The precipitated antimony pentasulphide through a Gooch crucible which. for 0. to sulphate and a hot solution is cautiously added of (5 15 gms.3 gm. is placed in a 500-c.1 gm.

From ten to twelve times as much solid sodium hydroxide and a little sodium nitrate. whereby alloy.GRAVIMETRIC 250 Both of these wash liquids should be boiling hot with hydrogen sulphide. sodium peroxide. The residue is filtered off. The residue remaining * Z. after which the precipitate is gently ignited. the contents are fused and kept liquid for After cooling. the excess of oxalic acid nearly neutralized with ammonia and the tin deposited electrolytic ally as described on p. (6) Method of H. form of an monium nitrate water. or better. 231. 533 (1905).c. and 236). Rose. The crucible is heated at 280-300 and saturated in a current of carbon from air) to constant weight and its contents weighed as Sb 2 S 3 To determine the tin. leaving the insoluble part in the form of a fine meal. gr. the mixture is well stirred and filtered after standing twelve hours. 0. washed with am228. 44.. anal. pp. . transferred as completely as possible to a large silver crucible and the ash of the filter added. Procedure. One-third of the solution's volume of alcohol (sp. This method is based upon the insolubility of and the solubility of sodium stannate metantimonate sodium Principle. are added and the silver crucible is placed within a larger porcelain one in order to protect it from the flame: twenty minutes.833) is now added. the nitrate is evaporated to a volume of about 150 c. dried. in dilute alcohol. According to Vortmann and Metzl. concentration. 234. the crucible is placed in a large porcelain dish and its contents treated with hot water until the melt has disintegrated. Chem. the antimony and tin are left in the form of their oxides (cf.* antimony may be separated from tin by passing hydrogen sulphide into a solution containing hydrochloric and phosphoric acids of the proper dioxide (free .. Both metals are assumed to be present in the The alloy is treated with nitric acid.

It is. mixture consisting of equal volumes dilute hydrochloric acid (1:4) and 5-10 per cent. this solution the antimony is precipitated by hydrogen sulphide and determined as described on p. If considerable tin and little antimony were originally present. a single fusion of the oxides with caustic soda does not afford a complete separation. * A few drops alcoholic t A wash of sodium carbonate solution should be added to all the liquids. water.* until the filtrate when acidified with hydrochloric acid and tested with hydrogen sulphide no monate longer gives a yellow coloration (tin sulphide). f in which it is readily soluble. the alcoholic filtrate is gently heated to remove the alcohol. The second residue of sodium metantimonate is free from It is dissolved from off the filter by a mixture of hydrotin. separated from The filter is treated the filter and placed hi a silver crucible. From chloric and tartaric acids. 218. then with 1 vol. Ten grams of solid caustic soda are now added. oxides) this method gives very good results. however. alcohol +1 vol. and the melt treated in the same way as before. 233. the mixture fused. acidified slightly with hydrochloric acid. dried. and the tin precipitated as sulphide by hydrogen sulphide and determined according to p. and finally with water. vol. The contents of the porce- removed by heating lain crucible are solution subsequently dissolved in a and washed into the silver crucible. is washed first with a mixture of 1 vol. as the residue of sodium pyroantimonate always contains some tin. 251 LJ on the sides of the dish alcohol (1 is washed onto the filter with dilute The sodium metanti- alcohol + 2 vols.SEPARATION OF ANTIMONY FROM TIN. little caustic soda the water is then removed by heating the silver crucible at first on the waterbath and finally in an air-bath. tartaric acid is used. Remark. water. . alcohol + 1 vol. in a with crucible porcelain repeatedly fuming nitric acid until the paper is completely destroyed and the excess of acid is then in an air-bath. For the tin determination. alcohol + 2 vols. water). 3 vols. therefore. 3. If the oxide residue which was first fused with sodium hydroxide and nitre consisted solely of tin and antimony As a rule.

so that the sodium metanis subsequently rendered impure by the presence of these The antimony determination therefore gives too high reIn this case the method of W. antimony. or greenish yellow * Chem. As soon as all has dissolved. concentrated the After cooling. and treated as above described. 1900.c. lead and a little copper bismuth and zinc. alloy will usually dissolve in the cold after standing a while. 252 most antimony and tin alloys contain lead and other metals whose oxides remain to small extent with the tin and antimony on treatment of the alloy with nitric acid.. Analysis of Bearing Metal. 18. p. By this treatment sodium antimonate is formed. sodium peroxide is added to solution in small amounts until the liquid colorless. if much copper is . to which 3 c. Hampe * should be used. beaker and dissolved in 15 c. it will be necessary to heat for some time on the water-bath. the solu- when tion (it should be yellow. the precipitate is washed and dissolved in a little warm sodium sulphide. and usually small amounts of iron. of concentrated nitric acid are immediately added. however. timonate metals. this separates out to some extent.GRAVIMETRIC ANALYSIS. cipitate antimony is after which the 0.c.c.833) added. gr. The alloy is dissolved in aqua regia (as described below in the analysis of bearing metal) and the tin and antimony separated from the remaining metals by means of colorless sodium From the solution of the sulpho-salts the tin and antisulphide. The This alloy contains tin. (sp. One gram of borings are placed in a 400-c. becomes In order to completely prethe from the one-third as much alcohol solution. are mony precipitated by making barely acid with dilute sulphuric acid. sults. concentrated hydrochloric acid. precipitate is filtered off while the tin remains in solution. and when treated with more sodium peroxide a distinct evolution of oxygen takes place. rich in lead. Ztg.

1 gm. * This stirring is indispensable because lead chloride separates out very slowly from a supersaturated alcoholic solution containing other The complete precipitation is best recognized by the fact that chlorides. dried at 150 and weighed. It is now treated.ANALYSIS OF BEARING METAL. deep porcelain dish t evaporated off at as low a temperature as is It possible.f crucible. of tartaric acid and enough caustic potash make the solution barely alkaline. 0. iron and zinc. low in lead are not treated with alcohol in this way. present) is diluted with 15 times as small portions with constant stirring. the precipitated lead chloride is filtered into a weighed Gooch washed with absolute alcohol. In the nitrate The alcoholic nitrate poured into a large. When dryness and the alcohol the alcohol gone. I In evaporating off the alcohol there is a tendency for the solution to creep over the edges of the dish so that it is advisable to employ a deep dish and to evaporate the liquid in small portions. evaporated to a small volume and then there is all the solution is is is is added one gm. complete only when driving off all the tin the alcohol there is is in the quadrivalent always some stannous must be subsequently oxidized by means of KC1OS . with freshly prepared hydrogen to In sulphide water until no further precipitation takes place. necessary to avoid evaporating the solution to in as that case some SnCl 4 will be volatilized. Bi. In such decompose the alloy with chlorine gas. tin. Zn and the last of the Pb are precipitated as sulphides (precipitate a) while all the Sn and Sb remain in solution (solution &). added in After standing for twelve hours.* much 253 alcohol. as recommended by Finkener. Fe. t Alloys cases it is best to The separation condition. bismuth. this way all the Cu. of potassium chlorate is added. In is chloride formed which and HC1. copper. as described in the analysis of tetrahedrite on page 359. no mark is left upon the sides of the beaker when the stirring rod is rubbed against it. and stirring frequently. will be found a few milligrams of lead in the of presence antimony.

washed with hydrogen sulphide water. according to p. by acidifying with acetic acid. transferred to a 400-c. according to p. 183. and boiled Then 3 gms. excess of ammonia and determined as Bi 2 O3 according to p. evaporated with the addition of 4 or 5 drops of concentrated sulphuric acid. determined electrolytically. of tartaric acid to expel the hydrogen sulphide. or as cuprous sulphide. until the yellow color disappears. To determine the iron and zinc.c.2) and evaporated with hydrochloric acid to remove the nitric acid. and 6 gms. 174. 187. Treatment of Solution To determine the antimony and is diluted to exactly 250 c. H and zinc (Filtrate c). of purest potassium hydroxide are added. 1. beaker. . then 2 or 3 c.12) to 25 parts water. Then. gr. is withdrawn in a pipette. the alkaline solution measuring flask. dissolved in nitric acid of chlorides diluted so that its acidity corresponds to 1 part HC1 The Cu. and Bi are (sp.GRAVIMETRIC ANALYSIS. the Filtrate c is oxidized by boiling with a few drops of concentrated HNOa and the iron precipitated p. precipitating as sulphide and weighing as such. precipitated as sulphides by hydrogen sulphide. after acidifying with sulphuric acid. gr. hydrogen peroxide is allowed to run slowly into the solution. 87.c. 143. The precipitate is dissolved iron in nitric acid. b. 100 c. acidified with acetic acid. 1. and after thoroughly mixing. Pb. 254 Treatment of Precipitate The a. in excess are added and the solution boiled a few minutes.c.c. filtrate from the bismuth precipitation. and the last of the lead determined as sulphate according to FromTthis filtrate the bismuth is precipitated with an p. In the ammoniacal the copper is according to p. whereby any precipitated sulphide is redissolved. 179. in a tin. and the solution precipitate is filtered off. At this point some 30 per cent. (sp. filtered and washed with water containing The filtrate contains the 2 S. The by an excess zinc is of ammonia and weighed determined in this last filtrate as Fe2Os.

233. p. p. 255 gm.^ The moist sulphides are dissolved in freshly-prepared ammonium sulphide. of pure oxalic acid are added. So that no arsenic trichloride will be lost by volatilization. 18. (1894). In the nitrate from the arsenic pentasulphide all of the tin is found and can be precipitated as sul- phide after diluting largely with water and passing hi hydrogen sulphide. (a) Method of Fred. is acid solution is the earlier editions of this book.SEPARATION OF ARSENIC FROM TIN. is not altogether satisfactory. /?. on account of the lead sulphide precipitate being contaminated with tin. 248. t Ibid. 136. From the nitrate for each 0. of metal present (Sb-j-Sn). Chem. 1900. (6) Method of W. Rossing's method. Remark. The precipitated sulphides are dissolved ammonium taric acid and ammonia are then added and the arsenic tated with magnesia mixture as * Z. freshly-prepared almost to dryness and oxidized with hydrochloric acid and potassium Tarchlorate in a flask connected with a return-flow condenser. From this solution the arsenic is precipitated as sulphide under the conditions described on p. Usually the lead results are too high and the tin too low. At the end The electrodes are of six hours the deposition is complete. Separation of Arsenic from Tin.1 For this purpose the evaporated to a volume of about 200 c. 45. 1 magnesium ammonium precipiarsenate. Hampe. (1893). washed as described on p.c.. J Chem. dried and weighed. the solution boiled ten minutes and the antimony separated from the tin as described on p. It is finally changed to the oxide as described on p. anal. 41.* which was recommended in the tin oxalic determined electrolytically. J as soon as possible in solution the is evaporated sulphide. Neher. . as (1902). 5 gins. evaporated in an Erlenmeyer flask nearly to dryness and oxidized with hydrochloric acid and potassium chlorate. 243. 32. Ztg. and electrolyzed with a gauze electrode.

ammonia. however. is filtered off. the precipitate is dissolved in hydroAfter chloric acid and reprecipitated by the addition of ammonia. they are precipitated as sulphides with hydrogen sulphide. If the metals are present in solution. and. After standing twelve hours. one-third as much alcohol (sp. (a) Method of Rose. 67. Separation of Antimony from Arsenic and Tin. so that Hampe to prefers to dissolve the precipitate in hydrochloric acid once more. It is then fused * and kept liquid for about of the dish are transferred to a silver crucible. is off filtered and twelve the another hours. The almost-dry residue is treated with concentrated sodium hydroxide solution and the contents which a little sodium hydroxide is added and the contents of the crucible dried in an air-bath. heated with fuming nitric acid in a large covered beaker until the sulphur is completely oxidized. the precipitate cent. precipitate standing 2 ammonia.6734 -p gm. 0. 66 or p. the melt is disintegrated with water. From the weight of the latter the amount of arsenic can be computed as follows: x= 2As or x =0. a larger porcelain one so as to avoid . 256 described on p. arsenic. gr. transformation is somewhat tiresome. and the excess of acid removed by evaporation on the water -bath.GRAVIMETRIC ANALYSIS. and after standing twelve hours the * The silver crucible is placed in contact with the flame. with cent. After cooling. to precipitate the arsenic by means of hydrogen sulphide. 206.833) is added in order to completely precipitate the sodium metantimonate. and then to determine the magnesium in the evaporated filtrate as magnesium pyrophosphate according to p. washed per again This precipitate can be converted into magnesium pyroarThis senate and weighed in this form as described on p. 207. washed into a porcelain dish. after solid twenty minutes by heating over a Teclu burner. in order washed with 2J per remove a little magnesia.

cases gold is deposited as metallic gold from after filtering and washing. IS 257 precipitate is filtered and subjected to the treatment described on The nitrate containing all the arsenic and tin is acidified p. These are separated after sulphide. oxidized with hydrochloric acid and potassium chlorate. 248) or that of Rose In the combined (p. GOLD. and from the magnesium ammonium and tin are precipitated by hydrogen arsenate the antimony the solution acid. filtrates 250). 197. Gold is At. If some is present. 255. there must be no free to be considered: nitric acid present in the solution. oxalic acid. SUPPLEMENT TO THE HYDROGEN SULPHIDE GROUP. and the arsenic separated from the (b) tin as described Method of on p. If the gold is to be precipitated by means of either ferrous sulphate or oxalic add. GOLD. it must be removed by repeated evaporation with concentrated hydrochloric acid and the solution then diluted with water. MOLYBDENUM. Without filtering. PLATINUM. VANADIUM. The gold is present in solution. formaldehyde. i. 3. Hampe. and weighed For the deposition of gold the following reducing agents are ferrous sulphate. 2. 255. Wt. TUNGSTEN. with hydrochloric acid. In almost its solutions all Gold is silver. whereby stannic arsenate is precipitated. SELENIUM. Au. Present in Solution. The gold is alloyed with copper and The gold is present in an ore. 251. the precipitated sulphides of tin and arsenic are filtered off.GOLD PRESENT IN SOLUTION. hydrogen sulphide is conducted into the liquid. and hydrogen peroxide. The moist sulphides &.2. making either according to the method of Clarke (p. To this . are oxidized as described on p. the arsenic determined in the same way. We have three cases to distinguish: 1. always determined as the metal itself. TELLURIUM.

or. p. even in the cold. however. The reaction takes place according to the following equation: 2 AuCl 3 + 3H 2 O 2 + 6KOH If the gold tions it passes it dilute soludeposited by obtained in such a finely-divided condition that it through the filter. the gold can Gold can be separated from platinum by acidified filtered. and weighed. Seemari)* If a gold solution is treated with potassium or sodium hydroxide solution and then with formaldehyde. The predried. the finely-divided gold collects together and assumes a reddish-brown color. and the gold is is cipitate lain first crucible. with hydrochloric acid and then with water. By boiling. In this way gold can be separated from If silver metals. 1968. Vanino and L. it is first removed by the addition of hydrochloric acid. and the covered added with a allowed to stand forty-eight hours in a warm place. with hydrochloric acid. hydrogen peroxide. which is of course never the case in a dilute hydrochloric acid solution. transferred as completely as possible to a porcethe ash of the filter added. * Berichte (1899). better still.GRAVIMETRIC ANA'LYSIS. oxalic acid or ammolittle sulphuric acid. method from very is until the excess of and 6KC1 + 6H 2 O + 3O 2 + Au 2 this is then hydrogen peroxide is completely destroyed. For the precipitation of gold by means of oxalic acid. iron is with water containing hydrochloric acid until the completely removed. the gold is soon precipitated quantitatively. is present. method. 32. It is then ignited and weighed. several hours on the water-bath. . scales of the deposited gold are filtered off and is The yellow washed. the ignited almost all slightly acid solution nium oxalate beaker is is diluted with water. and then with pure water. the precipitated silver chloride filtered off. the solution is boiled is be readily this . as above described. Deposition of Gold by Means of Hydrogen Peroxide (L. and the filtrate treated as above described. If. 258 dilute solution n large excess of clear ferrous sulphate solution is and the beaker covered its contents are heated for added. even platinum. The precipitate is then filtered is washed off. but not from silver.

When gold is present in alloys it is most rapidly and most The principle of the accurately determined in the dry way.COLD ALLOYED WITH COPPER AND 2. method is very simple. If less than three parts of silver are originally present for one part of gold. in the separation of gold from silver by means of nitric acid it is necessary to remember that the separation is only quantitative when the alloy consists of three or more parts of every gold cupellation one part of gold. 681. . unless the acid is made extremely dilute. while all the gold and silver are left behind in the form of If " a metallic button. The Gold is SILVER. Furthermore. the latter metal remains behind as a brownish scale. whose weight is obtained. 57. Consequently. magnesite better than bone-ash. if more silver is present. silver to The separation of the silver from. In order to obtain accurate results a number of precautions must be taken.. This second loss amounts to much less than the former one occasioned by the use of too much lead. a gold-silver alloy is melted in the air with lead upon a cupel" (a very porous vessel made of bone-ash)* the lead and copper are oxidized. Berg-Huttenw. small amounts of the noble metal are absorbed by metal is the cupel and this amount is greater the smaller the amount of lead used. it is left * is as a fine powder. According to R. as quartation or inquartation. Gruncl. of silver to one of gold. Furthermore. 259 Alloyed with Copper and Silver. in an unnecessary excess of lead must be avoided. the gold by means of nitric acid is spoken of as parting. Oesterr. By the cupellation of the alloy some noble always lost and the amount lost increases in proportion to the amount of lead used and the higher the temperature. the oxides fuse and are absorbed by the cupel. which consists of three parts. If the weight of the gold that is left undissolved is deducted from the weight of the gold-silver button the weight of the silver is obtained. If a gold-silver alloy. is treated with nitric acid. Z. that the richer a gold-silver alloy is has shown Experience in base metal the more lead is necessary for the cupellation. in the form of foil. it is necessary to add pure This operation is known silver until this proportion is reached. The silver is afterwards separated from the gold by the action of nitric acid which dissolves the silver but leaves the gold behind.

49. . 49 is heated to a cherry-red heat. and the cupel heated it has acquired the same color as the muffle. of lead are placed upon the cupel. 50. This is determined by The Preliminary Assay. so that the weight of litharge absorbed by the cupel is practically that of the original lead button. FIG. it is necessary to know the approxi- FIG. Fig. and when the gold and silver are present in the proper proportion.e.* is placed in the back part of it. the muffle is closed until until * A good cupel will absorb its own weight of litharge. 50 represents a cupel. After this 5 gms. mate composition of the alloy before an accurate determination can be made. a cupel weighing from 6 to 7 gms.. together with its cross-section. For this purpose the muffle shown in Fig. it is clear that accurate results can be obtained only when the correct amount of lead is present in the alloy that is cupelled.GRAVIMETRIC ANALYSIS. During the cupel- lation about one-tenth of the litharge formed is lost by volatilization. the muffle door is closed. 260 From what has been said. i.

. With the help of an iron hook the cupel is now carefully advanced to about the middle of the muffle and the door should be left open a ready access of air into the muffle. 1000 thousandths 900 Amount 1 of Lead Necessary for the Cupellation of 0. the color of the button is obso that there is served. placed in the is molten lead (with the help of a pair of tongs). After the approximate amount of gold present has been ascer" diately 1 tained . it contains less than three parts of silver to one part of gold.the is button is pure white. Amount of Gold Present in the Alloy. After about twenty minutes the lead will be all absorbed." * The hot cupel is then removed from the muffle and after cooling.f the analysis proper is made. silver are present to " parted and the residual gold weighed. which is shown by the "blick. of lead. the lead is alloy 261 melted and then 0. then three or more parts of In this case it is immeone part of gold. (a) // the button is greenish yellow or darker.THE PRELIMINARY ASSAY. of the accurately-weighed enveloped in a small piece of lead-foil. treated with nitric acid and the residual gold weighed. using the indicated in the following table: amount of lead as LEAD TABLE. 0.25 gm.25 gm. (b) If . in which case from four to six parts of "fine silver" are added (the proper amount can be usually told by the practised eye) and the button is cupelled The button now obtained in a new cupel with 1 gm. and the muffle closed until the alloy has melted and shows a bright upper surface. of Alloy.25 gm.

the alloy was white. the alloy was greenish yellow. Treatment of the Quartered Gold-Silver Button. the one to serve for the silver determination and the other for the gold. are taken. This it is again heated and placed in a little roll is pared with that obtained from alloys containing known amounts of gold. Afterwards these streaks are tested with dilute aqua regia. determination of the gold and silver. 262 '] \ The Final Assay. was very white. p. by placing it upon a piece of brass foil and rolling it between two steel rollers to a long strip (Fig.GRAVIMETRIC ANALYSIS. and on the subsequent treatment with nitric acid. and silver is it contains 550-750 thou- present to a considerable extent. little pieces would probably drop off. the alloy was a beautiful yellow or reddish yellow. 51. 51. * Cf. c. and this mixture is cupelled with the same amount of lead as the first portion. rolled f up as shown in Fig. 259. therefore.25 gm. it regains its original softness. once again as much pure silver is weighed out as the amount of gold found to be present by the preliminary assay (inquartated with one part of silver). if it was distinctly yellow or reddish yellow it is inquartated with 2J parts of silver. it contains more than fine of silver. t By hammering the gold-silver alloy. more than 700 thousandths of noble metal and the contains gold predominates. The For the former is definite cupelled with the correct button of the gold-silver If the original 500 thousandths If alloy is amount of lead and the weight determined. it . If the original alloy was greenish yellow. it however. thick This is heated upon a fresh cupel and quickly cooled (Fig. 6). two portions weighing exactly 0. If. 51. The gold-silver button is removed from the cupel with xhe "button tongs." cleaned with a stiff brush ("button brush"). sandths of noble metal. By again heating the metal and then quickly cooling. alloys containing the same amounts of gold are attacked equally readily. and hammered upon an anvil to a round disk about 1 mm. the metal becomes so brittle that cannot be converted to a smooth-margined roll. it is inquartated * with two parts of silver. If. a).

Determination of Gold in Ores. 1. beautiful yellow substance. a No. the button is washed by decanting three times with distilled water. The very finely ground and sifted ore is mixed in Principle.188) free ten minutes.DETERMINATION OF GOLD IN ORES. 1. and kept so for to boiling then poured off and replaced by the FIG. By subtracting of the gold and silver together. when the gold will pass into the cup. it is into a harder. 52. 7). little flask (Fig. from the gold and the crucible is placed poured back part of the muffle for a short time. from covered with 30-40 chloride. After this acid is poured off. the the of weight gold from the weight weighed. and some suitable slag-forming material. charcoal. off at right angles and skilfully turning the flask right side up. same amount of stronger acid (sp. gr. gr. 51. covered with an annealing cup (or lackan ordinary porcelain crucible may be used). heated The acid is c. whereby the gold dried and is changed from its former brown and soft condition The water is off in the is After cooling. The flask is filled ing this with water.c. the amount of silver is obtained. The charcoal reduces a part of the lead oxide to metal which alloys with the noble metal and sinks to the bottom in the form of a button. The flask is removed by first raising its mouth to the level of the water in the crucible and then sliding it then quickly inverted (Fig.295) and the above treatment repeated. 51. while the foreign sub- . and is //). 9 French crucible with lead oxide. 263 of nitric acid (sp.

Ricketts and Miller. of ore. * This amount is usually sufficient. with very rich gold ores 10-15 gms. etc. the most important reagent. the crucible is is the hammered the lead button cupelled and broken. it is necessary that the purity of the reagents used should be tested. usually act oxidizing: which case more charcoal must be added to the charge. Reddish-brown ores (Fe2 O 3) bluish-black. is .GRAVIMETRIC ANALYSIS. off.* In order that such a button may be obtained. The best results are obtained when the lead button weighs about 18 gms. 2 In such cases less charcoal (or in some cases none at all) should be added than would be otherwise necessary to produce the right amount of lead. . it is usually necessary to make a preliminary assay of the ore.). Litharge. an unnecessarily large amount of lead some gold is lost during the cupellation. may be used to advantage. for a gold assay are: Litharge (PbO). while with very poor ores as much as 120 gms. for it forms with the silicic acid of the ore a readily fusible silicate. or in case considerable sulphide sometimes necessary to neutralize its action is present. Notes on Assaying.264 stances should pass into the slag. in Testing the Reagents. New York. Cf. Sulphide ores act strongly reducing. After cooling. The ordinary reagents necessary i. Reducing ores are recognized by their color: they are gray. for with as is shown by the following equations: PbS+2PbO = S FeS2 + 5PbO = 2SO + FeO + 5Pb. 1897. when obtained from 30 gms. The amount of lead reduced from the litharge depends largely upon the nature of the ore. slag the silver-gold button parted in the same way as before. by the it is addition of oxidizing agents. The noble metal should be extracted with as little lead as possible. enough. But above all. or yellow (pyrite. is a basic flux.

" 15 1 gm. Sodium Bicarbonate (NaHCO. following experiment: Litharge Sodium bicarbonate (NaHCOJ KHC H O Argols (crude 120 gms. dry common salt. the crucible is removed from the the tongs. as is shown used must be dry and free from minium. its lightly tapped upon its down any small particles of lead adhermake all of the free metal collect together gently tapped by in order to knock bottom it resulting silver button is obtained must be deducted whenever the corresponding amount of litharge 2. and ing to the sides on the bottom and to form in the is broken. The reducing power is Litharge Sodium bicarbonate Charcoal Charcoal. As soon as the contents of the crucible have reached the state of quiet fusion. silver walls are is of a button. The covered crucible is are placed in a glowing coke-oven. 3. . however. 60 " 2 " 4 4 6) mixed thoroughly upon a sheet of glazed paper and the mixture placed in a No.).). Anhydrous Borax (Na^O. the above reaction. determined once for this is known. After cooling the crucible the lead button by hammering upon fire.REAGENTS FOR GOLD-SILVER ASSAY. so that low The results would be obtained in the silver determination. litharge should be free or all its silver by the from silver contents must be (which is almost never the case). determined as follows: 60 gms. same time. by at the The litharge it is 265 a desulphurizing agent. the slag removed from it upon an and it is cupelled more than the button weighed. The amount of anvil. is used in an assay. 9 French crucible and covered with a layer of finely-powdered. 4. for the latter oxidizes silver. a cupel weighing only a few grams The itself. carrying it into the slag. 2 and 3 require no testing.

After cooling. 1 gm. of lead were obtained in this exshows the amount of lead that periment. the . Ordinary table salt is heated in a large Hessian crucible until and the contents of the crucible are poured into a shallow iron mould with a raised edge. The solidified crust is finely powdered and preserved in a stoppered flask. 6. lead. lead. nitre. Nitre serves as an oxidizing agent. are mixed and fused as before and the weight of the lead button determined. Preliminary Assay. " . After the reagents have all been tested the next step is the it melts. 1 Sodium bicarbonate gm. or the oxidizing power of the nitre. of ore. terms of lead is determined: (KNO3) Its oxidizing Nitre Litharge Charcoal power expressed in 3 gms. 9 with a cover of ordinary common salt and fused. and if p gm. Since in an ordinary assay we start with 30 gms. charcoal would P gm. 266 are mixed. Common Salt. 5. Five grams of the finely-powdered and sifted ore are weighed out and mixed with: 80 gms. the weight of the lead button obtained is determined and this expresses in terms of lead the reducing power of the charcoal. 60 . then the difference reduce Pp was oxidized by 3 gms. the lead button obtained is weighed. nitre oxidizes about 4 gms. in a French crucible No. of charcoal should reduce about 30 gms. 20 " Litharge Sodium bicarbonate Borax 5 " placed in a crucible and covered with a layer of common salt. If under (4) it was found that 1 gm. and hammering off the slag.GRAVIMETRIC ANALYSIS. 1 gm. 15 gms. After fusing. lead. cooling. as in the testing of litharge.

GOLD-SILVER ASSAY.

267

weight of the lead button now obtained multiplied by 6 will give
the weight of the button from the real assay. We will distinguish
four cases

:

The lead button weighs 3 gms.

(1)

Consequently the button obtained from 30 gms. of ore would
weigh 18 gms. In this case the ore is assayed with the following
proportions of flux:

Ore

30 gms.

Litharge
Sodium bicarbonate

80

"

"

20

Borax

"

5

The lead button weighs

(2)

less

than 3 gms.

Evidently the ore acts reducingly, but not enough so to yield a
button weighing 18 gms. when 30 gms. of ore are used; it is,
therefore, necessary to add charcoal to the flux.
Example. Let us assume that the lead button obtained by the
preliminary assay weighed 1 gm., then the button obtained from
30 gms. of ore would weigh 6 gms. In order to obtain a button

necessary to add enough charcoal to supply
gm. of charcoal was found to reduce 30 gms.

weighing 18 gms.

it is

12 gms. of lead.

If 1

of

lead,

then

it is

necessary to add

12-r-SO gms.

= 0.4

gms. of

charcoal.
(3)

The lead button weighs more than 3 gms.

In this case the ore has a strong reducing power, and to obtain
the lead button of the right weight it is necessary to add some nitre.
Example. Suppose the button to weigh 6 gms.; this would

mean a 36-gm. button when 30 gms. of
too much lead would be produced.

ore were used;

We

i.e.

must add,

18 gms.

therefore,

enough nitre to oxidize this 18 gms. of lead. If the oxidizing power
gm. of nitre was found to be 4 gms. of lead, then 18 -=-4 = 4.5
gms. of nitre must be added to the flux.
Remark. Ores which have a very strong reducing power would
frequently require the addition of enough nitre to cause the contents of the crucible to boil over. In such a case, about 40-50 gms.
"
"
are placed in a roasting-dish and roasted in a muffle, and from
this roasted ore the portions are taken for the preliminary and
of 1

GRAVIMETRIC ANALYSIS.

268
final assays.

The

results,

however, must be expressed in terms of

the unroasted ore.
There

(4)

The

is

no lead button formed.

The
either neutral or possesses an oxidizing action.
1
from
results
of
and
the
charcoal,
repeated, using
gm.

ore

is

assay is
obtained the final assay

now

is

based.

Final Assay.
*
For the
assay from 30-120 gms. of ore are taken (accordof
and
the
the
amount
to
gold present)
corresponding amount
ing
of sodium bicarbonate is added. The amount of litharge also varies
with the amount of ore, and in some cases as much as 240 gms. are
final

necessary, although as a rule 80 gms. are sufficient. Otherwise the
procedure is exactly the same as in the preliminary assay. The lead
button is cupelled and the weighed silver-gold button is parted as

described on p. 263.

PLATINUM, Pt. At. Wt.

195.0.

Platinum is best determined as metallic platinum.
The following three cases will be considered
:

The platinum

acid solution
present
other
but
with
other
or
alone
either
metals,
platinum
together
metals are absent.
1.

in a hydrochloric

is

The platinum is present alloyed with gold and silver.
The platinum is alloyed with small amounts of the
num metals together with small amounts of base metals.
2.

3.

I.

plati-

The Platinum

is Present in Hydrochloric Acid Solution Either
Alone or Together with Other Metals.

The platinum is either precipitated from the solution as ammonium chloroplatinate, (NH 4) 2 PtCl 6 which is decomposed by ignition
,

and the residual platinum weighed; or the platinum is precipitated as metal by the addition of reducing agents to the solution

;

or finally the platinum

precipitated as sulphide by conducting
hydrogen sulphide into the hot solution and changed to platinum
by ignition. The two former methods serve to separate platinum
*

"

"

is

Usually assay tons are used as units in weighing out the ore, and
the weights are calibrated in terms of this unit instead of the gram. An
"assay ton" contains the same number of milligrams that there are ounces
troy to a ton, so that by weighing the button obtained in milligrams, it is
at once known how many ounces per ton the ore carries.

PLATINUM.

269

from most other metals, while the latter serves to separate plationly from the metals of the alkali, alkaline earth, and ammo-

num

nium sulphide groups, and not from members

of the

hydrogen

sul-

phide group.
(a) Precipitation of

The
tralized

Platinum as

Ammonium

Chloroplatinaie.

much as possible, is nearly neuwith ammonia, an excess of ammonium chloride and considsolution, concentrated as

erable alcohol are added, and the mixture allowed to stand twelve
hours under a glass bell-jar. It is then filtered through an asbestos

tube 10-15 cm. long, washed with 80 per cent, alcohol until
a few drops of the filtrate leave no residue on being evaporated
to dryness on a platinum foil.
The precipitate is dried by conducting a stream of air warmed to about 90 C. through the tube.
After cooling the tube is weighed, a plug of ignited asbestos * is
introduced, and the tube is again weighed; in this way the weight
filter

A stream of dry hydrogen is now
conducted through the tube, and the latter is heated at as low a
temperature as possible until no more hydrochloric acid is evolved
and all the ammonium chloride has been driven off, after which the
tube is cooled in a desiccator and weighed.
of the asbestos plug is found.

Instead of filtering

precipitate upon asbestos an unused.
The moist precipitate is
weighed paper-filter may
with
the
in
a
filter
placed together
large porcelain crucible

the

be

apex of the filter-paper points upward, and the
is then ignited.
This ignition must be performed
with great care, as otherwise there can be a considerable loss durso that

the

covered crucible

ing the process. At first the precipitate is dried by gently wanning the covered crucible, and when the odor of alcohol has disappeared, the temperature is raised very slowly until the crucible is at

a strong red heat.

During the whole operation there must be no
vapors from the crucible. The decomposition is
is no longer a penetrating odor
when
there
complete
arising from

visible escape of

When this point is reached, the cover (whose
under side will be covered with carbon) is removed for the first
time and leaned against the crucible and the contents of the latter
the covered crucible.

*

vent

Ammonium
loss of

chloroplatinate decrepitates during the heating.
it is heated between two asbestos plugs.

substance

To

pre-

GRAVIMETRIC ANALYSIS.

270

are ignited with free access of air until the carbon from the filterpaper is completely burned. Often a slight deposit of platinum*
will be found in the upper part of the crucible and upon the cover,
so that the latter

must always be weighed with the

crucible.

seems likely that the precipitate of ammonium
chloroplatinate is contaminated with other substances (e.g. sodium chloride, etc.) the precipitate can be dissolved in water after
It has been washed with alcohol and dried.
The platinum may
then be determined, as described on p. 50, by precipitating with

Remark.

If it

mercury, washing with dilute hydrochloric acid and then with
water, and finally weighing.

The results obtained by this method are satisfactory but somewhat lower than the true values; the following process is more
accurate:
(6)

The

Precipitation of Platinum by Reducing Agents.

solution

placed in

is

freed from

an Erlenmeyer

flask

any excess

of acid

by evaporation,

into the neck of which

is

ground

The solution is neutralized with amof
an
excess
formic
acid
and a little ammonium acetate are
monia,
and
the
contents
of
the
flask
after being diluted to a volume
added,
to

fit

a return-flow condenser.

of 200 c.c. are heated to about 80 C. on the water-bath until the
evolution of carbon dioxide has nearly ceased. The flask is now
connected with the return-flow condenser, and its contents boiled for
twenty-four hours. The precipitated metal is filtered off, washed

with dilute hydrochloric acid, then with water, dried, ignited, and
weighed.
2.

The Platinum

is

Alloyed with Gold and Silver.

An alloy is seldom found which contains only the above three
noble metals ; usually copper is also present. The first step, then,
is to separate the noble metals from the others by cupellation with
*
By means of the dry distillation of the filter, carbon monoxide is formed,
and by the decomposition of the ammonium chloroplatinate chlorine is set
These two gases act upon the metallic platinum and form volatile comfree.
pounds (RCl r CO, PtCl r 2CO, and 2PtCl2 .3CO), which, however, are later

decomposed by the aqueous vapor. This causes the deposit of platinum in
the upper part of the crucible. In order to avoid loss, a large crucible should
be used.

PLATINUM.

271

on p. 259, after which the hammered and rolled
treated with pure concentrated sulphuric acid. [Nitric
acid cannot be used, for some platinum would be dissolved with
lead as described

button

is

After boiling for ten minutes, the silver will be completely dissolved, provided at least two parts of silver are present
If more
for each part of platinum, which is usually the case.

the

silver.]

platinum is probably present than corresponds to the above ratio,
pure silver should be added, and the mixture cupelled once more
with 1 gm. of lead.
After the alloy has been boiled for ten minutes with sulphuric
it is allowed to cool, filtered, and the treatment with sulphuric
acid repeated once again. The metal remaining behind (in the
form of a roll or as a powder) is washed three times by decantation

acid

with water, ignited, and weighed as described under gold. This
gives the weight of the gold and the platinum together, and by subtracting this amount from the original weight of the noble metals
obtained after cupellation, the weight of the silver is obtained.

Separation of Gold from Platinum.

an alloy of gold and platinum is treated with
metal is attacked. If, however, the alloy contains three parts of silver to one of gold and platinum taken together, and the alloy is treated at first with acid of sp.gr. 1.16 and
then with acid of sp. gr. 1.28, the platinum gradually goes into
solution with the silver.
Procedure. The gold-platinum alloy is cupelled with three times
its weight of pure silver and 1 gm. of lead, the resulting button is
hammered and rolled, after which it is treated with nitric acid (of
the strength stated above), and the residual metal weighed. It is
again cupelled with three parts of pure silver, and the same procPrinciple.

If

nitric acid, neither

This is continued until a constant weight is finally
ess repeated.
obtained for the residual gold ; the third operation usually accomplishes this.
Instead of effecting the separation of the gold from the platinum
in this way, the two metals may be dissolved in aqua regia, and

the gold precipitated by means of ferrous sulphate, as described on
This is a good method.
p. 257.

GRAVIMETRIC ANALYSIS.

272

According to Vanino, and Seemann,* the separation is effected
quickly by precipitating the gold from an alkaline
solution by means of hydrogen peroxide.
In order to determine
the platinum, it is precipitated from the boiling acid nitrate by

much more

hydrogen sulphide and weighed as metal after ignition in a porcelain crucible.

Analysis of Commercial Platinum, according to Deville and Stas.
Five grams of the platinum alloy f are heated for five hours
at a temperature of

about 1000 G. with ten times as much lead

in a crucible of purified gas-carbon;

this crucible

is

embedded

in

one of clay which is filled with charcoal. After cooling, the lead
button is treated with very dilute nitric acid until there is no
longer any gas evolved.
In this way a solution, A, is obtained, containing about 98.4
per cent, of the lead used, all the palladium and copper, and small

amounts of platinum, rhodium, and iron, and a residue, B, consisting of a black metallic powder, which is filtered off, and will contain
the remainder of the platinum and rhodium with all of the iridium
and ruthenium.
1.

The

Treatment of the Nitric Acid Solution A.

by the addition of slightly more than the
and filtered. If the lead sulphate is pure white, it is washed with dilute sulphuric acid. If it
is not absolutely white, it is washed with a solution of ammonium
carbonate until it becomes so small amounts of lead are dissolved
by this operation. This last wash liquid, therefore, is concentrated, to precipitate the lead carbonate, filtered, and after making
acid with hydrochloric acid, added to the main filtrate.
The solution is evaporated to about 100 c.c., and when cold is
poured into a saturated solution of ammonium chloride. The
mixture is heated to boiling and allowed to cool again. The ammonium chloroplatinate is filtered off and washed with a saturated
lead

theoretical

is

precipitated

amount

of sulphuric acid,

;

solution of

ammonium

the platinum

is

chloride; in this way, the greater part of
obtained.

* Berichte 1899,
p. 1971.
f All commercial platinum contains other platinum metals, especially
iridium.

PLATINUM.

The

273

from the platinum precipitate is boiled with formic
acetate as described on p. 270, b.
In this case
the remainder of the platinum, the palladium, and the rhodium will
be precipitated. These metals are filtered off, and the copper and
iron are determined in the nitrate in the usual way.
The formic
filtrate

acid and

ammonium

acid precipitate (consisting of a black metallic powder)

is

dried and

fused with potassium bisulphate in a porcelain crucible. The melt
is treated with water, the solution decanted from the unattacked

ammonium carbonate and
of
remove
traces
lead
(to
sulphate), then with dilute
and
with
acid,
finally
water; it is then dried and
hydrofluoric
filtrate
from
The
the
platinum contains palladium and
weighed.
rhodium. The former is precipitated by the addition of mercuric
cyanide, and boiling until the odor of hydrocyanic acid has disappeared. The voluminous, yellowish- white precipitate of palladouo
cyanide is washed first by decantation, then upon the filter, dried, and
ignited at first cautiously and then strongly over the blast until the
platinum and washed alternately with

nitric acid

paracyanide

is

completely destroyed; finally heating in a current

hydrogen (as in the case of copper sulphide, p. 183) in order to
reduce any palladium that has been oxidized by the previous treatment. As soon as the flame is removed, the supply of hydrogen is
at once cut off in order to prevent its being absorbed by the metal.
of

The palladium is weighed after cooling.
The rhodium is precipitated from the filtrate by means of formic
acid, as before, and the deposited metal is dried, ignited in a stream
of hydrogen, allowed to cool in the gas,
2.

and then weighed.

Treatment of the Residue B.

The washed residue is warmed with dilute aqua regia (in this
case 2 vol. nitric acid, 8 vol. hydrochloric acid, and 90 vol. water),
and in this way solution C is obtained, which contains the rest of
the lead, platinum, and rhodium, and residue D, consisting of
lamella? of iridium and ruthenium.
3.

Treatment of the Solution C.

After evaporating to a small volume, the lead is removed by sulphuric acid, the solution again evaporated, taken up in hydrochloric acid, and the platinum present is precipitated by pouring

GRAVIMETRIC ANALYSIS.

274

into a cold saturated solution of

described under
little

ammonium

rhodium, and after washing

ammonium

chloride exactly as
precipitate contains a
with a saturated solution of

The platinum

272.

1, p.

it

placed at one side for the time being.
The nitrate, together with the wash water, is evaporated until
more platinum and rhodium separate out on cooling, and this prechloride, it

and washed as

is filtered off

cipitate

is

before.

together with the precipitates, are now placed in a
small, weighed porcelain dish, dried, and reduced at as low a temperature as possible, in a stream of illuminating gas, and heated

Both

filters,

somewhat in a muffle so as to remove the carbon from the filter.
The metal thus obtained (platinum + rhodium) is weighed. For the
separation of the rhodium from the platinum, the spongy metal is
heated in the same dish with potassium bisulpnate, gradually raising the temperature until a dull-red heat is obtained. After coolmelt is extracted with water, the unattacked platinum (it
may still contain small amounts of rhodium) is filtered off, washed,

ing, the

and again fused with potassium bisulphate. This operation is
repeated until the rhodium is completely extracted, which is known
by the melt showing no yellow color after ten minutes.

The platinum
under

is

washed, ignited, and weighed as described

1.

The Combined

filtrates

from the platinum contain rhodium and

platinum. Ammonia, acetic and formic acids, therefore, are added once more, and the solution boiled for a long time.
The precipitated metal is filtered off, ignited, weighed, afterward
still

a

little

fused at a distinct red heat with potassium bisulphate, and the
If a residue remains after this
cold melt extracted with water.

treatment,
regia.

The

it is filtered off,

If it dissolves, it is
filtrate

weighed, and treated with dilute aqua
if it does not, it is rhodium.
;

platinum

from the ammonium chloroplatinate, which conis diluted, formic acid and ammonium aceis gently boiled for two or three days in an

tained some rhodium,
tate are added, and it

Erlenmeyer

flask

connected with a return-flow condenser.

.The

in spite of the condenser, and the evapfrom
time to time with a dilute solution of
is
orated part
replaced
In
this
formate.
ammonium
way small amounts of platinum and

liquid evaporates

somewhat

rhodium are precipitated, which are

filtered off

and separated by

PLATINUM.

275

fusion with potassium bisulphate as before. In the filtrate there
are likely to be present traces of platinum, rhodium, and iron.

The iron is first removed by the addition of chlorine water and
afterward ammonia; the ferric hydroxide is filtered off, ignited, and
weighed. In order to remove the last traces of platinum and rhodium, this last filtrate is evaporated to dryness, the residue heated
with nitric acid in order to remove the ammonium chloride completely, and then boiled for a long time with formic acid and ammonium acetate. The traces of metal thus obtained are washed
with hydrofluoric acid and added to the main portion of platinum
and rhodium.
4.

Treatment of the Residue D.

The undissolved, gray lamellae consisting of iridium, ruthenium,
and small amounts of iron obtained by the action of dilute aqua
regia, are filtered off, dried, ignited in an atmosphere of hydrogen
or illuminating gas, and weighed.
The weighed metal is then fused in a pure gold crucible with
potassium nitrate and carbonate. For this purpose, a previously
melted mixture of 3 gms. potassium nitrate and 10 gms. potassium
carbonate is placed in the crucible, the metal added, and the mixture heated for two hours at a dull-red temperature. In this way
the ruthenium

changed completely into water-soluble potassium
and the iridium is oxidized to Ir2O 3 the latter
ruthenate,
4
2
some
to
extent, a soluble compound with the alkali.
forms,
The melt is treated with water, and the solution, together with
is

K RuO

;

,

the suspended Ir 2 O 3 ,* is poured into a stoppered cylinder, the precipitate allowed to settle, and the clear liquid decanted off into a
retort.

The residue remaining in the cylinder is covered repeatedly with
a dilute solution of sodium hypochlorite and sodium carbonate,
The decanted liquid
until the yellow color is completely removed.
added to the main solution in the retort. This solution conruthenium and a part of the iridium. It is saturated
with chlorine in the cold, distilled, and the distillate received in a
mixture of alcohol (distilled over potassium) and pure hydrois

tarns all the

chloric acid.
* Cf.

W.Palmaer,

Z. anorg.

Chem.,

10,

332 (1896).

GRAVIMETRIC ANALYSIS.

276

After the distillation is complete, the alcoholic distillate is evaporated to dryness and the ruthenium chloride thus obtained is
reduced to metal by heating in a stream of hydrogen. After
It must dissolve
weighing, the purity of the ruthenium is tested.
completely in a concentrated solution of sodium hypochlorite.

The liquid remaining in the retort is evaporated to a small volume, the insoluble residue remaining in the cylinder (that was
washed with sodium hypochlorite and sodium carbonate) is added,
and the mixture boiled with caustic soda solution, with the addiall of the iridium is precipitated.
precipitate, consisting of iridinm oxide and small

tion of a little alcohol, until

The dark-blue
amounts

of ferric hydroxide,

ignited.

The

ferric

is

filtered off,

oxide contained in

washed, and strongly
then extracted with

it is

hydrochloric acid containing some ammonium iodide, and the residual iridium oxide is washed successively with water, chlorine
water, and hydrofluoric acid in order to remove gold that came
from the crucible and silicic acid from the caustic soda. It is then
ignited in hydrogen and the iridium weighed.

The iron present in the hydrochloric acid extract is precipitated
Its purity is tested by
as ferric hydroxide, ignited, and weighed.
heating in a stream of hydrogen and hydrochloric acid, to see if it
can be completely changed to ferrous chloride and volatilized as
such.
F. Mylius and F. Forster* have recommended that platinum
be tested for small amounts of impurity by taking three separate

The first portion is tested for
palladium, iridium, and ruthenium according to the lead procedure just described of Deville and Stas. The second portion
serves for the iron determination; the metal is dissolved in aqua
portions each weighing 10 gms.

platinum metals precipitated by formic acid, and the
In the third portion, rhodium,
iron determined in the filtrate.
regia, the

silver, copper,

num

and lead are determined by

as PtCl 2 CO at 238

C. (temperature

volatilizing the platiof boiling quinolin) in

a stream of carbon monoxide and chlorine, and determining the
above substances in the residue.
Remark. The determination of the iron in a separate portion is
to be recommended, for in the lead procedure some iron is always
obtained from the carbon crucible.
* Berichte 1892,
p. 665.

SELENIUM.

SELENIUM,

At.

Se.

277

Wt.

79.2.

Selenium is usually determined as the element
Three cases are to be considered:

The selenium is present as alkali selenite or as selenious acid.
The selenium is present as alkali selenate or as selenic acid.
The selenium is present as potassium selenocyanide.

I.

II.

III.

The selenium

I.

The

itself.

is present

as selenite or as free seleinous add.

with hydrochloric acid, saturated with
sulphur dioxide gas, boiled, filtered through a Gooch crucible, and
washed first with water, then with alcohol. The residue is dried
solution

is

acidified

and weighed.
The precipitation of selenium by sulphur dioxide is
always quantitative whether the solution is concentrated or dilute,

at 105

C.

Remark.

whether

it

contains

much

or

little free acid.

in the separation of selenium

importance
latter element

This latter fact

is

of

from tellurium, for the

is not precipitated by sulphur dioxide when considerable hydrochloric acid is present (cf. p. 279).
Phosphorous acid does not precipitate selenium from cold,

dilute, strongly acid solutions; this fact is

separation of selenium
II.

acid.

The selenium

As selenium

from mercury

(cf. p.

made
281).

is present as alkali selenate or

in the

form

use of in the

of selenic acid

is

as free

selenif-

not precipitated

by sulphur dioxide, phosphoric acid, or hydrogen sulphide, it
must be first reduced to selenous acid by long-continued boiling
with hydrochloric acid

(cf

.

Vol.

1)

;

the above procedure

is

then

followed.
is present as potassium selenocyanide.
The
as
is
treated
with
much
as
concentrated
possible,
hydrosolution,
chloric acid, boiled, allowed to settle, and the precipitate filtered

III.

The selenium

through a Gooch crucible, dried at 105 C., and weighed.
Remark. From very dilute solutions of potassium selenocyanide, selenium separates out only very slowly according to this

method;

it

is

therefore advisable to concentrate the solution as

much

as possible, but when this cannot be done, the boiling with
hydrochloric acid should be continued for some time and the liquid

allowed to stand before

filtering.

GRAVIMETRIC ANALYSIS.

278

In practice, selenium is obtained usually in none of the above
forms, but as impure selenium (selenium sponge) or as selenide,
and by the treatment of these substances one or the other of the

above selenium compounds
If the

is

selenium or selenide

obtained.
is

acted upon

by concentrated nitric

acid,* or aqua regia, all of it is dissolved in the form of selenous acid
(not selenic acid). After evaporating the solution several times
with hydrochloric acid in order to remove the excess of nitric
acid, the selenium is precipitated

under
If

by sulphur dioxide

as described

1.

the finely powdered selenium or selenide

is

intimately mixed

with two parts sodium carbonate and one part potassium nitrate, placed in a nickel crucible, covered with a layer of
sodium carbonate and potassium nitrate and heated gradually
until it fuses, all the selenium forms alkali selenate and on extracting the melt with water it goes into solution; in this way it
separated from most of the remaining oxides. The solution,
however, often contains small amounts of lead. In order to re-

is

move

the latter, the filtrate is treated with hydrogen sulphide,
filtered; the solution is freed from hydrogen sulphide
boiling, strongly acidified with hydrochloric acid, boiled until

and again

by

no more chlorine

is

evolved and the selenium

sulphur dioxide according to

is

precipitated

by

II.

The mixture must be heated very slowly, as otheris likely to be lost by volatilization.
Selenium and very many selenium compounds may be satisfactorily determined as follows: The dry, finely powdered sponge is
Remarks.

wise some selenium

fused at as low a temperature as possible in a current of hydrogen f
with twelve times as much potassium cyanide. After the mass

has fused quietly for about fifteen minutes it is allowed to cool in
hydrogen. It is then extracted with water, the solution is heated
to boiling,
*

aqua

and analyzed according to

Mercury cyanide

is

unacted upon by

III.

nitric acid,

but

is

dissolved

by

regia.

A Rose crucible (Fig. 37, p. 185) is used, or a round-bottomed flask
jwith a long neck made of difficultly fusible glass, from which the air is replaced
by hydrogen. In the latter case the delivery-tube must be so wide that the
Beck of the flask is nearly filled with it.

SELENIUM AND TELLURIUM.
It is necessary to boil the solution of

279

potassium selenocyanide

before acidifying it, for small amounts of potassium selenide
(K 2 Se) are almost always present, and on acidifying with hydrochloric acid this is decomposed with evolution of hdyrogen selenide.

On

the potassium

boiling,

selenide

is

changed to potassium

selenocyanide according to the equation:

K 2 Se + KCN + H 2 + O = 2KOH + KCNSe.
TELLURIUM, Te.

At. Wt.

127.5.

is usually determined as the element itself.
sulphur dioxide is conducted into a hydrochloric acid solution containing tellurous acid, black tellurium is quantitatively

Tellurium
If

precipitated, provided the solution does not contain too muck acid.
If tellurous acid is dissolved in 200 c.c. of hydrochloric acid, sp. gr.

be precipitated on passing sulphur dioxide
into the cold solution.
If, however, the solution is diluted with
an equal volume of water and sulphur dioxide is passed into the
The preboiling solution, all the tellurium will be precipitated.
cipitate is filtered off, washed with water until free from chlorides,
1.175,

no tellurium

will

then with alcohol, dried at 105 C. and weighed. The oxidation of
the tellurium during the drying is so slight that it can be disregarded.*

Separation of Selenium and Tellurium from the Metals of
Groups III, IV, and V.

By conducting sulphur dioxide into the solution fairly acid with
hydrochloric acid, the selenium and tellurium will be quantitatively precipitated while the other metals remain in solution.
*

The presence of nitric acid prevents the complete precipitation of the
by means of sulphur dioxide and similarly the presence of sulphuric
To remove nitric acid, sodium chloride is added and the
is harmful.

tellurium
acid

solution evaporated to dryness repeatedly with hydrochloric acid.
to Brauner the addition of sodium chloride

According

absolutely necessary, as otherof tellurium will be volatilized as chloride.

wise an appreciable amount
A. Gutbier (Ber. 34, 2724 (1901)

is

) reports that all these difficulties are overprecipitating tellurium from a hot solution by means of hydrazine
hydrate or hydrazine hydrochloride, but not the sulphate. See also P.
Jannasch and M. Miiller Ber. 31, 2393 (1898).

come by

;

GRAVIMETRIC ANALYSIS.

280

Separation of Selenium and Tellurium from the Metals of Group
(a)

From

Sulphur dioxide

is

II.

Copper, Bismuth, and Cadmium.

passed into the boiling solution, acid with

hydrochloric acid, whereby all of the selenium and tellurium and
usually some of the bismuth are precipitated. The precipitate
after being washed is dissolved in nitric acid, the solution evaporated to dry ness, taken up in concentrated hydrochloric acid,
diluted with a little water and precipitated with hydrogen sul-

The precipitate, consisting of the three sulphides, is washed
and then treated with sodium sulphide solution whereby selenium
and tellurium pass into solution while the bismuth remains behind
as its brown sulphide and is filtered off.
The solution containing the selenium and tellurium is acidified
with nitric acid, carefully evaporated to dryness and the residue
boiled with 200 c.c. of hydrochloric acid, sp. gr. 1.175, until there
The deposited sulphur is
is no longer any evolution of chlorine.
then filtered off through a Gooch crucible, and the filtrate saturated with sulphur dioxide gas all the selenium is in this way preThe latter is filtered off through a Gooch crucible and
cipitated.
washed successively with a mixture of 90 vol. HC1 (sp. gr. 1.175)
and 10 vol. water, dilute hydrochloric acid, and finally absolute
alcohol.
The precipitate is dried at 105 C. and weighed. The
filtrate is diluted with an equal volume of water and the tellurium
phide.

;

by passing sulphur dioxide into the boiling solution.
This precipitate is washed with water until free from chlorides,
then with absolute alcohol, after which it is dried at 105 C. and
precipitated

weighed.

Remark.

The above method

is

suitable for the separation of

selenium and tellurium from small amounts of bismuth, but does
not effect the separation of selenium (and tellurium) from copper.

copper selenide is formed according to
compound is not decomposed quantitasodium
sulphide.* In this case, the method of B.
tively by
Brauner and B. Kuzmaf may be used.
In this case, more or

less

the conditions, and this

* Cf. E.
Keller, J. Am.
t Berichte, 1907, 3362.

Chem.

Soc., 19, 771.

SELENIUM AND TELLURIUM.

281

The tellurium and selenium are precipitated in a pressure
by means of SO 2 the precipitate, which is contaminated
with copper, antimony and bismuth, is filtered (using a Gooch
flask,

,

crucible) washed, dissolved in nitric acid, the solution evaporated
to dryness and the residue taken up in caustic potash solution

The alkaline solution is placed in an Erlenmeyer flask
(1:5).
upon a water-bath, and little by little 4-6 gm. of ammonium
persulphate are added, whereby the potassium tellurite is oxidized
When all
to potassium tellurate and the selenite to selenate.
the persulphate has been introduced, the solution is heated to
boiling to decompose the excess of persulphate, then acidified
with sulphuric acid and allowed to cool. Now, 100 c.c. of
2 S-

H

water are added, the excess of the H 2 S expelled by passing C0 2
through the solution, and the precipitated CuS (Bi 2S 3 Sb 2 S^)
The filtrate is
filtered off, and treated as described on p. 235.
,

boiled with

hydrochloric

acid

tellurous acid, and the solution
analyzed as described above.

The

first filtrate

to
is

reduce

the telluric acid to

reduced by means of

from the impure Te and Se

will

SO and
2

contain the

greater part of the Cu, Bi, etc.
(6)

From Antimony, Tin and

Arsenic.

If considerable antimony is present, tartaric acid is added to
the solution, and the selenium and tellurium are then precipitated

by boiling with sulphur

dioxide.

Muthmann and Schroder

According to

*

this

method

of

not quantitative; some
antimony is always precipitated with the tellurium. A. Gutbier,f
however, finds that a perfect separation can be accomplished by
separating tellurium from antimony

means

is

of hydrazine hydrochloride (not the sulphate).
(c)

From Mercury.

The mercury selenide, or telluride, is dissolved in aqua regia, chlorine water

is

added, and the solution

Phosphorous acid

is

*Z. anorg. Chem.,

is diluted largely with water.
added, t and after twenty-four hours standing,

14,

433 (1897).

t Z. anorg. Chem., 32, 263 (1902).
} Selenous and tellurous acids are not precipitated by phosphorous acid
from dilute hydrochloric acid solution, but are precipitated from hot con-

centrated solutions.

GRAVIMETRIC S.N4LYSIS.

282

the mercury is precipitated completely as mercurous chloride, and
is determined as such
according to p. 170.

The filtrate containing selenium and tellurium is concentrated,
taken up in water, and the selenium separated from the tellurium
according to the method of Keller (see below.)
(d)

From Gold and

Silver.

The separation

of selenium and tellurium from silver offers no
inasmuch as the latter can be precipitated by hydrochloric acid and determined as the chloride.
The gold is precipitated as described on p. 257 by oxalic acid
and the selenium and tellurium in the filtrate by means of sulphur
difficulty,

The three metals may also be precipitated together by
dioxide.
sulphur dioxide, weighed, and the selenium and tellurium afterward volatilized by roasting, leaving the gold behind.
Tellurium may be separated from gold by precipitating the latIn the case of selenium, however, it is
ter with ferrous sulphate.
also precipitated quantitatively by ferrous sulphate from solutions
strongly acid with hydrochloric acid.

Separation of Selenium from Tellurium.

A.
Keller's

method

is

Method

of E. Keller.*

based upon the fact that tellurous acid is not

precipitated from solutions strongly acid with hydrochloric acid

while selenium

by sulphur

is

precipitated quantitatively.

The mixture

Procedure.

dioxide

is

evaporated to dryness.

of

the

dissolved

in

The dry mass

two elements precipitated
nitric acid and carefully
is

treated with 200

c.c.

of

hydrochloric acid (sp. gr. 1.175), boiled to remove the nitric acid
and saturated with sulphur dioxide. The precipitated selenium
is filtered

through a Gooch crucible, washed

HC1

first

with a mixture

and 10 vol. water, then with dilute
then
with
water
until free from chloride, finally
acid,
hydrochloric
with absolute alcohol. The selenium is then dried at 105 C. and
weighed. The filtrate is diluted with an equal volume of water,
of 90 vol.

(sp. gr. 1.175)

* Jour.

Amer. Chem.

Soc., 19, 771.

SEPARATION OF SELEHIUM FROM TELLURIUM.

283

heated to boiling, and the tellurium precipitated by sulphur dioxand treated in exactly the same way us the selenium.

ide

Accc rding to Keller, this method gives thoroughly satisfactory
amount of tellurium present does not exceed
Even then the separation can be effected by increasing the
5 gms.
results, as long as the

amount

of acid to 450 c.c.

B.

The Potassium Cyanide Method.

The precipitate of selenium and tellurium produced by sulphur

much of pure (98 per cent.)
in
an
of
cyanide,
atmosphere
hydrogen, as described on
potassium
-The tellurium is almost wholly changed to potassium
p. 278.
dioxide

is

telluride,

fused with twelve times as

K Te
2

(a small

amount

of potassiuift tellurocyanide is
is changed for the most part

probably formed), while the selenium
into potassium selenocyanide,

and to a

slight extent into

potassium

selenide.

The brown melt is dissolved in water, and a slow current of air is
conducted through the solution whereby the K 2 Te is quantitatively
decomposed according to the equation

K Te+H 0+O = 2KOH+Te.
2

2

After standing twelve hours the tellurium is filtered off through a
Gooch crucible, washed with water, then with absolute alcohol,
dried at 105

and weighed.

heated to boiling * in order to change any
potassium selenide into the double cyanide; it is then acidified
with hydrochloric acid under a good hood (hydrocyanic acid!},
filtered, and the selenium determined according to p. 277.

The

colorless nitrate is

Remark.

This method gives slightly low results for tellurium
This is due to the fact that a little
for selenium.

and high values

potassium tellurocyanide is formed by the fusion and this compound is not decomposed by the current of air, but is subsequently
the solution.
precipitated with the selenium on acidifying
* Cf.
p. 27'..

GRAVIMETRIC ANALYSIS.

284

Determination of Selenium and Tellurium in Crude Copper.

Many copper ores contain selenium and tellurium, so that the
crude copper obtained from such ores always contains these elements. The amount present may be determined, according to
Keller,* as follows: According to the amounts of selenium and
tellurium present, from 5 to 100 gm. of the copper are taken for
the analysis
The sample is dissolved in nitric acid and an excess

ammonia

is added whereby the phosphorus, arsenic, antimony,
bismuth, selenium, and tellurium are precipitated together with
the ferric hydroxide, while the copper is held in solution by the

of

tin,

The precipitate is filtered off and washed with
ammonia- wattr until the copper is completely removed. The
precipitate is dissolved in hydrochloric acid and this solution saturated with hydrogen sulphide in the cold, whereby selenium and
tellurium together with arsenic, antimony, tin, and bismuth are
thrown down as sulphides and are separated by nitration from the
The precipitate thus obtained is treated
iron and phosphorus.
with sodium sulphide and filtered. The filtrate containing all the
selenium and tellurium in the presence of arsenic, antimony, and
tin as sulpho salts is acidified with nitric acid and carefully evaporated to dryness. The residue is dissolved in 200 c.c. of hydrochloric acid (sp. gr. 1.175) and treated as described on p. 282, A.
excess of ammonia.
dilute

At. Wt. 96.0.

MOLYBDENUM, Mo.

Form: Molybdenum Trioxide,
If the

MoO

3.

is present as ammonium
molybdate, a
heated in a spacious porcelain or platinum
carefully and later to a dull red heat; this leaves

molybdenum

weighed portion
crucible, at first

is

molybdenum trioxide behind in the form of a dense powder,
appearing yellow when hot and almost white when cold.
There is no danger of losing any of the molybdenum by volatili-

the

zation, provided the dull red heat is not exceeded.
If the molybdenum is present as alkali molybdate,

to mercurous

molybdate or to

its

sulphide,

described below.
* Jour.

Amer. Chem.

it is

changed

and then analyzed as

Soc., 22, 241.

necessary to effect the separation in a hydrochloric acid solution. as the sulphide can take place in two different ways: either the acid solution may be precipitated by hydrogen sulphide gas. The liquid is then heated to boiling. Precipitation of The Molybdenum as Molybdenum Sulphide. it is . for th? basic mercurous carbonate suffices to remove the slight amount of free nitric acid. after which the residual molybdenum trioxide is weighed. heated on the waterhydrogen sulphide. (a) Precipitation of Molybdenum Sulphide from Acid Solutions. for the separation of Mo from Ba.g. is filtered and washed with a dilute solution of mercurous nitrate. consisting of mercurous carbonate and mercurous rnolybdate. transferred as completely as possible to a watch-glass. the black precipitate. Sr. * In many cases. Remark. and Ca.. and the whole is heated very care- fully over a low flame until the mercury is completely volatilized. and the precipitate remaining on the filter is dissolved in hot dilute nitric acid into a large porcelain crucible. the main portion of the precipitate added to the residue. or the solution of ammonium sulphoprecipitation of molybdate may molybdenum be acidified with dilute acid. The greater part of the alkali is neutralized with nitric acid. e.* is placed in a small pressure-flask and saturated in the cold with The flask is closed. and to the slightly alkaline solution a barely acid solution of mercurous nitrate is added until no further precipitation is effected. It was formerly customary to add a slight excess of mercurous nitrate solution and then to add mercuric oxide to neutralizD the excess of nitric acid (the solution of mercurous nitrate contains free nitric acid). frequently necessary to determine molybdates obtained by fusion with an alkali In the course of analysis molybdenum 285 it is carbonate. The molybdenum solution. The precipitate is dried. slightly acid with sulphuric acid. is allowed to settle. The solution is then evaporated to dryness. Precipitation of Molybdenum in alkali as Mercurous Molybdate. According to the above procedure of Hilbbrand.PRECIPITATION OF MOLYBDENUM. the addition of mercuric oxide is wholly superfluous.

on the water- bath. covered with a watch-glass. The crucible is then covered and very carefully heated over a small flame until no more hydrocarbons are expelled. evaporated to dryness of the cr^ible. as described above. 286 bath until the precipitate has completely after it has become dilute sulphuric acid cold.GRAVIMETRIC ANALYSIS. the sulphide is changed to oxide. The Separation of Molybdenum from the Alkalies can take place by precipitation as mercurous molybdate or as phide. . The molybdenum oxide thus obtained always contains traces of SO 3 and consequently cible. After cooling. nickel one. when it is acidified with sulphuric acid and the precipitate treated as described under (a). and settled. a little mercuric oxide suspended in water the mixture is is added to the contents well stirred. the watch-glass is removed and the open crucible heated until it is brought to a constant weight. and filtered The precipitate is washed with very finally with alcohol until the acid has The moist filter is placed in a large and dried upon the water-bath. and dried at 100 C. * To avoid loss by decrepitation. * and carefully heated over a small flame whereby the sulphide is for the most part changed As soon as the odor of sulphur dioxide can no longer to the oxide. porcelain crucible perature as possible. the carbon burned from the sides of the crucible at as low a tembeen completely removed. sul- . (6) Hydrogen Sulphide is results. and the residue of molybdenum trioxide is weighed. The mercuric oxide is added It remove particles of easier to transform the in order to is much the oxide as follows : The sulphide unburned carbon. The has a bluish appearance. The operation is finished when no more sulphur dioxide is formed. trisulphide into through a Gooch cru- molybdenum is filtered washed with water containing sulphuric acid. and. The cover is then removed. are excellent. by raising the temperature gradually. nevertheless. the mercuric oxide is removed by gentle ignition. passed denum into the Ammoniacal Molyb- Solution until it assumes a bright-red color. and then with The crucible is placed within a larger alcohol. be detected.

Copper. 286. After filtering. Separation of Molybdenum from the Metals of the Ammonium Sulphide Group. as described on p. The filtrate is acidified with sulphuric acid and the molybdenum precipitated as sulphide by mean? The of hvdrogen sulphide. ammonium sulphide. 6). solution. the arsenic precipitated by magnesia mixture (see p. fused with sodium carbonate. digested Molybdenum from the Metals of Group II. while the alkaline earths remain From the aqueous solution the molyb- undissolved as carbonates. . which must contain the arsenic as arsenic acid. the in solution in the form of its sulpho salt. the precipitate has settled orless. the molybdenum sulphide is filtered off and convened to oxide. denum is determined as previously described. as is the addition of acid molybdenum sulphide by precipitated III will of (see p. The in solution as its sulpho salt. it is better pressure (see p. and filtered. (6) From Arsenic. and Bismuth. Separation of (a) The From solution is sulphide. molybdenum 28? The meh ex- solution contains all the as alkali molybdate. whereby the metals be precipitated and the molybdenum will remain Group After filtration. The molybdenum is precipitated as sulphide (preferably from a sulphuric acid solution) by treatment with hydrogen sulphide under If the solution contains titanium. 206) and filtered off. Cadmium. the solution acidified with sulphuric acid and heated in a pressure-flask until is and the supernatant liquid appears colAfter allowing to cool. Lead. 286) to first add ammonia and . 286.SEPARATION Of MOLYBDENUM. the is tracted with water and filtered. treated with caustic soda and then with sodium some time molybdenum remains in a closed flask. while the other metals are precipitated as sulphides. is treated with ammonia. Molybdenum from Separation of The substance the Alkaline Earths.

285. o^ by means of mercurous nitrate as mercurous tungstate. hydrochloric acid.0. Tlie residue is moistened with a chloric acid. The aqueous solution of the alkali tungstate is treated with an equal volume of concentrated hydrochloric acid. acidify with hydrochloric acid. and then precipitate the molybdenum as sulphide. diluted. filtered little hydro- and washed with G per cent. The yellow tungstic acid is ignited and weighed. or with 10 per cent. It is even volatile there advisable to heat the crucible finally over a good Teclu burner or over the blast-lamp. by ignition the yellow trioxide is obtained and weighed. If the tungsten is present as alkali tungstate. Since the trioxide is not is no loss to be feared during its ignition. the tungsten is present as ammonium tungstato. tion as solution with hydrogen sulphide. p. or as tungstic acid. the tungstic acid may be precipitated as such. TUNGSTEN. 2 88 Separation of Molybdenum from Phosphoric Acid. as mercurous tungstate. Wt. . The phosphoric acid is precipitated from the ammoniacal solumagnesium ammonium phosphate (see phosphoric acid) and the molybdenum is precipitated as sulphide from the filtrate Another way is to saturate the ammoniacal (cf. it is readily changed by ignition If in the air to yellow tungsten trioxide. In the filtrate the phosphoric acid is precipitated as magnesium phosphate under the customary conditions. its trioxide. boiled. ammonium nitrate solution.GRAVIMETRIC ANALYSIS. ammonium 184. but there remains in the filtrate a weighable amount which can be recovered by repeated evaporations with hydrochloric or nitric acid. a). Tungsten is determined as At. In this way the greater part of the tungstic acid is precipitated. evaporated to dryness on the water-bath and heated for an hour in the hot closet at 120. W. Precipitation of Tungstic Acid.

O.. the solution is boiled to expel all the carbonic acid. the filtrate evaporated to dryness with ammonia. or with ammonium nitrate solution. however. diluted with water to 100 saturated mercurous nitrate solution dried. 501 (1882). If. der Pfordten. Precipitation of Tungsten as Mercurous Tungstate. The concentrated solution is treated with a few drops of methyl orange. nitric acid is added until the indicator turns pink. using the flame of a Bunsen burner. Cf. Ann. ignited in a porcelain crucible hood. according to Philipp. 21. it is is and the latter decomposed by the is nitric acid treatment.) under a good weighed as 3 Remark. formed which : Na 2 WO 4 +3WO 3 = Na 2W 4 O l3 . allowed to cool. hard to decompose by acids.TUNGSTEN. but on evaporating with acid some more of the acid tungstate is formed. After standing three or four hours. The washing of the precipitate with acid. 152 (1883). washed with water containing mer- curous nitrate (5 c. 15.. is quantitatively precipitated by Ber. the precipitate is filtered off.* the acid tungstate is converted into ordinary tungstate. then. II. t Jahresber. according to Berzelius. perfectly true.c. which would result if pure water were used. The yellow precipitate settles quickly and the supernatant liquid should appear clear as water.f In the majority of cases it is a question of separating tungstic acid from a solution obtained after fusing with sodium carbonate.c. and then an excess of mercurous nitrate solution is added. which can be transformed into This is insoluble tungstic acid only by repeatedly evaporating the filtrates to dryness with hydrochloric or nitric acid. The tungstic acid W0 * . 222. . and c. is necessary in order to prevent the formation of hydrosol. v. 289 The reason why the tungstic acid is not removed completely by the first treatment with nitric or hydrochloric acid is that there is always a small amount of an acid tungstate Remark. 143.

therefore. t Since benzidine tungstate is appreciably soluble in hot water containall cases to postpone the ing benzidine hydrochloride. precipitate is ignited in a platinum crucible. 38. when the erable to nothing else is present which above. 2go The process is prefa single treatment with mercurous nitrate. The washing with dilute hydrochloride is continued until the evaporation of the filtrate on platinum foil leaves no weighable The precipitate is ignited wet as described above. according to G. when formed in the cold hard to filter and. In this sulphuric case te mixture of crystalline benzidine sulphate and amorphous benzidine tungstate is formed which can be filtered after standcold solution The benzidine sulphate is entirely volatile.1 N. If the tungsten is present as tungstate after fusing with sodium carbonate. *Ber.* If a neutral solution of sodium tungstate is treated with benzidine hydrochloride. the melt is dissolved in water. a white flocculent precipitate of benzidine tungstate is formed and the precipitate is insoluble in water benzidine hydrochloride. tends If the precipitate is formed from a to run through the filter. 783 (1905). to 800 in an electric oven. Knorre. v. it is necessary in nitration until the solution is cold. so that equally good results are obtained by either of the above two procedures. and the residue of 3 The precipitation can also take place satisfactorily from a loss The moist WO before adding the precipitant.. it comes down in a more compact condition and after cooling | can be easily filtered and washed without containing it is with water containing benzidine hydrochloride.GRAVIMETRIC A NA LYSIS. . conditions. or alkali acid sulphate is added to the solution. heated is weighed. a little dilute if.c. which can be benzidine of a Benzidine filtered in five hydrochloride gives a precipitate minutes. few drops residue. a little methyl orange is added to the clear solution. however. and finally 10 c. ing five minutes. of 0. sulphuric acid. same under the precipitates Precipitation of Tungsten as Benzidine Tungstate. then hydrochloric acid until the pink color is obtained. hot solution. on being washed with pure water.

it is necessary to add at least one cubic centimeter of the benzidine solution for 10 c. If the analysis is X Preparation of the Wash Liquid. the residue is fused with four times as much sodium carbonate. hydrochloric acid (sp.2). heated until solution is completed and a brown liquid is formed. 1. the melt precipitate * Instead is of dissolving the benzidine in hydrochloric acid.TUNGSTEN. the washing is accomplished with a dilute solution of benzidine hydrochloride. Kunz found 0. acid. be dissolved in of hydrochloric acid have been added.1029 gm.. The method is excellent. treated with 25 c. gr. of 0. 28 gms. Knorre observed that on dissolving tungsten steel in hydrochloric or dilute sulphuric acid. which * Of this soluis filtered and diluted to a volume of one liter.1026 gm. in aliquot parts of a solution supposed to contain 0. are sufficient to precipitate 0. 38.6 c. tion. To complete the ignited wet separation. Determination of Tungsten in Tungsten (a) Method Steel. 5.1 gm. contaminated with more or less iron. of G.. 291 Preparation of the Benzidine Solution. it oxidizes quickly in the air. forming grayish-yellow tungstic which on further washing with water gives a turbid filtrate. Remark. instead of using water. and 0. Ten c. of 1 liter of water to which 6 c. the tungstic acid does not pass through the filter if. 783 (1905). Knorre.c.f V. of water into a beaker. 0. of WO. W. Twenty grams of commercial benzidine are triturated in a mortar with water. out of contact with the air.c.c. benzidine hydrochloride may .c. all the tungsten remains behind as metal. v.. 0. greater part of the iron is separated from the tungsten. By the treatment of the tungsten the steel with acids. of the above solution are diluted with distilled water to a volume of 300 c.1 sulphuric acid added. the washed in a platinum crucible. of WO 3.c. If the finely divided tungsten is filtered off.c.1029 gm. t Her. therefore. carried out with the aid of sulphuric acid.1028 gm.1033 gm. washed with about 400 c.c.

Now a steel with a high percentage of tungsten is so hard that it is practically impossible to get borings or filings without the steel tools becoming badly worn. Ztg. the remainder of the bisulphate added in two separate portions. The heating is now carefully continued until finally * Chem. the ferric oxide filtered It sten determined as described on p.. has little effect upon it is otherwise with a potassium bisulphate fusion. it should suffice to hammer the sample in a steel mortar until a coarse powder is obtained.GRAVIMETRIC ANA LYSIS. Unfortunately a coarse powder dissolves extremely slowly in dilute or concentrated acids and fusion with sodium carbonate and potassium nitrate. which Procedure. may be in the form of coarse pieces. Wolter.* L. is fused in a 40-45 c. whereby even platinum crucible with thirty times as much potassium bisulTo prevent too violent effervescence. with a high percentage of tungsten. or with sodium peroxide. 289. one-third of the bisulphate is added and the well-covered. who has carefully studied the determination of tungsten in tungsten steel. of the coarse material. is place more slowly and the temperature is raised until the bottom of the crucible begins to redden and dense white vapors are evolved. is then removed for half a minute because a fairly The flame violent reaction fact is now when taking place within the crucible. inclined crucible is heated over a small flame until white vapors are evolved. found that most of the methods hitherto recommended are not practical because they required the metal to be in too fine a condition. a strong effervescence can be this point is After cooling somewhat. off. in such cases the sample to be analyzed becomes con- taminated with foreign material and the accuracy of the analysis For this reason if it is required to analyze a steel is affected.5 gm. In reached. Welter's Method. 1910. .2-0. is and the tungprobable that aluminium-tungsten alloys can be analyzed in a similar manner. 2. (6) L. The reaction now takes heard. large particles.c. large particles of tungsten steel are readily attacked. From 0. 29 2 extracted with a water. at first only phate.

Separation of (a) Molybdenum from Tungsten. and the water added is measured so that the volume of the solution will amount to about 60 or 75 c. and very cautiously heated over a free flame until no more ammonium salts are evolved. the weighed tungstic acid will always contain silica. The way greater part tungsten filtrate from the tungstic acid precipitate still contains tungsten. dilute ammonium tungstate in the crucible is evaporated covered with a watch-glass. of concentrated hydrochloric acid and boiled until the precipitated tungstic acid has become a pure yellow.TUNGSTEN. the solution is filtered through a small filter and the precipitate washed with 10 per cent. the crucible and cover boiled with water. which is somewhat turbid with tungstic acid. of a Bunsen burner. the mass is allowed to cool. proposed by M. 293 the whole crucible is heated to redness. then WO flame of a Bunsen burner. Am.. ammonium nitrate solution. the steel contained silicon. acid. 22. This method.c. F. After about fifteen minutes the reaction will be finished. ammonia. The Sulphuric Acid Method. again treated with hydrofluoric acid. it is covered with a few drops of hydrofluoric If evaporated to dryness. Soc. carefully washed. The liquid. When this point is reached. Ruegenberg and E.* depends upon the fact that unignited molybdic acid is readily dis* J. After igniting the residue over solution of to dryness on the water-bath. 772. but only tungstic acid. Chem. Smith. After standing half an hour on the waterbath. The lemon -yellow precipitate is dissolved on the filter in hot. .c. the solution caught in a weighed platinum The crucible. evaporated once more and finally ignited over the flame The crucible will now contain no silica. this In order to recover the later. is treated with 20 c. and the filter washed with ammonium nitrate. it is weighed as In 3 of the the is obtained. The molten mass in the crucible should show merely a gentle evolution of gas and there should be no black particles of unattacked steel visible. it is treated as described on paga 288. the full .

filtered. 1. and the residue washed into a weighed platinum crucible with ammonia. If only a little sulphuric acid is used for the separation. W. These ignited oxides cannot b? separated by treatment with sulphuric acid. After cooling.378). they can readily be brought into solution by heating for half an hour on the water-bath with concentrated ammonia in a pressure-flask. Dissert. and weighed. 286.GRAVIMETRIC ANALYSIS. After digesting for half an hour. freshly The mixture is covered with concentrated sulphuric acid in a porcelain dish and heated over a free flame. then two or three times with alcohol. the sulphuric acid driven off for the most part. Giessen. According to W. molybdenum as sulphide. however. Hommel. whether dissolved or * Inaus. and then evaporated. By this means. color disappears and the tungstic acid is of a pure yellow color. the contents of the flask. are Present in the Form of their Ignited Oxides. the liquid is diluted with three times its volume of water. (a) precipitated state. and afterward diluting with three times as much Procedure. ignited. shaking frequently. Hommel* tested this method in the author's laboratory. the separation is complete. and weighed as is precipitated from the The molybdenum 3. . and could not obtain good results except by digesting the moist oxide3 with concentrated sulphuric acid. gr. After cooling. usually a small amount of the tungstic acid is oxidized to the blue oxide. water. 1902. so that the yellow precipitate of tungstic acid is tinted with On adding one or two drops of dilute nitric acid. filtrate by passing hydrogen sulphide into the sulphuric acid solution in a pressureflask. (/?) it is always safer to precipitate the Tungsten and Molybdenum. ignited (after burning the filter by itself) in WO a porcelain crucible. Both acids are present in a moist. the filtrate from the tungstic acid can be evaporated in a platinum dish. while tung- stic acid is not. and the precipitate is treated as described on p. the green green. washed with water containing sulphuric acid... 294 solved by warming with sulphuric acid (sp. In case large amounts of molyb- denum are present.

173. but readily soluble in nitric acid . Pochard. The oxides two elements. Procedure. sodium chloride is cator over caustic potash. the sublimation of the molybdenum begins. 1101.2HCl. volatilized. however. tube drying-oven (to serve as an air-bath) (see Fig. the operation is usually complete. As soon as the temperature has reached about 200 C. are much sodium carbonate. their is sodium placed in a is bent vertimade of difficultly fusible and is connected with a Peligot tube containing a downward cally The horizontal arm of the tube is passed through a little water. and is connected with apparatus for generating hydrochloric acid gas. while the tungsten trioxide remains behind in the boat. The boat. or and the latter of which one end glass. and 46. white. the absorption of the MoO 3 . 295 washed into a porcelain dish. and treated as described under (a). which and molybdenum. or the latter with sodium chloride. of the salts. 114. was originally present as sodium tungremoved by treatment with water.2HCl in the water of the Peligot tube. and the filtered present (when the tungsten state) this is WO 3 is weighed. and treat the melt as described under (a). 19. are weighed into a porcelain boat. p. . and then through sulphuric acid. Comptes rendus. is removed. Mo 3O 5Cl 8 is often formed: = 3[MoO. the brick-red acid chloride. p. (6) If a mixture of the Sublimation Method* trioxides of tungsten heated at 250-270 or of their alkali salts. This substance is insoluble in hydrochloric acid. the as MoO 3 . evaporated to dryness.. now containing tungsten trioxide. in a current of volatilized completely molybdenum collects on the cooler parts of the tube as a is beautiful. C. it is weighed after drying in a desicIn case. The hydrochloric acid before reaching the tube is slowly passed through a flask containing concentrated hydrochloric acid. and in case only the former is present. From time to time the sublimate collecting in the tube is driven toward the Peligot tube f by carefully heating with a free flame. 3c). is dry hydrochloric acid. so that it will be possible to see whether any more molybdenum is being After heating for an hour and one-half or two hours. woolly sublimate. p.. It is still better to fuse the ignited oxides with four times as not.2HCl] + 2HCI 4H 2 O + Mo3 O 5Cl 3 * t By .TUNGSTEN.

After coolThe residue coning. the sublimate in the is washed out by means of water containing a little nitric acid. and sometimes small amounts of niobic and tantalic acids. an excess of sulphuric acid is added. The monoclinic Wolframite is an isomorphous mixture of and Ferberite. niobic. either by FeWO 4 . by hydrogen sulphide in a pressure-flask. and the precipitated tungstic acid is finally filtered off and changed by ignition to the trioxide. nation of the tungsten. dissolved in ammonia. evaporating with nitric acid or nitrate. MnWC>4. sodium carbonate in a platinum crucible over a good burner for from one-half to three-quarters of an hour. Hiibnerite. and stannic acids. This method gives correct results. The molybdenum sulphide is filtered off and changed by roasting in the air to the trioxide. Analysis of Wolframite (Wolfram). but often contains small amounts of silicic. Rose. tantalic. and changed to the oxide by gentle ignition. tube (c) The The Tartaric Acid Method alkali salts of the of H. About 1 gm.GRA yiME TRIC ANAL YSIS. and silicic acid (stannic acid). The tungstic acid is separated. and weighed as impure 3 oxide obtained in this way almost always contains silicic WO The The acid and sometimes stannic acid. resi- . tains iron. the tartaric acid is first destroyed by repeated evaporation with nitric acid. manganese. The solution contains all the tungstic acid. but is not so satisfactory as the preceding one on account of the time consumed in removing the tartaric at Remark. two metals are dissolved in considerable and the molybdenum precipitated according to p. 285. of the extremely finely-powdered mineral is fused with 4 gms. For the determitartaric acid. besides calcium and magnesium. by precipitating with mercurous precipitate is ignited. 296 For the determination of the molybdenum. To remove the former the . as above described. calcium. washed into a porcelain crucible. the melt is boiled with water and filtered. and finally the nitric acid solution of the entire sublimate is careThe residue is fully evaporated to dryness in a porcelain dish. and magnesium. evaporated to dryness.

The latter is filtered off. boiled and any silica filtered off. The tin is volatilized as stannic chloride. sodium carbonate fusion is dis- the insoluble residue from the solved in hydrochloric acid. must be taken. To determine the iron. the crucible is placed within a second larger crucible. first on the water-bath and finally over a free flame. This last operation is conducted as follows after the treatment with hydrofluoric acid is : The residue obtained mixed with six to eight much ammonium chloride.* and the latter is covered and ignited This operauntil the ammonium chloride is completely expelled. The inner crucible is then heated tion is repeated three times. 297 is heated with hydrofluoric and sulphuric acids. In the filtrate. dry ammonium chloride. and the residue is weighed. about 5 gms. times as its contents become of a pure-yellow cooled and weighed. the dry residue moistened with concentrated hydrochloric acid which is allowed to act for ten minutes. washed with water containing acid * This is the crucible. after ammonium which a constant weight it is is obtained.. the iron is separated from the other metals by the basic acid acetate process described on p. may be effected (according to Rammelsberg) by repeated ignition with pure. to prevent the oxide any is stannic oxide from formed when collecting on the outside of tin chloride comes in contact with . moist air. For the determination of niobium and tantalum. while the tungsten remains behind. 152. however. The manganese is precipitated heating with bromine (see p. The separation of tungsten from tin. then diluted with water. finely-powdered material is treated with hydrochloric acid to which about one-fourth of its volume of nitric acid has been added. manganese. and digested on the water-bath until the residue is colored a pure yellow. 77. The ignition with chloride and weighing of the residue is repeated until with ready access of air until color. a The larger portion of the substance. calcium and magnesium. The difference shows the amount of silicic acid present. 123) and the calcium and by as described on p. the solution evaporated to dryness. magnesium separated Remark.TUNGSTEN. Stannic acid is usually present in such small amounts that it is not usually due determined.

stannic. and the tungsten determined by one of the methods already described. enclosed mineral as well as silicic. until the iron reaction can is . comparatively however. . f. the * Preusser. they are first roasted in the air. 500 (1882). discovered by Wohler in 1824. p. The residue cf tin dioxide and niobium pentoxide (and perhaps tantalum pentoxide) is placed in a porcelain boat and final residue is and freed from free silica The metallic tin is exin a current of hydrogen. If. 15. Iron alloys rich in tungsten are acted upon only slowly by ignited tracted aqua regia. Zeit. anal.GRAVIMETRIC ANALYSIS.* Decomposition easily by a potassium bisulphate fusion is still better (see p. with sulphuric and hydrofluoric treatment by acids. 292). 1889. whereas the whole of the tungsten remains in solution in the form of alkali and ammonium tungstates. 350. or better still in the presence potassium nitrate. 298 no longer be obtained. Analysis of Tungsten Bronzes. 2.f offered for a long time considerable difficulty on account of the fact that acids do not decompose them very readily. is weighed. niobic. with hydrochloric acid. In the filtrate obtained after filtering off the deposited silver. the tungsten bronzes can be converted without difficulty into normal alkali tungstate. consisting of Nb2O 5 (Ta2O 5 ). Ann. and the residue.. It is obvious that the alkalies cannot be determined in the same of sample. % Berichte. weighed. when the residue taken up in ammonia and filtered in this way the tungstlc acid The residue is usually dark-colored and consists of is removed. Chem. residue is once more treated with ammonia. it is ignited. 173. water is tantalic acids. so that PhilippJ proceeded as follows: The bronze is treated with ammoniacal silver nitrate solution. By fusion with alkalies in the air. whereby the W(>2 is oxidized to WOs with the precipitation of an equivalent amount of silver. The now from tungsten. The analysis of these alkali salts of complex tungsten acids. t Pogg. they are brought into solution. and filtered the added.. and possibly It is treated with aqua regia again.

and the alkali weighed as sulphate. the decomposition of the bronze results. the filtrate is evaporated to dryness with the addition of sulphuric acid.* which follows.c. Zurich. another gram of ammonium sulphate is added and 1 c.5 gm. 299 tungstic acid is precipitated by treatment \vith nitric acid and determined as WO$. and Inaug. About 0. centrated sulphuric acid. of the finely-powdered bronze is treated in a porcelain crucible with 2 gms. of con- yellowish white. by precipitating it as the chloride. fact that the commercial salt often contains some potassium persulphate. t If . Although the above method affords satisfactory results in the analysis of bronzes containing comparatively little tungsten. During the heating the contents of the crucible are frequently shaken about a little by cautiously moving the crucible. is applicable in all cases. the crucible is then allowed to cool. In the case of sodium and lithium bronzes. the fused mass appears greenish. of alkali-free ammonium sulphate and 2 c. rinsed into a porcelain dish. Dissert. ammonium persulphate is used the addition of sulphuric acid is The only objection to the use of the persulphate lies in the unnecessary. 1903. whereupon the contents "of the crucible are once more heated as before until sulphuric acid fumes come off thickly. The method of Brunner. itis wholly inadequate in the case of bronzes rich in tungsten.c. into normal tungstates by heating them with ammonium persulphate.TUNGSTEN. the mass in the crucible is allowed to cool. The greenish or yellowish-white fusion is softened by treat- ment with water and 50 c. After adding of concentrated nitric acid. The escape of gases from the crucible soon and when sulphuric acid vapors begin to be evolved. of concentrated sulphuric acid f and carefully heated over a very small flame. based upon the fact that the bronzes can be transformed very easily. Procedure. or ammonium acid It is sulphate. and without loss of alkali.c. whereas with a potassium bronze the color is ceases After a part of the ammonium sulphate has been volatilized. the contents of the evaporating dish are digested * on the water-bath for three or four hours. After removing the excess of silver.

140 (1906). . and transferred into a 250-c. In order to recover the small amount of tungstic acid remaining in the nitrate. which.c.c.c. water. precipitate. is dissolved in warm ammonia The water. the dry residue treated with 50 c. Chem. well mixed and filtered through a dry filter. 361 (1900). Borntrager. allowed to cool.. concentrated nitric acid and 45 c. the melt is softened with water fifteen minutes.f 100 c. evaporated to dryness in a porcelain dish. 41 and 42).* One gram of the finely powdered mineral is intimately mixed an iron crucible with 8 gms.c.c. the solution is diluted to the mark. of the filtrate are allowed to flow into a mixture of 15 c. ammonium chloride. of sodium peroxide. diluted with a little water. and the mixture is carefully fused over the Bunsen burner for about After cooling. besides the tungstic acid. filtered and washed finally with dilute nitric acid.c. the ammonium salts expelled by ignition and the residue of alkali sulphate weighed Separation of Tungsten from Tin. it is evaporated as far as possible on the waterbath. filtered and washed with the same solution. 100 g. carbon dioxide is conducted into the solution for a few minutes). Augenot's Method. angew. c. 288. after diluting with water. is * Z.c.GRAVIME TRIG ANAL YSIS. Chem. pp. This time the liquid is taken up with the above mixture of hydrochloric acid and ammonium chloride. concentrated hydrochloric acid and 100 g. For the determination of the tungstic acid. the ammoniacal filter well solution washed with the same reagent. fZ.c. (cf. and the allowed centrated nitric acid and 45 to flow into 15 c. 19. flask (if lead is present.c. 39. of con- of concentrated hydrochloric evaporated to complete dryness. carefully treated with an excess of ammonia. rejecting the first few c. 300 then. again evaporated on the water-bath and treated as described on p. Augenot proceeds according to H.. in of concentrated hydrochloric acid. the residue of pure yellow tungstic acid is filtered off. anal. of the filtrate. also contains silicic acid and stannic oxide. The final filtrate from the tungstic acid determination is evaporated to dryness. of a solution 1000 c.

dilute ammonia solution in order to make sure that it contains should be the case. the spongy contents of the porcelain crucible. and washed. the crucible is placed inside a larger one of platinum and ignited over a Teclu burner The resulting tungstic acid is said to be from silica and stannic oxide. no trace The of metallic tin. of pure zinc are added precipitated. In this way the whole of the tin is obtained in an acid solution. and the greater part of the tungsten remains undissolved in the whereby the tungstic acid stannic acid is form of the blue oxide. solution is now If this diluted with water and the tin precipitated stannous sulphide by the introduction of hydrogen sulphide The precipitate is filtered. a second 100 c. which does no harm.TUNGSTEN. The blue oxide on the filter. The tin then goes into solution as stannous chloride. whereby tungstic acid and stannic acid are At this point 2 or 3 gms. 233). Or. as and weighed as SnC>2 (see p.c. 8. The mixture is allowed to stand quietly for an hour at a temperature between 50 and 60. is then allowed to cool somewhat and some powdered potassium * Wiener Monatshefte. 234). 301 acid (using preferably a Munroe crucible). however. .c. in the presence of a small amount of tungsten. of the original It is treated with 45 c. the moist precipitate of stannous sulphide may be dissolved in potassium hydroxide solution and the tin determined by electrolysis (see p. the small particle of tin is dissolved in a little hydrochloric acid and the resulting solution added to the main solution of the tin. The latter is filtered off. For the determination of the tin. crucible are heated in a beaker with hydrochloric acid (1:2) until The solution there is no more evolution of hydrogen perceptible. 647 (1887). free is changed to the blue oxide and the reduced to metallic tin. is dissolved in hot. to constant weight. of concentrated alkaline solution is used. or in case the latter is not available. ignited in a porcelain crucible gas. and ignited in an electric oven. hydrochloric acid. * According to Donath and Miiller a mixture of stannic oxide and tungstic acid may be separated as follows: The mixture is ignited with powdered zinc for fifteen minutes in a covered After cooling.

determined in the filtrate as above. in the mixture of oxides as obtained after precipitation with mercurous nitrate. In such cases. as Friedheim * has shown. for in this case the silicic acid is so enveloped with tungstic acid that some of the former is not volatilized as fluoride. Thereby the tungsten is volatilized. . washed first with dilute nitric acid and then with one per cent. such as obtained by evaporation with nitric acid. dried. tin is 3. When a mixture of tungstic and silicic acid is at hand. the hydrogen is replaced by air. In such cases. soc. which can be recovered in a receiver containing dilute hydrochloric acid. f Bull..-f The mixture of the ignited oxides is introduced into a platiboat and heated to redness in a stream of dry hydrogen chloride. probably as an num acid chloride. excellent results may be obtained by the Method of Perillon. solution of ammonium nitrate. is Frequently the tungsten is reduced to a blue lower oxide. and the contents of the boat are heated chloride In a current of air. however.. the silicic acid may be removed by treating the ignited residue with hydrofluoric acid is and a large excess of sulphuric acid. 45. replaced The tube by hydrogen chloride. is again allowed to cool. 1'industrie miner. The separation does not succeed. the silica remains behind in the com- bustion tube.GRAVIMETRIC ANALYSIS. Chem. which not volatile in a current of hydrochloric acid gas. the air and the tube once more heated * Z. anorg. after the apparatus has been allowed to cool. Separation of Tungstic Acid from Silica. The WO and weighed as ignited. 302 chlorate is added little by little until the blue tungsten oxide is completely transformed to yellow tungstic acid. and after standing twenty-four hours the tungstic acid is filtered off. It is diluted with one and onehalf times as much water. 398 (1905). when the liquid no longer shows any blue tinge. 1884.

to receiver is in the chloride evaporated dryness with nitric acid. is a volumetric process. and chromium are present. Vanadium is determined as the pentoxide. is WO the current of hydrogen chloride gas is perfectly free from platinum boat will be strongly attacked. V2 O 5 The most convenient method for determining vanadium . If phosphorus. In practice. the melt is extracted with water. whereby the sodium vanadate goes into solution while most of the metals nitrate. The bisulphate method of effecting the separation accurate (See Vol. are left behind in the form of oxides or carbonates. and it is a matter of separating it from the aqueous solution obtained after fusing with sodium carbonate and potassium nitrate. the form of the sodium salts of the corresponding acids. I). and will be discussed in the chapter on volumetric analysis. arsenic.33 VANADIUM. If vanadic sulphide is carefully roasted in the crystalline mass.2. it is also a mixture of six parts sodium carbonate and one part potassium After cooling. to redness. the is less At. 51. and chromic acids). can be easily changed to the pentoxide by ignition. the latter is a reddish-brown fusible substance which solidifies as a radiating. the vanadium is separated from the other metals present by fusing with air. V. VANADIUM. therefore. is Unless and the precipitated 3 filtered. it changed quantitatively to the pentoxide. If vanadium is present as ammonium or mercurous vanadate. Wt. tungsten). air. the vanadium is usually met with as the sodium salt of vanadic acid. ignited and weighed. The process repeated if necessary until finally a The tungsten acid residue of pure white 8162 is obtained. In the analysis of most minerals containing vanadium. . on treating the melt with water in also dissolve these elements arsenic (molybdenum. and of separating it from the other acids which are likely to accompany it (phosphoric.

In neutralizing the alkaline solution of the vanadate with nitric acid. 22. The precipitate is dried. The alkaline solution is nearly neutralized with nitric acid and to it is added. 69.. Chem. { obtained correct results by working as well as E. by which it is precipitated as lead vanadate. J Z. the gray-colored precipitate is allowed to settle and is filtered and washed with water to which a few drops of II mercurous nitrate solution have been added. 32. drop by drop.. according to which the vanadium is precipitated as mercurous vanadate. order to avoid passing over the neutral point. t Dissertation. II Berichte. 1903. The Mercurous Nitrate Method of Rose. Berlin. 3164. and that of Roscoe. but Gooch and Gilbert. 304 from the Solution Sodium Vanadate. which was saturated with ammonium chloride. nitrate used should leave no residue on being ignited. Champagne. The Berzelius-Hauer method. and the residue of V2 O 5 is weighed. * Pogg. 1890. 1. The mercurous . prakt. The method gives good results. Precipitation of Vanadic Acid of There are two good methods for the separation of vanadic acid from a solution of an alkali vanadate: the Rose method. Hillebrand recommends fusing with a weighed amount of sodium carbonate and adding the amount of nitric acid that has been found necessary by a blank test to neutralize this. 388. for in this case nitrous acid (from the nitrate fusion) will be set free and the latter reduces some of the vanadate to a vanadyl In salt and the latter is not precipitated by mercurous nitrate. is in an ammoniacal solution.' GRAVIMETRIC ANALYSIS. Ann. 175 (1902). The liquid is then heated to boiling. was found by Holverscheidt f to give always too low results. a nearly neutral solution of mercurous nitrate until. the solution must on no account be made acid. Remark. ignited under a good hood.. Chem. anorg.* in which the vanadium precipitated as ammonium metavanadate. a further addition of the reagent causes no precipitation. after the precipitate has settled. 54 and J.

driving off the excess of sulit is phuric acid. from 50 to 100 c. The filtrate containing all the vanadic acid is evaporated in a porcelain dish to a small volume. The Lead Acetate Method 2. Suppl. and the vanadium determined in precipitated the filtrate by evaporating the latter. After cooling. After being dissolved in as little nitric acid as possible. rapidly settle to the the beaker. and weighing the residual V 2 O 5 Procedure. and it it. 8. Principle. orange-yellow lead vanadate is quantitatively The lead vanadate.35 VAHADIUM. finally heating over the free flame until dense fumes of sulphuric acid are evolved. the lead washed. The solution from the sodium . evaporated further on the water-bath. carbonate and potassium nitrate fusion is nearly neutralized as before with nitric acid. when the will collect together. but OD absolutely clear.. constant composition. Pharm. white and free from vanadium it will be so provided enough sulphuric acid was used and the mass was not heated until absolutely color with lead .c. and finally in an air-bath until all the sulphuric * Ann. and the supernatant liquid will appear The precipitate is at first orange-colored.c. voluminous precipitate bottom standing It is of gradually becomes yellow and finally perfectly white washed with water containing acetic acid until it filtered off. is which enough into nitric acid is added An excess of sulphuric acid is added evaporated on the water-bath as far as possible. . dry before diluting with water. and the solution added to the main part is of the precipitate. however. 102 (1872). of water are added. as lead sulphate. If of Roscoe* a solution weakly acid with acetic acid is treated with lead acetate. the lead sulphate is filtered off and washed with dilute sulphuric acid until 1 c. an excess of lead acetate solution is stirred into it. so that the amount of vanadium present cannot be determined by weighing the precipitate. to to completely dissolve to the solution. does not possess a precipitated. Chem. of the filtrate will The show no yellow sulphate should be hydrogen peroxide. transferred to a weighed platinum crucible. dish. the part remaining on the filter is dissolved in as little as possible of hot dilute nitric acid.. half a cubic centimeter of the filtrate will leave The now washed no residue on a porcelain precipitate evaporation.

306 acid is removed. For their separation. the solution is saturated with hydrogen sulphide and the precipitate of arsenic trisulphide is filtered off. these are decomposed only at a faint-red heat. Instead of decomposing the lead vanadate by means of sulphuric acid. Lead may also be separated from the vanadic acid as lead chloride. 308) The separation of is in the analysis followed. vanadium as the sulphide by acidifying a solution of an alkali vanadate that has been treated with an excess ammonium not admissible. both elements go into solution. whereby the vanadic acid is reduced to vanadyl salt and the arsenic to arsenious acid. In this case the procedure recommended of vanadinite (p. H. and after extracting the melt. obtained by fusion with sodium carbonate and nitre. and the reddish-yellow hydrate of vanadic acid is changed by gentle ignition into the pentoxide of vanadium.GRAVIMETRIC ANALYSIS. the solution evaporated to dryness. the rest remaining precipitated in solution in the form of vanadyl salt. The open at a faint-red heat and its crucible is then ignited for some time * contents finally weighed as V 2 5. Rose called the attention of vanadium sulphide is is of chemists to the inaccuracy of this method. with water. vented its Separation of Vanadium from Arsenic Acid. A few drops of nitric acid are added.by means of hydrogen sulphide and determining the Remark. brown . vanadium in the filtrate. For this purpose the blue-colored filtrate from the lead sulphide precipitate (which contains some vanadyl salt) is boiled to expel the excess of hydrbgen sulphide and the deposited sulphur is filtered off. The author has carefully tested the method and found it useless. for only a part of the as the brown sulphide. Most minerals containing vanadium also contain arsenic. but this has not pre- being recommended in some of the most recent works on analytical chemistry. the solution is acidified with dilute sulphuric acid and sulphur dioxide is passed into the hot liquid. After boiling to remove the excess of sulphur dioxide. The filtrate is freed from * On expelling the sulphuric acid. Holverscheidt recommends precipitating the lead as sulphide. there is finally formed some green and crystals of a compound of vanadic acid with sulphuric acid.

of 8 per cent.1 gm. Carbon dioxide is passed into the boiling solution until the excess of sulphurous acid is removed. the precipitate washed with dilute mercurous nitrate solution and In this weighed. of cool. P2 O5 no trace of the latter could . of hot 25 per cent. A. hydrogen sulphide by boiling. solution of ammonium nitrate and 50 c. nitrate solution this solution and 1 c. Vanadium from Phosphoric Separation of If the solution of the soda-nitre fusion contains Acid.c. ammonium c. to about 60 C. the melt is dissolved in water. of ammo- nium molybdate are added.c. To ammonium molybdate solution is warmed solution are added Remark.c. below).. evaporated with nitric acid in order to form vanadic acid again. the solution is then made alkaline with sodium carbonate. .c. the and allowed to stand (cf. i vo'. after which the precipitate is dissolved by for one hour. nitric acid. the solution made When P2 5 is acid with sulphuric acid and boiled with sulphurous acid in order to reduce the vanadic acid to vanadyl sulphate.c. .ume. passing 10 c. now about 100 c. of the proper wash liquid (see p. set aside The clear liquid is then decanted through a filter. ammonia through the filter into the the beaker containing the bulk of the precipitate and the filter is finally washed with 30 a 34 per cent. The phosphoric acid is determined by the method of Woy (page 440). To of water. and the vanadium determined by one of the above methods. phosphoric as well as vanadic acid. Gressly tested this method in the author's labora15 gm. the latter will be recognized by the pure blue color which the solution assumes.c. but only sinters The ignited oxides are fused with an equal weight of together. when it is allowed to ' the cold solution. washed three times by decantation with 50 c.c. way the sum V O5 +P O5 of the 2 2 obtained. is present the V2 O5 does not melt.c. both are precipitated by mercurous nitrate. The amount df phosphoric acid found is deducted from the sum of the oxides and the difference gives the amount of V2 5 Remark. 200 c. and the phosphoric acid repreci pita ted by the addition of 20 c. tory and made the interesting observation that if about of V2 O5 was present with 0. sodium carbonate.37 VANADIUM.c. the solution heated until it begins to boil. more 20 of c. 437). of a 75 per cent.

vanadic acid. of ammonium molybdate dissolved in 500 c. 306. The above-described separation gives correct results only when present as vanadyl sulphate. sp.c. of nitric acid. filtered. Separation of The acidified Vanadium from Molybdenum.GRAVIMETRIC ANA LYSIS. the vanadium is present it is tion is allowed to stand after the addition of the ammonium molyb- date. of the finely powdered mineral is dissolved in dilute nitric acid (in order to avoid loss of chlorine the solution is kept cold). The filtrate from the silver chloride is treated with hydrochloric acid in order to precipitate the excess of silver. 285 and 286) and weighed as Mo0 3 of hydrogen sulphide from the filtrate. Analysis of Vanadinite. of water) and this solution poured into 500 c. About 1 gm. gr. as described on After removing the excess pp. and the solution thus freed from silver is evaporated . and the prethrough a Gooch crucible. Determination o] Lead. the precipitate therefore should not be allowed to stand long before filtering. The chlorine is precipitated with silver nitrate and the weight of the silver chloride determined as described on p. solution containing the alkali salts of the two acids is with sulphuric acid and the molybdenum precipitated in a pressure-flask cipitate filtered off by means of hydrogen sulphide. . washed with hot water. if vanadic acid is If the soluprecipitated with the phosphoric acid. with nitric acid and determined as described under the Separation of Vanadium from Arsenic Acid. the mineral often contains arsenic and phosphoric acids. Determination of Chlorine. Besides lead.c. the vanadium is oxidized . 317. On the other hand. and the solution is diluted with considerable water. and chlorine. 308 be detected according to the procedure of Woy. the vanadyl sulphate is gradually oxidized to vanadic acid. not even on boiling the solution. an immediate precipitation was produced if a stronger solution of ammonium molybdate were used (75 gms. p. 1:2. (Pb 5 ( VO 4 )3 C1).

its anhydride is weighed with the vanadium and the amount of P 2O 5 is deteras described on p. this precipitated by the addition of sulphuric acid. 309 The dry mass is moistened to dryness to remove the nitric acid. the last portions of lead and arsenic are precipitated by hydro- with sulphurous acid. and afterward more strongly with ready access of air (uncovered crucible) until the reduced. at first red pentoxide. filtered through a Gooch at 110 C. 307. dried to precipitate completely the lead chloride. on the water-bath. From the filtrate. The arsenic sulphide is then changed to gen sulphide. and the lead For portion. the residue adhering to the sides of the dish is dis- solved in a little ammonia and added to it. Determination of Vanadium. The dry mass is vanadyl washed by means of as little water as possible into a weighed platisalt to num crucible. If phosphoric acid is present.VANADIUM. and weighed as crucible. this amount is deducted from the mined weight of the two oxides. Phosphoric Acid. 206. PbCl 2 . with hydrochloric acid. and is repeatedly evaporated in order to oxidize the blue brown vanadium pentoxide. with sodium sulphide and the arsenic precipitated from the solution thus obtained by the addition of hydrochloric acid. and previous filtered precipitate is digested and preferably is . the solution is diluted with water. The determination of arsenic is best carried out in a separate purpose the mineral is dissolved in hot nitric acid. alcohol is added in order and the latter is washed with alcohol. 95 per cent. after The reduction by dissolving in ammoniacal hydrogen precipitated as magnesium ammonium arsenate determined according to p. arsenic acid. The filtrate from the lead chloride contains the vanadium The as vanadyl salt. and Arsenic. The crucible is then gradually to expel the ammonia. dark-colored oxide is changed over to the brownishheated. peroxide. the latter is alcohol nitric is acid driven off by careful heating added to the solution. the greater part of the excess of the acid is removed by evaporation. The temperature is then raised until the vanadium oxide begins to melt.

. Survey Bull. latter. and considerable silicate as First of all. taken up filtered. is * See U. F. chromate.f The aqueous sodium vanadate and often phosphate.to proceed as follows: Five gms. The almost neutral solution in water. the residue is evaporated to dryness with hydrofluoric and sulphuric acids. of soda is determined by a blank test.GRA yiMETRIC ANALYSIS. but contains chromium. the dry mass is fused with soda and nitre again. in small is it often of of iminterest and although very amounts. f If considerable vanadium is present. 310 Determination of Vanadium and Chromium in Iron Ores and Rocks. J The amount of nitric acid necessary to neutralize 20 gms. sodium carbonate and 3 gms. For this portance purpose best. S. molybdatc.J solution contains It is very important that the solution is not made acid at this point on account of the reducing action of the nitrous acid set free from the nitrite formed during the fusion. the aluminium and the greater part of the silicic well. and the residue is filtered off. Geol. a little nitric acid cautiously added. of the finely powdered mineral are mixed with 20 gms. besides place. in the mineral. the insoluble residue always contains vanadium and must be fused with soda-nitre again. molybdate. The residue of . acid are removed by nearly neutralizing the alkaline solution with nitric acid. Method of W. if the corresponding elements are present If the precipitate is too bulky. also its chromate. mercurous carbonate. in to be able to determine it such cases. aluminium hydroxide and silicic acid almost never conIf it is desired to determine the tains vanadium. potassium nitrate and fused over the it is The green fusion (containing manganese) is extracted blast-lamp. The and is evaporated nearly to dryness. with water. Hillebrand* As vanadium often occurs in many ores of iron and in rocks. aluminate. a few drops of alcohol are added to reduce the manganese. vanadate. 411. and the aqueous solution of the melt added to the main solution. and then a drop of mercurous nitrate in order to see if the precipitation is complete. and phosphate. cold alkaline solution is now treated with an almost neutral solution of mercurous nitrate until no further precipitation takes The somewhat voluminous precipitate contains. arsenate.

arsenic. and from amount used the from must be subtracted vanadium of amount the the difference present is calculated. Anal. the solu- now reduced by means of sulphur dioxide and the titration The mean of the two experiments gives the vanadium repeated. for a measurable amount of permanganate is used up in oxidizing the chromium.).c. The precipitated sulphides off. and traces of platinum precipitated by hydrogen sulphide in a pressure-flask. On cooling the mass is colored a beautiful blue if molybdenum is present. the filter together with the precipitate is carefully ignited in a porcelain crucible. and titratanalyzed solution.VAKAD1UM. with water containing ammonium 311 the precipitate washed nitrate. The filtrate from the above precipitate is freed from the exhydrogen sulphide by boiling and passing a stream of carbon dioxide through it. . The amount in the analysis. if yellow-colored. it is filtered into a 25-c. and the hot solution is then titrated cess of the N to a pink color with ~^r potassium permanganate solution (cf Vol. In case more than 5 mgm. platinum crucible at as low a temperature as possible. The ignited residue is fused with a little sodium carbonate. of chromium are present a correction must be made. tion is value. the melt extracted with water and. The liquid is heated to boiling. dried. a few drops of sulphuric acid are added and the crucible heated again until the acid is almost com- are filtered pletely removed. This method gives correct results only when the amount chromium present is very small. flask and the amount of chromium determined colorimetrically by comparing its color with a carefully prepared solution of potassium chromate. The solution is then slightly acidified with sulphuric acid. and the molybdenum. reducing of permanganate now used ing with permanganate. . and ignited in a filtered. which is true in the majority of of cases. This is determined by takof chromate as the ing a solution containing the same amount with it sulphurous acid. In order to obtain absolutely accurate results.

meanwhile passing a current of carbon dioxFor each gram of iron taken.c. 312 Determination of Vanadium and From Chromium in Pig Iron. allowed to cool. finally boiling it until there is no more evolution of gas. Vol. 1. and the solution filtered. of ide through the liquid. and. the is amount of determined colorimetrically * by placing the solution in a graduated cylinder and comparing its color with a potas- chromium present * The is colorimetric determination When considerable is only suitable chromium when small amounts are present (chrome steel) the results obtained by the colorimetric determination may be as much as 2 per cent. solution is acid. The residue is fused with a little sodium carbonate. gr. the melt extracted with water. and the vanadium as vanadate in the presence of alkali silicate and phosphate. the liquid is heated to boiling. The residue is filtered off. being care- acid set free will The barely alkaline then treated with an almost neutral solution of mercu- rous nitrate until no further precipitation takes place. too In such cases the chromic acid is titrated with ferrous sulphate (see high.GRAVIMETRIC ANALYSIS. as much of the precipitate as transferred to a platinum crucible.). The hastened by warming. 5 c. In case the filtrate colored yellow. of water are used. It is now diluted with an equal volume of water. After drying. The fusion is leached with water and the solution thus obtained contains all the chromium as chromate. which mercurous is is ignited to remove the mercury. Five parts of sodium carbonate and one part of nitre are then added to the contents of the crucible and the mixture is heated to quiet fusion. the filter burned by possible itself and its ash added to the main portion of the precipitate. filtered and washed with water containing a little nitrate. present. of the iron are dissolved in dilute hydro- chloric acid in a flask. solution is an excess of barium carbonate is added and the mixture allowed to stand for twenty-four hours with frequent shaking. The aqueis now nearly neutralized with nitric make the solution acid as the nitrous ous solution ful not to reduce some of the vanadium and chromium.c.12 and 10 c. sp. without filtering off the slight residue. hydrochloric acid. dried and ignited in a platinum crucible in order to burn off the carbon. rapidly washed with cold water. is . Anal. 5 to 10 gms.

) Molybdenum. the solution is diluted and filtered. solution is then acidified with sulphuric acid and hydrogen sulphide is conducted into the boiling solution to precipitate ar- The senic and platinum. Method of A. moved and After filtering.VANADIUM. 30. f and transferred with the aid of a little more of the same acid to a separatory funnel of about 250 c. sp. still when the conditions be removed so that a large of the iron can can be taken for analysis. The method is given in this edition of the book as illustrating the removal of the greater part of the iron from a ferric chloride solution by shaking with ether.1. Determination of is re- \ ^-.c. acid solution is evaporated to a sirup. Molybdenum.c. The ether separation. Chem. 1. Although it is difficult to effect a perfect separation in this are right. the latter dissolved in a little hydrochloric acid. is provided with tightly fitting stop-cock c. Blair. 313 sium-chromate solution containing a known amount of chromium. as well as the greater part of the iron. Procedure. follows the iron so that when a small amount of the former is present.. the hydrogen sulphide the hot solution titrated with ganate solution (cf. as is the case in steels. The resulting solution is evaporated to dryness and the residue dissolved by treatment with hot concentrated hydrochloric acid. . t Am. The separation works best with acid of this concentration.potassium perman- Volumetric Analysis). Two grams of the steel are dissolved in nitric acid with the addition of hydrochloric acid if necessary. gr. 1228. almost of sample steel all way. Vanadium. method has not been This particular laboratory and not given in the German edition. is discussed in many other text-books and deserves tested in the author's is mention. A. Chromium. the ether solution may be regarded as containing all of the molybdenum. If silica is The hydrochloric present. in this analysis.* and Nickel in Steel. however. Soc. of ether are added to the cold About 80 * J. capacity which and glass-stopper. (TRANSLATOR.

the precipitate is allowed to settle. the lower layer is The stopper of the transferred to a second separatory funnel. chromium.c. the solution evaporated nearly to dryness. The vanadium is determined in this last filtrate.c. sp. of hot water are added and the tion is heated with the addition of a little sulphurous acid to reduce any chromic acid that may have been formed. water. of a 10 per as lead vanadate the addition by cipitated cent. treated with 10 c. contains the vanadium. gr. acid solution containing manganese and copper. result in the reduction of some of the iron by . When 1. boiled and filtered. The hot solution is slowly poured.GRAVIMETRIC ANALYSIS. solution of lead nitrate. run into a beaker and freed from dissolved ether by evaporating on the water bath nearly to dryAn excess of nitric acid is added and the solution again ness. the contents of the funnel once more shaken.c. cooled. more of ether. first funnel is carefully rinsed with hydrochloric acid. nickel and iron with the greater part of the manganese and any copper that may have been in the sample.c. solution of sodium hydroxide. treated with 50 of hydrochloric acid. and the the vanadium. dilute hydrochloric acid. After boiling a few minutes. It is made barely acid with nitric acid. and finally on the about 300 filter until the volume of the The precipitate contains the hydrated oxides of chromium. and the lower layer added to the contents of the second funnel. and evaporated until fumes c. some silicate and aluminate (from the reagents) and sometimes a little chromium. is washed twice by decantation. the two liquids are in equilibrium. When the soluis almost sirupy. nickel.1. * The warm solution would the ether. The solution in the latter is shaken with 50 c. concentrated sulphuric acid. It is preof 10 c.c. 314 solution* and the mixture is shaken vigorously for half a minute. filtrate is The filtrate c. into a boiling solution 10 per cent.c. once more made alkaline with a few drops of sodium hydroxide. while stirring vigorously. 20 c. The lead vanadate is filtered and washed with hot The precipitate is dissolved in hot. all is evaporated to remove all the hydrochloric acid. eventually adding enough acetic acid to make the sojution decidedly acid and boiling for several minutes. evaporated again.

13". Compt. the solution heated to between 60 and 70 and titrated with permanganate.* and the titration with permanganate makes the vanadium pentavalent again. hydrated manganese dioxide (alumina and silica from the iron and part of the Tne filtrate is boiled to drive off the ammonia. and filtered. the filtrate contains the chromium and the rest of the manganese. phurous acid added to reduce any chromic acid. The evaporated solution The precipitate consists of is diluted to 50 c. of sodium carbonate and half a gram of potassium nitrate. of water of sulphuric anhydride are evolved.. the solution diluted hydrogen sulphide. is is evaporated with sulphuric all expelled. 315 When cold 150 c. and the chromium precipitated by the The precipcareful addition of ammonia to the boiling solution. it is . To the filtrate. are added. Consequently 2 atoms V The are equivalent to 1 atom of oxygen in the titration. The two niters are ignited and the precipitates fused with about 2 gms. The fused mass is treated with water and the solution filtered. MOLYBDENUM. The ignited oxides are dissolved in hydro- chloric acid. and the solution evaporated to small volume with the addition of a few drops of ammonia from time to time. 570 (1903). The evaporation of the vanadate solution with hvdrochloric acid and subsequent treatment with sulphuric acid results in the reduction of the vanadium from the pentavalent to the tetravalent condition. The filter containing the insoluble residue from the above fusion is returned to the same crucible in which the fusion was made and ignited.DETERMINATION OF YANADIUM. whejeupon rend. manganese. copper. The residue contains the nickel.c. The two precipitates obtained by the sodium hydroxide treatment contain chromium. ETC. sulreagents). the excess of reducing agent boiled off. enough ammonium nitrate is added to convert all the sodium salts to nitrates. The and the copper precipitated by filtrate acid until the hydrochloric acid *Campagne. nickel and copper besides iron and manganese. washed and weighed as Cr 2 O 3 . itate is filtered off. vanadium is the interfere when little iron does not a of presence of reduced in the above manner.c.

c. of water. The heating and weighing is repeated until the pre- The crucible is then placed in cipitate ceases to lose in weight. After slowly cooling. cover and the heating is continued until the ignited precipitate becomes bluish white in color. 136). reduced by the careful addition of ammonium acid sulphite. The ether solution from the two separatory funnels is shaken with water. The lower layer is.c. the precipitate is filtered into a Gooch crucible and washed with water containing a little sul- several hours. the cold solution treated with 10 c. which causes the separation of an ether layer from the solution containing the iron and molybdenum. the solution of ferric chloride containing all the molybdenum is evaporated nearly to drynees. cooled and weighed. pressure The bottle is stoppered and heated on the water bath for bottle. The Gooch crucible is placed within a larger porcelain crucible so that the bottom of the former does not touch that of the latter. the excess of sulphurous acid boiled off. and the cold solution saturated with hydrogen sulphide in a 200 c. therefore. The Gooch crucible is then heated to faint redness. the suction bottle and washed with ammonia until the washings are free from molybdenum. of concentrated sulphuric acid and evaporated until the sulphuric acid fumes The cold sulphuric acid solution is diluted with 100 c. drawn off. 316 diluted and treated with a nickel determined by large excess of ammonia and the electrolysis (see p. phuric acid and finally with alcohol. The The crucible is again heated and difference in weight corresponds to the amount weighed.GRAVIMETRIC A NA LYSIS. freely.c. . of molybdenum trioxide. covered with a watchglass and heated gradually until there is no more odor of sulphur The watch-glass is then replaced by a porcelain crucible dioxide. small amount of ferric oxide always A remains on the felt.

. Thus one liter of 1 per cent. is heated to boiling and the silver precipitated by the addition of hydrochloric acid. The determination considered. Chem. As much dried first obtained. . Wt. 107. X At. of 10 per cent. the silver chloride can be filtered upon an ordinary washed filter.00154 g. and 1 1. first with water containing a little nitric acid until the chloride test can no longer be obtained. Ag. it 3 lead of Forms : 7 THALLIUM). The ash of the filter is added to the main portion of the precipitate. HC1 dissolves 0. If it is is transferred to a weighed porcelain burned (as described on page 21) in a platinum spiral whereby some of the silver chloride adhering to it will be reduced to metal. the AgCl is less weighed.88. filtered through a Gooch crucible and washed. Whitby.0555 g. S. till a constant weight is not desired to use a Gooch crucible for this determination. AgCl. the solubility of AgCl rises rapidly. drop by drop. * G. HC1 dissolves 0. washed as before and dried at 100 C. silver. After cooling in a desiccator it is One liter of Solubility of Silver Chloride* 0.SILVER. dried on the waterand then heated over a free flame until the silver chloride fyath of the precipitate as possible crucible.0003 g. AgCl at 20 and 0. anorg. slightly acid with nitric acid. water dissolves In water consoluble than in pure water but as the quantity of hydrochloric acid is increased. 108 (1910). The precipitate is allowed to settle in a dark place. then twice with alcohol or water in order to remove the nitric acid. HC1 dissolves only 0. The solution. Z. AgCl.0002 g. AgCl at 21. of 5 per cent. but 1 1. LEAD. METALS OF GROUP I.0217 g. until no more precipitate is formed. and mercury has already been remains for us to discuss the determination of SILVER. The precipitate is and finally at 130 C. taining a little hydrochloric acid. at 100. AgCl and Ag. Determination as Silver Chloride. 67. at 100 C. It is moistened with a little nitric acid and a drop or two of concentrated hydrochloric acid. MERCUROUS MERCURY (AND SILVER. the filter begins to melt.

bonate. the chloride. or the In the latter case. but this method not be described in this book. Upon the silver salt is placed a small disk of platinum foil. bromide. for it offers no particular advantages over the determination as silver chloride with a Gooch cruwill cible. and the crucible then weighed. If the method. cyanide the substance must be heated very cautiously at first in a covered crucible. The porcelain crucible containing the silver halide is placed in a crystallizing dish and near it is placed a second crucible containing a little mercury and a small piece of zinc. obtained by the ignition of silver oxide. The crystallizing dish so that the crucible is is filled with dilute sulphuric acid (1:20) it is then entirely covered with the acid and Next morning all of the silver salt The crucible is removed from the washed with water. Lagutt obtained excellent results. ignited. dried. Silver can also be deposited electrolytically. the cover is removed from the crucible and the contents are ignited Metallic silver is is completely burned. and weighed as metal. Separation of Silver from Other Metals. and iodide may be effected very conveniently by passing the electric current through the substance after it has been melted together. in a stream of hydrogen. until the carbon From The reduction of the chloride. E. By this allowed to stand over night. the residue dissolved in a little water . Ag. bromide (but not the iodide) and sulphide. and weighed. and escape reduction. acid.GRAVIMETRIC ANALYSIS 3i8 Determination as Metal. precipitated from a nitrate solution by means of 2 S. the other end of the wire dips in the mercury in the other crucible. the silver H is the nitrate is evaporated to dryness. ignited To determine the thallium. carsalt of an organic acid. When the organic substance is completely charred. has not been fused to a compact mass small particles the silver precipitate are likely to float around during the opera- simple silver halide of tion. will be found to be reduced. which is fastened to a platinum wire. As almost all metal chlorides * are soluble in dilute hydro* Thallium chloride If thallium is present is difficultly soluble in water. the metal may be obtained by igniting in a current of hydrogen.

mercurous salts these are oxidized before the addition of the hydrochloric acid by boiling with nitric acid. suver is 319 separated from the other metals by the addi- If the solution contains tion of hydrochloric acid to the solution. and the thallium precipitated by the addition of potassium iodide. dried at 150 and weighed as Til. .SILVER. then with alcohol. For the separation of silver from gold and platinum in alloys consult pages 259 and 270. chloric acid. The thallium iodide precipitate is washed with dilute potassium iodide solution.

AND HYPOCHLOROUS HYDROCHLORIC ACID. and silver slowly added with constant stirring until the precipitate and further addition of the reagent produces no more precipitation. boiling changed to cipitate allowed to settle in the dark. HYDROCYANIC. B. the prenitrate is collects together through a Gooch and then treated exactly as described in the determination of silver. If only metals of the alkali or alkaline earth groups are present. Ferrous salts. and ferric salts. Wt. HC1. The liquid is now heated to boiling. it is not always possible to follow the above procedure. the cold solution is made slightly acid with nitric acid. SULPHOCYANIC.GRAVIMETRIC DETERMINATION OF THE METALLOIDS (ANIONS). The chloride solution is present either as free hydrochloric acid or as a chloride soluble in water. It is present in the form of an insoluble chloride. in case only little ride 320 . 36. for are substances on which are present exampb. HYDROFERROCYANIC. HYDRIODIC. Mol. it is evident that the precipitate of silver chlo- would b3 contaminated with these substances and too high This is particularly true of stannic results would be obtained. page 317. HYDROBROMIC. If. HYDROCHLORIC. Form : ACIDS. A. HYDROFERRICYANIC. The Chloride is Present in Aqueous Solution. on the other hand.47. If the aqueous solution contains a chloride of a heavy metal. filtered crucible insoluble basic salts. We can distinguish between two cases: A. Silver Chloride. GROUP I. AgCl.

The solution is then heated to boiling and. Each beaker is quickly stoppered and then weighed. if enough nitric acid is present to prevent the reduction to silver. Determination of Tin. As both the solid salt and its concentrated solution are very necessary to weigh out the portion for analysis hygroscopic. the danger of forming basic salts still remains to be feared. Four more weighing beakers are now tared and into each is placed about 2 c. 321 reduce silver nitrate to metallic silver on heating the solution. the salt is completely dissolved to a homogeneous syrup by shaking.c.2). and precipitated in the cold utes. of the syrup. whereby the is colored red. from a stoppered vessel. sp. Example Tin chloride to the formula is : Analysis of Commercial Tin Chloride. beaker. diluted to about 300 c. Ammonia solution (free from chloride) is now added until .c. of water are added. boiled for one or two min- and washed with water containing ammonium nitrate.) is placed in a tared weighing beaker. it is better to first remove the heavy metal by precipitation with ammonia. is In all cases. obtained either as a solid salt corresponding 2 O. closed and weighed. and the beaker is again weighed. with silver nitrate.c.c. and weighed as SnO2 Determination of Chlorine. caustic soda or sodium carbonate. About 10 c. In such cases the precipitation is effected as before from a cold solution and the subsequent heating omitted. The filtrate from the tin hydroxide precipitate is acidified with nitric acid.the color of the solution is changed to yellow (an excess of ammonia must be carefully avoided for tin hydrox- liquid ide is with somewhat soluble in ammonium ammonia).c. or as a concentrated aqueous solu4 SnQ + 5H tion. ACID. however. and a few drops of methyl orange are added.HYDROCHLORIC nitric acid is present. nitrate (5 c. The contents of one of the weighing beakers is washed into a 400-500-c. . filtered. The solution of concentrated is then treated ammonia exactly neutralized with nitric acid. 1. It is best to proceed as follows: it is A large sample of the substance (about 10 gm. . gr.

) antimony or stannous compounds are present. of the Solution SnO 2 found=p. This amount of substance yielded p gm. Anal. . taken for Analysis = a. SnO 2. of the solid salt. It has been proposed to add tartaric acid to the solution. of substance taken. then the amount a of the solution taken for analysis x= A-a = -5- n will contain : wt. then dilute with water and precipitate the chlorine with silver nitrate. corresponding to: SnO 2 :Sn =p:x? . = Sn02 and in percentage : In the same way the amount of chlorine present is found to be: 100C1 p'-B_^ 3Sa"?Z %l This analysis may be volumetric process. A of the solution contain gm. and weighed. the above procedure cannot be used. AgCl found = p'. however. The amount of tin and chlorine present is computed as follows after crucible. : Weight Weight Weight Weight Weight Since B of Solid Salt =4. gm. dried at 130 C. then with cold water or alcohol. it is filtered through a Gooch washed with cold water containing a little nitric acid. 322 the precipitate has settled. If accomplished much more rapidly by a (Consult Vol. of the Solid Salt of the of the + Water =B. to proceed as precipitated by hydrogen sulphide as its .. follows: The antimony is It is better.GRAVIMETRIC DETERMINATION OF THE METALLOIDS.

silver chloride.HYDROCHLORIC ACID. For the determination of chlorine * Mercurous chloride in rocks. The mass is treated with water. (This does not apply to a sampleapatite contaminated with silica or silicates. In such cases. a little containing all the chlorine made is hydrogen peroxide or potassium per- is added (both reagents must be free from chloride) and boiled until the excess of the peroxide is destroyed. 1 gm. filtrate slightly ammoniacal. chlorine in apatite may be determined by treating the finely powdered mineral with nitric acid and silver nitrate on the is solution. Silver chloride should be mixed with three times as much sodium carbonate and heated in a porcelain crucible until the mass has sintered together. It is less rated with practical to proceed as follows : The ammonia and the hydrogen solution is satu- is sulphide precipitated by the addition of ammoniacal silver nitrate solution. According to this method.f sodalite. is boiled with sodium carbonate solution * (free from chloride) and the chlorine determined in the filtrate as before.g. e. upon by potassium or sodium hydroxide. solution the this treatment traces of hydrogen sulphide remaining in the By carbonate solution are oxidized to sulphuric acid. chlorine may be determined in the presence of large amounts of hydrogen sulphide without difficulty. many minerals such as apatite. the deposited silver sulphide is filtered off. after which the precipitate is filtered The and washed. of the finely- decomposed only slowly by sodium carbonate. and rocks 'containing the latter. the solution is acidified with nitric acid.) water-bath. Analysis of an Insoluble Chloride. trate as under (a). Many chlorides. but readily acted Everything goes into solution with the exception of silver which is filtered off and weighed. f According to Jannasch. the substance must be fused with sodium carbonate. and the silver chloride precipitated from the filtrate by acidifying with nitric acid. are not decomposed by boiling them with sodium carbonate. After cooling. of . the excess of the latter is removed by passing carbon dioxide through the solution. washed with ammonia. and the chlorine determined in the fil- The substance . 323 sulphide. B. chloride. and the chlorine determined as silver chloride as described above. the insoluble silver filtered off.

a part of it remains in solution as soluble silver chlorate: 6C1+ 3H 2 O+ 6AgNO 3 = 5AgCl+ AgClO 3 + 6HNO 3 The 1. the solution is acidified If silicic acid with nitric acid and allowed to stand overnight. is no separation and . Free Chlorine. cooling. After has . If it is desired to determine gravimetrically the amount of chlorine in a sample of chlorine water. there be feared from 1 gm. The cold filtrate is acidified with nitric acid and the. is extracted with hot water. its salts This may : A definite amount of the chlorine water is transferred by means of a pipette to a flask containing ammonia and after mixing the soluAfter cooling the liquid is acidified with tion is heated to boiling. The ammonia connitric acid and precipitated by silver nitrate.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. 324 powdered material is much sodium fused with four or five times as carbonate (or with a mixture of equal parts sodium and potassium carbonates) at first over a Bunsen burner. and washed with hot water. The ammonium latter and quantitatively on warming nitrogen: (a) (6) is chloride and partly to am- decomposed partly into ammonium in the cold chloride 2NH 4 OH + 2C1 = NH 4 C1 + NH 4 OC1 + H 2 3NH 4 OC1 + 2NH 3 = 3H 2 O + N 2 + 3NH 4C1. or to one of nitrate. the solution is boiled. chlorine determined as above. verts the chlorine partly to monium hypochlorite.* the chlorine is precipitated at once from the cold solution. Hillebrand. . methyl orange is added. F. for all of the chlorine is not precipitated as silver chloride. of the substance. If there is no separation of silicic acid on acidifying the water extraction of the fusion with nitric acid. of silicic acid to .precipitated out by the next morning. a little ammonia is added. * According to W. afterward over a Teclu The melt burner or the blast-lamp. therefore. it is not feasible to simplify add silver nitrate. must be changed to hydrochloric' acid before attempting to precipitate with silver be accomplished in several ways chlorine. filtered.

phosphoric. and arsenic are oxidized in the same way to sulphuric. Ann. u. If Determination of Chlorine in Non-electrolytes (Organic Compounds). it is first set free as such. f. 136. the is heated under the same conditions with nitric acid in the presence of silver nitrate. the acid. After cooling the solution is acidified with nitric acid.HYDROCHLORIC The 2. If. chlorine water treated with dilute caustic soda solu- is tion. the solution contains both free chlorine and hydrochloric total chlorine is determined by one of the above methods. Sulphur. is partly oxidized by the nitric acid. phosphorus. Pharm. A. Method Principle. chlorine water acid. and the chlorine precipitated by means of silver nitrate. The 3. on the other hand. tains halogen. anal Chem. (1865). sulphur. The method is are decomposed compounds of Carius* based upon the fact that all organic by heating with concentrated nitric If the substance conacid at a high temperature under pressure. the solution is ACID. diluted with water. Chem. d. or arsenic. acid formed The latter. and arsenic acids and any metals present form nitrates. and Zeit. hydrogen peroxide is added. p. and the liquid boiled until the excess of hydrogen peroxide is removed. while the free chlorine is determined in a separate sample by a volumetric process (see lodimetry). however. 129. * 4. The therefore a reversible one. phosphorus. It is then acidi- with nitric acid and the chlorine precipitated by a soluble fied silver salt. 451. an aqueous solution of sodium arsenite is added (arsenic trioxide dissolved in sodium carbonate) until a drop of the liquid will not turn a piece of iodo-starch paper blue. 325 treated with an excess of sulphurous is made ammoniacal. . p. the halogen hydride is converted into silver halide as fast as it is formed and the halogen is in this case quantitatively changed into its silver salt. reaction is substance but on account of the reducing action of the nitrous it is then changed over into its hydrogen compound.

Aliphatic substances are usually decomposed by heating four hours at 150-200 C. with walls about 2 mm. of the tube is thick-walled capillary and the end fused together (Fig. c).GRAVIMETRIC DETERMINATION OF THE METALLOIDS. gr. The time and temperature must be .15-0. 1. long and 5 mm. wide). and shoving the paper it reaches about the About 40 c. As soon as the tube a plQ 53 containing the substance has reached the remains suspended (Fig. one end. 53. In this only the lower half of the tube is wet with the acid. A glass tube made of difficultly fusible glass (about 50 cm. may ferred to the tube piece of glazed paper into the tube until middle of it.2 gm. 53. 6). substances of the aromatic series usually require from eight to ten hours' heating at 250-300 C. while in some cases an even longer heating at a higher temperature is necessary." and gradually heated.5 gm. It very important that the substance should not come in contact with the acid before the tube is closed at the upper end. of pure nitric acid (sp. now heated very cautiously in the flame of the blast-lamp until the tube begins to soften and thicken (Fig. 326 Procedure for the Halogen Determination.. in diameter. The tube is then inclined way to one side and from 0. About 0. It is then drawn out into a 3-5 cm. long. of the substance contained in a small glass tube closed at one end is introduced into it (this smaller tube should be about 5 cm. After the tube has become cold. carefully shoved into the iron mantle of a "bomb furnace.c.5) free from chlorine are poured into the tube through a funnel whose stem is about 40 cm. long. it is enveloped in asbestos paper. 53. thick) is sealed at long. of silver nitrate (or in the case of powdered much be used) is transthe powder pouring by through a cylinder made by rolling up a substances rich in halogen as as 1 gm. thoroughly cleaned and dried by sucking air through it. 2 cm. it is wise there is likelihood of The upper end some halogen escaping. as otheracid. a).

I Before heating. is again and heated to the desired temperature. after three hours more 250-270 C. a scratch is made upon it with a file jus. 327 found out for each substance by experiment. the iron removed. and finally after another three hours a temperature of about 300 C. the tube and the hand should be wrapped in a towel to avoid accidents. the insoluble silver halide is filtered off through a Gooch crucible. out In most cases a drop of is tube brought in found the of will be the latter. When the contents of the tube are at the atmospheric pressure. The contents of the tube are then carefully poured into a fairly large little tube in which the substance was inner and the part of the tube as well as its capillary weighed out. as is often the case even with careful work. In such cases it should be heated to only 200 C.. is attained. with substances rich in sulphur. The point of the capillary is now more strongly heated % until the glass softens. beaker without breaking the thought that the precipitate is contaminated by fragbroken glass. carefully heated with a this means the and free flame. about 300 c. After cooling. and this is touched with a hot glass rod. allowed It is then fused together to cool. The decomposition is complete when on cooling the contents of the tube neither The heating is so crystals nor drops of oil are to be recognized. They are easily distinguished from crystals of the undecomposed substance. and heated to boiling. f Such a high pressure is often attained that the tube bursts as soon as it heated very hot. when it will be blown out The gas escapes in consequence of the pressure within the tube. the capillary opened and the gas set free. The liquid in the beaker is diluted to is washed out with water. liquid is driven back into the by in the furnace. its weight is determined.t below the capillary. and by other part of the tube. and after washing and drying at 130 C. the tube is allowed to cool completely mantle together with the tube is then slightly inclining the mantle the capillary of the into the open air. the clear liquid is decanted through a filter. the residue washed by If it is ments of * Sometimes. whereby the tube usually breaks and the upper part can be removed. is reached.c. .! After the heating is finished.* regulated that after three hours the temperature of about 200 C. crystals of nitrosyl sulphuric acid are formed and adhere to the sides of the tube.HYDROCHLORIC ACID. with a hissing sound.. In order not to lose point liquid of the is outer the point capillary this.

and the pletely reduced to metallic silver. The solution is filtered through the same filter. and the contents of the crucible are again evaporated to dryness. completely washed with dilute and then once with alcohol in order to remove the nitric As much of the precipitate as possible C. The residue is then warmed with dilute nitric acid upon the water-bath. residue washed by decanting several times with water until the iodine reaction can no longer be detected. and its ash placed nitric acid. heated to boiling. the liquid is reduced (in order to change any on a few the water-bath. and after allowing the silver chloride or bromide to settle in the dark. the solution is filtered through a small filter. The mass in the crucible is then covered with pure dilute sulphuric acid. The method of Carius is by far the best for the determination of halogens in organic substances when only one of the halogens is . This method is also suitable for obtaining lead and mercury from organic compounds in a form which can be precipitated by hydrogen sulphide. a to is transferred watch-glass. After this time the silver iodide will be com- The zinc is removed. is filtered through an ordinary washed filter (not a Gooch crucible). the filter burned. and the crucible allowed to stand overnight.328 GRAVIMETRIC DETERMINATION OF THE METALLOIDS. and the residue (except when it is silver iodide) is dissolved in warm ammonia water. and then weighed. the fresh beaker. substance. filtrate is acidified with nitric acid. but the filtrate is this time collected in a After washing the filter with dilute ammonia. and the latter is washed with water and dried. heated until it begins to fuse. decantation with very dilute nitric acid to the disappearance of the silver reaction. dried at 130 C. in order to dissolve the silver. silver into the nitrate). a piece of chemically pure zinc is added. and weighed. it cannot be dissolved in ammonia In this case the in this way separated from splinters of glass. is In the case of silver iodide. it filtered through a Gooch crucible. drops of water and a drop of evaporated pure hydriodic acid are added. acid. and dried at 100 A little dilute nitric acid is added in a weighed porcelain crucible. This second weight deducted from the former gives the amount of silver iodide present.. This filter is ig- nited in a crucible and the residue (the glass) is weighed. together with the glass. when the main part of the precipitate is added.

and gently tapped so that a small canal is formed above the lime. and wide closed at one end). determined as silver. The carbon is filtered off. mine. and Iodine. so that some silver sulphide is likely to be precipitated with the silver halide. 339). then about 0. from which the by silver is precipitated as silver sulphide. Mol. and the halogen precipitated with silver nitrate.. 80.5 1 gm. Separation of Cyanogen from Chlorine. " lime the ACID. The tube is then placed in a small combustion furnace (cf Carbon) and heated. the contents of the tube are transferred to a large beaker and the lime dissolved in dilute nitric acid free from chlorine. First of all the front end of the tube. Wt. Biltz (Chem. long is introduced. and precipitated with silver nitrate. more of lime. whereby the silver halide goes into solution. free from substance. Hydrobromic acid is determined exactly the same as hydroThis is also true of the determination of free brochloric acid.* In the analysis of substances rich in nitrogen. the liquid is boiled to remove the excess of the reagent. from chloride) from 5 to 6 cm. filtered. AgBr. two or three of them are present method " is to be preferred. separates the halides from sulphide treating the precipitated silver salts with an ammoniacal sodium thiosulphate solution. HYDROBROMIC Form: ACID. and finally 5 cm. Silver Bromide. long. The Lime Method. is heated to a dull redness.HYDROBROMIC present. placed on its side. and . The substance is then mixed thoroughly with the lime by means of a copper wire whose end is wound into a spiral. it is possible that some soluble calcium cyanide will be forme:!. of substance. If 329 at the same time. 1903.93. Bromine. then the back end. In this case the solution is treated with hydrogen peroxide (free from halogen) before enough nitric acid has been added to make the solution acid. HBr. Rep. and afterward the other burners are lighted one after another until finally the whole tube is at a dull-red heat. p. If the lime contains calcium sulphate. Ztg. by adding ammonium sulphide. Into a glass tube made of difficultly fusible glass (about 40 cm. a layer of lime (free cm. and bromine in non-electrolytes. After cooling. In this case care must be taken that the silver precipitate contains no silver cyanide (cf. then acidified. this is reduced to sulphide. * W. 142). The tube is nearly filled with lime.

therefore. Forms. Suppose a grams substance gave p grams silver iodide and p' grams silver chloride. weighed and the equivalent amount of silver added to the weight of the main part of the precipitate. (6) Determination as Palladous Iodide. acid at one's the main disposal. Wt. This important method for the separation of iodine from bromine and chlorine is carried out as follows: The solution is acidified with hydrochloric acid. and palladous chloride solution is added until no more precipitate is formed. sired to filter the silver iodide through an ordinary way instead of through a 328 Gooch If it is de- washed filter crucible. Mol. After standing one or two days in a warm place.330 GRAVIMETRIC DETERMINATION OF THE METALLOIDS. in a grams substance p+ iodide. (a) Determination as Silver Iodide. is is placed in a weighed porcelain crucible and heated until it begins The filter ash is placed in another to melt and then weighed. HI. whereby crucible. the procedure described on used. The determination the same of hydriodic acid is carried out in exactly as the analysis of hydrochloric acid. the brownishblack precipitate of palladous iodide is filtered through a Gooch . 127. the silver and any unreduced iodide are changed to silver chloride. and Palladous d Iodide. PdI2 . and treated with nitric and hydrochloric acids. converting the reduced metal to iodide by dissolvIn case there is no ing in nitric acid and adding hydriodic acid. HYDRIODIC ACID. then The silver chloride is iodide is We have. and the amount of iodine present may p' A grams silver be calculated in the usual manner. Agl. hydriodic portion of the precipitate p.93. Silver Iodide. Example.

(a) The iodine is determined as above as palladous iodide. and in a second sample the sum of the chlorine and iodine is determined from the weight of their insoluble silver salts. of solid potassium nitrite (free from halogen) is added. which escapes from the solution on In one sample.c. This method depends upon the fact that in a dilute solution of the three halogens.. is allowed to settle.c. in the form of their are the together precipitated halogens fore. and the of the substance should . SEPARATION OF THE HALOGENS FROM ONE ANOTHER. water in a liter flask) is treated with 2-3 c. of dilute sulphuric acid.5 gin. i. 0. the PdI 2 may be changed to palladium by igniting in a current of hydrogen. of the flask are now treated with silver nitrate solution.SEPARATION OF IODINE FROM CHLORINE. crucible. and weighed as PdI 2 According to Rose. (6) Method of Gooch. Procedure. dried at 100 C. or through a tared 331 that has been dried at 100 filter C. resulting precipitate Gooch crucible. otherwise some chlorine escapes.. The mixture of the halogen salts (about 0. . Separation of Iodine from Chlorine. washed with warm water.5-1 gm. thereboiling. and from the weight of the palladium the amount of iodine calculated. in a second sample the amount of the chlorine is deter- mined after setting free the iodine by means of nitrous acid. and the solution is boiled until entirely colorless in most cases this The contents is accomplished in about three-quarters of an hour. nitrous acid sets free iodine alone: 2KI+ 2KNO + 4H2SO = 4KHSO 4 + 2NO+ 211. and weighed. and the amount of iodine determined by difference. silver salts. The Palladous Iodide Method. In order to obtain correct results by this method.0+ 12 4 2 . the solution must be very dilute when it is boiled to expel the iodine. be dissolved in 600-700 c. It is filtered through a .

the flask is immediately closed. he collects in it a mixture of caustic soda and hydrogen peroxide. reaching to the bottom. where. From 5-10 c. p. which are gradually Procedure. and Prakt. with evolution of oxygen. 182 fiir et seq. Leit. This second tube is connected with an Erlenmeyer flask for a reAbout ceiver. however. whereby it is transformed to sodium iodide and is subsequently determined as silver iodide. The Peligot tube is likewise filled with a suitable amount of caustic soda and hydrogen peroxide. The iodine is changed into sodium iodide and sodium hypoiodite by means of the dilute alkali : 21+ 2NaOH = NaI+ NaOI+ H The sodium peroxide to hypoiodite. sodium nitrite solution are now added to the solution containing the halogens. and the contents of the flask are heated over a free flame while water vapor is at the same time conducted into it. 50 c.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. 1. 144. The solution containing the two halogens is placed round-bottomed flask and diluted to a volume of 600-700 Like a wash-bottle. is 2 O. in a 1^-liter driven over into the Erlenmeyer flask.c. .c. through which vapor can be conducted into the flask. Chem. and this is in turn connected with a Peligot tube. In the other solution the chlorine is determined in the usual way. an equal volume of hydrogen peroxide free from chlorine is added. the space above is filled with violet vapors of iodine. this flask is provided with one glass tube c. 332 (c) Method of Jannasch* Jannasch proceeds in exactly the same way as Gooch. As soon as the liquid begins to boil. 2 When all the iodine is driven over into the receiver (which is always the case after the solution in the flask has become colorless * Zeit. but instead of letting the iodine escape.c.c. of pure 5 per cent. they are completely absorbed by the hydrogen peroxide solution. and with another shorter tube for the escape of gas. anorg. of 10 per cent. of dilute sulphuric acid (1:5) and 10 c. caustic soda solution are placed in the Erlenmeyer flask. der Gewichts-analyse. reduced by the hydrogen sodium iodide: NaOI + H 2 O = H 2 O + O 2 + Nal. p. and the mixture cooled by surrounding the flask with ice or snow.

the contents of the distillingflask are transferred to a beaker and the chlorine determined as silver chloride.* The solution. the addition of silver nitrate results in the formation of there some silver iodate. * If the above directions are closely followed. whereby it is completely decolorized. Jannasch recommends a slightly different procedure. and this can be changed by sulphurous acid to iodide. He adds silver nitrate directly to the alkaline solution in the Erlenmeyer flask. and the silver nitric acid are iodide filtered through a Gooch crucible and weighed." If the solution is acidified. the liquid is boiled. due to insufficient cooling of the contents of the receiver. the liquid within it is washed with hot water into the Erlenmeyer and the current of steam is stopped. soluble (though difficultly so).SEPARATION OF IODINE FROM CHLORINE. and the latter is not reduced by hydrogen peroxide. An excess of silver nitrate and a little then added. therefore. Brunner. the liquid is acidified with a little sulphuric acid. In such cases the results obtained are too low. 333 and has been boiled for twenty minutes longer). and accurate results will be obtained. but the addition of sulphurous acid changes it to iodide without loss. there should not be much separation of iodine. the delivery-tube between the distilling-flask and the Erlenmeyer flask is removed. This method has been carefully tested in the author's laboratory by O. For the chlorine determination. and this amount of iodine escapes determination. It may be caused by the presence of a small amount of nitrous acid which is not oxidized to nitric acid by hydrogen peroxide or if the contents of the Erlenmeyer flask are not kept cool. In this case there is a separation of a considerable amount of iodine on acidifying the solution. this always causes a yellow coloration due to free iodine. appreciable amounts: of sodium iodate (NaIO3 ) are formed. . the presence of the iodate is shown by the separation of a little iodine. Remark. howfor silver iodate is ever. In the latter case. In this way accurate results are obtained provided is no iodate formed by the absorption of the iodine. cooling. is treated with a few drops of sulphurous acid. and in the above form has been found to give very exact results. The contents of the Peligot tube are added to the Erlenmeyer flask and the solution heated to After boiling in order to remove the excess of hydrogen peroxide.

the precipitate is filtered through ring. and weighed after cooling. of the acid (free from chlorine) and precipitated in the cold by the addition of a slight excess of The liquid is heated to boiling.5 gm.x and from this p q (AgCl) this it follows: 3- In AgBr + y = + my = equation m=- . If this value is substituted in equation (3). 334 Determination of the Halogens by Indirect Analysis. Determination of Bromine together with Chlorine. q the weight after the silver has been completely changed to chloride. asbestos filter-tube made of The difficultly fusible glass. begins to melt. the tube is fastened in a slightly inclined position. long. salts of the silver of chlorine. halogen salt is The solution acidified containing with a little nitric about 0. --= 0. During the first half hour the precipitate should not be heated hot is enough to melt dried at 150 it. and a current of dry chlorine gas is passed through it.224 (p-q) we obtain .4. then AgCl 1. and after cooling again.7633. a 15 cm. (a) In this method the sum of the weights of the silver two halogens is first determined and afterwards the bromide converted to silver chloride by heating in a current Principle. silver salts. after which the chlorine after cooling the residue is again weighed. x 2. however. (AgBr) y. At the same time the tube is heated cautiously by moving a small flame back and forth. Procedure. with frequent stirsilver nitrate.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. the temperature finally. until and it If and p represents the combined weight is of the is replaced two raised by air. precipitate For the transformation of the bromide into chloride. the asbestos is shoved forward a little in the tube by means of a glass rod (in order that the gas may pass through it more readily). C.

x + my = q (AgCl) and from this it follows: m= 0. Determination of Iodine together with Chlorine. AgBr + mx + x y ny = p = g(AgCl) and o x= nm^p 0. nm in which n- =0. Agl If this value is substituted in equation (Agl) y=2M7(p-q) (AgCl) x=p-y. AgBr . p represents the weight of the silver bromide and and q as before the corresponding weight of silver this case iodide. x + y = p 2.DETERMINATION OF IODINE TOGETHER WITH CHLORINE- 335 and (AgCl) x = p-y from which the amount (6) of bromine and chlorine may be calculated. The same procedure is used as above described If p represents the weight of silver iodide + silver chloride and q the weight after the silver has been converted to chloride.6105 and 3. 2. chloride : Agl 1.7633.6105. we obtain and (c) In silver Determination of Bromine in the Presence of Iodine. (3). then AgCl Agl 1.

x from which follows from 3 - y. the iodine is If (t) is multiplied iodide is subtracted from (P). the Presence In one portion of the substance the total weight (P) of the halogen salts is determined. the sum of the weights of the silver chloride is obtained (P p). . and this is changed over into chloride whose weight (Q) is obtained.GRAVIMETRIC DETERMINATION OF THE METALLOIDS.996-. Instead of determining the iodine as palladous iodide it may be removed 'as on page 331.7951. and if this is subtracted from (Q).303. and Chlorine in One Another. determined as palladous iodide. If (p) is silver bromide and amount the of silver chloride sponds to the q) will (Q be obtained which corre- amount that would be obtained from the weight (p-p). 336 values for If these m and n are substituted in equation (3).545. is we have designated by x and : AgBr + y = (P-p) + my = (Q-q) p. the corresponding weight Again. of Bromine. (d) Determination of Iodine. If. 334. 6. x 2. and (AgCl) t -(P-p)-y. then. by treatment with nitrous acid and the weight of the silver bromide + silver chloride obtained. of silver chloride is obtained (q). we obtain (Agl) z=4. (a) : -P--- (AgBr) y = 4. if is (t) multiplied by 0.p-6. by 1. In a second portion of the substance. the amount the amount of silver of silver chloride bromide by AgCl 1.2 and (AgBr) y = p-x. whose weight is (t). the corresponding weight of silver obtained (p).

the cold solution is treated with an excess of silver nitrate. By the decomposition of the silver cyanide. Free hydrocyanic acid as well as the cyanides of the alkalies and alkaline earths are decomposed quantitatively by silver nitrate with the formation of insoluble silver cyanide. the filter burned in a platinum spiral. above calculation.c. To confirm the result. HCN. and weighed. at first gently and finally until the silver begins to melt. p. 337 and iodine follows from the bromine and iodine volumetrically lodimetry.02. AgCN. bromine. 27. mandelic acid nitrile. Wt. of a 10 per cent. of ACID. anal. the precipitate allowed to settle and it is then filtered through a weighed filter. 34. it is desired to determine gravimetrically the amount of cyanide present in an aqueous solution of hydrocyanic acid or of an alkaline cyanide. Bitter-almond water contains cyanogen as free hydrocyanic ammonium cyanide. of concentrated ammonia * Z. difficultly volatile is formed. contents the igniting Determination : of Hydrocyanic acid in Bitter-almond Example paracyanide Water. Ag. of bitter-almond water are treated with 10 c. weighed. If.HYDROCYANIC The amount of chlorine. but is acted upon by the latter if the solution is made ammoniacal readily after the addition of the silver nitrate and then made acid. For the determination consult Part II. . silver nitrate solution. Mol. it is then of the precipitate. but this is gradually burned away by of the open crucible. therefore. but the greater part is present as acid and as C6 H 5 CH(OH)CN.c. the silver cyanide is placed in a porcelain crucible. its ash added to the main portion and the contents of the crucible ignited. stirred. HYDROCYANIC ACID. The latter compound is not decomposed aqueous solution by means of silver nitrate. dried at 100 C. a little dilute nitric acid is added. and Metallic Silver. Chem. 2-3 c. Forms: Silver Cyanide. in The gravimetric determination of the cyanogen present formed according to the method of Feldhaus * as follows is per- : 100 gms. Ill (1864).

sulphide with the formation of insoluble mercuric sulphide and hydrocyanic acid: Hg(CN) 2 +H 2 S=HgS + 2HCN. Liebig's volumetric method is much more satisfactory for this determination (see Part II. This reaction. therefore. the solution is immediately acidifi3d with nitric acid. If it is desired to determine the amount of cyanogen in a solid alkali cyanide. as an indicator. 338 are added.and f erricyanides of e. Some complex cyanides silver nitrate. The zinc sulphate. as it were. there is always a slight loss of hydrocyanic acid. however. and the solution then acidified nitric acid and the precipitate treated as above. it must be performed in an alkaline solution. only slowly) . Mercuric cyanide precipitated by is a non-electrolyte and is consequently not but it is acted upon by hydrogen silver nitrate. cannot take place in neutral or acid solutions on account of the volatility of the hydrocyanic acid. the alkalies (and mercuric cyanide) are not. a weighed amount of the salt is dissolved in containing silver nitrate. inasmuch as the pure white precipitate will not be formed until the mercury is completely precipitated. The hydrogen sulphide water is added until the upper liquid shows a pure white precipitate of zinc sulphide. If this should cause a turbidity. Method of Rose. the following procedure is necessary: The twice as solution of the mercuric cyanide is treated with about much zinc sulphate dissolved in ammonia.GRAVIMETRIC DETERMIANTION OF THE METALLOIDS. and the determined as HCX described above. are quantitatively decomposed by those of nickel. enough ammonia is added to clear it up and hydrogen sulphide water is then slowly poured in. Precipitation Analyses). Determination of Cyanogen in Mercuric Cyanide. In order to avoid the introduction of an excess of hydrogen sulphide into the solution. serves. The precipitated sulphides are now . zinc. If the cyanide is water with dissolved in water before the addition of the silver nitrate.g. and copper (the latter while others such as the f erro. This causes at first a brown precipitate which becomes black on stirring. the precipitate allowed to settle.

339 The filtrate con- tains all of the hydrocyanic acid and is treated with an excess of silver nitrate. and in this way the total definite amount of weight of the silver salts is determined. Forms: Cu2 (CNS) 2 Ag(CNS). HCNS. Determination of Hydrocyanic Acid and Halogen Hydride in the Presence of One Another. the precipitate is filtered into a Munroe crucible. Cu2 (CNS)2. acidified with nitric acid filtered and the weight of the silver cyanide determined as described on page 337. according to Neubauer and Kerner. Mol. which is neutral or slightly acid with hydrochloric or sulphuric acid. 101. and dried at 130 to 140 to constant weight.* The solution is treated with silver nitrate in the cold.09. SULPHOCYANIC ACID. * Ann. is treated with 20 to 50 c. washed with cold water containing sulphurous acid. . Chem. filtered off and washed with dilute ammonia. 344. Wt. of a saturated solution of sulphurous acid. After standing a few hours. Pharm. d. then once with alcohol. (1857). dried at 100 C. solution of the alkali sulphocyanate. heated until it is completely melted. p. and copper sulphate solution is slightly greenish tint introduced with constant stirring until a is imparted to the liquid.SULPHOCYANIC ACID. The results are good. and then reduced with zinc and sulphuric The metallic silver and paraacid as described on page 328. and the off filtered are halogen determined in the filcyanogen the precipitate is trate according to page 320 et seq. 59. The .c. BaSO 4 . u. The above separation can be more satisfactorily effected by means of a volumetric process (See Precipitation Analyses). A placed in a porcelain crucible. the precipitate filtered. i. Determination as Cuprous Sulphocyanate.

heated for from thirty minutes to an hour on the water-bath. Determination as Silver Sulphocyanate. 340 2.) by means of barium chloride. then deep red. to treat a solid alkali sulphocyanate with strong nitric acid in an open vessel. for on account of the violent action some of the hydrocyanic acid is volatilized and escapes oxidation. The solution is at first colored yellow. In the absence of all other compounds containing sulphur. to accomplish this the solution must be kept boiling gently . of a one-tenth normal potassium sulpho- cyanide solution) and add 10 c. method. crucible. It is better. may be determined with accuracy by oxidizing thiocyanic acid and precipitating the sulphuric acid formed as barium sulBromine water is the most suitable oxidizing agent for phate. dried at 130 Determination as Barium Sulphate.c. The sulphur is then by no means entirely oxidized to sulphuric acid. which has been slightly acidified with nitric acid. an excess of bromine water. and weighed. and finally becomes colorless. the filtered into a precipitate is then with a little alcohol. Heberlein found in the author's laboratory. it The alkali sulphocyanate solution is treated with this purpose. Instead of bromine. Philipp obtained good results by this 3. reddish brown. This excellent method for estimating sulphocyanic acid is only applicable in the absence of the halogen acids. washed with water. AgfCNS).c. keeping the beaker surrounded with ice.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. of fuming nitric acid. and the sulphuric acid precipitated (according to the directions on p) 464 et seq. nitric acid may be employed as the oxidizing agent. and weighed as barium sulphate. as E. the solution acidified with hydrochloric acid. After stirring well. Munroe to 150 R. to dissolve the alkali sulphocyanate in water (Heberlein used 20 c. The dilute solution of the alkali sulphocyanate is treated in the cold with a slight excess of silver nitrate solution. or hydrocyanic acid. It will not do at all. however.

taken up with water and the silver precipitated ticles of filter and filtered off. boiled two hours and then treated as above. of a stream of nitric acid (sp. treated with an excess of fuming nitric acid. 130. In this way Heberlein sulphocyanate is found 100. hydrogen as chloride peroxide are used).40). After acidifying with * by W. of one-tenth normal sulphocyanate solution. Ghemie. Borchers. according to Heberlein. then heated two hours on the water-bath. of the theoretical amount of better effected silver salt * precipitate sul- The oxidation phocyanic acid. . the oxidation of the sulphocyanic acid is sure to have been complete. f Hydrogen peroxide in ammoniacal solution also oxidizes sulphocyanic acid completely to sulphuric acid but the oxidation requires more time than in the case of nitric acid.79 taken.c.37-1. gr. f Borchers precipitates the sulphuric acid without removing the silver means of barium nitrate. if the solution of the alkali placed in a flask connected with a return-flow condenser. of 3 to 4 per cent.c. 341 It is then evaporated almost to dryness. of water. taken 200 c. 120 c. Repertorium der anal. no violent reaction and no loss of sulphocyanic The contents of the flask are heated to boil- ing for three-quarters of an hour. The oxidation is more certain. If at the end of this time. By this method. The procedure given here is better.2 per cent. by and of the sulphpcyanic acid is still first precipitating the acid in the form of its filtering it off (it is when a sulphate is only necessary to wash the The funnel contain- also present). p. 1. hydrogen peroxide (for 20 c. precipitated hot with barium chloride solution and the barium sulphate filtered off and weighed. the alkali sulphocyanate is treated with a large excess of 3 to 4 per cent. up in ACID.SULPHOCYANIC for two hours. of the potassium sulphocyanate lein found 99.c. The sulphuric acid is precipitated in the filtrate as barium sulphate and the latter is weighed. red vapors are still evolved from the flask (usually due to small par- paper) it makes no difference. 1881.1 and 100. the apex of the filter is broken with a glass rod and the precipitate washed into the flask In this way by means there is acid to be feared.94 per cent. Heber99. the solution made ammoniacal. ing the precipitate is then placed over a small flask. and finally boiled. The contents of the flask are evaporated to a small volume in order to remove the excess of nitric acid. allowed to stand twenty-four hours at the ordinary temperature.

If this of silver nitrate required amount of silver nitrate is obtained. accurate procedure for the analysis of cyanides is to de- termine the carbon and nitrogen by elementary analysis (which * Loc. 215. and sulphocyanide may through a Gooch crucible. From page 330). 342 hydrochloric acid the sulphuric acid is precipitated with barium chloride and the barium sulphate formed is weighed.* The amount of silver nitrate necessary to precipitate both of the acids is determined volumetrically in one sample of the substance (see Precipitation Analysis) and in a second portion the weight of the barium sulphate formed after the oxidation of the sulphocyanic acid is determined. Wt. In one portion the amount of sulphocyanic acid present is deterA as barium sulphate after oxidation with nitric acid. A third poras chloride silver to changed tion is fused with sodium carbonate and potassium nitrate and the iodine determined from the melt as palladous iodide (see acid and silver nitrate (Carius silver salts are filtered off. silver nitrate. The oxidation effected even is more slowly by potassium per- carbonate. Mol. f page 325) after which the weighed. Acid together with Halogen Hydrides (Volhard). cit. Form: The most Silver Cyanide. AgCN.9. second portion is heated in a closed tube with concentrated nitric mined Method. HYDROFERROCYANIC ACID. Determination of Sulphocyanic and Hydrocyanic Acids in the Presence of One Another (Borchers). the halogens be precipitated by 160 and weighed. H 4Fe(CN) 6 . computed (see the data thus obtained.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. the three halogens are page 336). From the latter weight the amount of sulphocyanic acid present can be computed and also the amount of silver nitrate that amount is would be required to precipitate subtracted from the amount to precipitate both of the acids. dried at t Instead of using the Carius method. the equivalent to the hydrocyanic acid present Determination of Sulphocyanic it. filtered . and subsequently halogen described on page 334. see) .

On filtering off the insoluble oxides. This method depends upon the fact that all salts of hydroferrocyanic acid on being heated with yellow mercuric oxide give up their cyanogen to the mercury. or. where v is This volume v can be determined only approximately. flask and after the decomposition was up to the mark.. measuring off a definite volume of the filtrate. forming soluble mercuric cyanide. how- Even then the operation is tedious. so that the attempt has been made to avoid the washing of the precipitate by diluting the liquid containing the precipitate suspended in it ever. In order to obtain exact results. when the precipitate is filtered off. By washing with a solution containing a dissolved salt. 100 c. after first precipitating out the The amount of cyanide found then -calculated over into the amount that would have been obtained in case the whole of the solution had been used for the analysis.c. but the volume of the suspended oxides. 343 Determination as Silver Cyanide (Rose-Finkener).. but on washing some of the precipitate usually passes through the filter. and that in complete. 338) is . and subsequently determining the cyanogen as silver cyanide mercury as sulphide (see p. cases is In this way an considerable.c.c. the first-men- tioned procedure should be followed. to a definite volume.. treated with an excess boiled until the blue color has completely disappeared. filtering through a dry filter. a clear filtrate. it is possible to obtain. of cyanide were found. so that the cyanogen determination by this method will never be abso- for the v lutely certain. Thus Fe/"[Fe"(CN) 6] 3 + 9HgO + 9H 2 O= = 9Hg(CN) 2 +4Fe(OH) +3Fe(OH) 2 3 A weighed amount of the substance of mercuric oxide and the is liquid is .HYDROFERROCYAN1C ACID. of the filtrate p gms. the amount . decomposed error is introduced which in some Let us assume that the Prussian blue was in a 100-c.c. at first a clear filtrate is obtained. The amount of cyanide in the portion weighed out is not 2 p gms. diluted volume of the liquid before filtering was not 100 c. preferably mercuric nitrate. the liquid was 50 c. while the iron Prussian blue is changed to insoluble decomposed as follows: ferric is hydroxide. better still.

Soluble may be satisfactorily determined by permanganate (cf. 52. Colorimetric Determination. Mol. Oxidation Methods). the residue after evaporation and the solution analyzed as usual. Mol. in drinking-waters). NITROUS.02.9. they can all be used in testing for this acid. AND HYPOPHOSPHOROUS ACIDS. will GROUP II. while according to the following procedure y^^ mgm. Part II. Wt. CYANIC.47. Wt.. ACETIC. . of nitrous acid in a liter can be detected. Thus in the production of tri-amido-azo-benzene (Bismarck brown) less than T fg. under Oxidation Methods. For the determination of the iron ferrocyanides titration with potassium and Reduction and other metals. To carry out the determination not two solutions are necessary. HYDROFERRICYANIC ACID. upon depends Inasmuch as azo-compounds are formed only when nitrous small acid is present. HYDROSULPHURIC. 344 carbon and nitrogen should be determined by elementary of analysis. in a liter can be detected with certainty. Hypochlorous acid is always determined volumetrically and be discussed in Part II of this book. of Peter Griess. gasometric- The two former methods will be dis- cussed in Parts II and III of the book. The H Fe(CN) 3 ferricyanides are analyzed in the 6 is . HNO 2 NITROUS ACID.g. one of sulphanilic acid and one of . Mol. same way as the ferro- cyanides. Wt. Nitrous acid is or colorimetrically. but the different substances do not prove equally sensitive as reagents. and the formation of intensively colored azo-dyes.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. 47. HYPOCHLOROUS ACID. sul- dissolved in water. HC10. either determined volumetrically. the substance heated with concentrated is phuric acid. This method serves only for the determination of extremely amounts of nitrous acid (e. ally.mgm. 214.

. % Lunge.NITROUS ACID. .5 gm. and after being sucked free is . chim. [2] 2. the reagent becomes red.3 gm. of colorless solution is poured off from the bluish-violet the water. After this.4047 gm.c.2 to 0. it is washed with a small amount of distilled water. of sulphanilic acid is dissolved in 150 c. 1899. Ilosvay if acetic acid were used the reaction was much more sensitive. gm.c. 345 Both substances are dissolved in acetic acid * and prepared according to the directions of Ilosvay f as follows 1.e. is weighed out into a liter flask and dissolved in hot distilled water.1 These two solutions are now mixed. 100 c. and 150 c. of the clear liquid are pipetted into a second ing cold. 0. Heft 23. and in must be decolorized by shaking with zinc-dust before this case it using. After becomof it is diluted to exactly one liter with pure then water. 2. of dilute acetic acid are added. { It is not necessary to protect the reagent from the action of light. 317. and the precipitate allowed to settle. a little more than the theoretical amount) in order to convert the silver nitrite into silver chloride and sodium nitrite. f. Besides the above reagent. Griess used dilute sulphuric acid to set free the nitrous acid. Zeitschr. it is trated solution of commercial potassium nitrite is treated with silver nitrate solution. showed that t Bull. residue. p. As long as the solution remains If it comes in contact with nitrous colorless it can be used. angew. the solution * P. 0. from mother-liquor. About 0. but it is desirable to keep impure air away from it. which is often present in the air. The silver nitrite is placed in a calcium chloride desiccator and allowed to dry in the dark. of dilute a-naphthylamine. silver nitrite the precipitate In order to obtain absodissolved in as little hot lutely pure water as possible and quickly cooled The mass of crystals is placed in a funnel provided with a platinum cone. acid. of sodium nitrite of known necessary to prepare a solution For this purpose a concenstrength. : acetic acid. of pure sodium chloride is added (i.c. thoroughly shaken. As soon as it has become dry (shown by its having assumed a constant weight) exactly 0.c. the precipitated silver nitrite is filtered off and washed a few times with cold water. of solid a-naphthylamine is boiled with 20 c. Chem.

the blue color produced can be distinctly seen. with relatively larger amounts (e..g. then the water con- of nitrous acid as the standard. of nitrous acid is present in a liter.g. As soon as a distinct red coloration is apparent. the color is so intense that it is unsuited for a colorimetric determination.c. Meanwhile in three other cylinders are placed respectively 0.g.c. If TV mgm. 346 liter flask and diluted up to the mark with water 1 c. and 1 c. TromsdorfT recommends for the determination of nitrous acid in drinking-water the use of zinc iodide of starch.01 free mgm.4 c.. the colors are compared with that produced by the water to be analyzed. N O 3 2 from nitrous .mgm. the water contains considerable nitrous acid (e. of and the contents of the cylinder mixed with the stirrer shown in Fig.5 c. however. If the color of the unknown water lies between two of the standards e. 0. over 0. This method is not to be recommended because in the first place .c.5 c.c..3. in a cylinder. of the solution containing a known amount of sodium nitrite.3 then the red will coloration be dark so that the mgm.1 c. 287). with T% mgm. and comparing the blue color produced by the nitrous acid (cf.2. of the known solution.GRAVIMETRIC DETERMINATION OF THE METALLOIDS.. the cylinder is placed about 70-80 C. of this acid.c. per liter). 0. solution contains 0. the red coloration will appear within one minute. the color of the tains the then three more standards are prepared conand 0.. When unknown same amount solution is. 50 c. 61. p. 25.c.c. 0. of the standard taining. the reagent. say. each is diluted with water up to the mark and treated with the reagent in the same way. aid of the in water at of nitrous acid is pres- the water tested. such as is of the water to be shown on examined are placed p. Procedure for the Determination. If as much as y^.c. Vol. treated with 5 c. colorimetric determination cannot be performed with certainty. I. between that produced with 0. If In this case a definite volume of the water is diluted with distilled water and the nitrous acid present in this diluted water is deter- mined as before. matched. unless a concentrated solution of naphthylamine is used.1 and 0. as much ent in a liter of as 1 mgm. per liter. per liter) the solution is simply colored yellow.

2 There are four cases to be considered: I. Through the other hole in the stopper is placed a glass tube reaching to the bottom an * Usually two of these tubes are used in order to the gas escapes absorption. desired to know the per cent.09. The determination of sulphur in sulphides soluble in water. Wt. Determination of Free Hydrogen Sulphide. The determination I. i. 347 far lass sensitive than the Griess method. IV.tube is connected with aspirator.HYDROSULPHURIC ACID. which are likely to be present in a drinkingwater. 55. (a) Determination of Hydrogen Sulphide in Gas Mixtures. The determination of free hydrogen sulphide. but it is possible to accomplish the same end by a gravimetric process. HYDROSULPHURIC ACID. 2 Mol. lodhietry).e. The other end of the absorption. Forms: Barium Sulphate. The determination of sulphur in sulphides insoluble in water but decomposable by dilute acids with evolution of hydro- gen sulphide. 34. and second because can easily lead to error inasmuch as a blue color will be often produced when there is no nitrous acid present. * which contains a solution of ammoniacal hydrogen peroxide free from sulphuric acid. H S. of hydrogen sulphide mixture of gases. will also cause the solution of zinc iodide of starch to turn blue. H S. of sulphur in insoluble sulphides. II. Through one hole of the stopper is passed a right-angled glass tube which reaches just below the bottom of the stopper in the bottle. and colorimetrically. make sure that none of . . The source of the gas is connected by means of rubber tubing In case it is present in a with the ten-bulb absorption-tube shown in Fig. page 359. BaSO 4 Hydrogen Sulphide. III. Traces of hydrogen it is it peroxide or ferric salts. and its other end is connected with the absorption-tube. the analysis is best made volumetrically (se Part II. a large bottle of about 4-5 liters capacity filled with water and closed by means of a double-bored stopper.

and is connected with a rubber tube to serve as a siphon . 125. the air in the rubber tubing between the source of gas and the absorption-tube is removed by conducting the gas to be analyzed through it. * According to Leduc. slowly heated to boiling. and 760 mm. prea at boiling temperature with a boiling solution of cipitated barium off. Before beginning the experiment. a little hydrochloric acid is if necessary. * y = ' d'P the volume of the hydrogen sulphide absorbed. it is filtered and weighed as barium sulphate. run out. The upper end of this tube is likewise bent. The amount follows of hydrogen sulphide present in the gas is computed as : of water which has flowed out of the aspirator of the gas that has been sucked through the volume represents the apparatus less the amount absorbed by the ammoniacal hy- The volume drogen peroxide solution. siphon a beaker. chloride. in a platinum crucible. after from 2-5 liters of the water have is closed by screwing up the cock on the The contents of the absorption-tube are poured into arm. Let V represent the volume of water in which has flown from the aspirator and p the weight of liters barium sulphate found. and kept at this temperature The solution is then evaporated on for from five to ten minutes. Water is now allowed to run slowly from the aspirator into a vessel graduated in liters.* we have: BaSO 4 :22. Since one gram molecule of barium sulphate corresponds to one gram molecule of hydrogen sulphide and the latter assumes at C. Comptes rendus. as 22. Both at the beginning and end of the experiment it is necessary to note the temperature of the room and the barometer reading. 571 (1897) the density of H 2 S from which the molecular volume is computed (referred to air =1) is 1. pressure a volume of 22. When this is accomplished the tubing is connected with the absorption-tube.159:p:Fi. on the lower end of the rubber tube is a screw-cock.159 liters.1895.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. the aspirator the water-bath to a small volume. and the sulphuric acid filtered the solution added.159 liters. ignited wet After the precipitate has settled. The mean of these readings is used for the calculation. 348 of the bottle. .

and the sulphuric acid determined as barium nent brown color is sulphate. K o+ (6) M Determination of the Amount of Hydrogen Sulphide Present in Solution. when the sulphuric acid is as barium sulphate. Determination of Sulphur in Sulphides Soluble in Water. the amount of sulphuric acid formed is determined as barium By means of a pipette a definite out and allowed to run 'into sulphate. and sulphate. and 760 mm. when it is warmed. 349 Now the volume (V) of the gas that passed through the apparatus at and B mm.DETERMINATION OF SULPHUR IN SULPHIDES. sulphide. II. _7-(B-uQ273 ~ 760(273 + The volume of the gas ' and we have: 100 =V = TT37\f the P er cen ^. likely to the sulphide sulphur is precipitated by means of cadmium acetate and the sulphur in the precipitate is determined as under III. by volume of hydrogen sulphide present. be the case after standing in the air for some time. while FI is measured at C. slowly heated to boiling and kept at that temperature until the excess of the reagent is destroyed. pressure. (a) The solution is treated with an excess of ammoniacal hydrogen peroxide water. After heating to boiling and acidifying with hydrochloric acid. therefore. It is necessary. volume of the solution is ammoniacal measured hydrogen peroxide with constant stirring of the latter by means of the pipette itself. and was t mm. acidified with hydrochloric acid. (3) The solution precipitated with barium chloride is and weighed treated with bromine water until a perma- obtained. to pressure. 760 reduce V to drawn through the apparatus is then. or the cadmium sulphide is oxidized with either bromine water or . C pressure. If as is the solution contains thiosulphate.

c. After a rapid current of hydrogen has passed through the apparatus for about five minutes. in which case the gain in weight represents the amount of . in P. Principle. and hydrogen is conducted from T throughout the whole apparatus for five minutes more in order to remove as The 100 * In case hydrogen peroxide is not at hand. is now connected with the delivery-tube from the evolution-flask K. to 1 liter). . sulphide. of dilute sodium hydroxide solution (250 gm. In the case of sulphides rich in sulphur 0. and sulphite sulphur will be discussed in Part II of this book under lodimetry. 2 2 10-20 c. 100 c. gr. lodimetry). or the hydrogen sulphide is absorbed in caustic soda solutioa and the sodium sulphide formed analyzed according to II or finally the gas may be absorbed in a weighed tube containing pumice soaked with copper sulphate solution. Instead of oxidizing the sodium sulphide to sodium sulphate it can be titrated with iodine (cf. the receivers V and P are partly filled with an of hydrogen peroxide * (about 3-4 per cent. of the substance should betaken for the analysis.c.c. The sulphuric acid formed is then precipitated with a hot solution of barium chloride.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. of Sulphur in Sulphides Soluble in Dilute Acids. of bromine water are added. a) the conand the receiver is broken and the air is ing less sulphur a correspondingly larger The substance is placed in nection between the flask K by conducting hydrogen gas through the delivery expelled from tube and out through the open stop-cock of T. Evolution and Absorption of the Hydrogen Sulphide. 350 fuming nitric acid.c. The determination of thiosulphate. The Determination III. and the sulphuric acid formed determined as barium sulphate. the receivers should contain c.25-0. and absorbed in ammoniacal hydro- gen peroxide solution as under I. V. of the sulphide The hydrogen sulphide is evolved by treatment with dilute acids. 1. whereas of those contain- amount should be taken.50 gm. receiver. After the decomposition is complete the contents of the receiver are transferred to a beaker. an Erlenmeyer flask (Fig. of the solution in V and about about placing ammoniacal solution H O ). 30-50 c. 54.19) and boiled while carbon dioxide is passed through it until the excess of bromine is completely expelled. gas absorbed. the solution acidified with hydrochloric acid (sp.

35 1 After this. ing somewhat. the hydrogen sulphide will surely completely be driven over into F. concentrated acid -f 1 vol. then dilute hydrochloric acid (1 vol. about as possible of the air from the receivers* into introduced 20 c. the contents of are heated to a gentle boiling and a slow current of hydrogen * is conducted through the apparatus from T for K twenty minutes. t By the absorption of the hydrogen sulphide hi the ammoniacal solution ator.ANALYSIS OF SULPHIDES.f * The hydrogen is evolved from zinc and sulphuric acid in a Kipp generThe gas is washed first with an alkaline lead solution in order to remove traces of hydrogen sulphide and then with water. At the end of this time.c. . when the flame is removed and the current of hydrogen is continued for fifteen minutes longer. of boiled water are through T so that the much K substance is entirely covered. of boiled water) is slowly added to the contents of the flask and the decomposition is promoted by warm- - %M FIG. 54. When the evolution of the gas has ceased.

in which is on being passed hydrogen is also present. bromine 2. yellow color can be disulphide. may be present in four different conditions: 1. or aqua regia. 3. especially cast iron. By far the greater part is evolved as hydrogen sulphide when the metal is treated with hydrochloric acid. an extremely stable sulphur compound which is not very much affected by ammoniacal hydrogen peroxide. . Chem. 19. Another part of the sulphur present is not volatilized by the action of hot dilute hydrochloric acid. This method yields excellent results and can be applied to the Determination of Sulphur in Iron and Steel. distinctly seen in the delivery -tube. * Cf. 352 The contents of the two receivers are washed into a beaker and slowly heated to boiling in order to effect the complete oxidation of the thiosulphuric and sulphurous acids and to expel the The solution is finally acidiexcess of the hydrogen peroxide. J. fied with hydrochloric acid and the sulphuric acid determined as barium sulphate. always colored somewhat yellow owing to This. it is a sign that the greater part of the hydrogen sulphide has been driven over. Another part is evolved probably as methyl sulphide (CH 3 ) 2 S. 114 (1897). where it dips into the solution in the receiver and later disappears owing to further oxidation: of hydrogen peroxide the the formation of a little latter is ammonium (NH ) 2S 2->(NH 4 ) 2S 2 3-^(NH 2S0 ->(NH 4 2 S0 4 4) 4 When 3 ) . Another very small part of the sulphur may be present in the form of an insoluble sulphide which is not oxidized by nitric acid or aqua regia and can only be obtained in solution after fusion with sodium carbonate and potassium nitrate. in hydrochloric acid. Soc .* the sulphur present in different kinds of iron and steel. The sulphur in this compound changed completely into hydrogen sulphide through a tube heated to redness. 4. the color can no longer be detected. but can be oxidized to sulphuric acid by treating the contents of the evolution flask with nitric acid or aqua regia. Am.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. As Phillips and Blair have shown.

The residue is. and the sulphuric acid in the final filtrate determined as barium sulphate in the usual way. are sufficient. any deposited silicic acid filtered off. or basic Bessemer. In the case of certain other steels and cast irons. a large amount of the substance must be taken for the analysis. K into hydrogen sulphide. To this end. (Cf.DETERMINATION OF SULPHUR IN IRON AND STEEL. The sulphur present in steel or cast iron made by the Thomas-Gilchrist. After the air has been replaced by hydrogen. 54). process can as a rule be determined accurately by this method. except in this case a stronger acid should be used (HC1 sp. The insoluble residue which is obtained especially in the case of irons containing considerable silicon. the resulting solution evaporated with hydrochloric acid. should be used. filtered off. often contains considerable amounts of sulphur.. cases. the melt extracted with water. this tube is heated to dark redness by means of a small furnace of from four to six burners. in the flask the flask should be connected with a return flow condenser. 381). the results are likely to be In order to carry out an accurate determination in such low. while with steel 5 gms. a tube made of difficultly fusible glass (about 30 cm. however. care must be taken that enter water the red-hot no tube. wide) is inserted between the evolution flask and the absorption flask V (Fig. therefore. For pig iron 2-5 gms. Remark. the liquid should only be boiled very gently. 353 Inasmuch as the amount of sulphur present is so small. whereby the sulphur in the methyl sulphide passing through the tube is converted completely . p 357). . 1. the use of this tube drops of K p. and the boiling is continued for at least twenty minutes after the gas evolution has ceased. When is adopted. or what is better. The determination is carried out in the same way as before. gr. washed. dried.12) this is allowed to act upon the iron at once without first covering it with water. and with wrought iron as much as 10 gms. long and 1 cm. fused with sodium carbonate and potassium nitrate (cf.

have recommended the following method. sample of drillings is dissolved in concentrated nitric After the iron is completely dissolved. Colorimetric Determination of Sulphur in Iron and Steel. where a and a' represent the amount of substance taken for the analysis duplicate it. a grams of substance produce a certain shade then it would take 2a grams of a substance containing half as much sulphur to If other words. and then filtered. p. gas flame should not be used at any stage in the process. the liquid boiled for a few minutes. washing the precipitate with hot The filtrate containing 1 per cent.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. 50 at a red heat.c. sodium carbonate are added. On account of the uncertainty in obtaining all the sulphur present in iron or steel by the above evolution method. the Committee on Standard Methods for the Analysis of Iron American Foundrymen's Association.c. the residue thus obtained is taken up in 50 c. A 3-gm. which is that proposed by Bamber. The filtrate is diluted to and the resulting solution is c. and a volume of about 100 precipitated hot with barium chloride solution. the the amount of hydrogen sulphide. 354 Bamber Method for Determining Sulphur in Iron and Steel. nitrate are added. 6 (1866. 2 gms. Stahl und Eisen. or. . the solution is evaporated to dryness in a platinum dish and the dry residue is ignited over an alcohol lamp After the ignition. of iron is passed into a flask containing cadmium acetate amount whereby the latter is colored yellow owing to the formation of intensity of the color is proportional to cadmium sulphide.c. the relations holds.. Wiborgh. of concentrated hydrochloric acid. in * J. of potassium acid. sodium carbonate solution. c. of a 1 per cent. During the determination great care should be taken to prevent For this reason a the absorption of fumes containing sulphur. 240.c. of water and 2 c. filtered.* The hydrogen sulphide evolved from a weighed Principle. solution of all the sulphur is evaporated to dryness with hydrochloric acid. as = aV.

with a side- arm funnel T and with a groundbetween the cylinis about 20 cm. then. to the c. The water must not be boiled too strongly and the cloth must not be allowed to puff up. edge are placed of the Upon this upper two rubber rings same inner diameter as the Between these two glass cylinder. at the glass connection The der B. is laid a circular piece of cloth that has been dipped in a solution of cadmium acetate.1 gm. the contents boiled a few minutes to remove the air. flask. K FIG. of different shades representing For this purpose.5-6. cylinder latter The upper edge of the rounded over and ground is perfectly smooth. bottom. is placed upon the flask. of iron) through the .c. with the cadmium acetate cloth in position.c. a scale In the first place. sulphuric acid (1:5) contents of the flask (3 is After boiling for three or four minutes cautiously added.0 cm. for each 0. different It consists of Erlenmeyer A flask a 250-300-c. and a weighing-tube containing a definite amount of a substance whose sulphur content is known is thrown into the The cylinder. and the gentle boiling is continued until is uniformly moistened with the aqueous vapor which the cloth seen to pass through it. and upon the rings C upper rubber ring is placed a wooden which is held firmly against ring H the edge of the cylinder by means of three clamps (only two are shown in the illustration).DETERMINATION OF SULPHUR IN IRON AND STEEL and s and s' 355 the percentage of sulphur present. long. Wiborgh sulphur. wide at the top and about 8 mm. must be prepared percentages of uses the apparatus shown in Fig. 55. the flame is removed. drop by drop. for in that case it will become distorted and afterward an unevenly colored is surface will be obtained. 55. and is from 5. The flask A is filled not quite half full with distilled water.

prepare Tint No. so that the side which was toward the flask is on In the same way a scale of six different shades is prepared top.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. How much of it should be weighed out in order to of sulphur. 0-8 0-4 0-2 0-1 0-08 0-04 0-02 Tint No. The piece of cloth is now removed and placed upon a piece of white filter-paper. 1 ? From the table we know that this shade can be prepared by . Tint No. Present. and is there is no more gas evolved from the substance. 3. Present. 0-8 0-4 0-2 0-1 0-08 0-04 0-02 To 0-08 0-04 0-02 2. Amount 4. 0-025 0-050 0-100 0-200 0-250 0-500 1-000 Tint No. 356 The evolution of hydrogen sulphide begins at once recognized by the cadmium acetate cloth becoming yellow. corresponding to the following table Tint No. 5. 0-035 0-070 0-140 0-280 0-350 0-700 1-400 suppose we wish to prepare the scale from a sample of steel containing exactly 0. 0-8 0-4 0-2 0-1 0-08 0-04 0-02 0-0025 0-005 0-010 0-020 0-025 0-050 0-100 0-8 0-4 0-2 0-015 0-030 0-060 0-120 0-150 0-300 0-600 0-005 0-010 0-020 0-040 0-050 0-100 0-200 0-8 0-4 0-2 0-1 0-08 0-04 0-02 0-01 0-02 0-04 0-08 0-10 0-20 0-40 0-8 0-4 0-2 0-1 0-08 0-04 0-02 Tint No.17 per cent. Out. : Tint No. illustrate the use of this table. Sulphur Weighed Per Cent. After the acid has all been added. the boiling is continued until funnel T. Amount Weighed Per Cent. and then for ten minutes more in order to completely expel it from the solution. 0-1 6. 1. Sulphur Out.

0118 gm.0235 gm.8 gm. Determination of Sulphur in Insoluble Sulphides. of the substance (according to its supposed sulphur content) is weighed out and treated in the same way. In the same way the amount necessary to produce Tint No. as is the case in iron and steel laboratories. however.8X 0. of the steel in order to prepare Tint No. (6) In the can take place: Wet Way. Fresenius' Method: Fusion with Sodium Carbonate and Potassium Nitrate. or the sulphide is acted upon whereby the absorbed by one of in a suitable apparatus with nascent hydrogen. weigh out 0. of the extremely finely powdered sulphide is in a spacious nickel crucible with twelve times mixed intimately 0. of sulphur is present.0025 = xX 0. 357 weighing out 0. that an accurate value is obtained only when all the sulphur is present in a form such that it is evolved as hydrogen sulphide on treatment with acid. 1. About gm. Remark. the table shows us that 0. therefore. For the determination proper.DETERMINATION OF SULPHUR IN INSOLUBLE SULPHIDES.0025 per cent. evolved as hydrogen sulphide and sulphur is the above-described methods.017 We must. It is to be noted. 2 be found to be 0.. The above process is very simple and to be recommended in case a large number of sulphur determinations are to be will made. IV.1 per cent. is OXIDATION IN THE DRY WAY. etc. sulphur.2 gm. from 0. (A) 1. If with a sample of 0.8 gm.5 . For this analysis the sulphur is either oxidized to sulphuric acid and determined as barium sulphate.1-0. and it follows from what has been said : 0. 5 is obtained.~of an iron containing 0. The oxidation of the sulphide (a) In the Dry Way. a shade corresponding to Tint No.

c..c. and In this case a nickel crucible should be used. XX (1881). concentrated hydrochloric acid and again evaporated to dryness.c. Remark.. the total amount most reliable method for determining and serves for of sulphur hi insoluble sulphides testing values obtained by other methods. finally washed with water to the alkaline The filtrat e is treated in a the reaction.c. concentrated hydrochloric acid. p.5 gm. 358 much sodium carbonate and one part a thin layer of the mixture and with covered potassium nitrate. 04. important. filtered. 1448. the residue boiled with pure dilute as of a mixture of four parts .GRAVIMETRIC DETERMINATION OF THE METALLOIDS. of the substance with 25 gms. The contents of the crucible are heated gently at first and finally until there is no more * Glaser See Chem. the melt is extracted with water. of disappearance covered beaker with an excess of hydrochloric acid boiled to sodium carbonate solution and expel the carbon dioxide.c. and filtered if necessary. After cooling. recommends sodium peroxide. anal. heated to boiling and precipitated normal barium chloride solution! which is diluted and added as quickly as possible while stirring vigor- filtrate is diluted to with 24 c. In order to remove all of the nitric acid. of a mixture of six parts sodium carbonate and one part potassium chlorate.c.. This is the (cf. . The 450 c. of to 100 c. Chem.. ously sulphuric acid). 224. then gradually increasing the temperature until the contents of the crucible are melted it is then kept at this temperature for fifteen minutes. Ztg. of the solid BaCl 2 % Z. water. is ble in 2. In order to avoid the tedious operation of destroying the nitrate which is necessary in the method of Fresenius. It This is accomplished.* heated at first gently.! by placing the crucian inclined position within a hole in a piece of asbestos board. treated with 100 c. Bockmann fuses 0. This last residue is moistened with 1 c. the dry mass is treated with 10 c. Chem. Z. t 122 gm. 594 (1895). 18. Method of Bockmann. to conduct the fusion in such a manner that none of the combustion products of the sulphur in the illuminating-gas comes in contact with the contents of the crucible. -2H 2 O dissolved in a liter of water. however. anal. as suggested by Lowe. and evaporated to dryness.

but according to the author's experience it is equally good. 56. or Hg2 and is which M . which is 30 cm.5 gms. 56. Zn.c. wide and made of difficultly fusible glass. In order to purify the gas it is passed through the washThe first contains water and the other two contain conbottles A.DETERMINATION OF SULPHUR IN INSOLUBLE SULPHIDES- 359 evolution of oxygen. or Bi. . . and C. of this sort of is to effect the determination an analysis we will consider the Analysis of Tetrahedrite (Fahlerz).5-1 gm. . Fig. V and Z are placed about 100 c. long and 1^ cm. Oxidation by Chlorine (Rose). B. and a slow but steady stream of chlorine * is conducted through the apparatus. This method is held to be less accurate than that of Fresenius. 3. of tartaric acid have been added. From 0. Sb. Tetrahedrite is mula "IMS-RjSj in a sulpho-salt corresponding to the general foris Cu 2 Ag2 Fe. * The chlorine is generated in a Kipp apparatus from chloride of lime and hydrochloric acid. R As. After cooling the melt is extracted with water. FIG. of the finely-powdered mineral is introduced by means of a long weighing-tube into the bulb of the tube R. the filtrate acidified with hydrochloric acid and precipitated at a boiling temperature with barium chloride. This very important method is used less to determine the amount of sulphur present in insoluble sulphides than it solution of the sulphide for the separation and As an example of the metals. of hydrochloric In the receivers acid (1:4) to which 3.

V volatile chlorides. the bismuth as chloride. diluted with water. lead. are driven over into possible by carefully heating with the flame. B contains all of the sulphur as sulphuric acid. R begins to diminish. 360 As soon as the chlorine reaches the substance in R. ammonia. and determined as the chloride. the tube R The as easily much as After allowing to is broken by first scratching with a file near the drawn-out part and then touchOver each of the open ends of the ing it with a hot glass rod. almost amounts of iron. the decom- R The contents of become heated and the volatile position begins. lead. The heating is continued until only brown vapors of ferric chloride are given off. insoluble in acid. however. the decomposition is assisted by heating with a small flame kept in constant motion. a part of the iron and zinc and often small amounts of lead. filled a calcium chloride tube order to remove traces of acid. moist test-tube is placed and allowed to stand this way overnight. When the action chlorides collect in the front part of the tube.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. consists of silver. treated with ammonia on the filter and the silver precipitated from the ammoniacal filtrate by acidifying with hydrochloric The residue. and the residue consisting of silver chloride and the gangue is filtered off. considerable The Solution all of the zinc. The contents of V and Z are poured into a beaker and the drawn-out part of R is washed out with hydrochloric acid containing tartaric acid. centrated sulphuric acid. and the gangue. allowed to settle. This is warmed for a long time with dilute hydrochloric acid. is ignited wet in a platinum crucible and weighed. the arsenic and antimony as their pentoxide compounds. washed thoroughly with hot water in order to make sure that all lead chloride is re- moved. as little as possible of these should pass into the receiver. tube a clean. The Residue A and copper chlorides. It is also well to introduce with pieces of calcite between C aud R in . cool in an atmosphere of chlorine. Treatment of the Residue A. in this way the sublimate absorbs water and can be easily washed off in the morning.

and the iron separated from the zinc. and the lead the from separated copper as sulphate according to p. These are precipitated by the addition of ammonia and ammonium sulphide. the residue filtered and the bismuth determined in the filtrate according to p. precipitate insoluble in ammonium sulphide usually consists almost entirely of mercuric sulphide and sulphur. consisting of sulphides of arsenic. 1. the solution oxidized with nitric acid. The filtrate from the hydrogen sulphide precipitate is combined with that obtained from Solution B after hydrogen sulphide has been consisting of copper passed into it. 150). A stream of carbon dioxide is passed through the solution for some time in order to remove the greater part of the excess of chlorine. 157. 361 Into the nitrate from the silver chloride. (preferably and weighed. antimony. filtered off. The precipitate. Treatment of Solution B. hydrogen sulphide is passed until the solution is saturated with the gas. and the arsenic and antimony separated from the mercury and bismuth by means of ammonium sulphide as described on p. which likewise contains these metals. boiled. the precipitated sulphides filtered off and the arsenic separated from the antimony as described on p. dissolved in hydrochloric acid. . The filtrate from the hydrogen sulphide precipitate contains and zinc and is combined with the corresponding filtrate iron from the Residue A. 241 et seq. the precipitate and lead sulphides is filtered off.DETERMINATION OF SULPHUR IN INSOLUBLE SULPHIDES. then a few times with carbon bisulphide. however. gr. 200. dried at 100 C. preferably by the barium carbonate method (see p. mercury. and hydrogen sulphide is then passed into it at the temperature of the water-bath. in which case The it is washed first w ith r alcohol. 235. the mixture of the two sulphides is treated with nitric acid of sp. From the ammonium sulphide solution the arsenic and antimony are precipitated by acidifying with dilute hydrochloric or sulphuric acid.2-1. is filtered oft after standing twelve hours. while the mercury is determined as above in a Paul's drying-oven) described.3. and possibly bismuth. If bismuth is present. an equal volume of water added. then with alcohol again.

Chem. hydrochloric acid.. at first [IV]. this Aqua regia is most frequently used in practice and in the pro- recommended by J. As an example we will cite the first Determination of Sulphur in Pyrite.c.c. de Chimie through a with cold water and then of not more than 150 c. in a with a watch-glass. 9. gr. 15. f First of all. At first 300 the acid but at the c. purpose aqua regia. 1906. 358. hydrochloric acid and potassium chlorate. Rome. gr. . of concentrated hydrochloric acid and again evaporated 'to dryness. 1. the solution filtered and the residue washed with hot water. p. gr. Of the fine powder. (B) For OXIDATION OF SULPHUR IN THE WET WAY. ammoniacal hydrogen peroxide have been proposed.4 and 1 volume of hydrochloric acid of sp.c. 0. the sample must be ground to an impalpable powder.2. VI. Vol. pyrite in the cold. of a mixture consisting of 3 parts nitric acid.c. G. and Zeit. small filter * J. 3 volumes of nitric portion acid of sp. gr.. sp.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. sp. is and beaker which is 1 part covered allowed to act upon the last the reaction is completed by heating upon the water-bath. Phann. de IX. t The procedure is given here as recommended by the Report of the Sixth International Congress of Applied Chemists. and. of concentrated hydrochloric acid and 100 c. bromine. fur anal. 1. The hot filtrate. is treated with 10 c.c. or sulphur will separate out during the solution of the sample. The dry mass is now treated with 1 c. Vol. Lefort. 81. 99. The determination B Solution of the sulphur in an aliquot part of the not to be recommended on account of the fact that is the metals present are likely to contaminate the precipitate of barium sulphate.c.42. fuming nitric acid. p. The residue is treated with 5 c. 1. in some cases. p. of hot water.* viz.2. et. 362 It best to determine the sulphur in a separate portion by and potassium nitrate as described is fusion with sodium carbonate on p. Lunge's Method.5 gm. Then the solution is transferred to a porcelain evaporating dish and evaporated to dryness on the water-bath. 1.

c. of concentrated hydrochloric acid added in excess. for fifteen " 363 filtrate is neutralized with hydrochloric acid. using methyl orange as indicator. however. of the danger of losing some sulphur as hydrogen sulphide. Thereupon the solution is heated until it begins to boil. whereby the churned/' until a volume of about 450 c. barium chloride The reagent is added as quickly solution and diluting to 100 c. After washing. kept at is treated with 20 about 70 and washed with hot water. which as a rule agree If the closely with those obtained by the Fresenius method. The ferric hydroxide c. the most.c. To test the ammonia precipitate for sulphur. it is not sufficient to permit the determination of sulphur in roasted pyrite.c. ammonia. ignited and weighed. then transferred to a filter and washed free from chlorides. The barium sulphate precipitate is washed three times by decantation with boiling water. precipitate is filtered precipitate is reached. ammonia and minutes. when it is treated with a boiling-hot solution made by taking 24 c.c. Such . obtained in this way. Remark. dried. it should be filtered off and weighed with the main part of the barium sulphate precipitate. The above method gives excellent results.c. transfer it from the filter into a beaker by means of a stream of water from the wash bottle and dissolve The it by the addition of as little hydrochloric is precipitated with and the filtrate and washings treated as in the Should any barium sulphate be case of the main analysis. contained barium or any considerable amount of lead. as possible by suction. It is still better to filter the precipitate through a Munroe crucible. on account sulphuric acid. the crucible placed within a larger porcelain or platinum crucible. the precipitate is dried as much acid as possible. is well The of 10 per cent. pyrite. resulting solution filtered. In such cases the Lunge method will give lower results but on the other hand it represents more nearly the quantity of sulphur in the pyrite which is available for the manufacture of In spite of the strong oxidizing power of the above mixture of nitric and hydrochloric acids. and 1 c. of 10 per cent. as possible at one time while stirring the solution vigorously.DETERMINATION OF SULPHUR IN INSOLUBLE SULPHIDES. heated gently and weighed. some sulphate will always remain undissolved with the gangue.

and a fusion allowed to cool somewhat.. barium In the following calculation. a crystal of potassium nitrate and the heating is continued. Chem. in the form of fine borings. transferred to a added. evaporated * J. containing the greater part of the sulphur. ammonia water which is contained The contents of the flask are calibrated flask. it is filtered latter frequently contains platinum crucible. the ash of the filter paper is made with 2 gms.. rejecting the first few c. the dried. and the acidified sulphuric acid precipitated by the addition of 5 c. the resulting solution filtered. of precipitate is The 10 per cent. is poured. bromine. the filtrate with hydrochloric acid. while constantly stirring. heated to boiling. well shaken.c.c. mixed by pouring back and forth several times into a dry beaker. 675 (1901). The crucible should be inclined within an asbestos shield to protect its contents from being contaminated with any sulphur from the gas flame.c. are introduced gradually into an Erlenmeyer flask containing a cooled mixture of 200 c. As soon as all the metal has dissolved. 23. of iron or steel. crucible is is is dissolved in water. in order to expel the slight excess of bromine.c. Soc. diluted with water up to the mark. new beaker. About 5 gms. Determination of Sulphur in Cast Iron and Helmer *) Steel. the contents of the flask are heated to boiling. the weight of this chloride solution. free from sulphur. and the solution is from any residue.c. and then filtered through a dry From the strongly filter. the melt added. After the sodium carbonate has melted. in a 500-c. products are fused with a mixture of two parts sodium carbonate and one part potassium nitrate and the analysis carried out as described under the Fresenius method. to 100 Am.c. . of the filtrate. called p.c. ammoniacal 300 are transferred by a pipette into a while c. c. into 130 c.364 GRAVIMETRIC DETERMINATION OF THE METALLOIDS. original solution of the iron. Inasmuch as the an appreciable amount of sulphur. treated with five or six drops of dilute filtrate. water and 8 c. (Noyes and . sodium carbonate. After cooling.c. avoiding any contamination from a gas flame.

the ferric oxide is dissolved by heating with 50 c. A great advantage the sulphur which of the then found to be is is gained by not having to wash the ferric hydroxide precipitate. dissolved in a water. round- bottomed flask "with 50 c. the solution evaporated nearly to dryness. concentrated nitric acid. steel. weighing a is is cent. A very slight error is introduced by neglecting the volume of the ferric hydroxide precipitate.25 gm. of hot. is added. * Stahl und Eisen. of potassium nitrate. 887 (1905). All obtained with the exception of that small amount combined with an organic radical. ( sample of iron or + X Xl(M ? -13. and the After residue ignited until no more brown fumes are evolved. Method of Krug* 5 gms. sulphur. is complete.4 and the contents of the flask are gently heated. concentrated hydrochloric acid. normal barium chloride solution. of borings are treated in a 500-c.c. . The weight of this precipitate is taken as p\ in the following computation. accurate and easily carried out.. Determination of Sulphur in Iron and Procedure. sp. gr. 25. The iron must be introduced into the bromine in very small portions in order to prevent overheating which would result in the formation of a basic salt that is hard to get back into solution. but this is negligible in the deteris mination of such small amounts of sulphur.73xteg-per a BaSO 4 Xa *ft & This method Remark. and the treatment with hydrochloric acid and evaporaThe hydrotion repeated until no more chlorine is evolved.c.DETERMINATION OF SULPHUR IN INSOLUBLE SULPHIDES.c. Steel. the acid is gradually heated up to the When at the end of an hour or two the solution of boiling point. 365 hydrochloric acid and the sulphuric acid precipitated by the addition of 5 c. 0. the liquid evaporated to dryness. the iron little cooling. After the reddishbrown vapors cease to form. 1.c. The sulphur content gms.

a few drops of hydrochloric acid and a little water are added. Krug established the fact that a mixture of pure ferric chloride. 1. Furthermore. After cooling the ferric chloride introduced into a double separatory funnel. In testing this method. could and all Johnston and found to be more accurate.2. of tenth-normal sulphuric acid. and any residue of silica. solution until a little layer The mixture is well is formed on top) and 100 c. of dilute hydrochloric The ether acid. of ether.c. gr. The solution is filtered and the hot filtrate treated with hot barium chloride solution.1 which has been saturated with ether. and the ether contained in it is removed by evaporating on the water bath to dry ness.. the results were compared with the bromine method of iron. introduced into the second separatory funnel and the contents The upper well shaken. but keeping the volume below 60 c. corresponding to 5 gms. etc. this time the cooling is unnecessary. of fuming hydrochloric acid and ether mixture (prepared by gradually pouring ether into cold consolution is centrated hydrochloric acid. be treated with 10 c. To the residue.1. 1. washing out the dish with hydrochloric acid. The upper olive-green ether layer contains nearly all of the iron. sp. of ether cooled under the water tap and thoroughly shaken. the lower one is added to the contents is carefully ether solution 75 c. . sp. 30 c. carbon.c. gr.366 GRAVIMETRIC DETERMINATION OF THE METALLOIDS. whereas the lower hydrochloric acid layer will contain all the sulphuric acid and some dissolved ether. The lower layer is withdrawn to a porcelain evaporating dish. of the latter recovered after the ether separation. is filtered off into a porcelain evaporating dish. chloric acid solution is then rinsed into a beaker. Remark.c. the lower light yellow solution contains all the sulphuric acid. The nitrate is evaporated until a film of ferric chloride forms on the solution.c. 1.c. sp. layer will contain an ether solution of practically all the remaining iron.c. gr. The lower layer withdrawn into the other separatory funnel and the is washed once with a few c. of pure ether are now of the other separatory funnel. which is redissolved by the addition of a few drops of hydrochloric acid. Dr. solution is shaken with this last mixture and after standing until two layers again separate.

. 6). 347. 1937. To is purify the gas dioxide might contain.5 gm. In 1891 the author independently came to the same conclusion and worked out a method which permits of the determination of sulphur not only in pyrite but in all other insoluble sulphides. The Iron Method* (a) In 1881. per sulphate serve to remove traces of hydrogen sulphide that the carbon f Kipp generator. in diameter (Fig. Groger showed that by heating pyrite with iron out of contact with the air the former is quantitatively changed into ferrous sulphide. In this way part of the sulphur is usually given up to the iron. FeS2 + Fe=2FeS. and the compound itself is reduced to compounds which are acted upon by hydrochloric acid with evolution of hydrogen sulphide. long and 10 mm. M. which can be easily made from an ordinary piece of combustion tubing. The crucible is now placed in the opening of the piece of asbestos board A (Fig.30. 54. 54.DETERMINATION OF SULPHUR IN INSOLUBLE SULPHIDES. (C) 367 EXPULSION OF HYDROGEN SULPHIDE FROM INSOLUBLE SULPHIDES. The carbon dioxide prepared from marble and hydrochloric acid in a it is passed through a wash-bottle containing water. of iron powder that has been previously ignited in hydrogen is placed in the crucible. p. b) and upon it is placed the gas-delivery tube B which has been prepared from difficultly fusible glass. About 3 gms. the latter absorbed in ammoniacal hydrogen peroxide solution. from 0. and the mixture is finally covered with a thin layer of iron powder. and Potassium permanganate and copfinally through a calcium chloride tube. then through a tube filled with pumice soaked in copper sulphate solution. small glass crucible about 30 mm. Procedure.with iron powder. XXIV. A stream of dry carbon dioxide f is passed through the apparatus for a few min* Berichte. then through one containing potassium permanganate. as de- is The heating with iron is accomplished in a scribed on p. First of all the finely powdered sulphide is heated out of contact with the ah. of the sulphide is thoroughly mixed with it. and from the latter all of the sulphur will be given off as hydrogen sulphide on treatment with hydrochloric acid.

p.5 cm. 2377. the sulphates of the . Harding. t Berichte. 2085. utes and the crucible ally there is lost by is have ceased to glow. p. The rest K its is carried out as described on p. so that a blank experiment is first made with a weighed amount of the same. however. and for the experiment proper the same amount of iron is used. 3 68 is gently heated with a small flame. the barium sulphate* present in insoluble sulphides is usually small. about 0. (6) The Tin Method. 57). Procedure. deep in tinfoil * Only barium sulphate is reduced with heavy metals are easily reduced. with metallic tin and concentrated hydrochloric acid give off all their sulphur as hydrogen sulphide. amount of is it often only partially reduced. and the crucible is kept at this temperature for ten minutes. who first studied Into the evolution tube (Fig. J Berichte. the temperature is raised until a dull-red heat is obtained. 350. The author was disappointed in not being able by this method to distinguish between the sulphur present in insoluble sulphides and that present as sulphate (barium sulphate). thick. % this method. XIV. it is completely reduced to sulphide by this method. the analysis. this method serves for the determination of the total amount of sulphur. The amount of sulphur found to be present in the iron is subtracted from the amount found in of the procedure Remark. Upon this the substance is placed enclosed (s) and then a layer of granulated tin about 6 cm. the crucible together with and is connected with contents is placed in the 400-c. used tin and hydrobromic acid. After cooling in the carbon dioxide. If the amount of sulphate present is small.c. flask the absorption vessels V and P as shown in the figure. Usua distinct glowing visible. is placed a layer of finely -powdered tin (g) long and 2. Commercial iron powder always contains a small amount of sulphur. while if a large amount of sulphate as sulphide is present. which is 20 cm.5 cm. As. XXV. but no trace of the sulphur As soon as the contents of the crucible volatilization.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. wide.} Almost all insoluble sulphides on being treated Principle. difficulty.

57. prefer- ably by placing it in a small paraffin bath. It dissolves after about fifteen minutes. The capsule of tin soon dissolves. Concentrated hydrochloric acid is now added through the drop-funnel until the tin is at the most half covered with the is closed shown in the figure. and the tube connected with the receivers P and V. after which the step-cock FIG. as The flask V contains an ammoniacal solution of hydrogen peroxide. of water in order to remove any stannous chloride that may be carried over with the gas. 369 (Z) is added. The contents of the tube are then warmed slightly. and the substance is seen to be floating in the acid.DETERMINATION OF SULPHUR IN INSOLUBLE SULPHIDES. while P contains 2 to 3 cm. and the acid becomes . A current of pure hydrogen is conducted through the apparatus for about five minutes. acid.

on the other hand. except is is of sulphur. conducted in precisely the same manner aa 325 for the determination of halogens. Wet Way p. although a longer time is required than is the case with pyrite. etc. galena. This method affords an accurate means for deter- into mining the sulphur present in insoluble sulphides as sulphide in the presence of sulphate. cinnabar. while the iron method effects the decomposition with ease. chalcopyrite. p. By these last two methods. 350.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. in which case only the sulphide sulphur is determined. Thus the amount of pyrite in clay-slate that contains gypsum can be determined by this method. 351. is determined. The oxidation (a) (b) In In the the is Oxidation in the (a) This operation was described on *With large effected Wet Way. 54. Arsenopyrite. Finally. although usually the treatment with aqua regia or fusion with soda and nitre is used. however. one receiver is often insufficient. In connected with a Peligot tube containing ammoniacal hydrogen peroxide as shown in Fig. copper. cases may Determination of Sulphur in Non-electrolytes. 359). until the tin is completely covered with it and the heating is continued for half an hour. Remark. More acid is then added to the contents of the tube. it may be mentioned that arsenic sulphide may be decomposed by the above method. . The heating is now continued until there is no more yellow coloration to be detected in the delivery-tube which dips into the receiver V. 370 perfectly clear. amounts such cases the tube b (Carius). . Dry Way. it is oxidized to sulphuric acid and determined as barium sulphate. In order to determine the amount of sulphur present in organic compounds. is either unacted upon of only decomposed with difficulty. By this means all of the sulphur will be driven over V* and is there held in solution as ammonium sulphate and analyzed as described on p. the total sulphur More accurate values for the pyrite present in such be obtained by decomposition in a current of chlorine (see p. meanwhile first heating the contents of P to boiling and passing a current of hydrogen through a.

The only method for examining cyanates consists of determining the amount of carbon and nitrogen present by a combustion (see Elementary Analysis). and weighed it is as barium sulphate. hydrochloric acid is added. Hydrocyanic Acid. The carbon and hydrogen can be determined by Elementary Analysis (which CYANIC ACID.. a weighed crucible with the addition of a little water. COOH always determined volumetrically. 371 added to the contents of the After the closed tube has been heated and opened. Part II. solu- . Wt.02. amount of the substance is added and the contents of the crucible again heated very gradually. of the acetate see).03. contents are transferred to a beaker. 43. .g. frequently stirring the mixture with a silver wire until the organic substance is completely decomposed. c. (6) Oxidation in the Dry Way (Liebig).c. Determination of Cyanic Acid. CH3 ACETIC ACID. A mixture of eight parts potassium hydroxide (free from sulis melted in a large silver phate) and one part of potassium nitrate After cooling. the substance is heated with phosphoric acid when the free acetic acid distils over and is then titrated Free acetic acid (cf. In one portion of the substance the carbonic acid is deter- mined by the addition of calcium chloride to the ammoniacal tion and weighing the ignited precipitate as calcium oxide. in wood-cements. and the liquid is evaporated to a small volume in order to remove then diluted with water to a volume of about 200 and precipitated hot with a boiling solution of barium chloride the nitric acid. and Carbonic Acid in a Mixture of their Potassium Salts. Mol. is Acidimetry). HOCN. phur present in difficultly volatile substances. This method is particularly suited for the determination of sule. its in this case there is no silver nitrate tube. For the analysis of acetates. the melt is dissolved in water.ACETIC AND CYANIC ACIDS. After cooling. acidified with hydrochloric acid and the sulphuric acid formed is precipitated and weighed as barium sulphate. 60. | Mol. Wt.

7 2. After this the phosphoric acid is precipitated by magnesia mixture and the pre* If the hypophosphite were at once treated with nitric acid. washed with water itate and from the weight of the mercurous chloride the hypophosphorous acid present is calculated as follows: dried at 110 C. Determination as Mercurous Chloride.c. amount present as potassium carbonate and potassium deducted. adding water.02.c. Magnesium Pyrophosphate. 2.5-1 gm. then acidifying with nitric acid and deter- mined as mining the weight of the silver cyanide as described on p. solution of the salt. . Forms: Mercurous Chloride. dark place the precipis filtered through a Gooch crucible. by the addition of water the ortho-salt is formed. of the substance in about 100 c. amount of H P0 + 2H + 4HgCl = 2Hg Cl + 4HC1 + H P0 2 8 2 2 2 2 3 4 2Hg2Cl 2 :H 3 P0 2 =p:* =~ 2Hg2 Cl 2 in which p (6) by the weight of the Hg2Cl2 obtained in the analysis. standing for twenty-four hours in a warm. of on the water-bath to a small volume. of concentrated nitric acid to the aqueous First of acid is all.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. which is slightly acid with hydrois treated with an excess of mercuric chloride.. 328. . In a third portion the potassium is determined by evaporating with sulphuric acid and weighing the residue of potassium sulphate If from the total amount of potassium as described on p. 41. 66. the phosphorous acid is converted into phosphoric adding 5 c. Hg Cl Mg P 2 2 (a) 3 ? Mol. 37 2 In a second portion the cyanogen of the cyanide is detersilver cyanide by treating the aqueous solution with an excess of silver nitrate. present the cyanide is H PO HYPOPHOSPHOROUS ACID. The chloric acid. Determination as Magnesium Pyrophosphate. Wt. the difference gives the amount of potassium combined with the cyanic acid. solution of from 0. by After this means insoluble mercurous chloride is precipitated.* evaporating a few drops of fuming nitric acid and again heating. metaphosphoric acid would be obtained.

The oxidation can be accomplished by means of chlorine. BaSO 4 . H SO 2 3 Mol. The amount of sulphuric acid from the peroxide is deducted from the total value found in the analysis. after which the temperature is gradually raised till the boiling-point is reached. . The alkaline solution of the sulphite is treated in the cold with potassium percarbonate. CARBONIC. cipitate GROUP HI. acidified with hydrochloric acid and precipitated with barium chloride after making acid with hydrochloric acid.SULPHUROUS ACID. Oxidation with Chlorine or Bromine. OXALIC.* The solution of sulphurous acid or of a sulphite is treated with an excess of ammoniacal hydrogen peroxide. The sulphite or free sulphurous acid is first oxidized to sulphuric acid and then precipitated with barium chloride. the excess of the reagent is subsequently removed by boiling and the sulphuric acid is precipitated with barium chloride. SELENOUS. . IODIC. TELLUROUS. MOLYBDIC. 82. SULPHUROUS. 373 is weighed as magnesium pyrophosphate as described under Phosphoric Acid. BORIC. gently heated. Form: Barium Sulphate. heated to boiling in order to remove the excess of the peroxide. * The hydrogen peroxide must always be tested to see if it contains sulphuric acid. The solution is then acidified with hydrochloric acid and presolid cipitated with barium chloride. Wt. Oxidation with Hydrogen Peroxide. if it is found to be present. SULPHUROUS ACID. or of a sulphite.09. the amount is determined and afterward an accurately measured quantity is used for the oxidation. TARTARIC. PHOSPHOROUS. Chlorine or bromine water is allowed to flow gradually into the aqueous solution of sulphurous acid. hydrogen peroxide. METAAND PYROPHOSPHORIC ACIDS. bromine. or potassium percarbonate. With potassium percarbonate a similar procedure is used.

The analysis of these acids was discussed under Selenium and Tellurium. In this case an indirect analysis must be made. may be determined very accurately by a volu- Part II. effected exactly as that of is page 372). PHOSPHOROUS ACID. the total amount of magnesium pyrophosphate is found.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. 2 82. each acid present can be calculated as follows Suppose we have a solution containing the two acids.02. and Magnesium Pyro7 . 3. We have then from which it follows -i on mv . and let chloride produced from it ox represent the amount of mercurous and mx the amount of magnesium pyro- Further. it is to be noted that hypophos- (cf. Mg P 2. Let us denote by x the amount of hypophosphorous acid present in V c.Wt. nesium chloride is p. 3 2 3 2 Determination of Phosphorous and Hypophosphoroua Acids. 374 Sulphurous acid metric analysis (cf. : -of the solution.2HC1 + HgA. Hg2Cl2 cor- : H P0 + 2HgCl + H = HaPCVr. Aftei oxidizing one portion of the substance to phosphoric acid. H P0 3 Hg Cl phosphate. responds to 1 mol. H PO 3 3 1 mol. mercuric chloride is allowed to act upon a second portion and the weight of the mercurous From these data the amount of chloride formed is. In this case. The total amount of the mercurous while the total amount of magnesium pyrophosphate is q. pyrophosphate. let y represent the amount of phosphorous acid present in the same volume of the solution and vy the corresponding amount of mercurous chloride and ny that of mag- phosphate. 2 2 This determination phorous acid Mol. Selenous and Tellurous Acids. however. determined.c. lodimetry). Forms: Mercurous Chloride.

(a) For the analysis which contains no Determination in the Dry Way.02. H 3 P0 3 H 3 P0 2 Carbonic acid mv and v have the following values: 687 CARBONIC ACID. measuring on n. 375 and y=p m In these equations. and an oxidation would take place. Second. when the difference will represent the amount of gas.0. as.1.CARBONIC ACID. of the substance in this case the DETERMINATION OF CARBONIC ACID BY DIFFERENCE. of the substance is weighed into a platinum and gradually heated to a high temperature. or magnesium is present a final heating over the blast-lamp is necessary.4733-g. the carbon dioxide may be expelled from a weighed amount ratus . m= Mg 2 P 2 1 ' 2Hg2 Cl 2 _ i. on the other hand. 7 m^T " q onmv is effected by C02 . we may weigh the substance.* In case dioxide. o. even the difficultly decom- The posable cadmium carbonate can be analyzed by this method. m. Mg2 P 2 7 ^^HsPOT 1 ' 358 H CO 2 3 . A. Wt. expel the carbon dioxide and then weigh it again. ~ ^HggO. 62. for example. First. or a volatile mixture of carbonates constituent other than the carbon gm. determined gravimetrically as is more accurate determination its = p. of a carbonate. This analysis may be accomplished in two ways. but a and expelling this gas volume. Mol. strontium. * Carbonic acid cannot be determined by this method when the oxide suffers change.1742. while with other carbonates the heat of a good Teclu burner is sufficient . and then absorbed in a suitable appacarbon dioxide is r/eighed directly. carbonates of barium and the alkalies. in the case of FeCO. 1 crucible calcium. residual MnCOg where . Gravimetric Determination of Carbon Dioxide. do not lose their carbon dioxide on ignition.

which has a ground-glass connection with the tubes * In the German edition of this book. The whole apparatus is then weighed. is This ascertained.) By afterward weighing the apparatus and subtracting this weight from that first obtained. of the and the amount ond portion by of carbon dioxide is determined in a sec- (6). which in an improved form is shown in Fig. however. when carbon dioxide is evolved and escapes from the apparatus. instead of Mohr's. (Care must be taken that no moisture escapes with the gas. In this book. ly well. that of Mohr. It is all made of very thin glass and weighs comparatively little. namely. The alkalimeter consists of the small.376 GRAVIMETRIC DETERMINATION OF THE METALLOIDS. wide-mouthed. analysis is easily accomplished.. Geissler. 58. The weighed carbonate is placed in an apparatus containing acid. only one of these so-called alkalimeters will be described.* Shrotter. besides having a flat bottom. those Bunsen. If the substance contains the sum ignition. .) answer the purpose equalof FIG. flat-bottomed flask F. Bunsen's alkalimeter is described The above apparatus has the advantage of having a stopcock to separate the acid compartment from the flask. upon which it will rest unsupported. 58. and a large number of different forms of apparatus have been devised for this purpose. (6) Principle. but in such a way that the former does not at first come in contact with the latter. although it must be stated that many other forms (e.g. water besides carbon dioxide then is determined by the loss on water + carbon dioxide Determination in the Wet Way. after which the acid is allowed to act upon the substance. etc. Fresenius-Will. the weight of the carbon dioxide Procedure.

Through a hole in each stopper a short piece of glass tubing with rounded ends is introduced. is placed in a 1 to 1. but it should be gently heated while a cur- rent of dry air is sucked through it. This space with molten sealing-wax. leaving the outer 2 or 3 in the tube is filled Before beginning the determination the apparatus must be It is not advisable to dry the flask by washing clean and dry. in baking-powders. are transferred to the flask and from weighing-tube.5 gms. by stirring-rod within rubber tubing. Another wad of cotton is then placed upon it. During the aspiration the small calcium chloride tubes are connected with ively. The tube should be kept closed when not in use to prevent the gradual absorption of moisture from the air. A At the bottom and B.4 is now filled two-thirds full a little water is added. .CARBONIC ACID BY DIFFERENCE. unless the calcium chloride is saturated with carbon dioxide before the analysis t This method is is made (see foot-note. with alcohol and ether. As aspirator an inverted wash-bottle may be used. page 380). and cooled in a desiccator. a paper about 3 cm. ready the finely-powdered substance. The tube . from which the water is allowed to run out slowly through the shorter tube. and the cork is shoved far into the tube with the help mm. wide is introduced into the neck of the tube. and taken to see that none of the latter adheres to the glass after the tube care is above the filled portion. but in this case softened cork stoppers are placed at the end of the tubes after the second wad of cotton. The paper cylinder is removed cylinder of glazed is about three-quarters full of calcium chloride. not in use. and through this cylinder some pieces of sifted calcium chloride* are poured. some carbon dioxide will be absorbed by it and consequently low results obtained in the analysis. when air-tight connection is made. and the tube is closed tempo- in the tube. t all been dried is at 100 * As commercial calcium chloride always contains a little free lime. so that When no moisture can enter the c and d respect- flask. which has C. Two ordinary calcium chloride tubes are filled in the same way about two-thirds full. of B is placed a loose 377 wad of cotton. often used for the determination of the carbonic acid Such substances are decomposed by water so that they should be kept dry until after the apparatus has been weighed. of a stirring-rod. empty. the top is placed rarily at d by means of a piece of stirring-rod within rubber tubing. so that a perfectly These tubes are also closed.

The whole apparatus. 58. meanwhile aspirating a current of dry air through Not more than three or four bubbles of air per c and out at d. The objection the size and error in making the two weighings. the analysis of or Lunge-Marchlewski Fresenius-Classen the cases such In etc. second should be allowed to pass through the flask. decomposition will be nearly complete in most remains to remove all carbon dioxide absorbed by It now cases. as shown in Fig. 380 and 388. DIRECT DETERMINATION OF CARBON DIOXIDE. As soon as the evolution of carbon dioxide begins to take place quietly. there is likely to be an method is better. may be . 378 with hydrochloric acid (1 part concentrated acid to 4 of water) by means of a small funnel or thistle tube. Remark. This is effected by and contained the liquid hour. but it is esti- unreliable for as are present in cements. * There operation. and the stop-cock T must be turned so that none of the acid will run into the flask. gently heating the solution by means of a small flame until the acid just begins to boil. The stop-cock T is then opened so that the acid in A slowly drops into the flask. in the apparatus. B. Here again the determination can be carried out both dry and wet ways. the apparatus is allowed to stand without watching for about half an At the end of this time all of the acid will have passed into the and the flask. it is unquestionably true that it is easier to expel carbon dioxide from a solution than it is to absorb it quantitatively. This method affords excellent results in the mation of large amounts of carbonic small amounts such acid. (See pp. after which it is again weighed without the stoppers. is some danger To prevent of losing a little hydrochloric-acid gas during the this the calcium chloride may be replaced by pumice carbonate impregnated with anhydrous copper sulphate. The loss in weight represents the amount of carbon dioxide originally present in the substance as carbonate. As soon as the boiling begins. is now placed upon the balance-pan and accurately weighed. or the decomposed by means in the of sulphuric acid. stoppered and allowed to stand near the balance for half an hour or more. the flame is removed and the slow current of It is then air is still passed through the apparatus until it is cold.) to this method lies in the fact that owing to weight of the apparatus.GRAVIMETRIC DETERMINATION OF THE METALLOIDS.* On the other hand.

Example: Analysis of White Lead. and made of difficultly fusible glass. 380) the . way in . White lead. long and 1-1. f though. lead oxide. The analysis is conducted as above described except that in which is connected with the this case the calcium chloride tube soda-lime tubes sents the is amount weighed. no other volatile acid can be present Water is kept back by the calcium chloride the same time.5 cm. therefore.DETERMINATION OF CARBONIC ACID BY DIFFERENCE. a slow meanwhile passing but steady current of air through the apparatus. and the latter is shoved into the middle of a horizontally held glass tube which is about 20 cm. This method can be employed for the analysis of carbonates with the exception of those of barium and the Remark. air and the soda-lime tubes are subsequently increase of weight represents the amount of carbon dioxide. The gain in weight of the former repreof water in the substance. t this Even the carbonates of the alkalies and of barium can be analyzed if they are mixed with potassium bichromate. Through one of the calcium chloride tubes a slow stream of air (free from carbon dioxide)* is conducted and the other is connected with two weighed soda-lime tubes (cf. It is a basic carbonate of lead and contains. while it is often contamifree nated with sand. provided it is from acetate (which must be shown by a qualitative test). of the substance are weighed out into a porcelain boat. current of The weighed. wide. carbon dioxide. (a) From one to Determination in the two grams 379 Dry Way. The substance is heated gradually until it glows strongly. while * The air is if the passed through two wash-bottles containing caustic potash solution. can be accurately and expeditiously analyzed by the above method. of course. the gain in weight of the latter shows the amount of carbonic acid present. at tube. and water. When there is no further heat effect to be detected in the soda-lime tubes. the substance is allowed to cool in p. Both ends of the tube are provided with calcium chloride tubes connected with it by means of tightly-fitting rubber stoppers. all alkalies.

ignited. 2NaOH + COj=Na 2CO 8 + H. * / is a protection tube whose left arm is filled with calcium chloride and Fig. 59. with a condenser and connected with the dryingcapacity provided tubes a.f The substance is weighed out into the dry flask. and c and with the weighed soda-lime tubes d and e. (b) Determination in the Wet Way. covered with a little through the apparatus in order to remove any carbon dioxide may be present in the flask or in the three drying-tubes. a.c. 6. it must be saturated with this gas before the determination dioxide t For this purpose a dry current of the gas is conducted through is made the tubes for one or two minutes. As commercial calcium chloride always contains lime which will absorb carbon dioxide. and weighed. The first drying-tube. after Fresenius-Classen. the outer end of the tube is then closed of a glass rod within a piece of rubber tubing and the other end At the end kept connected with the Kipp generator for twelve hours of that time the excess of carbon dioxide is removed by passing air through The air is freed from carbon dioxide and the tubes tor twenty minutes dried by passing through two bottles containing concentrated caustic potash solution and then through a long tube filled with calcium chloride. contains glass beads wet with concentrated sulphuric acid. that While the air is being led through the apparatus. After weighing the latter the lead oxide is treated with hot. when it will dissolve to a clear solution if pure.O. the soda-lime tubes are carefully wiped with a linen cloth and weighed. while any sand will remain behind as an insoluble residue. By deducting the latter from the original weight of the residue in the porcelain boat. by meansis .third filled with calcium chloride in order to absorb the water set free by the absorption of the carbon by the soda-lime. while b and c contain granular calcium chloride. dilute nitric acid. The apparatus necessary for this determination It consists of a decomposition-flask is shown in about 400 c. the weight of the pure lead oxide is obtained. water in order to prevent loss of the substance and a slow current of air (free from carbon dioxide) is conducted Procedure. 380 residue in the porcelain boat is weighed the amount of lead oxide determined. of whose right arm contains soda-lime. is If there is a residue it is filtered off. The current of air is now stopped.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. the weighed tubes are connected with c * The right arm of the last soda-lime tube is one.

bubbles per second pass through a. As soon as this has taken place. provided not more than 0. a slow current of air is passed through the apparatus so that not more than 2-3 FIG.DIRECT DETERMINATION OF CARBON DIOXIDE. the contents of the flask are slowly heated to boiling and while the solution is boiling gently. the flame is removed and a somewhat more rapid current of air is conducted through the apparatus for twenty minutes more. by the heat effect there. Almost all of the car- bonic acid tained is absorbed in the first soda-lime tube. 59. The stream of acid is regulated so that not more than 3-4 bubbles per second of gas pass through a. perfectly cold was taken for the analysis. in this way the water vapor is condensed and flows back into the flask instead of reaching the sulphuric acid in a. in . When all e. after which a slow stream / of hydrochloric acid (1:3) 381 allowed to flow upon the substance is from the funnel T. may be ascer- should remain of the carbonate of the carbon dioxide has been absorbed the tube d quickly cools. on the one hand and with on the other. and allowed to stand in the balance case for twenty minutes.5-1 gm. stoppered. as The second tube. consequently the contents of the latter tube seldom have to be renewed. When all of the acid has been added. The soda-lime tubes are then removed. During the whole operation. causing an immediate evolution of carbon dioxide gas. cold water is allowed to flow through the condenser.

of pumice in pieces about the size of a pea are placed in a and covered with a concentrated solution of 30-35 gms. there should be no turbidity. the lime is placed in a tube of difficultly fusible glass and heated in a small combustion furnace. and copper sulphate * is introduced this serves to absorb all of the between a hydrogen sulphide evolved. In this way 4 gms. the amount of carbonate present is determined and an accurately weighed amount is used for the analysis. but also for the analysis of carbonates in solution provided little or no free carbonic acid is present. t To prepare this lime absolutely free from carbonate. It cannot be heated higher than the above temis formed which would be absorbed perature as otherwise some sulphur dioxide by the soda-lime. of porcelain dish copper sulphate. . is Determination of the Total Amount of Carbonic Acid in Mineral Waters. Remark. as in the case of conducted as follows: many mineral waters.3 GRAVIMETRIC DETERMINATION OF THE METALLOIDS. From * 3 to 4 gms. the substance contains besides the carbonate a sulphide is decomposable with acid. The Fresenius-Classen method is suitable not only for the determination of carbon dioxide in solid substances. they are then weighed. should always be made with this lime. a tube containing pumice If which impregnated with and b. are taken for the satisfactory. for four or five hours. of commercial lime can be freed from carbonate in one-half to three-quarters of an hour. from 3-10 gms. The results obtained by this method are perfectly For the analysis of substances containing small amounts of carbonate. That the carbon dioxide is actually removed can be shown at the end of that time by passing the escaping air A blank experiment through baryta water. 2 order to acquire the temperature of the balance. At this temperature the copper sulphate is partly dehydrated and in this condition it absorbs hydrogen sulphide more readily than when in the hydrous condition. In case considerable amounts of the latter are to the analysis be estimated. The solution is evaporated to dry ness with constant stirring and the residue allowed to remain in the hot closet at 150-160 C. analysis. meanwhile passing a current of dry air free from carbon dioxide over it. If it is desired to use commercial lime for the determination. of freshly-burnt lime f and the same amount Sixty gms.

while through the other hole a glass tube about 50 cm. A double-bored rubber stopper is taken of such a size each will that it will fit fit above flasks and through tube which reaches about 3 cm. * are of crystallized calcium chloride placed in to six Erlenmeyer flasks whose necks are of 383 each of from four such a size that the apparatus shown in Fig. long is passed which likewise reaches about 3 cm. The gain amount water taken for the analysis. particularly when magnesium carbonate is present. Often. This is . the shorter tube is again closed with the thumb.DIRECT DETERMINATION OF C. and fastened by means of The flasks are then allowed to string to the neck of the flask. bonate. the flask is removed from the water. To make sure that the solid stopper not loosened while carrying the flask back to the laboratory. the thumb placed over the shorter of the tubes. The thumb is now removed from the shorter tube. stand several days with frequent shaking. so that the flasks must be The addition filled by a of calcium chloride serves to decompose any alkali carnot quantitatively decomposed by lime alone. the filled not easily accessible. they are taken to the spring and are treated one after another as follows: The solid rubber stopper is quickly replaced by the one fitted with the two tubes. below the stopper. liquid the filter is immediately thrown into the flask. and the flask is dipped well below the surface of the water. when the spring. 59. and the latter is now connected with the apparatus shown in Fig. The flasks are they closed by means of tightly-fitting rubber stoppers and accurately weighed. when the precipitate is allowed to settle and the flask and contents are weighed. The carbon in weight represents the The supernatant dioxide is determined as in the previous process. As soon as the almost full.water will pass into the flask and the is replaced air will escape through the long tube. This method is the flasks can be spring * is of is capable of yielding excellent results provided as above described. and the stoppers are once flask is more quickly interchanged. quickly poured off through a folded filter. 59. however.4RBON DIOXIDE. it is is covered by a piece of parchment paper. into the neck of each of the one of the holes is fitted a short glass above the stopper and the same distance below. but so that the longer tube still reaches into the air above. To fill the weighed flasks with the water to be analyzed.

consists of evolving carbon dioxide from cedures carbonates by the action of acid. and computing its weight from its volume. and also for the determination of carbon in iron and steel. Fetter sson. collecting the gas over mercury FIG.-f This excellent method. (a) Method of 0. The method * Cf. and was used by him for the determination of the carbonic acid in sea-water (Skagerrak). 384 method and usually a small amount of carbonic acid is during the operation. the modified method of Pettersson f Berichte. in carbonates. Petterson's apparatus is shown in Fig. A much more expeditious and accurate different lost procedure which can be performed within one hour at the spring. upon which the two following proare based. 1402. on p. 60. p. 393.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. consists in the determination of the total amount of carbonic acid present in mineral waters 2. 60. . 23 (1890). by measuring the volume of the Gas-volumetric Determination of Carbonic Acid.

means of a flame. of moist hydrogen at 720 mm. and the liquid hi K is heated by once more opened. the measuring-tube. a small piece of filled up aluminium wire * rest of the thrown in. and 15 C.0142 gm. b is closed and is tube. and the screw-cock d is a is opened. mark with the water to be examined. a is closed. noted as well as the temperature of the cold water which surrounds After this b is opened and is raised.GAS-VOLUMETRIC DETERMINATION OF CARBONIC ACID. and the air hi the The cocks M until the mercury rises removed by raising up to the crossing point. The decomposition-flask K water up to the mark just below the side- flask mark is not shown in the illustration). c is opened. unabsorbed gas is once more brought into the measuring- the gas The As soon as the mercury has reached and vertical tubes. By weighing the both empty and with this amount of water. when d is closed and then a. By this means the hydrochloric acid in N is introduced into the flask K. The air in the measuring-tube (which does not contain an appreciable amount of carbon dioxide) is removed by opening c and raising M. the juncture of the horizontal allowed to remain in the Orsat tube for three minutes. with the All of the rubber tubing should be firmly fastened to the glass by means of wire. the flame is raised until the mercury within it stands filled is with that in the measuring. the volume of the flask when arm (the to this The flask is now filled to the mark is obtained. The acid is allowed to run into the flask until the upper part of the apparatus is reached. and d are closed. taking care that none of the caustic potash solution comes After (the latter should not quite reach the stop-cock b). bringing the gas once more to the atmospheric pressure. after which c is again closed. As soon as the meas- measuring-tube is in the capillary M M uring-tube is almost removed from K. slowly opened.c.tube. is brought very low. and its position in the latter At the same time the barometer reading must be then read. its volume * 0. level is M with the gas. with it . A lively evolution of gas at once ensues. Now a is is lowered. 3 85 of determining the carbonic acid in a water containing small amounts of free carbonic acid but considerable carbonate will suffice to show how the apparatus is filled with distilled is used. aluminium evolves 20 c. and the apparatus as shown in the is flask is connected figure. a. b. which contains whereby the gas passes into the Orsat tube M caustic potash solution (1:2). After this c is closed.

* Cf. of substance V c. Tabellen. Soc. 62. these readings of the barometer and thermometer remain rule. Proc. Let us assume that from a gms. by repeatedly lowering M. In case it is desired to determine the amount of carbonate in a solid substance. otherwise it necessary to reduce the gas volumes in is The difference between C. allowed to carried out exactly as described above. chem. mm.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. Phys. pressure by the following formula : 7(5-^0-273 760(273+0 In this formula. weigh FX0. and 760 mm. raising Finally the upon the substance and the determination act is acid is closing a. M.529 = 0. a smaller decomposition-flask should be used.001977 gm. f Landolt-Bornstein. each case to the two volumes represents the amount of the carbonic acid The unabsorbed gas is removed through c and this whole operation of collecting the gas and absorbing the carbon dioxide is repeated until finally no more gas is given off from the liquid gas.c. First of all C. In order to compute the weight of the carbon dioxide from this volume. pressure. pressure weighs 0. is then The percentage the original substance V X 0. pressure. Computation of the Analysis. constant. and 760 mm. we start with the fact that the density of carbon dioxide 1 c. which was measured moist at the volume is reduced t C. w ' represents the tension of aqueous vapor ex- pressed in millimeters of mercury.001293 gm. of air at is 1. of carbon dioxide were obtained.1977 - =per cent. inK.c. and 760 mm. and V c.c. to and B. and 760 mm. C0 2 weighs 0.c. C0 2 .t consequently at 1 c.1977 gm. of G0 2 in . Lord Rayleigh.529 * referred to air as unity. 204 (1897). 386 As a as well as the temperature and barometer reading is noted. Roy. The aluminium wire is added to the weighed substance and the exhausted apparatus is opening and then c.001293X1.

Remark. expelled. a different gas simultane- Formerly it was customary . By boiling The addition an acid of aluminium solution. carbonic 387 is absolutely necessary.GAS-VOLb'METRIC DETERMINATION OF CARBONIC ACID. 61. acid is not completely FIG. this is only effected when ously passes through the solution.

measured gas must be reduced which ordinarily requires a knowledge . there under the same pressure as that in the compensation-tube (this is the case when the mercury level is the same in A and C). . 6. i. Method (6) of Lunge and Marchlewski* Lunge and Marchlewski carry out the determination according same principle as that of the above process.. Chem.. therefore.c.of the temperature and the barometric pressure. In this method the reduction is accomplished without paying any attention to the actual readings of the thermometer and barometer by means of the compensationtube C. By raising the le veiling-tube B so high that V c. but Petterson accomplished the same purpose by generating hydrogen within the liquid itself. decomposition-flask N.c. 388 to pass air through the apparatus.c. therefore. and 760 mm.. is a gas volume V" in the measuring-tube A If. f. at C.. the three last are connected together as shown in the It figure. pressure. in A corresponds.c. by simul- to the taneously evolving hydrogen (aluminium and hydrochloric acid).GRAVIMETRIC DETERMINATION OF THE METALLOIDS. the volume of the to C.c. 1891. and 760 mm.c. and absorbing the carbon dioxide by means of caustic potash in an Orsat tube. p. 229. however. and the le veilingtube B. The volume of the gas T" *Zeitschr. measuring-tube A. the 140-c.c. which contains a known amount of air. is compressed to 100 c. measuring the gas. any gas would be equal to 100 c. to the vol- angew. In the case of all gas-volumetric methods. we can reduce this volume to the standard conditions by simply raising B until the volume of the gas in C is just 100 c. pressure. the compensation. pressure. The apparatus which they recommend consists of the is shown in Fig. 61.tube C. 40-c.e. this amount of air has V and atmospheric pressure P' (with the mercury at the same level in B and C) we know that this volume of C.. viz. taking care that the mercury remains at the same height in the tubes A and C. we have accomplished the reduction in a mechanical way. and 760 mm. at a volume of at t . If. that amount of air which in a dry condition assumes a volume of 100 c.

F'P' = 1.5 C. P f . In the measuring-tube A. by equation 2 we have: V'-P' Fp'. 10 =14.9) C According!}' 112.5 ' -273(731-14. 389 of this gas at C.9 c. then 100X760X290.. . and 760 mm. the reduced gas volume that is desired.9 c. 5=731 mm. pressure.c. of assume J=17. To illustrate. A drop of water is added by means of a pipette. In the compensation-tube we have the volume at atmos- V and after compression the volume becomes and the pressure is P from which it follows: pheric pressure P' F = 100 ' c.Pp F"-P'~F "-P or F':F"-Ff':TV' " F is. Before using the apparatus for the determination. F 'P . By 1 dividing equation F"-P' = F "P V" at the atmos- volume becomes . This is apparent when we remember that at a constant temperature the product of the ume pressure into the volume remains a constant for any gas. 2.tube with the correct amount of air.c. the tube is im- .c. dry air measured at of the the laboratory moist at when measured temperature pressure and the prevailing barometric pressure. for it has been compressed to the same degree as the gas in C. . this and is accomplished as follows: First of all a calculation is made to determine what would be C. of air are introduced into the tube by removing the stopper and lowering the levelling-tube until the mercury in the compensation-tube stands at exactly 112. let us the volume of 100 c..GAS. therefore.VOLUMETRIC DETERMINATION OF CARBONIC ACID.c. we have the volume pheric pressure F ". 9 (tension of aqueous vapor). and and the pressure P after compression this so that . it is necessary to fill the compensation. and 760 mm.

with the funnel tube Connection is also made with the tube A after it has been completely filled with c.c. and the air in raising A After repeating this is expelled. slowly opened and the water water. 62. of hydrogen. after this h is turned so that A is connected with the capillary d. B is lowered. when 10 until m is once the of c. The contents of the flask are heated to boiling over a flame and kept at this temperature until all of the aluminium has dissolved.c. Procedure for the Analysis. process three or four times until finally only two or three centimeters of air re- main in A.. of M . is weighed out into the decompositionflask. opening h so that e is connected with A.08 gin. Such an amount of the substance in will to be analyzed most 30 is added. The air from now exhausted by lowering B. A rubber stopper containing a glass tube is latter then pressed sure C down may vary as After this the temperature and preswill the reduced volume of the air into D. always be equal to 100 c. then closing h by turning it 90. until the stop-cock h is reached.e.c. when M is is filled with distilled allowed to run into the latter is N immediately .c. i. enough to furnish approximately 100 c. h is FIG. have run The carbon dioxide evolution begins at once and the mercury level quickly falls in A. N is mercury by raising B. that at the carbon dioxide will be generated. much as it . and carefully B until the mercury stands at an equal height in A and B. more acid closed. and the flask is connected and capillary n. In order to transfer the gas remaining in the flask m is N into the tube A. About 0. of aluminium wire.V. then into the flask . and an air-tight seal is made by covering the with mercury. the hydroadded to M.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. During the whole operation the mercury level in B must be kept lower than that in A. chloric acid (1:3) is m carefully opened. 390 mediately stoppered.

allowed to stand there for with an Orsat tube filled gas in A is three minutes. as in the Petterson method.14-0. the driven over into the latter. or a corresponding amount of any other carbonate.. It is also well to make these readings in the above-described procedure. * In the decomposition flask K. is fastened to the neck of the flask. of water is allowed to flow through the funnel. Chem.c. in order to be sure that the volume in the compensation-tube has remained constant. nan be computed according to the formula C. where its volume at and 760 mm. to test the volume of the gas in the compensation-tube from time to time make sure that it really corresponds to 100 c.15 g. The reduced volume is After this the capillary d then read. angew. under the For a single determination the author prefers to dispense in order to with the compensation. however. CO2 = 0. is connected with caustic potash (1:2) (Fig. and then the capillary is connected * Z. 1906. 63.c. of air standard conditions of temperature and pressure. It is necessary.015 g. . (c) Method of Lunge and Rittener. 1849. of calcite. is placed 0. Fig. for example. Remark. as. where carbon dioxide determinations must be made daily. however. mark. T. and the per cent. About 1 c. Per cent.. in which F is the amount of carbon dioxide absorbed in theOrsat tube and a represents the amount of substance taken for the analysis. the collected gas must be kept surrounded by water at a definite temperature. pressure is determined as before. in cement factories.c. and again transferred to A. and the temperature and pressure must be observed.1977. the mercury stands at the same height in A and C and so that the level in the latter tube is exactly at the 100-c. 391 The gas is then compressed by raising the tube B until closed.. weighing about 0. This is the most exact of all methods for the determination of carbon dioxide in solid substances and is accomIt is particularly to be recommended plished most quickly. and a small piece of aluminium wire. In this case.GAS-VOLUMETRIC DETERMINATION OF CARBONIC ACID. The difference in the two readings represents the volume of the carbon dioxide. 62).tube.

whereupon the stop-cock h t is closed. in the burette run two or three minutes. hydrochloric acid is added through the funnel dioxide from the flask. dilute acid that it may be added much more quickly than prescribed above. hydrochloric acid (1:4) is allowed to flow upon the substance until the latter is decomposed completely. . after which h : | T' is by letting the closed. By carefully opening the lower stop-cock h^ the salt solution is allowed to rise in the burette until the liquid there stands at the same height as in the levelling tube. 63. serves to expel the last traces of carbon As soon as all aluminium is dissolved. t Provided the temperature and pressure are the same as before the If this is not the case. pressure before the difference is found. The with the dry Bunte burette. added from wire is T until the aluminium reached and the flask is heated The hydrogen now evolved again. or siderite. The apparatus is allowed to stand for 20-25 minutes so that the temperature of the gas will be that of the surroundings and then. a. dolomite. which contains a FIG. the until the liquid reaches the stop-cock h y which is then closed at once. Now from the funnel T. The stop-cock of the funnel T is Bunte burette are opened. such as magnesite. of the burette is now connected by rubber tubing with the levelling tube N. by suitably raising or lowering the levelling tube with ^i open. * taking care that no water Acid is then gets into the burette. The lower end. the burette reading is taken and the temperature as well as barometer reading noted.392 GRAVIMETRIC DETERMINATION OF THE METALLOIDS. . The funnel T | of the burette is filled with strong caustic potash * In the case of carbonates. closed and the two cocks lower stop-cock. saturated solution of common salt. then the liquid is heated to boiling. they are decomposed so slowly by cold. h l} is and a partial vacuum pump of the now connected is produced with the suction pump. both volumes must be reduced absorption of the CO 2 to and 760 mm.

64. 386. Example: Weight of substance = a Volume of hydrogen + air + CO 2 =V t Tempera ture = Barometer =B Hydrogen + air = TV Tension of aqueous vapor CO = Vt-V 2 The volume reduced and 760 mm. and the contents of the burette mixed by shaking. of the tension of pure water at the same temperature. to .8uQ273 f 760(273 + and the percentage of CO F X0. which is closed before the last few drops of liquid leave the funnel. Tension of salt solution = 0. ' t is. 386) per cent. . The computation of the weight of carbon dioxide is carried out exactly as described on p. therefore: _ (F TV). By repeating the operation it is whether to the tell absorption of carbon dioxide has been easy The residual volume is read with the usual precaucomplete.GAS-yQLUMETRIC DETERMINATION OF CARBONIC ACID. for this purpose the author has modiapparatus the Pettersson apparatus as shown in Fig. of carbon dioxide in mineral waters not suited. except that the vapor tension of the saturated salt solution only amounts to 80 per cent. CO2 is. mm. For the determination this fied is (d) The Modified Method of Pettersson. = w mm. For decomposition-flasks.c. 393 solution (1:2) and a partial vacuum is produced in the burette. tions and the difference between the two readings * gives the volume of the carbon dioxide. by lowering the levelling tube and opening the stop-cock h^ The caustic potash solution is allowed to run into the burette by opening the upper stop-cock h.8w mm.(-0. capacity are used (according to the supposed amount of carbonic . Erlenmeyers of from 70-200 c.1977 = 2 in the substance (see p.

The water in R is now removed by filter-paper and the flask and contents weighed to the nearest centigram. By deducting water. 394 acid) and the exact capacity of each flask is etched upon it. determine each flask is The tube R is shoved into the stopper until the small opening can be seen just below the bottom of the rubber stopper. and in this way an air-tight seal is made. 64. and the latter is pressed as far as possible into the Erlenmeyer flask full of means some of the water passes from the flask into the tube R. To provided with a tightly-fitting stopper this. of gray (not red) rubber containing one hole. The bottom of R is fused together.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. but near the bottom a small opening is blown. b. through which the small tube R is introduced. By this . The latter is then raised as is shown in Fig.

tightly fastened with wire. About 0. a sharp line is cut in the wax by means T of a knife and the capacity is written upon the wax w ith a pointed file. The its original and air is position as The tube R shown in the figure. in shown the is nected with the flask as figure and the screw-cock H rubber connections must be All closed. 6) and the spring-water within the tube is washed out by a stream of distilled water from a washbottle.c. paper strip is covered with a thin coating of Along the edge of the paper where the bottom of the rubber stopper came on the flask. now pressed into the flask so that the small the lower surface of the stopper.* The flask is then connected with the bulb-tube P (of about 40 c. which in turn is connected with the measuringtube B. from ened to the stopper is flask. filled by dipping into the spring. the flask dried. 395 this.GAS-VOWMETRIC DETERMINATION OF CARBONIC ACID. then removed from the Orsat tube by suction through the right-hand capillary and the stop-cock is changed to the stop-cock times. of aluminium is placed in the flask. the filled flask is closed by the rubber stopper with the tube R so that the bottom of the stopper reaches just to the mark again. The flask is now ready to be used for the analysis. are cooled its contents . the weight of the water. 64. These lines are etched upon the flask by exposing them to the action of hydrofluoric acid for two minutes. below reaches opening * is With water containing much carbonic acid. a piece of rubber tubing is placed in the bottle containing the water to be analyzed so that it reaches to the bottom and the water then After this is siphoned off into the flask for two or three minutes. the flask and by ice in order to prevent the glass breaking. from whence it is driven into the Orsat tube by turning N M This operation is repeated four raising N. The tube R is raised (Fig. the volume of the By means of a piece of gummed paper fastflask. the weight of the empty flask together with the rubber stopper and R. so that the air passes The bulb P is exhausted by lowering into B. the position of the lower edge of the rubber flask is emptied. The latter is placed in a condenser through which a stream The reservoir N' is now conof ordinary water constantly flows.04 gm.e. is obtained. capacity). which is flask as well as the wax. dried. i. and the neck of the The noted. When this is not possible. and the wax melted and wiped off with filter-paper. The excess of the latter is then washed off.

GRAVIMETRIC DETERMINATION OF THE METALLOIDS. acid solution and the last portions of the gas are carried over into the measuring-tube B. measuring. N is gas. this is closed. As soon as the acid has reached the stop-cock M. and the contents of B are brought under is removed. in the flask. after which its position in B is noted. M N until the mercury in the two atmospheric pressure by raising tubes is at the same height. none of the liquid in the flask is carried over with the escaping As soon as the aluminium has completely dissolved. and after reading the volume of the gas as before it is led into the Orsat tube. the barometer read. which is afterward hastened by gentle warming. it is necessaiy to have a sensitive .* and the gas is driven over into the Orsat tube and allowed is This boiling. while that present as normal carbonate together with the rest of the bicarbonate remains to remain there. the liquid in the latter is usually turbid at this point The owing to the precipitation of alkaline-earth carbonates. H is opened.. its contents are read and driven over into the Orsat tube as before. The addition of the K clears up and acid. reservoir air reaches the contents of K. and a small amount of acid is allowed As soon as the acid to run into K. and driving over of the gas is repeated until only a slight gas evolution can be made In this way all the free carbon dioxide and a part to take place. of that present as bicarbonate is driven off. As soon as the measuring-tube is almost entirely rilled with gas. at the spring. is repeated until finally the liquid in the aluminium begins to evolve a steady stream of hydrogen. When the measuring-tube B is nearly filled. 396 in Usually carbon dioxide is immediately evolved and the mercury at once begins to sink slowly. The temperature of the water surrounding B is taken. after which H is again closed. so that the flask is filled with the hydrochloric lowered. a lively evolution of carbon dioxide ensues. The le veiling-tube N is placed in a low position. H is opened. the flame is closed. when the contents of the flask are heated to boiling but care is taken that . The evolution of the gas is B hastened by gently heating the contents of the flask. N f is now filled with hydrochloric acid (1:2) and the removed from the rubber tubing by raising N' high and pinching the tubing with the fingers. After remaining * If this analysis is made aneroid barometer at hand. etc.

This differ- ence represents the volume of the carbon dioxide gas. By correctly adjusting the current of water flowing through the condenser. Determination of Carbonic Acid in the Presence of Other Volatile Substances. For a single determination more than one hour is seldom required. From the volume of the absorbed carbon dioxide the per cent. The apparatus * can be readily transported. the temperature at which the gas is measured will remain constant during the entire experiment. both in winter and. See Part II. If it is desired to determine the amount of carbonate present in commercial chloride of lime. . 397 there three minutes the unabsorbed gas is once more transferred to B and its volume subtracted from the total amount of gas which has been expelled from the water that was analyzed. nor the indirect method will give by the The determination can easily be effected following procedure: The chloride of lime is decomposed with hydrochloric acid and an ammoniacal solu- the gases evolved (CO 2 -f C1 2 ) are passed into * It can be purchased from Bender and Hobein of Zurich. at any desired height it is In order to maintain well to fasten it to a ring- stand. present is computed as was shown under the Pettersson method.DETERMINATION OF CARBONIC ACID. Acidimetry. The author has travelled with an outfit fully at the spring during the last six years over the highest mountain passes under many disadvantages of weather. summer. (a) Determination of Carbonic Acid in the Presence of Chlorine. so that neither the direct correct results. chlorine will be evolved with the carbonic acid on treatment of the solid substance with hydrochloric acid. Determination of Carbonic Acid in the Air. By this method the author has determined success- the amount of carbonate in a great many of the most important waters of Switzerland. Remark. without its the tube N meeting with any accident.

. 0. 398 After standing several hours is filtered off quickly.96) are added. while the carbon dioxide ammonium is absorbed by the ammonia forming latter is precipitated by the calcium carbonate. the chlorine is changed into ammonium chloride with evolution of nitrogen : 4NH3+ 3C1= 3NH4C1+ N. precipitate in the determined and the carbonate precipitated calcium water. DETERMINATION OF CARBON. Graphite. On treating an iron containing carbide carbon with chloric or sulphuric acid. (1) DETERMINATION OF CARBON IN IRON AND STEEL. . Determination of Carbon Dioxide in the Presence of Alkali (6) Sulphides.* in a warm On Remark. tion containing calcium chloride. but from carbonate. only a part of it is dilute hydroevolved in the form of * One part of crystallized calcium chloride is dissolved in five parts of water. washed with the place. concentrated. Sulphites. and the carbonate deterfree mined preferably by the Fresenius-Classen method (p.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. ten parts of ammonia (sp. In Organic Compounds. gr. and the chloride as calcium carbonate. 380). (1) Carbon (a) (b) exists in As As two forms in iron and steel: Carbide Carbon. and the mixture allowed to stand at least four weeks before using. conducting the mixture of chlorine and carbon dioxide into the ammoniacal solution of calcium chloride. It is heated to boiling to destroy the excess of the hydrogen peroxide. (2) In Iron and Steel. or Thiosulphates. The solution to be analyzed is treated with an excess of a solu- tion of hydrogen peroxide containing potassium hydroxide. carbonate by one of the usual methods.

742. with steel 9 per cent. Stahl u. in which case the difference represents the carbide carbon. In the analysis of iron and steel it is customary to determine directly the total carbon and the graphite. 581. 52. To prevent such losses. unless precautions are taken. however. Principle. but characteristic Ledebur * on boiling with strong hydrochloric acid the latter to volatile hydrocarbons. methane. the iron goes into solution and the carbon is oxidized to carbon dioxide. hydrogen. 3 per cent. 1894. in a suitable apparatus or its is absorbed either latter is and the volume measured.. The carbon is oxidized to carbon dioxide. t . () Those in which the greater part of the iron and the residue subjected to combustion. p. Sarnstrom. Eisen. The Chromic-Sulphuric Acid Method. With ferromanganese the loss amounts to 22. of the total carbon. Thereby. In of a excess of chromic a considerable acid. is removed.und Hiittenm. and Corleis. method the borings. 1888. For the oxidation of the carbon a great many methods have been proposed they can be classified as follows (a) Those in which the oxidation is effected with the un: . 76 per cent. carbon monoxide. This carbon is called by "hardening carbon" to distinguish it from "ordinary carbide carbon" which is left behind as a brown or gray mass when the iron is treated with dilute hydrochloric or sulphuric acid.DETERMINATION OF CARBON. 399 smelling hydrocarbons. changed substance itself. are treated with a mixture of chromic and sulphuric acids and heated to boiling. Sarnstrom f recommended leading the In and this free * Stahl und Eisen. Berg. and 2 per cent. 1885. large spite amount of the carbon is likely to escape in the form of hydrocarbons and carbon monoxide. is also changed Graphite is unattacked by acids under all circumstances. With ferromanganese the escaping gases contain. which should be as fine as possible from grease. 18 per cent. Determination of Total Carbon.5 per cent. Ztg. oxygen. besides carbon dioxide and traces of heavy hydrocarbons.

In fact the use of the combustion tube is unnecessary in an because only 2 per cent. Many experiments long. The apparatus required Corleis decomposition flask * A is A shown in Fig. of the total amount In the analysis of ferrolost in this case. suffices if the sample is covered with a coating of copper during the treatment with chromic and sulphuric FIG. although objection has been raised to the long combustion tube that is required. however. Ledebur f even found that the results obtained with irons rich in graphite were a little too high on account of the formation of some sulphur dioxide. steel anlaysis.* 80 cm. have shown that the method of Sarnstrom gives exact results. acids. which is heated in a combustion furnace. 400 escaping vapors over copper oxide in a combustion tube. Corleis has succeeded in simplifying the method by showing that a very short combustion tube. the use of the hot tube is to be recommended.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. ordinary of carbon present is manganese. heated by a single Bunsen flame. but this error can be overcome by passing the gases through chromium trioxide just before they enter the combustion tube. 65. and similar alloys. small platinum tube heated to glowing also suffices. 65 and consists of a with condenser. filled with copper oxide. t Leitfaden fur Eisenhiitten-Laborat. .

flask is heated to boiling and kept at this temperature for ten minutes. The tubes a. A saturated solution of ordinary chromic acid Reagents. They are opened for a moment. but calcium chloride is satisfactory. tube C filled with granular cupric oxide.* while the current of air is continued for five minutes more. and with the U tubes. the other two containing calcium chloride. 4i The flask is connected. is 15 cm. as described on p. and It is placed in a little box made b. as shown in the drawing. quickly closed.c. c. at the bottom of which is placed a little concentrated caustic potash solution. allowed to stand five minutes in the balance-case. rubbed off with a piece of chamois skin or a clean linen cloth. The soda-lime tubes d and e are removed. 150 c. and c are drying tubes. stoppered soda lime tubes. the red-hot copper oxide tube. is made The of difficultly fusible glass. 6. The tube B is about 10 cm. 2. of copper sulphate solution and 200 c. The flame is then removed and a current of air free from carbon dioxide is passed through the apparatus for ten minutes at the rate of about three bubbles per second. of concentrated sulphuric The mixture in the acid are poured into the flask. the first containing glass beads wet with concentrated sulphuric acid. The flask is then connected with the tube B. of chromic acid solution. long and chromium contains trioxide between two asbestos plugs. and then weighed. e. long. the upper third of the right-hand arm The tube / is a safety tube of each containing calcium chloride. A solution of copper sulphate of the salt in 1 liter of water. It is not advisable to use chemically- which pure chromic acid for this purpose. on one side with a soda-lime tower. A. and / are filled exactly Tubes a.c. through the opening 25 c. made by dissolving 200 gms. W. containing some sulphate. and mixed. and allowed to stand ten minutes in the balance room.c.DETERMINATION OF CARBON. * Corleis used phosphorus pentoxide for a drying agent. is not weighed. and Procedure. and on the other side with a system of tubes. . The ground-glass stopper a is removed. 380. d and e are glass- of asbestos paper. 1. but is used to avoid any chance of carbon dioxide or moisture entering the weighed tubes from the air. d. closed. for the latter often contains organic substances.

hours while a slow current of air is conducted through the apparatus. * For cast iron 0. and are passed through the apparatus. the decomposition-flask is opened. and runs along the side of the flask on the inside ending in a quite fine point near its bottom. of water). however. a funnel-tube is fused into the neck of the flask.c. they are connected with the apparatus again. CrO in 100 c. according to the amount of carbon present)* is introduced quickly from a glass-stoppered weighing tube. 61. 3 acid of specific gravity 1.65 and saturated with chromic acid. After weighing the soda-lime tubes. Since the use of the copper sulphate solution prevents the loss cent. A chromic acid solution (100 gms. should be used. it is evident that the combustion-tube can be dispensed with for technical purposes. 3.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. neutral solution of copper sulphate. and the weighed substance (from 0. and for wrought . 1. suffices iron 5 gms. of the total amount of carbon pres- more than about 2 per ent. The upper end of the condenser is connected with the measuring-tube by means of a capillary tube about 36 cm. The flame is then removed. Combustion Carbon in the Wet Way and Measuring the of the Carbon Dioxide. 402 By means of this preliminary boiling. of Volume This operation is best carried out by means of the Lunge- Marchlewski method. removed and subsequently weighed of about two liters more of air when the soda-lime tubes are as before. which is subsequently weighed again to determine the amount of sample. A saturated. after which the contents of the flask are slowly heated so that after from 15-20 minutes the The solution is kept boiling for one or two liquid begins to boil. but for steel from 1 to 2 gin. Furthermore. Sulphuric Reagents. ground to fit the condenser-tube. the decomposition-flask is larger and there should be a ground-glass connection between the flask and a condenser. 2. The apparatus necessary is shown in Fig. In this case. long.5 gms.5 to 5 gms. traces of organic matter contained in the apparatus are removed. The flask is immediately closed and the copper oxide tube heated to glowing.

The amount and the necessary quantities following table: Per Cent. solution. C. 403 Sulphuric acid of specific gravity 1.COMBUSTION OF CARBON 4. also saturated with chromic acid. of iron or steel to be of weighed out the reagents are shown in the . Pure sulphuric acid of 6.71. 5.10. IN specific gravity 1. THE WET WAY. Commercial hydrogen peroxide Procedure.

* Verhandlg. 66. Chromic acid solved in 300 c. Beford. of chromic acid and heated an hour in a large flask upon for a sand-bath in order to completely destroy any dust. are added. of carbon present will be obtained. solution has a specific gravity of 1. d. d. He found that Hempel iron in chromic-sulphuric acid under diminished pressure in the presence of mercury all of the carbon would be readily oxidized to its dioxide.704. 1000 c.0005392 by pressure. in order to determine small amounts of organic matter which are invariably The amount of carbon dioxide found under present in them. 1. Method of HempeL* objects to the above procedure on the ground that by dissolving the iron in the mixture of chromic and sulphuric acids some hydrocarbon is likely to escape oxidation. sp. formed. 404 temperature and the the amount factor 0.c. Vereins z. of water and 10 gms. of dis- 30 gms.2. 1893. The flame is then taken away and a current of air is slowly conducted through the solution in order to dioxide that remove any carbon may have been After cooling the solution FIG. that may be present.c. After the analysis has been completed. these conditions must be subtracted from that obtained in the analysis proper. Fig. by dissolving Reagents Required. is diluted with water until it specific gravity of 1. 100 gms. 66 represents the apparatus used. The resulting 1. 2. of concentrated sulphuric acid are mixed with 500 c.c.. etc. using the same amounts of each reagent. Gewerbefleisses. has a . of chromic acid are water and solution. Sulphuric acid. of sulphuric acid.704. gr. a blank determination measured under the standard conditions of If this is multiplied must be made.GRAVIMETRIC DETERMINATION OF THE METALLOIDS.

Wiborgh. of sulphuric acid are added through boiling for half M is now opened for the first time and C.c.f the * Zeit. the stop-cock at the contents of the flask boiled for half an hour longer.) start only carbon dioxide M by pouring water into C and gas in the flask is carried over into lifting the tube p until the gas in the flask is entirely expelled..HEMP EL'S METHOD FOR THE COMBUSTION OF C4RBON. a Into the funnel C little water is acid solution. . (1893).. t Ibid. Chem. From this amount of carbon present can be computed. which is immediately heated to boiling over a small flame. M the measuring. The difference represents the is amount of carbon dioxide formed by the oxidation. perfectly air-tight. of the iron or steel is placed in the decomposiB. XXXII XXIX (1890). Gas Analysis. about 2. after which the carbon dioxide absorbed in a HempeFs potash pipette and the volume of the unabsorbed gas is determined. About gm. Other methods for the determination of the volume of the carbon dioxide formed from the carbon in iron or steel are those of J.tube is entirely with mercury. but toward the end of the operation there The flame is removed. of chromic sure that the ground-glass connection between the flask condenser is cup there.* Otto Petterssoii and August Smitt. p. and the apparatus is connected together as is 0. filled and the poured into the are placed 30 c. p. 385. by means of which the air in the In order to make flask B is exhausted as completely as possible. in proportion to the temperature of the solution.c. 120 c. The total volume of the gas is read. of mercury are added by means of a small pipette. and by carefully lifting the latter a little the chromic acid is allowed to run into the flask. anal. After an hour.5 tion-flask shown in the drawing. and the apparatus is connected at p with a suction-pump. f. 405 Procedure.3 gms. (At the is generated. the is a fairly lively evolution of oxygen. 198. The measuring of the gas in this apparatus will be described more in detail in Part III. By raising the levelling-bulb N. the stop-cock is closed. the stop-cock at p is closed.

tube S.* The sample of iron or steel is heated in a stream Principle. Leitfaden fiir Eisenhiitten . water. nor carbon dioxide. 67. anal. Procedure.. tained in the carbon determination. cast iron. To cf. in an apparatus The specimen is subjected to the action like that shown in Fig. but tungsten of For steel. 16. regulate the current of gas. slag.. { * Z. 401 (1869). J The flow of the acid is regulated a glass rod covered with rubber tubing by raising the may be used.c. because these substances all tend to convert a part of the carbon into carbon monoxide. Wohler's Chlorine Process. more hydroneeded which is allowed to flow into the flask through a Bulk's f dropping funnel. is principal requisite for the success of the process is pure This must not contain oxygen. the chlorides washed out by water.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. whereby low results are ob- chlorine. the following method is used. 467 (1892). The residue is filtered through asbestos. 46 The methods are suitable for the already described carbon in wrought iron. not in alloys such as ferro-silicon. the A. Chem. of chlorine B is the liter flask in which the chlorine is generated. Ledebur. Chem. Instead of S .. of pure chlorine gas whereby iron. of pyrolusite and 500 c. such materials. and the carbon burned to carbon dioxide either in the wet or in the dry way. The due to inclosed chlorides. steel. silicon. it contains about 200 gms. of concentrated hydrochloric acid. as silica. and sulphur are volatilized while the carbon remains behind in the presence of small amounts of non-volatile The silicon present not affected by the treatment. anal. The contents of the flask are heated over a very low flame and in this is chloric acid is the current begins to slacken. Laboratorien a continuous stream of chlorine way When evolved. f Z. 8. ferro-chrome or determination etc. phosphorus.

long. b. long and 1 cm. . which is unaffected by the carbon in the iron or steel. A. containing caustic If the stream of chlorine becomes too strong. on coming in contact with the hot charcoal. soda flask is stop-cock is opened a little so that the excess of chlorine is absorbed by the sodium hydroxide. made of difficultly- FIG. which is provided a with stop-cock and leads to a cylinder. wide. a tube 40 cm. C. the solution. of coarse charcoal which has previously been well ignited and cooled in a desiccator. The chlorine is purified by means of the tubes sulphuric acid. to carbon monoxide. 15 cm. C a. h. The chlorine gas is next passed into the combustion tube D. b concentrated or beads. It contains a layer. pumice. fusible glass. The charcoal is placed in the tube between two loose plugs of The tube is heated to dark redness in a small ignited asbestos. acid. The last traces of moisture are removed by passing the gas through the tube d containing glass beads moistened with concentrated sulphuric acid. c. If the chlorine gas contains small amounts of oxygen (air) or carbon dioxide. moistened with sulphuric d. c glass is and a contains water. these are changed. 67. combustion furnace. 407 connected with the right-angled tube.WOHLERS CHLORINE PROCESS.

68. is bent into a right leads into concentrated sulphuric acid in the flask e. is sprinkled as a thin layer * upon a previously ignited porcelain boat. The boat is shoved into the combustion tube and the evolution of chlorine is started as described above. which should be as fine as possible.5 gm. The formation and volatilization of the ferric chloride takes place at a relatively low temperature. 4 o8 about 40 cm. the filtrate comes through perfectly free from asbestos fibers. is placed a little glass wool. Of ferro-chrome about 0. lighting the burners one at a time from right to left. and. in the case of ferro-silicon. wide and 5 cm. The substance. on such a filter. the heat is gradually raised until the tube begins to get red and then the residue in the tube is allowed to cool in the stream of chlorine. The silicon all until after about twenty minutes. and angle The sulphuric acid serves as a seal and prevents air from getting This is into the tube. because otherwise the metal will become covered with a coating of non-volatile chromic chloride which prevents it from being acted upon by the chlorine. which is about 1 cm. tube. and upon this a suspension of ignited asbestos fibers in water is poured until. The carbonaceous * residue can be oxidized in the apparatus This is especially important in the case of ferro-chrome. The residue is washed.G Ml/IMETRIC DETERMINATION OF THE METALLOIDS. As soon as no more brown vapors escape from the tube. wide. and of ferroabout 1 gm. with the aid of YIG. should be taken. 68. long. light suction. The boat is removed from the combustion tube is not heated at the air will have all . with cold water until no chloride can be detected in the into filtrate. Fig. long by 1.5 cm. From the beaker the insoluble residue is washed an asbestos filter prepared as follows: In the funnel R. when been expelled then the heating is begun very gradually. . the contents are rinsed with cold water into a beaker.

of sulphuric acid.* Solution of the Iron. 65. Further- more. aqueous solution of chromic acid.71 chromic acid. sium-cupric chloride containing 300 gms. which is likewise saturated with In the analysis of ferro-chrome. Warming accomplished by means of in a glass-stoppered bottle. of concentrated hydrochloric liter has proved most satisfactory. the solution is filtered through ignited asbestos and preserved acid to the The solution of the borings takes the solution is stirred. the Committee on Standard Methods of the American Foundrymen's Association (Chemical Engineer. shown 5 c. Before using. which is best place very slowly unless a mechanical stirrer.c. for analyzing special samples of iron and steel which are available for distribution and serve as standard samples of known chemical composition. In this case. . should contain of a saturated. The contents is converted into soluble chromous of the boat are then treated exactly as described above. 1. of the double salt away (2KCl. there is always some insoluble chromic chloride in the boat which cannot be removed by washing. 49 in Fig. * The dry combustion methods are much used in the steel laboratories of the United States and by the Bureau of Standards at Washington. therefore. C. the substance after being heated in a stream of chlorine. A number of methods have been proposed for dissolving the iron and leaving the carbon behind in the form of For this purpose a solution of potasan insoluble residue. sp. and 60 c.CuCl 2 ..COMBUSTION OF CARBON IN THE DRY WAY. 5. 416 (1097) ) have recommended the use of a dry combustion method for settling all cases of dispute.c. gr. p.2H 2 0) and 75 c. 400 but in this case the flask A. is heated in an atmosphere of hydrogen. whereby the insoluble chromic chloride chloride. Combustion of Carbon (a) in the Dry Way. D.c.

. * J. The residue is filtered.. or the tubulated one of Gooch. of the sample and 200 c. are made of shown that one of nickel answers the purpose equally well. Fe+CuCl 2 ==FeCl 2 2Cu + 2CuCl 2 = 2Cu 2 Cl 2 . 1. D. ever. of the potassiumcupric chloride solution are used. dried and usually burned in a current of oxygen. C.c. Chem. Eng. or in a special form of crucible. The presence of potassium chloride aids the solution of the copper. They apply equally well for the determination of the total carbon in steel except that in the latter case usually 3 gms. this serves to convert any carbon to carbon dioxide which is then absorbed in potassium any of the hydroxide solution before coming in contact with carbon from the sample. the solution also helps. The combustion may take place in a porcelain or platinum tube. such as the jacketed crucible These. Ind.410 GRAVIMETRIC DETERMINATION OF THE METALLOIDS. The following directions are taken from the Report of the Committee on Standard Methods of the American Foundrymen's Association and corresponds closely to the method used by the Bureau of Standards at Washington. such as for example a short porcelain tube filled with copper oxide. the carbon dioxide being absorbed in a weighed bulb containing potassium hydroxide solution. in preparing standard samples for distribution. 415 (1909). it is advisable to make use of a preheating tube. but it should never be heated above The following reactions take place: 60 to 70. To make sure that the oxygen used contains no carbon in any form. probably on account of the formation of a double salt. how* and are but platinum Ruppel has expensive devised by Shimer.

The train used consists of a pre-heating furnace containing copper oxide. one of anhydrous cuprous chloride. This combustion tube contains four or five inches of copper oxide * platinum gauze. then the weighed absorption bulb should be connected with the train and a blank determination made. care must be taken to press chloride loosely lumps well against one another. is placed the furnace. t free The silver foil is from hydrochloric unnecessary acid. gr. then one containing granular calcium chloride. followed by a bulb containing potassium hydroxide solution (sp. A Geissler or Liebig bulb is connected with this last tube and contains potassium hydroxide solution (sp. 41 * Determination of Total Carbon in Cast Iron. Before using the apparatus. especially the prolong of down the calcium the absorption bulb. A negative filled. between plugs of end with a tube connecting anhydrous cupric sulphate.27) with a prolong of calcium chloride. gr. as when the tube is some moisture is likely to get by. in 100 c. The combustion tube is connected at this in front of this plug.5 mgm. if the carbonaceous residue is washed . and the solution eventThe beaker in which the on ignited asbesots.27). 1. and one of granular calcium chloride. In filling the calcium chloride tubes. and the front or forward end is is customary to follow the direction considered the end toward the gas that nearest to the weighed potash is bulb.c. One gram of the well-mixed drillings are meanwhile dissolved double chloride solution. 1. of the ually filtered * In describing a combustion train it The back or rear end of the flow of gas.DETERMINATION OF TOTAL CARBON IN CAST IRON. The bulb should not gain in weight more than 0.f about two inches long. reservoir. the contents of the tube should be heated for half an hour in a stream of oxygen. A calcium chloride tube is used between this last tube and the aspirator bottle to prevent any moisture working backward. blank is often obtained by beginners for this reason. The plug at the front end of the furnace should be at about the point where the tube leaves A roll of silver foil. the latter is connected with a ten-burner combustion furnace in which either a porcelain or platinum tube is placed.

with the carbon upon it. the third burner from the forward end is lighted and a few minutes later the fourth burner. After applying suction. ignited Care should be taken that the carbon on the asbestos asbestos.75 of an inch in diameter and 0. solution took place is washed thoroughly with 20 c. but where many determinations are being made it involves considerable expense. The potassium hydroxide bulb at the front of the train is then detached and weighed with the usual precautions. at first turning them low and gradually raising the heat until the tube is hot. followed by a suspension of the same asbestos in water. A crucible. longer. lighted. METALLOIDS.c. . of dilute hydrochloric acid (1:1). pad is about 0. The filter is then dried at a temperature between 95 and 100. As soon as this end of the tube is hot. and transferred to the filter by means of more of the same acid from a wash-bottle. of the carbon residue. the oxygen is stopped and a current of air swept through the tube at the same rate for twenty minutes finally all are lighted hot. the oxygen turned on and allowed to pass through the Absorption bulb at the rate of three bubbles per second. lighted. reaches far enough into the tube to get the full heat from the The burners under the pre-heating furnace are now furnace. the asbestos is gently The of tamped down with the flattened end of a stirring rod.GRAVIMETRIC DETERMINATION OF 4*3 THE. The dried asbestos.25 finished an inch thick. but no The two forward burners under the combustion tube are faster. although it is well copper wire is in a free end of wire the bottom of the funnel with placed long the of the stem. is pushed into back end of the furnace and the funnel wiped out with dry. Finally the residue is washed on the filter with hot water until free from chlorides. This unquestionably works well. An excellent substitute can be prepared from a funnel such as was described for use with a to shorten the sides Gooch somewhat. Blair recommends the use of a perforated platinum boat for the filtering. which should be near the forward end Light each burner in succession until and turned high enough to heat the tube red After twenty minutes have elapsed from the time the last burner is turned on full. Loose down below bottom reaching ignited tight coil of asbestos is placed upon the coil of wire. gradually turning down the burners under the combustion tube.

if a combustion boat con- taining the borings of sample is placed in a cold. whereas those obtained by dry combustion of the iron in potassium-cupric chloride are from and pig with chromegiving exact after solution 10 to 40 per cent. the layer of which being not less than 0. In the ^ it center of this tube is placed a disc of platinum gauze and for three toward the crucible a roll of silver or four inches in the side and for the same distance on the other side some copper oxide. 7th ed. When platinum is used it is advisable to superficially place the drillings in a little depression of sand. A. Chem. 739. Ind. of an inch inside diameter should be followed by a copper tube and 10 inches long with its ends cooled by water jackets. The Chemical Analysis of Iron. or in one of fused quartz. 21. 4*3 When the Shinier or similar crucible is used for the combustion. platinum-lined * A. but experiments have shown that tungsten steels the direct method is capable of results. t Oesterr. { in a porcelain tube. that there is difficulty in burnthe carbon on account of the sample becoming coated all of with oxide.. heated with a fish-tail burner before the aspiration of air is started. Zeitschr. however.. . Ind. It ing has been claimed. The combustion may be carried out in a platinum tube. No. b. according to Blair. Shimer. 1. 1894. but according to Schneider f this may be overcome by mixing the finely divided sample with three parts of lead and one of copper. Eng. too low. According to Campbell and Gott. deep.25 in. Blair. J.DETERMINATION OF TOTAL CARBON IN CAST IRON.. W. J P. in one of the special forms of crucible. it is possible to effect the combustion the finely divided substance fact.* this by heating a current of oxygen. (1908). J. 1. In most cases Direct Combustion of the Sample. The ends of this tube are plugged with glass wool and the tube foil. Chem. 738. In true not only of ordinary steels itself in is iron. Eng.

beaker and is no further evolution of gas. W. The latter is collected in a weighed calcium chloride tube. 1. Determination of Graphite. 1. Campbell and Gott. J. gr. followed by hot water. according to Liebig.1). then with a hot solution of potassium hydroxide (sp. 1. From the weight of carbon dioxide and finally drying at absorbed. the asbestos and graphite are transferred to a combustion-tube and the carbon burned in a current of pure oxygen as described above.c.c. After 110. the former in a weighed vessel tains either caustic potash solution or dry soda-lime. which con- The combustion (a) (b) is performed. (Elementary Analysis. In an open tube] In a closed tube. gr. the filter and residue washed an asbestos ignited through filtered with hot water. with hot water again until free from chloride. loc. Eng. Ind. the amount of graphite is calculated. 741. . Chem. * J. of nitric acid heated gently until there means the carbide carbon The solution is dissolved while the graphite is not attacked.. Ind. Chem. cit. 1.. H. One gram of pig iron is treated with 35 (sp.13) in a 300-c. Keen. which oxidizes all of the carbon to carbon dioxide and the hydrogen to water.) The organic substance is burned in air or in oxygen Principle. Determination of Carbon and Hydrogen in Organic Substances. and the products of the combustion are passed over glowing copper oxide. 4H porcelain tube and then heated at a temperature of about 900 complete combustion . By this is c. Eng.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. It is very convenient to heat the tube by means of an electric furnace. dilute hydrocohloric acid.* will Such a furnace can be constructed at a cost not exceeding $30. take place without endangering the platinum by any spattering of the oxides formed. 741.

in the foot-note. plates of asbestos board to protect the rubber stoppers ends of the tube from the heat of the furnace. 60. 381. 5. Two in the left). Procedure for the Combustion of Organic Substances Free from Nitrogen. from 12-15 An open tube made of difficultly-fusible glass mm. two tubing. as described on p. of coarse and 50 gms. (a) Combustion in an Open Tube. 350 gms. The outside of the tube is rubbed with a piece of chamois skin or old linen. it must be 10 cm.DETERMINATION OF GRAPHITE. 70) is filled from the left was described on p. The length of the tube depends upon that of the combustion-furnace. which 415 is 1. as shown in the figure. Dry rubber 8. Sulphur. on the calcium chloride tube (Fig. FIG. Requirements. side as ground-glass stoppers. Halogen. 71) or (see p. 69. 377. 6. The calcium chloride tube (Fig. A d and two soda-lime tubes e). Geissler potash bulb (Fig. closed with a plug of glass-wool and the end of the tube fused together.* It is more practical to use a calcium chloride tube fitted with 1. and Metals. A A A drying apparatus (Fig. wide. 380. ETC. 3. far the greater majority of all By in this combustions are carried out way. screw-cock. Or the tube is stoppered and an air-tight seal neatly with sealing-wax. of fine copper oxide. longer than the furnace. made by pieces It is covering it . After filling the tube. and the of rubber * two ends are stoppered with short tubing each containing a piece of stirring-rod. 2. 4. its contents are saturated with carbon dioxide. Preparation and Combustion. 70). 7.

on the left). and the bulbs are two-thirds full by sucking through the rubber tubing. the tube is washed. dried. free the air ide centrated caustic potash solution. 71. The apparatus is wiped with wash-leather and weighed without the stoppers. 4. k. 72. after taking the same precautions as with the weighing of the large calcium chloride tube. 71) is filled with caustic potash solution (two parts solid KOH in three parts of water) as follows: The small soda-lime tube d is replaced by a piece of rubber tubing. 72). 4i 6 allowed to stand in the balance-case for fifteen minutes and is then weighed without the stoppers. the soda-lime tube two calcium chloride tubes ad 6 and k' a. The Geissler bulb (Fig. 69. 2. of copper gauze is introduced into the right-hand end of the tube so that . both ends of which are rounded by heating in the blast-lamp. and the c. after cooling. The drying apparatus (Fig. K k FIG.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. the soda-lime tube d is again connected (its right half is filled with soda-lime and the outer half with calcium chloride). The Combustion-tube (Fig. consists of a wash-bottle. which serves to and oxygen used for the combustion from carbon dioxand water vapor. Tha filled FIG. of the tube c is then cleaned by means of a piece of filterpaper. and filled as follows: First a short roll. end and the two ends are closed with pieces of rubber tubing each containing a piece of stirring-rod with rounded ends. c is dipped into the solution of caustic potash. D. FIG. 70. containing con- 3.

d. Commercial oxygen often contains the latter. is next added. in which case it is necessary to pass the gas through a The gas should come from a gas"preheating" furnace before using it. the copper oxide is at a dull-red heat. 72. Gradually the. K. The burners are now turned down and the oxygen current disAll of the flames are extinguished after some time continued. While the tube is cooling.15-0. Usually some water condenses in the right-hand end of the tube. fit tightly in the tube. At is of the tube is left open for the passed through the apparatus the flame is turned low and first heated equally. and when the presence of oxygen can be detected at the right end of the tube (by its igniting a glowing splinter). When all the water is removed. This roll serves as a plug and must. k' Finally another roll of copper gauze. but which is with a tightly The lacking in Fig. 417 5-6 cm. If the substance is a difficultly-volatile oil it is weighed into a * The oxygen must be free from hydrogen. is on the right and placed in a combus- is left now tion-furnace. as is shown in Fig. with the tiles covering the tube. 69. 69.) time being. about 45 cm. so that about 5 cm. until. . (The tube should be provided with a glass stop-cock. never from the bomb itself.COMBUSTION OF ORGANIC SUBSTANCES. A right end slow current of oxygen * and the furnace is the whole tube is lighted. this end of the tube is closed with a rubber stopper through which an open calcium chloride tube is placed. temperature is raised. extend beyond the at each end. a short piece of rubber tubing. about 5 cm. a. as shown in Fig. of the latter are left empty. about 10 cm. the calcium chloride tube and the potash bulb (or soda-lime tubes) are weighed (the stoppers being replaced immediately after the weighing) and from 0. ometer. on the The tube left. and after this is placed another plug of copper gauze. long and large enough to fill the tube loosely '. The left end of the tube furnace is closed fitting rubber stopper through which a glass tube and is connected with the drying apparatus by means of passes. A layer of coarse copper oxide. except those under the right half of the tube. is placed so that a space of about 10 cm. long.2 gm. this is expelled by carefully holding a hot tile under the tube. of the substance is weighed into a porcelain or platinum boat. therefore.

41 8 ( small glass tube open at one end. the tube containing it is placed so that its capillary pointed towards the left.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. bubbles bustion-tube is The two outer burners on the left are now lighted and the copper oxide spiral d (the copper was changed to the oxide by the ignition in oxygen) is slowly heated just to redness. the bulb is warmed. In case the suba liquid. in horizontal lies a then turned so that the capillary position. is tube. while that between the drying apparatus and the comit opened just enough to permit two. the combustion is usually complete. 69. or at the most of gas per second to pass through the apparatus. The stopper removed from the left (and now cold) end of the combustion- lary. Connection is made with the drying apparatus on the left and with the absorption-tubes on the right. with the tiles in place. the boat with the substance in it is placed in the tube and the copper roll right after it. the drying apparatus is closed.* * getting into this tube from the with an unweighed calcium chloride tube. is empty. and the boat It is well. the latter is connected with an airgasometer. this is weighed. and in the case of a volatile liquid the stance is is end of the capillary is broken off with a file just before introducing The stop-cock between the tube and into the combustion-tube. so that the liquid rises in the bulb as it cools. end is melted together. The tube is now graduheated from right to left. taking care that the gas evolution is never greater than four bubbles per second through the potash bulb this can be easily regulated by means of the stop-cock or by When the contents of the entire tube turning the gas-burners. a bulb is blown into a small capillary tube. have been brought to redness. and the stop-cock in the drying apparatus is wholly opened. the weighed. If it is readily volatile. ally . and the capillary is introduced into the liquid to be ana- The bulb is lyzed. as is shown in Fig. however. the long copper roll is removed by means of a piece of wire with a hook in the end of it. To prevent moisture from connect it air. and the tube is again is no liquid in the capil- Care must be taken that there Everything is now ready for the combustion. three. until the hot tube the to pass oxygen through gas can be detected train combustion of the end at the right-hand (a glowing splinter The flames are then turned down and a current of ignites at n). it is well to . the a little that adheres to the to latter is warmed slightly liquid expel sides of the tube.

per cent. If. and. the combustion of By many organic substances containing nitrogen. however. 300 p' -^--p* Cent ' C Determination of Carbon and Hydrogen in Nitrogenous Organic Substances. The spiral is heated veniently pass till it glows by holding it in a large gas flame. correct results will be obtained.and nitro-compounds. p that of the water. wide. wiped off with a piece of chamois skin or a clean linen cloth.02 X== X. so that if such substances were analyzed according to the previous process. but it is . The alcohol quickly boils away. The calcium chloride tube and the potash bulbs are now removed. The gain in weight represents the amount of water and carbon dioxide respectively. WV P and 101 in p ---per cent. results will is as the latter is not absorbed.02= p:x 44:12=p 2. / / / :x 3 =44 P =li P . then of : H O:H 2 2 CO2 :C =p':z and =p:x 18. room twenty minutes. 419 through the apparatus until the oxygen is completely little water always collects in the front (right) end and this must be driven over into the calcium chloride tube by holding a hot tile under it. an unreduced copper spiral introduced in the front (right) end of the combustion-tube.H 12 . of the tube. making it as large as will conabout copper gauze into the combustion-tube. after which time they are weighed without the stoppers.COMBUSTION OF ORGANIC SUBSTANCES. both the carbon and hydrogen be too high. especially nitroso. The copper spiral is prepared by rolling together a piece of 10 cm. and p' that of the carbon dioxide. this serves to reduce the oxides of nitrogen to nitrogen itself. oxides of nitrogen are formed which are partly absorbed in the calcium chloride tube and partly in the potash bulb. and while still hot thrown into a test-tube containing one or two cubic centimeters of methyl alcohol.02: 2. and from this the amount for hydrogen and carbon can be calculated as follows If a represents the weight of the substance. allowed to stand in the balanceair passed A expelled.

FIG. 73. and reduced completely to bright metallic copper. The spiral is taken out with a pair of crucible tongs and dried by quickly passing it through a flame a few times. warm it is introduced into the front end of the combustion-tube. and the copper oxide spiral at FIG. To carry out the combustion. d heated and then the reduced spiral at the other end of the Then beginning at k (Fig. one burner is lighted after is first tube.420 GRAVIMETRIC DETERMINATION OF THE METALLOIDS. 75. the substance introduced into the tube. 69) is closed. FIG. the stop-cock between the combustion-tube and the drying apparatus (Fig. and while still the latter is is . 74. 72). . some of it oxidized to aldehyde by the hot copper oxide. which has been previously burned out as described in the pre- vious analysis.

Fig. turned down. silver spiral should 180-200 spiral * is C. 69) is filled with finely granular. the oxygen replaced by pleted as in the previous case. The mixture is then transferred to the combustion tube. anal. but only to about In case a silver spiral is not at hand. M. Fig. and the flask closed by inserting a tin-foil covered cork which is fitted with a calcium chloride tube. its end reaching outside the furnace. Chem. until finally the entire contents of the tube are heated to and no more bubbles escape through the potash dull redness Xow bulb. and this is ignited in a stream of oxygen. The combustion is then carried out in the usual manner. end of the combustion tube with the aid of the funnel T (Fig. The oxygen is then replaced by air and the tube allowed The finely granular to cool until it can be held in the hand. Substances hard First of all the left to air. n. copper oxide is next transferred to the small flask K. a long copper used. which is then stoppered and its contents well ghaken. conducted exactly the same as in the case of nitrogenous substances. 74. and oxygen opened somewhat can be detected at The flames are then gradually for the first time the stop-cock passed through the tube until is by a test with a glowing splinter. in an open tube. weighed into the glass-stoppered mixing tube M. For another method of conducting a combustion Z.* Combustion of Organic Substances Containing Halogens. whereby the substance becomes intimately mixed with the copper oxide to which it adheres.COMBUSTION OF ORGANIC SUBSTANCES. 421 another. flask While the copper oxide in the the substance to be analyzed is is becoming perfectly cold. The analysis is not be heated to redness. but not pulverized. 73) . is it and the analysis com- burn are treated somewhat differently. except instead of a reduced copper spiral The one of silver is used to keep back any halogen set free. (Fig. 75. consult . copper oxide. and the mixing tube is shaken repeatedly with small portions of the remaining copper oxide in the flask until finally it can be assumed that all of the substance has been transferred to the combustion-tube. 611 (1903). Dennstedt. From one-sixth to one-fifth of the copper oxide in the flask is transferred to the mixing tube. 40.

which contains copper oxide and copper spirals air. The substance is burned in a combustion-tube. alkaline earths. for the former melts easily. and by adhering to the glass cause the tube to break. for the sulphur dioxide escapes and is partly absorbed by the water in the calcium chloride tube and partly in the potash bulb. may be carried out in either . Procedure. or a part of the carbon cadmium. is likely to Combustion of Organic Substances Containing Metals. Sulphur compounds cannot be burned in a tube containing copper oxide. In this case the substance is mixed in the boat with a mixture of ten parts of powdered lead chromate and one part of potassium chromate. When lead chromate is used. of the hydrogen and carbon in as in the determination exactly substances containing nitrogen.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. but This determination should really be discussed under Part III. it will be described here on account of its being an analysis by combustion. the combustion must take place at a lower temperature than with copper oxide. one of ignited lead chromate is used. remain in the tube as carbonate. but in this case the nitrogen Principle. forming difficultly-volatile lead sulphate which remains in the tube. This determination a closed or open tube. Dumas' Method for Determining Nitrogen in Organic Substances. so that absolutely worthless results are obtained. 422 Combustion of Organic Substances Containing Sulphur. and the combustion is conducted as is the case when sul- phur is will present. Instead of the long layer of copper oxide. If the substance contains alkalies. free from evolved is measured. The latter oxidizes the sulphur dioxide to sulphur trioxide.

tion-tube is closed at one end and is about 75 The combus- cm. It a layer of magnesite 15 cm. From time made whether the air has all been expelled. which is filled with mercury to a little above the lower end of r. whereby the air in the tube is expelled by the carbon dioxide and passes through the azotometer. and upon this rests a liberal amount of caustic potash solution (300 gms. long. p. 76. The heating must be accomplished so that there will be a slow but steady evolution of nitrogen. the bubbles of gas will all be absorbed by the When this is the case the flame is put out under M. heated at S and the process is continued as in an ordinary combustion until the whole tube (with the exception of the part where is found) is heated to a uniform temperature and more no finally nitrogen is evolved. after which a layer of M coarse copper oxide * about 40 cm. p. (a) 4*3 Determination in a Closed Tube. The tube is then coarse copper oxide is heated to a dull redness. The tube is then placed in a combustion-furnace and connected with an azotometer. and the stop-cock closed with the azotometer tube completely filled. S. 417. The experiment is begun (with the le veiling-bulb low and the stop-cock of the azotometer open) by heating the left half of the magnesite layer. ignited. is added at a in a boat and mixed with powdered copper oxide by means of a spiral wire (cf. XIII. as described on p. Berichte. caustic alkali. in pieces about the contains at size of a pea. long is added. and finally the reduced copper spiral (prepared as described on p. the magnesite layer is once more heated and the nitrogen the magnesite * The copper oxide must be previously t H. Schiff. long. KOH dissolved in a liter of water).DUMPS' METHOD FOR DETERMINING NITROGEN. The tube is heated first at R and the burners are lighted one after another toward the left until about three-quarters of the layer of to time a test The is levelling-bulb is to see raised. If all the air has been replaced by carbon dioxide gas. 421). 419). followed by a loose plug of ignited asbestos and The substance then a 10-cm. f as shown in the figure. When the combustion is complete. The necessary apparatus is shown in Fig. 885. layer of coarse copper oxide. .

At the same time the barometer and thermometer * readings are noted. the experiment is ended and it remains only to measure the nitrogen. eter is by the carbonic acid For this purpose the azotometer together with the connecting is removed from the combustion-tube and piece of rubber tubing FIG. of the substance were used for the * An accurate thermometer should hang at the side of the azotometer. 424 remaining in the tube completly driven over into the azotomset free. . set aside for at least thirty The weight of the nitrogen present is computed as follows: Let us assume that a gms. 76. after which the gas levelling-tube is raised until the solution in it stands at exactly the same height as that in the tube.GRA VIME TRIC DE TERMINA TION OF THE ME TALLOIDS. As soon as the volume of the gas in the azotometer remains constant. when the volume is read. The apparatus is then minutes at a place where a uniform temperature prevails. the tubing closed by means of a pinch-cock.

0012506 and XF gms. pressure. of the concentration used. with potassium hydroxide less than that of pure water. a Gas Analysis. The nitrogen. a = 0. ever.. its volume must be If the gas first reduced to C. howwas not measured over pure water but over a solution of potassium hydroxide. barometric pressure.. 425 B of nitrogen were obtained at t C. has been found to weigh of nitrogen will weigh c.0012506 gm. of nitrogen at 0.1 2506 * Cf. analysis and V c.c. In order to obtain the weight of the nitrogen. . and 760 mm. 273 760(273+0 would hold in which B represents the and reading reduced to a temperature of observed barometer w is the tension of water vapor measured in millimeters of mercury.0012506 -F X_ 0.* then VQ and 760 mm.c. and mm. Consequently the following formula holds with sufficient accuracy: = V(B-w)-273 760(273+0* As 1 c. in per cent.c. 0. Nitrogen under = 100 :x -V . had been measured over pure water the formula _ V(B -10).DUMAS' METHOD FOR DETERMINING NITROGEN. and the vapor tension of this solution is In fact. the diminution of the vapor tension as compared with pure water almost exactly compensates the correction which would be applied in reducing the barometer reading to 0.

=per cent. After the connection with the azotometer has been made. and it is covered with a piece of copper gauze in order that it may be heated more uniformly. then the long layer of coarse copper oxide. If the combustion-tube of Fig. 76 is imag- M off at and connected by means of the two-bulbed tube with a long test-tube. as shown in the upper part of the figure. ined to be cut The long test-tube contains sodium bicarbonate. N. is exactly the same as in the former case. except that in this case the carbon dioxide is generated outside of the tube. (b) The determination is carried out in practically the same way as before.04493 it becomes . in the fact that the combustion-tube can be used for a large ber of nitrogen determinations without refilling it each time. . this is followed by a copper boat containing the substance mixed with powdered copper oxide. The advantage of this method over the former the procedure Remark.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. Determination of Nitrogen in an Open Tube. and the constant values are united. for in this way it is possible to get a very intimate mixture of the substance with the powdered copper oxide. and finally the reduced copper spiral. the apparatus necessary for this determination will be seen. . 426 If the value for VQ is inserted in this last equation. lies num- With difficultly-combustible substances the author prefers to work with the closed tube. x = 0. At S is a long copper oxide spiral. the tube containing the sodium bicarbonate is heated and the air removed from the combustion-tube by means of the carbon dioxide evolved. The greater part of the water that is simulOtherwise taneously set free collects in the tw^o-bulbed tube.

MnSO + 2H O+ 2CO 2 4 4 2 2. results. This should be borne in mind in determining the purity of a commercial sample.023 gm. 58). The method is based upon the fact that oxalic acid Principle. A weighed amount of the oxalate is treated with Procedure. heated to boiling. and from the weight of the calcium oxide the of oxalic acid is calculated as follows amount : _HAO Determination as Carbon Dioxide. Remark. found. washed with hot water. 2 2 4. II.OXALIC ACID.05. one and a half times as much manganese dioxide (free from carbonate) either in the apparatus shown on page 376 (Fig. process (see The free acid crystallizes with two molecules of water and its molecular weight is then 126. 427 Wt. p. Both methods give good H 2 C2 4. 381). and precipitated with boilAfter standing twelve hours the ing calcium chloride solution. 90. ignited wet in a platinum crucible.02. and Carbon Dioxide.1. but oxalic acid determined conveniently by a volumetric Volumetric Part Analysis). for described the was determination of carbon as same the exactly were dioxide of carbon this If dioxide. p. 59. can be much more . precipitate is filtered off. CaO. on being heated with manganese dioxide and dilute sulphuric acid is quantitatively oxidized to carbon dioxide: H C O + MnO 2 2 4 2 -f H SO . = Oxalic Acid. Determination as Calcium Oxide. C02 . HCO OXALIC ACID. Mol. The neutral solution of an alkali oxalate is treated with a few drops of acetic acid. or The procedure is in that of Fresenius-Classen (Fig. corresponds to p gm. Forms: Calcium Oxide.

tilled saponified : B(OCH + 3H 3) 3 The = 3CH OH+ B(OH) 3 2 3 . The fused mass is cooled and weighed.2 gm. Chem. boric acid set free combines with the lime to form calcium If the paste of water and lime is evaporated to dryness. at s. it is completely Principle. If the alkali were all neutralized with acetic acid. f. 364). 44.c. % Instead of lime.01. which is WO To permit the escape of air from the flask.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. and as much of it as possible is transferred to the dry Erlenmeyer flask (Fig.weight over the blast-lamp. . Determination as Boron Trioxide.f . therefore. a liquid If the methyl borate is passed over a which boils at 65 C. About 1 gm. II * This is the formula of meta-boric acid. nited to a constant . with some of the lime adhering to it. and hydrochloric acid is added drop by drop A drop of dilute sodium hydroxide until the solution turns red. . weighed amount of lime in the presence of water. of the purest lime J obtainable is ig- borate. B 2 O 3 ) is treated with a few drops of either litmus or lakmoid solution. give up all their boron in the form of methyl borate. of flask as water. is connected with the distillation- shown The aqueous solution of the alkali borate (containing not more than 0. 3 carbonic acid. Alkali and alkaline-earth borates. the gain in weight. represents the amount of B 2 O 3 Procedure. f Zeit.5 gm. little or none of the boric acid would || pass over into the receiver during the subsequent distillation with alcohol. anal. on being diswith absolute methyl alcohol (free from acetone) and acetic acid. The crucible. Gooch and Tones use 4 to 7 gms. a cut is made in the side of the cork stopper. The slightly acid is added and then a few drops of acetic acid. in the flask is slaked by the careful addition of about The lime 10 c. 27 (1887.. 18. 428 BORIC ACID. of sodium tungstate in a platinum crucible to expel any fused with about 0. B 2 3 by the Method of Rosenbladt-Gooch.* Mol. and the flask in the figure. 77) which serves as a receiver. Wt. is placed in a desiccator and set aside for the present. It is absolutely necessary to neutralize the greater part of the alkali with hydrochloric acid and then the last of it with acetic acid. HBO 2 . pp.

solution.. Then 2-3 of acetic and the * as By c. prepared in this way. shown by the blue . the paraffin bath is lowered. 77. of about 200 c. R. of methyl alcohol is repeated the the repeated distillation.c. FIG. and after R has cooled somewhat.c. This process is repeated three times. 10 c. capacity. The liquid is distilled a paraffin bath at not over 140 C. also a few drops becomes liquid distinctly red again.c.DETERMINATION OF BORIC ACID. the contents of the retort become alkaline.. and the by placing distillate collected in the Erlenmeyer flask containing the lime in When all of the liquid has distilled over.* with 10 c. of methyl alcohol (free from acetone) are added through the funnel and the contents of R are again distilled off. color of the solution. is added by means 429 of the funnel T to the pipette-shaped retort. The funnel is washed three times by the addition of 2 or 3 cubic centimeters of water and the stop-cock R is closed.c. of water are added to the acid until distillation retort.

the methyl borate can be distilled into a dilute solution of ammonium carbonate. and finally more strongly until a constant weight is obtained. the retort should be removed from the by lowering the latter. even in the . During this process the alcohol must not be allowed to boil under any circumstances. the alcohol being all removed by the first sure that all of the of the receiver are then evaporation. after which the contents are washed into the platinum dish and evaporated to dry ness again. presence of considerable amounts of other salts. f Due to the excess of the acetic acid added. prefers the above method. The dark-colored lime and carbon remaining on the sides of the dish are dissolved in a little nitric or acetic acid and washed into the crucible.c. it is allowed to cool and is transferred by means of a little water it was originally weighed. gently The increase in weight represents the amount of B 2 O 3 This method affords faultless results. Remark. Then. however. capacity and evaporated on the water-bath to dry ness at as low a temperature as possible.* The stoppered flask is thoroughly shaken and allowed to stand for an hour or two in order to make three times more. and. The contents poured into a platinum dish of about 200 c. its entire inner surface is wet by the acid. to the crucible in which The contents of the latter are evaporated to dryness on the waterwith the cover upon it. and the latter evaporated with slaked lime in a platinum dish immediately after the distillation. as there is now no danger of losing the boric acid. 43 At the end of this time all of the boric acid be found in the receiver. a few drops of dilute nitric acid are added to the receiver. the retort is likely to break when the paraffin solidifies. The residue in the dish is then gently ignited over a small flame in order to destroy the calcium acetate f present . If this is not done. the crucible is ignited at first bath. will methyl borate is saponified.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. and. . Free halogen hydride or sulphuric acid must not be present. in order to remove the small amount of lime that remained adhering to the sides of the flask. by carefully inclining the flask. Instead of using lime in the receiver. * When the distillation is over. The author. This time the water in the bath may boil. paraffin bath. with which they would be weighed. for these acids form compound ethers with the methyl alcohol and distil over with the boric acid.

Determination of Boric Acid in Mineral Waters. acidified with acetic acid. washed thoroughly with hot water.c. a weighed amount (from 200 to 300 c. If this residue does * acid. In this way the calcium acetate does not creep up over the sides of the dish. This determination can be performed in the presence of fluorine provided acetic and not nitric acid is used to set free the boric acid. and analyzed as described on page 428. without regard to any separation of silica. page 32). and the aqueous solution containing the boric acid* is evaporated to a small volume.).1 gm. Remark. it is in no case advisable to use nitric acid and it is not permissible when chlorides are retort present. the solution is transferred to the Gooch and analyzed as above directed. . etc. of borie will be otherwise enough . If the of B O 3 in 2 water contains considerable boric acid (0.DETERMINATION OF BORIC ACID IN SILICATES.c. sodium carbonate solution is it is at once evaporated added to make it so. fused with four times as is much sodium carbonate. or more a liter). and. If Determination of Boric Acid in The finely-powdered substance Silicates. f If the water reacts alkaline. 43 1 one possesses a large platinum crucible (with a capacity of from 80 to 100 c. From 10 to 15 amount must be taken for the are evaporated in a large 1 the dish to about liter. and the filtrate and washings are evaporated on the water-bath until a moist residue is obtained. and there is no danger of any bumping. If the water contains only a little boric acid. 17. as is true in the great majority of cases. slightly acidified with acetic acid. for that matter. but. this fact taken into consideration.* deposited salts are filtered porcelain liters off (these never contain any borate). f the precipitated calcium and magnesium carbonates are filtered off. Sometimes the insoluble residue contains appreciable amounts In the method given under Volumetric Analysis. the melt is extracted with water.) is evap- orated to a small volume. Enamel. a large determination. ETC. the first evaporation can take place in this and it is then advisable to place the crucible within a ring-shaped copper or tin tube through which steam passes (Fig. the filtrate concentrated.

alcohol. and the filtrate is acidified with hydrochloric acid. 2-3 drops of the yellow solution are placed in a porcelain dish. boric acid hydrochloric acid. some of the boric acid will be volatilized with the alcohol. of sodium hydroxide is added. and allowed to stand twelve hours with The boric acid will then be found in the alcofrequent shaking. of boric acid is present. is diluted Accord- if as much as T oVo. Usually a larger residue is obtained. washed with 96 per cent. 432 not amount to more than 5 or 6 gms. after which just enough acetic acid is added to make the solution react acid again.mgm. it must be again treated with water and sodium hydroxide. acidified with acetic acid. 1 gm.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. tained is then made slightly alkaline with sodium hydroxide. diluted largely with water. and subsequent distillation of the alcohol. which ing to F. by means of more of the latter it is transcorked ferred to a flask. is repeated. up. it is gently ignited in order to destroy the organic matter. not too large. in which case the For this purpose the residue is is extracted from it. the alcoholic solution to be tested for boric acid and a few drops of acetic acid are added. and 1 gm. and the liquid evapacidified with a little orated until a moist residue is obtained. such that it cannot be conveniently analyzed directly. If boric acid is found in the alcoholic distillate. holic solution. and the alcohol once more distilled ofT. after which the solution with water and evaporated to dryness on the water-bath. it is redissolved. is analyzed as described on page 42X. the carbonaceous residue It isfiltered off. The residue is filtered off. after extracting with water.rngm. after the addition of water If the residue now obof sodium hydroxide. Henz. the alcohol distilled off (see Remark). This is again acidified with hydrochloric acid and the above extraction with alcohol. . Unless a large amount of water and the sodium hydroxide are added. a faint but distinct coloration will be evident. transferred to the Gooch retort. - en being treated with sodium hydroxide teristic is turned to the charac- blue-black color. will cause a strong reddish-brown coloration. while the presence of T Q. and distilled as described on page 428. for boric acid as follows : A few pieces of turmeric root are extracted with alcohol. thoroughly stirred with and absolute alcohol. It is always best to test the alcoholic distillate The solution thus prepared Remark.

02. Both iodic and decomposed. Form : HIO 3 Silver Iodide. This is especially true of is therefore not quantitative. and added until the solution. Wt. For the determination of the metal present in an iodate it is white heat. HCHO TARTARIC ACID. TARTARIC ACID.AND PYRO PHOSPHORIC ACIDS. sodium iodate. These acids are changed to phosphoric acid and determined as described on page 434. iodic acid as silver iodide. The composition trates is of free tartaric acid as well as that of the tardetermined by an elementary analysis. The determination 2 ACID.05. which at first sul- becomes yellow on account of the separation of iodine.MOLYBDIC ACID. is again colorless. lodimetry). 433 Mol. 150. IODIC ACID. molybdic acid has already been con- of sidered on page 284. For the determination of tion of the alkali iodate phurous acid is is Mol. which is only changed to iodide upon heating to a tion Potassium and silver iodates are much more readily but even then some iodide is lost. The precipitated silver iodide It is solution is heated to boiling and the determined as described on page 330. 175. the solu- acidified with sulphuric acid. .93. IODIC H MoO 4 MOLYBDIC ACID. After this an excess of silver nitrate and a considerable amount of nitric acid are added. Agl. periodic acids may be more accurately determined by a volumetric process (see Part II. 2 4 4 6. Mol. see page 4 14 etseq. . 162. above that for the decomposition takes place at a temperature The transformaat which the iodide itself begins to volatilize. Wt. 3 2 . not permissible to change the iodate to iodide by ignition. first changed to the chloride by repeated evaporation with con- centrated hydrochloric acid: KI0 + 6HC1 = KC1+ 3H O+ 203+ IC1. ETC. META. Wt.

. 1896. of ammonium magnesium little hydrochloric acid and diluting to a volume . Z.02. AND PERIODIC ACIDS. 7 Ammonium . a milky turbidity appears. Wt. of crystallized chloride in water adding a of one liter.. 44. The and Jorgensen. Mg P Pyrophosphate. the precipitation takes place in a hot solution. ARSENIC. 98. anorg. * but according to the experiments of Neubauer and of Gooch f it is evident that it is very difficult to obtain a pure precipitate of magnesium ammonium phosphate in this way sometimes it is contaminated with Mg 3 (PO 4 )2 and sometimes with Mg(NH 4 )4(PO 4 )2. K. Neubauer. Schmitz. 2 Phosphomolybdate. 4 2 Determination as Magnesium Pyrophosphate. as recommended by Schmitz. Gooch. anal. 20. some 2. however. anal. G.c. Z. A. 45. Chem. Z. 278 (1906). Jorgensen. a considerable excess of mixture." 1 and 10-20 c. VANADIC. 439. added very slowly. P 5 24Mo0 3 - 4)3 . (NH P0 i2Mo0 3 Anhydride. Procedure. according to B. PHOSPHORIC. Until recently. 279 (1904). 2 i. Forms Magnesium : H PO 3 Mol. pure. Z.. 333 (1905). PHOSPHORIC ACID. until a is precipitate begins to form. by dissolvchloride and 105 gms. Chem. Schmitz. THIOSULPHURIC. it must be redissolved in hydrochloric * H. ARSENIOUS. Chem. 4. 512 (1906). j B. anal. of a saturated solution of a little chloride. Jarvinen. according to Schmitz.. CHROMIC. 434 GROUP IV. Chem. Z. Chem.mixture" ing 55 gms. J Jarvinen. K. it was the usual practice to precipitate phos" " phoric acid in the cold with magnesia mixture and ammonia. 45. 43. Phosphomolybdic .|| a very Mg(NH 4 )PO 4 -6H 2 O is solution of alkali phosphate is treated with " hydrochloric acid. is prepared. coarsely crystalline precipitate of obtained. If. 135.5 per cent. || 1 The "magnesia. angew. while constantly stirring. f F.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. . and then the addition of the ammonia If is regulated so that about four drops are added in a minute. ammonia magnesia ammonium After heating the mixture to boiling.

and the solution is treated. It acid.2 gm.c. and weighed as described on p. until finally the liquid smells of ammonia. then to a filter and washed free from chloride. transformation is this to effect proportional to the necessary amount of nitric acid used. etc. It is best to use a is p gms. the together phosphoric acid. ammonia. of concentrated ammonia is added. ammonia. washed off. and to reprethe crucible with its cover.5 per cent. If it is desired to dissolve the ignited precipitate of concentrated hydrochloric acid. the liquid in the beaker being occasionally rotated. transferred its volume ignited Munroe If PC>4. and at the end of more it is ready to filter. as described above. after blowing away the vapors on top The solution is then allowed to cool. This change is always complete at the end of this time if the weight The time of the magnesium pyrophosphate was not over 0. of magnesia mixture are added. the crucible and its cover are removed. The precipitate is washed minutes ten times three by decantation with 2. It is dried. cipitate is placed in a beaker. crucible and an electric oven. the may be quickened.. addition of the first forms As the ammonia precipitate increases in amount. from 2 to 5 c. then the amount of can be computed according to the proportion. enough water is added to cover the crucible. In such cases the phosphoric . one-fifth of of the liquid.PHOSPHORIC ACID. 67-8. 2PO Solution and Reprecipitation of the Ignited Magnesium Pyrophosphate. After the liquid has been sufficiently heated. the heating is continued for and then an excess is three or four hours longer in order to make sure that the pyrophosphoric acid is completely changed to orthophosphoric acid. The method described on page 434 for the precipitation of phosphoric acid is not applicable when the substance contains alkaline earths or heavy metals. shall is 435 important that the precipitate which be crystalline. When the precipitate has dissolved. the weight of the precipitate 5. The beaker covered with a watch-glass and its contents are heated on the water-bath. with 2^ per cent.

and the ammonia. and only a small amount of Zeit. According to Hans v. has experienced. Determination of after Phosphoric Acid as Magnesium PyroPrevious Precipitation as Ammonium phosphate Phosphomolybdate. molybdic acid It never contains the supernatant liquid.. is treated with a slight excess of all ammonium molybdate and of the phosphoric acid boiling-point. p. ence of ammonium nitrate and sufficient nitric acid. for it is one of the quickest and most It accurate. Jiiptner (Oesterr. er . a boiling solution re- precipitated by the addition of nitric acid. irrespective of what If a solution containing phosphoric acid. and of these. but is always some what contaminated with small amounts of the bases in solution.. f According to Hundeshagen. he even recommends that be added for the determination of phosphorus in iron. the precipitate possesses the following composition: (NH 4)3 PO 4 12MoO 3 2HNO 3 - and always contains. shagen. a great many modifications. on the tartaric acid ground that it prevents the precipitate being contaminated with molybdie acid and ferric oxide. 1894. when H O. acid is phosphate. Chem. (Zeit. p. 79. It must also be noted that the solution may contain neither silicic * acid nor organic substances f Chem. I.. 164) and Eggertz prak. in the presPrinciple. 471) this is not the case. p. Chem. however. This method.. even when only alkalies are present. in the course of time. sufficient PaO 5 . (Jour. Hiittenw. f. that of Woy * will be described. p. 442. after decanting off mols. it is then obtained pure. and in some cases prevents it entirely. 28. 2 is present 24 more 3 molybdic acid than corresponds to the above formula. . may always applicable be mentioned that the molybdate method when the phosphoric is present as orthometals are in solution. 21.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. 496) the presence of tartaric and oxalic acids hinders the formation of the yellow precipitate.u. . anal. f. first proposed by Sonnenschein. If. the precipitate little is dissolved in more ammonium molybdate added. 43 6 acid should be precipitated first as ammonium phosphomolybdate and the phosphoric acid in this precipitate determined by one of the following methods. Zeit. as yellow ammonium is heated just to the immediately precipitated According to Hunde- phosphomolybdate. of MoO to 1 mol. fur Berg.

A 3 per cent.* The precipitate will dissolve somewhat if more nitric acid than the above quantity is used. HN0 3). date decreases the solubility of the precipitate in nitric acid . 25 per cent. beaker and to precipitate 0. in 4 liters of water (1 c. 436 given the yellow They do not [Translator. containing at If the solution contains more than this acid. Nitric acid. of ammonium nitrate solution are added and the solution is and 10-20 At the same time the required amount * These deshagen. an aliquot part is used for the analysis. A solution of 340 gms. 1 gm. is absolutely necessary.c. P2O 5 .1 gm. acid dissolved in 4 liters of water. the solution by Mo O (NH 4 ) 6 7 24 2 O.c.7 gms. sp.c. of nitric acid inactive. of HNO 3 but as much as 35. ammonium molybdate taken from experimental data furnished by Hunrefer to the formula on p. commercial ammonium molybdate. of P2Os c. precipitate. of obtained by dissolving of water.] I . 1. ammonium nitrate.001 2. P2 5 ). is 30 This amount of the neutral or slightly acid (HNOa) solution placed in a 400-c. is sufficient. As wash of nitric Woy's Method of Precipitation. but the addition of ammonium molybnitric acid present.6 gms. +4H gm.c. 1 .c.c.5 gm. of nitric acid heated until bubbles begin to of rise.1 gm. of the latter acid does no harm. phosphoric of the solution are taken. but its presence although about 5 per cent. gr. of P aO 5 requires 11. of this solution 1. The presence of ammonium nitrate not only facilitates the formaof tion of the precipitate. figures are c. liquid.PHOSPHORIC ACID. solution of ammonium molybdate obtained of 120 gms. In all cases 50 the most 0. 200 ammonium nitrate and 160 c. ammonium molybdate makes 55. 3. ammonium nitrate in 1 liter will precipitate 0. chloride (best none at all). gms. Solutions Required. amount of c.153 (containing 4. 437 but there must be considerable free gm.

of the wash liquid and then dissolved in 10 c. when the phosphoric acid is reprecipitated by the addition of 20 c.c. It is heated. Present in Grams.5 per cent. Now. hydrochloric acid ia added until the yellow precipitate produced dissolves only slowly on being mixed with the solution. 19 10 C. ammonia. added drop by drop through the same funnel that was used for the molybdate solution.c.f " " an excess of an acid solution of is added. . 30 c. until the liquid becomes slightly red in color. according to Schmitz. it is filtered off after per cent.*) is likewise heated until it begins to boil. To this solution 20 c.c. solution.GRAVIMETRIC DETERMINATION OF THE METALLOIDS.c. as before. the solution being rotated as before. magnesium ammonium phosphate *AMOUNTS OF REAGENTS REQUIRED. A few drops of phenolphthalein are added. The contents of the beaker are kept in motion for about one minute more and then allowed to stand for fifteen minutes. and 1 c. of 8 per cent. of ammonium molybdate are added. It is allowed to cool and then one-fifth of its volume of concenpure. 43$ solution (in this case 120 c. Amount of PzOs Nitric Acid. the precipitate is ready to filter.c.c. and then transferred to a separatory funnel and allowed to run in a thin stream into the middle of the phosphate . The precipitate is immediately formed and is now After standing ten minutes and dissolved which ammonia. After ten minutes. of the ammonium added. " 10 5 a 5 " f Loc. of hot nitric acid. while stirring the solution. the precipitate is washed once by decantation with 50 c. which is rotated while the molybdate solution is being The yellow ammonium phosphomolybdate is at once thrown down and the separation is quantitative. of water. until bubbles begin to rise. tit. and an approximately 2. ammonia solution introduced as quickly as possible from a burette. in warm trated of 2 ammonia is added.C. when the clear liquid is poured through a filter. magnesia mixture and the solution heated to boiling. nitrate solution.c.

constant) is multiplied present should be obtained. (NH ) 3 PO 4 12MoO. p. washed mixture until no further brown coloration is produced by K 4 Fe(CN) 6 and dried in a current of air at 160 C. anal. accord437). and this has been confirmed formed in the author's laboratory by experiments per- . until a constant weight is obtained. t Zeit.12MoCV 4 PO Theoretically this substance contains 3. P 2 O 5 in four experiments found 0. Steffan. precipitating the phosphoric acid in the cold with a 33 per cent. ing to the directions of Woy (p. of 2 5 If. is precipitated twice. in a Paul's drying oven.0378. gm. a small crystal ammonium nitrate and one of ammonium carbonate are added and the contents of the crucible again heated. 1640.0989 gm.PHOSPHORIC ACID. 0. having the following composition. dt.0992 .0994. 0. weight P2O 5 is Hundeshagen . with ammonium moly fa- through a Gooch crucible. 2. 2 transformed by heating for a long time at 160-180 C. the actual amount of The results obtained by Finkener. 03794 f was used. P 2 5 . found that the factor 0. Chem. XXXII (1893). f Loc.0994. into pure of the composition ammonium phosphomolybdate (NH ) 3 P0 4 .c. by 0.0995. the amount of yellow precipitate (dried until its . whereby the pre- cipitate will at once assume a homogeneous yellow color. date . of a potassium phosphate solution containing 0.782 per cent. Steffan worked precisely according to the directions of Finkener. J on the other hand. 2HNO3 4 is H O. f. the precipitate is filtered with the prescribed . accurate when the factor 0. The results of Hundeshagen and Steffan show that method gives very exact results. . 11 (1878). If of the precipitate should become slightly greenish. using 50 c. 0.03753 should be used. The precipitate produced as described under 1. A. Direct 439 of Phosphoric Acid as * Phosphomolybdate (Finkener) Determination Ammonium . Remark.. p. solution of ammonium this * Berichte. were only however. 144. The phosphoric acid Procedure. therefore.

P 2 5 this O O . whereby -P with 3. and in all cases it is best to remove the silicic acid before precipitating the phosphoric acid. . often effected in the same sample. not necessary. 0. 44 molybdate and It is. Determination of Phosphoric Acid as Phosphomolybdic Anhydride (Woy).946 per cent. .0099 gm. P 2 5 0.0992. is gently a greenish-black residue remains of the comignited. the precipitation from a hot solution with a 3 per cent. of P 2 O 5 O 24MoO The pre3 2 5 position follows: the bottom of a as is nickel cruUpon ignited cipitate The precipitate.0986 gm.* Determination of Phosphorus and Silicon in Iron and The determination of these two elements is Steel. O method gave 0. . steel. is placed a disk of ignited asbestos paper about 2 mm. so and the solution does not have Even when iron is present this that it is to be recommended for the determination of phosphorus in iron and 3.c. a too dilute nitric acid must not be used for dissolving the sample or there will be a loss of volatile phosphides and silicides. which cible is covered with a watch-glass and heated at first gently and finally bottom of the nickel crucible is at a dull-red heat. bluish-black color.0099 gm. Since phosphorus and silicon are present in the iron as phosphide and silicide. to work with such a concentrated solution of ammonium molybdate. result .0989 gm. thick. or the porcelain plate of a Gooch crucible may be used. of a potassium phosphate solution containing 0. P 2 5 and in a solution of 5 gms. in the analysis of 50c. produced in the same way as before. however. as Hundeshagen has shown.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. This method of iron is rapid and gives good results in the presence and aluminium. and the same Finkener. * Steffan found. it is allowed to cool in a desiccator. 0.0988. molybdate solu- tion yields just as accurate results to stand so long before filtering. of iron in the form of its nitrate. method gives good results. after which the covered crucible is weighed. filtering after standing twenty-four hours. 0. was obtained by the method of . When until the the precipitate has become of a homogeneous. Upon this is placed the Gooch crucible containing the precipitate.

c. This dissolves the oxide and phosphate. evaporated on the waterbath to a syrupy consistency. The silica thus obtained usually its purity must be tested in all cases. so that For this purpose it is sulphuric acid and 2 c. a drop of dilute contains ferric oxide.c. of nitric acid (1 vol. of water) and a watch-glass placed upon the beaker. sp. The silica is ignited wet in a platinum crucible and weighed. . boiled gently until vapors are evolved. gr. covered with 1 c. the residue is covered with 50 c. of pure hydrofluoric acid are added. of hydrochloric acid. which is accomplished when no more nitrate brown fumes are expelled.to adhere to the bottom of the dish. are placed in a 500-c. the contents of the dish are ignited until all of the ferric is changed to oxide.V STEEL. The dry mass should at the end be reduced to a loose powder. all upon the iron as the action slackens. concentrated acid.c. after which water is added. As soon evolved. foot-note).c. By this procedure all organic matter destroyed and the silicic acid is dehydrated. ether (cf. and 1 vol. 441 Determination of the Silicon.* ferric When all of the iron oxide has dissolved. good hood. washed with water containing hydrochloric acid and finally with pure hot water. About 5 gms. 236.c. the solution is evaporated to dryness. as in this case the latter will break during the subsequent ignition. and then heated over a free flame into dryness.4.PHOSPHORUS AND SILICON AND IN 7/?O. of concentrated hydrochloric acid and heated with formed by the oxidation of hydrocarbons is constant stirring almost to the boiling-point. of water. covered with 60 c. beaker under a. After cooling. after having been washed with p. A violent reaction at once takes place and brown vapors beaker the are is placed. the excess of * If graphite were originally present it remains with the silica.c. while the silicic acid remains behind. When this point surely is reached. gauze and its contents dissolved and no more brown wire is The contents of the beaker are then washed a 250-c. moistened with 2-3 c.c. 1. and after evaporating on the water-bath as far as possible. Care is taken during this operation that a cake of basic ferric nitrate does not . constantly stirring with a glass rod. porcelain casserole. After heating the liquid to boiling the silicic acid is filtered off through a small filter. allowed to stand for twenty minutes. of the iron borings.

One gram of borings is treated in a platinum or porcelain dish with 20 c. the graphite is completely the case when graphite oxidized. but a little pure sodium carbonate and potassium nitrate are added to the contents of the crucible and. evap- orated to dryness on the water-bath. gr. C. in water. D. the contents of the crucible are more strongly ignited and the This amount deducted from residue of ferric oxide is weighed. x.. moistened with a little concentrated hydrochloric acid. When all action has ceased . . If the impure = silica of iron taken for the analysis. 1. Si. pt from which the amount of silicon. sulphuric acid is removed by placing the crucible on a triangle in an inclined position and carefully heating by means of a moving flame. for analyzing samples of steel. is always not weighed. It is rapid recommended by the American Foundrymen's Association for the analysis of cast iron and has been used by the Bureau of Standards at Washington. a further purification of the silica is unnecessary.. The residual silica is ignited wet. general use. sp. is present) it is The melt is placed in a small porcelain dish and dissolved The solution is acidified with hydrochloric acid. er cent.c. though quite as exact. was grayish colored (as.2. As soon as no more vapors of sulphuric acid are given off. diluted with water and filtered. the weight of impure silica gives the amount of pure silica. by fusing.442 GRAVIMETRIC DETERMINATION OF THE METALLOIDS. can be calculated as follows: Si and in per cent. where a is the amount 100 Si ^-^-' SiO a Remark. and is much more than the above method. of nitric acid. Drown Method for Determining This method has come into very Silicon in Iron and Steel.

of water. sp.1. and silica. aicd. or almost As soon as this point is reached. washed with dilute hydrochloric acid. Both methods give equally good results. The filtrate from the silicic acid is diluted in a beaker to a volume of about 400 c. ignited and weighed. and ammonia is added until a permanent precipiThe liquid is then treated tate of ferric hydroxide is produced. 443 of 50 per cent.PHOSPHORUS AND SILICON IN IRON AND STEEL. (a) The Acetate Method of A. aqueous solution of sulphurous acid and slowly heated to boiling. ferric sulphate has dissolved. and the crucible again weighed. Blair.c. The liquid is then 20 c. gr. Determination of Phosphorus. and heated until all the The hot solution is at once filtered. A. If before this occurs the precipitate does not appear . is determined according to (a) The Acetate Method or (b) The Molybdate Method. which on further heating becomes a light green. 10-20 c. after which 1 or 2 c. cooled. distinct brown precipitate is formed. which on stirring becomes green. trated hydrochloric acid are added and a current of carbon dioxide conducted into the colorless solution until the excess of sulphurous acid is removed. of a saturated.c. is added very slowly with constant precipitate of ferrous-ferric To this solution stirring until the hydroxide dissolves with The addition is then continued drop by drop until a difficulty. judging from experiment/ performed in the author's laboratory. In the hydrochloric acid filtrate from the silicic acid all the The latter phosphorus is present in the form of phosphoric acid. The precipitate of ferric hydroxide soon dissolves and the liquid assumes a dark reddish-brown color. with 200 c. of hydrofluoric acid and a few drops of evaporated to dryness. of concencolorless.c. The solution is now cooled by placing the beaker in cold water. residue is placed in a platinum crucible without The contents of the crucible are drying. of chlorine or bromine is water is ammonia greenish added to oxidize a part of the iron.c. diluted with 150 c. sulphuric acid are added and the solution evaporated until copious fumes are evolved.c. 1. and then with The hot water. The difference in the two weights is the then treated with 4 or 5 sulphuric ignited c.c.c.

is the phosphoric acid is thus precipitated as basic ferric phosphate while the excess of the ferric salt is thrown down as basic ferric The through a large filter and washed precipitate filters readily and the filtrate is at first clear.c. filtered through a small filter and the residual silica washed with hot water. more of chlorine or bromine water added. The filtrate. of a 50 per cent. The solution is then filter containing the precipitate and the filtrate received in a small beaker. citric acid solution are added. the precipitate is filtered off and washed with 2*> per cent. the solution evaporated to dryness. when the solution is heated to All of boiling and kept at this temperature for one minute.c. one-half of the liquid's volume of strong ammonia is added and the mixture well stirred.5 gms. magnesia mixture repeated as above. The by warming with a mixture of bromine water. After standing twelve hours. and two drops and the precipitation with ammonia is this way a precipitate is obtained which pyrophosphate on ignition. This precipitate of magnesium ammonium phosphate always contains a small amount of iron and silicic acid (the latter from the glass) so that it is dissolved in hydrochloric acid. cjiloric acid and 1 or 2 c.c. Acetic acid is now added drop by drop until the precipitate redissolves. ammonia containing 2.c. is treated with 1 c. The precipitate adhering to the sides of the beaker is dissolved acetate. of ammonium nitrate in each 100 c. 5 c.c. but becomes turbid on standing in the air. amounting to not over 20 of the citric acid solution c. decidedly red in color. When perfectly cold. taken up in a little water. an equal amount of magnesia mixture and enough ammonia to make the solution faintly alkaline. and the addition of ammonia is repeated until the permanent green or brownish precipitate is obtained. the residue moistened with concentrated hydrochloric acid. it is dissolved in a drop or two of hydro-. or at any rate becomes white in color.444 GRAVIMETRIC DETERMINATION OF THE METALLOIDS. solution is filtered once with hot water. In of yields pure magnesium . of hydrochloric acid (1:1) Should this not be and 10 c.c. com- sufficient to effect plete solution (as is usually the case) enough concentrated hydrochloric acid is added to accomplish this. The filter is washed well with hot poured upon the water and the solution is evaporated nearly to dryness to get rid of the excess of hydrochloric acid. at the most.

c. acid.c. ever.c. (XH HSO phurous acid for this purpose. 439) . 445 Blair recommends the use of ammonium bisulphite of sulphurous acid for the reduction of the instead 3) 4 Much of the ammonium bisulphite of commerce.c. 1. howferric salt. is likely dissolves very slowly in the nitric acid owing to the formation of For this reason many chemists prefer to carry basic ferric salts. 1.c. sp. of molybdate solution and 30 c.01723 " " 2 2 4) 3 7 4 According to the above directions. by precipitated precipitate or by heated just to the boiling-point and rec.c. 437. water are added. some difficulty to be encountered at the stage where the dry residue is taken up in nitric acid. gr. sample of the borings is dissolved in 50 c. Again. is heated to boiling. and the phosphoric acid tated according to the procedure of Woy. gr. To nia. of c. and 10 c. = 0. of nitric In case . the excess of hydrogen sulphide expelled by of a current of carbon dioxide. 30 c. the dry residue is dissolved in as little nitric acid as possible. it Remark. After decanting off the clear Liquid. p.DETERMINATION OF PHOSPHORIC ACID IN SILICATES. out the analysis in accordance with the directions of the American Foundrymen's Association. and the solution then partly means oxidized as above described.27848 gm. Blair suggests that hydrogen sulphide be passed into the solution after the excess of the sulphurous acid has been removed. If the residue is overheated at all. of hot nitric acid. of nitric acid are added. The Molybdate Method. so that it seems safer to use sul- Remark. (b) The from the 441) is evaporated to dryness in a porcelain dish.2. sp.c. of ammonium nitrate solution and 10 c. filtrate silica (see p. by is precipi- the addition ammonium molybdate. of of the prescribed wash liquid and redissolved in a little ammothis solution 6 c.01639 P2 O5 -24MoO3 =0. in order to precipitate any The filtrate from the arsenic precipitate arsenic as the trisulphide. which are as follows: A 2-gm.c. P Mg P O " " (XH PO -12MoO3 = 0. 440) (p.13. contains phosphoric acid. the precipitate is washed once by decantation with 10-20 of 75 c.c. of hydrochloric. (p. The then analyzed by the method of Finkener is that of it is the addition of 20 Woy 1 gm.

c. It is then dried at a cent..c. of the concentrated When the two solutions are nitric acid and 1100 c. and filtered. 20 c.63 per cent. When at a temperature between 70 and 80 C. it is advisable to use half the above quantities of sample and reagents. sp. gr. The of concentrated nitric acid are added. 446 the sample contains a fairly high percentage of phosphorus. the first is poured slowly into the second with constant stirring and a few drops of ammonium phosphate solution are added.c. out.c. whereupon 65 c. cold. After a little ammonium phosphomolybdate precipitate has settled ready for use.2. at a temperature of about 200. of water. See Volumetric Analysis. 1. sp. of concentrated hydrochloric acid. stirring until all dissolved. of nitric acid. and allowed to cool somewhat. 1. .c. of ammonium molybdate solution are added and the solution agitated for a few minutes. of molybdic acid in 250 c. The temperature precipitate contains 1.c. are added and once more the solution It is is evaporated until a film forms. constant 100 and 105 to between weight. and 150 c.c.c. are added.c. so that the analysis should always be carried out with a reagent that has not stood very long. At this point 30 c. the reagent is decanted off and is The phosphorus in iron and steel is very conveniently analyzed by a volumetric method. of water is Another solution is prepared containing 400 c. of concentrated ammonia. evaporated to dryness and the residue baked until This baking acid. of phosphorus. 50 c. of nitric acid.c. the solution filtrate is is diluted to about 60 evaporated to about 25 c. and the evaporation is repeated until a film begins to form. then diluted with hot water to a volume of about 150 c. nitric acid and twice with alcohol. The precipitate is then filtered on a tared Gooch crucible which has a paper disc The precipitate is washed three times with 3 per at the bottom.c.42. The residue is dissolved by heating it with 25-30 c. serves to oxidize carbonaceous matter which otherwise interferes The solution free from is with the precipitation of the phosphorus. The ammonium molybdate solution used in these last directions is prepared by dissolving 100 gms.GRAVIMETRIC DETERMINATION OF THE METALLOIDS.c..c. gr. The solution does not keep very well.

the precipitate allowed to settle. made almost neutral. the solution is acid is formed. wide-mouthed filtrates c. the precipitate is much iron. The filtrate is precipitated with ammonia. or alkaline-earth metal. Tn the analysis of silicates (see p. 341. anal. Borntrager). but and the alkalies. In such a case the hydrochloric acid solution from the silica is evaporated several times to dryness contain with all of acid. 436. taken up with water. 250 denum containing molybdenum are saved. If the mineral water does not contain aluminium. Chem. 436-440) earth. The contents of a 5-6 liter flask is acidified with hydrochloric acid and evaporated to dryness. or alkaline The filtered and washed precipitate is dissolved in nitric acid and the phosphoric acid present determined according to one of the molybdate methods (pp. and the recovered as follows Into a large.* In practice the great majority of phosphoric acid determinaThe acid and amtions are carried out according to p. Recovery of Molybdenum Residues (H.SEPARATION OF PHOSPHORIC ACID FROM THE METALS. moniacal molybdenum flask is : of strong ammonia filtrates are added to this. are placed and the molyb- Either immediately or after some time a crystalline deposit of almost pure molybdic standing When the flask is nearly full. 105. and the * Zeit..c. p. dissolved in as little nitric acid and the phosphoric acid determined by one of the molybdate methods. f. XXXIII (1894). the residue is nitric as possible. 491) the phosphoric acid is found in the precipitate produced by ammonia in the filtrate from the silica together with iron and aluminium hydroxides. the residue is moistened with concentrated hydrochloric acid. . . Determination of Phosphoric Acid in Mineral Waters. phosphate aluminium. 447 Determination of Phosphoric Acid in Silicates. Remark. It is analyzed according to p. by which means the phosphoric acid is usually completely thrown down form in the of of iron. and the silicic acid filtered off. rich in phosphoric acid produced by ammonia will not the phosphoric acid.

and silicic These are filtered off and the solution diluted with disacid. is evaporated with the addition of sulphuric a syrupy consistency. the residue is acid to moistened with hydrochloric acid and taken up in water. and carefully heated over a free flame until the nitric acid is expelled. when the molybdenum After cooling. By the action of the nitric acid in the closed tube the phosphorus oxidized to phosphoric acid and this is determined as usual. Determination of Phosphorus in Organic Substances. Hydrogen sulphide is conducted into the hydrochloric acid by which means all the members of these groups are solution. 2. it has a specific gravity of 1. solution will be obtained. precipitated as ammonium In order to determine p. the pressure-flask * When Mid the is is for some time on the precipitated in large flocks. filtrate treated with hydrogen sulphide.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. tilled water until at 17 C. the metals. the flask stoppered and heated water-bath.11 = 14 Be. It then contains 150 gms. 448 upper liquid containing only a small amount of molybdenum is poured off. (a) Separation from the Metals of Group The phosphoric acid is phosphomolybdate according to first III. . or the molybdic acid will dissolve) and sucked as dry as possible. If this solution is diluted with four times as much water. Separation from the Metals of Groups I and II. The residue is poured upon a suction plate. saturated with hydrogen sulphide. After cooling. magnesia. 436. slowly opened and the molyb- silver is present it is precipitated as silver chloride.* precipitated as sulphides while the phosphoric acid remains in solution. the solution containing molybdenum. of ammonium molybdate in a liter. leaving behind a residue of iron and aluminium hydroxides. filtered off. The precipitate is dissolved by warming with as little ammonia as possible. The solution is placed in a pressure-flask. is SEPARATION OF PHOSPHORIC ACID FROM THE METALS. washed once with water (not more. i. a 3J per cent. The substance is decomposed by the method of Carius. but free from phosphoric acid.

The precipitate con- from phosphoric acid. remain in the with the molybdenum on account of the solubility of nickel sulphide in ammonium sulphide. is form of some of in the filtrate in the its sulpho-salt. it is acidiwith hydrochloric acid. the solution is made slightly ammoniacal and allowed to stand overnight in a stoppered flask. saturated with hydrogen sulphide. 5. The metals of this group will be found in the precipitate while the molybdenum Remark. Barium. 4. is The is 449 filtrate. is added until the solution is neutral. dish yellow in color. 3. then made slightly alkaline with it is acidi- ammonia and the phosphoric acid precipitated with " magnesia mixture " as described on page 434. nium carbonate Magnesium. the solution contains free alkali or alkali carbonate with nitric acid. so that method (a) will If nickel is present. In case the solution contains iron in the ferric form. denum sulphide is filtered off. dissolved in acids. of tartaric acid are fied added. 150 and 156.SEPARATION OF PHOSPHORIC ACID FROM THE METALS. Cobalt. Alkalies. Separation If fied from Chromic Acid. now free from phosanalyzed for the metals as (6) The phosphoric acid is separated as before. and for each gram of the mixed oxides 3 gms. Separation from Calcium. which is carbonate tion until a slight * If only alkalies are present there will be no turbidity. and the ammo- . tains the metals as sulphides free filtered. Manganese. and analyzed according to pp. the filtrate made slightly ammoniacal and saturated with hydrogen sul- After standing for some time the solution becomes redphide. and Zinc. when the precipitate is filtered off. and the Ammonium is added to the hydrochloric acid solupermanent turbidity * is produced. Strontium. Separation of Phosphoric Acid from Iron. It is washed with water containing ammonium sulphide. it will filtrate then give more accurate results. described on pages 82 to 167. phoric acid and molybdenum.

have been discussed under the respective metals.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. In the filtrate are now found the alkaline earths and alkalies. Mol. . BaS0 4 correspond to 1 mol. redissolved is c. Part II. This solution is acidified with hydrochloric acid and the sulphuric acid formed by the above treatment is precipitated as barium sul- phate.. way (seepages 43 and 76 H O 2 a. Ferric chloride then added drop by drop until the liquid above the yellowishwhite precipitate of ferric phosphate becomes distinctly brown The solution is diluted with water to a volume of 300 in color. which. 114. HS 2 2 3. or with ammoniacal per carbon ate solution.c. boiled for one minute. and then boiled to destroy the excess of the reagent. arsenic. is by igniting the residue obtained after evaporating to analyzed in the usual THIOSULPHURIC ACID. ff. and chromic.). while periodic acid is analyzed precisely in the same way as iodic acid. The aqueous solution of the alkali thiosulphate is treated with an ammoriiacal solution of hydrogen peroxide. BaS04 . heated for some time on the waterbath.16. Form: Barium Sulphate. filtered and washed with water containing ammonium acetate. Two mols. arsenious. vanadic. 45 by a few drops of hydrochloric acid. A much better procedure for the estimation of thiosulphuric acid will be discussed under lodimetry. The remaining acids of this group. after expelling the am- to 400 monium salts dryness. Wt.

V. can be used for the C^HieN^HNOa. 861 (1905). NITRIC ACID. 63. Ammonia.* i.HNO 3 Nitrogen Pentoxide. crystalline nitrate.c. Forms: Nitron Nitrate. C2oH 16N 4 . Z. 494. and dissolved in 80-100 c. The solution is heated nearly to boiling and treated with 10-12 c. and Volumetrically. Ber. but can be kept for a long time in a dark-colored bottle without its undergoing any change. angew. Busch. forms a fairly insoluble.c.1 nitric acid. Procedure. The base diphenyl-endo-anilo-hydro-triazole. The beaker containing the solution and precipitate is kept surrounded by icewater for about two hours. Enough of the substance is taken to furnish about gm. N2 O 5 . which is added all at one time. CHLORIC. . of 5 per cent. of 0. t The reagent A. ACIDS. NO. Gutbier. of water with the addition of 10 drops of dilute sulphuric acid. The precipitate is then transferred to a Munroe crucible and drained as completely as possible from the * M.c. Determination of Nitric Acid as Nitron Nitrate. AND PERCHLORIC HNO 3 .02. acetic acid.DETERMINATION OF NITRIC ACID AS NITRON NITRATE. is 38. NH 3 Nitric Oxide. which separation and quantitative estimation of this acid. of nitron (which can be obtained of Merck) in 100 c. Chem. 1905. Wt. G^HieN^ or -N called " nitron " for the sake of brevity. Mol. 45 * GROUP NITRIC. prepared by dissolving 10 gm. The solution usually has a reddish color. . of nitron acetate solutionf.. .

and boiling until the iodine is all expelled. 0. of water). 45 2 It is washed with 10 or 12 c. added in small portions. chromic.c. HNO 3 bromide.008 perchlorate.022 0.022 0. The solubility of the is given a little too high and that of the other salts a little nitrate too low. The following acids interfere with the determination by the nitron method.53 per cent. All of the above acids acids. It contains 16. therefore.19 nitrite. picric and oxalic Remarks. Nitrous acid is removed by dropping finely sulphate into the concentrated solution (0.61 2 2 7 2 3 3 These values are only approximate. chloric. 0. hydroferricyanic. 0.c.04 thiocyanate.125 HBr 0. 0.c. .005 HI 0. ice-water. and the precipitate drained The precipitate is dried at well after each washing.0099 gm. of pale yellow mother-liquor.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. 0. be removed from the solution before precipitating the nitric acid.2 5 or 6 c. hydriodic. 0. perchloric and the less common thiohydroferrocyanic.12 chlorate. of nitric acid nitrous. 0. cyanic.017 iodide.007 HCNS 0. idea as to the relative solubilities of the various salts of Chromic acid Some nitron is 100 obtained from the following table of slightly acid water dissolve at ordinary temperatures : c. until the yellow coloration entirely disappears. about 0. these acids must.011 HNO H Cr 0. Hydriodic acid is removed by adding an excess of potassium iodate to the neutral solution. powdered hydrazine gm. of nitron nitrate. corresponding to 0. of substance in is reduced by hydrazine sulphate.06 chromate. constant weight. hydrobromic. of 3 NO 110 to .0017 gm. form salts with nitron which are not very soluble.002 HC10 HC10 0. Hydrobromic acid is decomposed by adding chlorine water drop by drop to the neutral solution and boiling.

Chem. Vol. for the determination of nitric acid in alkaline solution to zinc.DETERMINATION OF NITRIC ACID. chloroplatinate or . as Busch and Gutbier have proved. This is not the It is probable case. amount nitron acetate and in his little left in solution is way compensated. * Reich. that the precipitate occludes a the error caused by 2. page 6) is to of aluminium. Determination of Nitric Acid as Nitrogen Pentoxide. it when there any other is volatile usually the case. Z.* This method is based upon the fact that when an intimate mixture of a dry nitrate is heated with an excess of silica. 453 On account of the appreciable solubility of the nitrate.. best. 2NaNO 3 + SiO 2 = Na 2 SiO 3 + N 2 This method cannot be used substance present. Determination of Nitric Acid as Ammonia. 86 (1862). nitrogen pentoxide is evolved and the amount is determined by the loss in weight. I. it was to be expected that the results would be a little low. the solution is distilled into a known of the acid is found by titration. Devarda's alloy ammonia by means (cf. however. which 3. After the reduction. 1. or. amount of acid and the excess or the ammonia is determined as platinum (cf. The usual method reduce is 5. b and as ammonium c). page 58. : NaNO 3 + 8H = 2H 2 O + XaOH + NH 3 .

of alcohol. of powdered Devarda's alloy are added.. . is constructed as proposed by F. 113.f Its left arm is connected by a curved tube with the middle bulb. of about 250 c.5 gm. }lbid. p. To this solution 5 c. XXXIX XXXIII (1900). 1. A. f. After K this the B flask is immediately connected with the distilla- tion apparatus as shown in the figure. The Peligot tube.. Pannertz.c. of caustic potash (sp. and 2 to 2J gms. capacity. Procedure of Devarda* About 0. so that a spurting back of the liquid is avoided. gr. (1894). of water. Twenty cubic centimeters tube is about 1 *Zeit.c. 318. inside the flask.454 GRAVIMETRIC DETERMINATION OF THE METALLOIDS. of the nitrate is placed in a 600-800-c. The delivery-tube (of potash glass) connecting the flask A K with the cm. Chem. in diameter and is provided with a small opening at o.c. p.3). to prevent any of the alkaline solution being carried over with the ammonia.c.c. 50 c. Erlenmeyer flask (Fig. 78) and dissolved in 110 c. anal.

of half-normal acid. consequently the ammonia formed from 0. the contents of the flask then the flame in order to start the reaction. of the nitrate was neutralized by 25 t c. of by a pinch-cock upon a piece of rubber tubing. with a few drops of methyl T The tubes A and B are which the upper end is closed same way. of follows: The tubes originally contained 25 c.c. A of the acid is of NH 3 .DETERMINATION OF NITRIC ACID AS AMMONIA.f of 1 mol. HNOs and one (63. while 5 c. this requires ." . has a capacity of about 250 cubic centimeters.c. When all is ready.02 gms. of half-normal sulphuric acid are added to the tube A 455 * and diluted so that the solution just reaches to each of the bulbs 0:1 the side. dent that * XH 1 The tube c. so that a piece of red litmus paper may be introduced here. Since 1 mol. the pinch-cock at r is is added to A. During the last ten minutes a slow current of air is passed through the tube r. the computed as is The amount changed to yellow. and t c. of half-normal caustic potash solution were used up in the titration. by the latter is liquid tube is colored is finished. and the red litmus paper in the T-tube should show no tinge of blue.) on being reduced yields half-normal sulphuric acid con- liter of enough sulphuric acid to neutralize \ mol. the contents of B are poured in.c.03151 gm. and kept at this The liquid in K about half of the liquid has distilled over into A about half an hour.c. temperature until . of tains 3. After an hour this will be shown to be complete by the cessation of the hydrogen evolution. f Ostwald has proposed that the molecular weight in grams of a substance be designated by the word "mol.5 gm. of the acid are placed in B. If the distillation has been correctly performed. When the distillation and the flame removed. it is evi- 63 02 equivalent to n =0. all of the ammonia will now be found in A no trace should reach B. K are gently heated is removed and the reaction allowed to proceed by itself. of half-normal sulphuric acid. and the excess with half-normal caustic potash washed with water that of the sulphuric acid is titrated solution until the solution nitric acid is opened A little methyl orange is added to A wherered. and diluted in the connected by means of a tube. orange. is then slowly heated to boiling.c.

of recrystallized potassium nitrate that has been dried at 160 C. which reaches into the flask just to the lower surface of the stopper. anal. Method of Schlosing and Grandeau. J Grandeau. The apparatus necessary a 150-c c. The method of Schlosing in its original formf was not much used on account of the apparatus required. below the stopper. Fifty c. and is provided with a pinch-cock.. IX (1870). f.03151 gm. 3 2 2 From the volume of the nitric oxide its weight is calculated.(25 -0=per cent. Grandeau used a separatory funnel instead of the tube a. 79 with a double-bored and consists of rubber stopper..GRAVIMETRIC DETERMINATION OF THE METALLOIDS. Solutions required 1. If a nitrate is heated with ferrous chloride and hydrochloric acid. c. [3]. of of HNO 3 01 present is (25-0 -0. prepared by dissolving in one liter of water 2. was proposed by Tiemann and Schulze.c. In the same way the tube a is connected with a straight tube. Through one of the holes is passed the tube b. 456 of nitric acid so that NO 3 0-03101 gm. The tube b is connected by means of a piece of rubber tubing 5 cm. ending in a restriction about 1 mm. 401. flask K fitted is shown in Fig. A nitrate solution of known strength. p. NO 3 . (25 25- 0. modified by Tiemann and Schulze* Principle. which is wired on to the tube. the nitric acid is reduced to nitric oxide: NaNO 3 + 3FeCl + 4HC1 = NaCl+ 3FeCl + 2H O+ NO. with a second tube whose lower end reaches up into the measuring-tube and is covered with rubber tubing as is shown in the figure.202.c. f Annales de chim." Analyse chimique appliquee a I'agriculture. wide and reaching 1J cm.03101= 100:3 x = 6. 1041. the lattei . through the other hole passes the tube a.5: . Chem. 0222 gms. Determination of Nitric Acid as Nitric Oxide. et de phys. * Zeit. 1 and = (25-0X0. N0 3 the per cent. 40 (1853). 479. but after being modified by Grandeau J it has become one of the best methods for the determination of nitric acid. long. p. and Berichte. VI (1873).

mm. 10 c. The water is is now poured out and exactly 50 c. the stopper fitted with the two in the flask.41 c.1.c. of specific gravity 1. . has been rein b.c. dissolving 20 gm. of iron Procedure. the liquid will quickly rise exerting a noticeable pressure. then 40 c.c. and its upper First of level is all. 79. when.c. A ferrous chloride solution obtained by (nails) in 100 c. The contents of the flask are heated to boiling with a free flame (a wire gauze is not used) until finally no more bubbles of air escape from the lower end of 6 into the bath containing boiled water.DETERMINATION OF NITRIC of this solution evolve at of C. The pinch-cock In! is then closed and the boiling is continued until the 50 c. its position is of the standard added to K. and the pinch-cocks In! and h" are placed nitrate solution tubes more are added and is opened. 457 pressure 22. 2. Hydrochloric acid. of concentrated hydrochloric acid. if no h' is pinched with the thumb air is present. of water are poured into marked on the outside of the flask by means K of FIG. a colored pencil. also marked. AUD and 760 AS NITRIC OXIDE. To make sure that the air is all expelled from the apparatus.c. NO.c. the rubber tubing at and finger. 3.

by opening h". 458 duced to a volume of 10 pinch-cock h" c. and the liquid in K of the vacuum thus produced the remainder of the nitric oxide expelled from the solution and the boiling is once more repeated.c.c. while the latter takes When its place. vacuum. and. of the acid are allowed to flow it is finally 3-4 c. The beaker containing the ferrous chloride is then replaced by one containing boiled water. A. 1907. 20 c. . with the same precautions as before. of nitric oxide to be noticed.* tents of the flask in a. which immediately closed. the lower end of a has become water in this way. and the conare heated fifteen minutes on the water-bath. gr. 50-c. The lower end of the tube a is placed in the ferrous chloride solution so that it reaches below the lower mark on the beaker. h is closed. acid (sp. although evolution no further is there solution shows that the gas has not been of the color brown the As soon completely expelled. is immediately filled with the latter up The vapors in the flask condense. as otherwise a little nitric is will distil over and not be reduced. f as the liquid no longer rises in 6. shown by the as closing together of the rubber tubing at h' and h". when the flame is removed and the The lower end of a. but the rubber tubing is at the same time pinched between the thumb and finger.c. and A filled with pure dipped into a beaker containing hydrochloric and about 20 c. 1. of the solution are allowed to pass into the flask K.c. 30 c. but should be inclined The specifically heavier ferrous chloride as much as possible. is dips into distilled water.c. the flame is ref allowed to cool. In order to accomplish this.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. As soon as the compressed rubber tubing begins to expand h is opened. Zurich. By means moved. forming a to the pinch-cock. placed over the lower end of b as shown in the figure. of water are added to replace the acid measuring-cylinder is now filled with boiled water. Wegelin. solution in the tube passes into the water. until the lower mark is * The heating on the water-bath is necessary. then 20 c.1) into K. more are added and the position in the beaker is again marked. . of the ferrous chloride solution are poured into a beaker and the upper level is marked on the outside with a colored pencil. K then heated to boiling with a free flame. the hand is removed from rubber the tubing and the nitric oxide begins to collect slowly in After half of the liquid has evaporated the measuring-tube. Inaug.c.c. The tube a should not extend vertically into the water. Dissert.

of the standard potassium nitrate solution contain 0. 459 The flame is removed. of solution. the barometer reading B pressure.06201 KXO gm. If at t' C. the amount of nitric oxide evolved will be about the same as that from 50 c. and the measuringtube containing the nitric oxide is placed in a cylinder containing pure water at the temperature of the room.c. then the reduced volume of the tion of the is unknown V nitrogen will be as before * 760(273+0 The following proportion 7 x= - 7*0. the same time the temperature of the water eter reading is noted. The volume thus obtained is is At taken and the barom- reduced to C.1011 gm. of 3 corresponding to 0.0620 1=V'Q : x = gm. of the gas is read. of the soluwhich should be prepared so that nitrate. h' is closed.c.06201 gm. w the tension of aqueous vapor at t. After standing fifteen to minutes the is tube raised twenty by means of the cork until the level of the liquid within stands at the same height as that and the volume in the cylinder without. now followed with 50 c. XO 3 in 50 c. its upper end is encased in a large reached. of 3> so that the volume VQ of the nitric oxide corresponds to 0. cork so that it floats on the water. reduced volume is If ^^-w) 273 V ~ * 760(273+0" Now 50 c. To prevent the tube containing the gas from sinking.c. of nitric oxide is obtained. Three or four experiments are performed with the standard solution.06201 _<> Vo * : now holds: 0. . the temperature was t. and B^ mm. N03 The same procedure XO .c. and wl is the pressure the volume tension of aqueous vapor at t.DETERMINATION OF NITRIC ACID AS NITRIC OXIDE. then the and millimeters. and 760 mm. of the standard solution. and the mean value is used.

except in the case of analysis is as before.47. This error is eliminated by the above pro- Remark. Forms: Silver Chloride.. In order to determine chloric acid as previously be reduced to chloride silver chloride by means it must of ferrous sulphate or zinc.. 205. with the 79. 100 to 300 c. a 7 difference that. Determination of Nitric Acid in a Drinking-water. Chem. so that low values would result. then computed In drinking-water the neutralization of the evaporated sample is not absolutely necessary.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. de minations one after the other without cleaning the apparatus or boiling it free from air in the meantime. Mol. to make sure that the carbonic acid which is completely absorbed. 84. followed by dilute hydrochloric acid. in that case the introduction of the hydrochloric acid would otherwise cause such a violent evolution of carbon dioxide that the flask might crack. HC1O. 460 It is not permissible to compute directly the weight which corresponds to the volume of nitric oxide obtained. From the water are evaporated to 40-50 c. ibid. until the solution is pink in color. See also Liechti and Hitter. a 10 per cent.. AgCl. Wt. 42 . CHLORIC ACID. instead of collecting the gas over water.c. besides volumetric and gasometric methods. * Z. Remark. anal. free from nitrate. L. of NO 3 cedure. 300 (1894). of in a porcelain dish. has been After the experiment performed with the water to be analyzed. solution of sodium hydroxide is used. and analyzed as described on page 457 Fig. it is repeated with an amount of the standard soluis set free tion sufficient to evolve about the The same quantity of nitric oxide. for some nitric oxide always remains in the flask. 33. Koninck * has devised an apparatus which prevents the liquid from sucking back into the decomposition-flask and at the same time permits the carrying out of a number of deterL. few drops of methyl orange are added. Sodium carbonate solution is now added until the liquid is barely alkaline (it becomes yellow) and the contents of the flask are washed into the decomposition-flask K. alkaline mineral waters . (1903).c.

CHLORIC ACID. too low results are obtained. L. Both methods afford exact results. nitric acid is added until the deposited basic ferric salt is dis0. Remark. working in the author's laboratory. The same end is more expeditiously by adding zinc-dust to the acetic acid solution. treated with 50 solved. obtained results which were from 0. chlorate contained in a weighed porcelain crucible with hydrochloric acid (1:3). but the former tion in for this reached to be preferred. The dilute chlorate solution is treated with acetic acid until it reacts distinctly acid.c. nitric acid is added in sufficient quantity to dissolve all of the excess of zinc. and After cooling. below the theochlorine residue little alkali is is retical value. 461 Reduction by means of Ferrous Sulphate.3 gm. About the salt is dissolved in 100 e. Some is and a always lost. and the contents of the latter are heated on the water- . it is not advisable to effect the reduc- way quantitative purposes. After cooling. fo_r it is accomplished in less time.1 per cent. A is covered watch-glass is placed upon the crucible. According to the two following methods. when the and weighed One of c. KC103 . the decomposition of alkali chlorate into chloride (a) The By is quantitative.3 to 1. grain of silver chloride corresponds to 0. Chlorates are not quantitatively decomposed into chlorides by ignition in open vessels or in a current of carbon dioxide.8550 gin. a 10 per cent. of water. an excess of powdered zinc is added. so that even when the with evaporated kydrochloric acid. Evaporation with Hydrochloric Acid. kept at this temperature for fifteen minutes. after which the solution is filtered if necessary and the chloride precipitated and determined as silver chloride. heated with constant stirring till it begins to boil. of chloride is precipitated by means of silver nitrate after the usual treatment.c. and the solution boiled for one hour. Reduction with Zinc. Although chlorates are reduced in neutral solution by means of zinc or Devarda's alloy. solution of crystallized ferrous sulphate. Blangey.

5 gm. with a watch- kept in constant motion.02 per cent. 100. page 325) . the is PERCHLORIC ACID. in a porcelain crucible with three chloride. or hydrochloric acid. 100. Blangey found that ignition with would accomplish the same result.47. as a mean of four experiments. the other hand. cover obtained. covered free flame. of the theoretical value. 4 one and one-Lalf to two hours are nec- . By mixed much pure ammonium and heated over a Chloride. Mol. until ammonium chloride is completely removed. so that an error amounting to as much as 1 per cent. twice igniting an intimate mixture of 0. some chlorine and alkali chloride Perchlorates cannot be reduced to chloride sulphate. 462 bath until the evolution of chlorine ceases. perchloric acid. of the theoretical value. After cooling in a desicIn this way L.GRAVIMETRIC DETERMINATION OF THE METALLOIDS. The liquid on the lower surface of the watch-glass is then washed into the crucible. HC1O 4 Form: . As a mean of two experiments. of ammonium chloride f in a platinum By * On evaporating with hydrochloric acid there is a loss without any evoit must be due to the volatilization of small amounts of lution . Blangey obtained 100.* are lost. L. AgCl. while L.of chlorine. Blangey cator. may be expected. ( zinc. On.06 per cent. (b) The Ammonium Ignition with alkali chlorate is times as glass.' Silver Chloride. of essary. Winteler has shown that perchlorates may be changed to chlorides by heating with concentrated nitric acid and silver nitrate in a closed tube (see Carius' method for determining chlorine in organic substances. Wt. and its contents are evaporated to dryness on the water-bath. NH C1 are used. The crucible then weighed. the crucible is again weighed. Decomposition of Perchlorates ammonium by Ignition with chloride Ammonium Chloride. The is placed upon it and it is then gently ignited over a free flame until the decrepitation ceases. f When 2 gms. potassium perchlorate with 1 J to 2 gms. by means of ferrous by repeated evaporation with concentrated On ignition.

NH *Thus on igniting 0. with ferrous sulphate. After (containing gm. dried. acid 0.3205 gm. Chloric. Pt) chlorplatinic on the ammonium to the chloride water-bath. for in that case the platinum is attacked. Blangey obtained in two experiments 100. f 100. To determine this.08 per cent. dryness evaporating was completely expelled and the residue was ignited twice more with the same amount of the latter. as described on page 461.2572 gm. the glass together with the deposit is weighed. Determination of Perchloric.06 and 100. of the theoretical values. 463 crucible covered with a watch-glass.0918 was added.c. of the theoretical amount. the difference between the wo weights represents the amount of alkali chloride. The residue of potassium by the following experiment: 0. was obtained instead of one weighing 0.2365 gm. as was proved KC1O 4 was mixed 1 c. f There is often a slight deposit of alkali chloride upon the cover-glass.24 per Determination of Perchloric Together with Chloric Acid. there will be no deposit at all upon the glass. Care should be taken not to melt the residual chloride. CHLORIC. the platinum evidently plays the part of a catalyser. of in a porcelain crucible with 1J of NH C1.4767 gm. It is worth mentioning that complete decomposition could accuracy of the results is not be effected by igniting three times in a porcelain * crucible. This rarely amounts to more than a fraction of a milligram.c. . 4 C1 a residue of 0. and Hydrochloric Acids in the Presence of One Another. the former is completely changed to chloride.PERCHLORIC. although the not affected. AND HYDROCHLORIC ACIDS. crucible (or in one of porcelain) with the addition of 1 c. and the chloride formed determined as A second portion is ignited in an old platinum silver chloride. The three acids are assumed to be present in the form of their alkali salts. is In this way as much ammonium chloride the total amount of chlorine obtained and from these data the amount of each acid can be calculated.. of hydrochlorplatinic acid and three times (as described above). chloride then weighed 0. and again weighed. of hydroand 4 gm.4395 gm. then the glass is washed. and if the ignition was performed with care. corresponding to cent. KC1O 4 with 2 gms. In one portion the chlorate is reduced.

393. Mol. . it filter it is being only necessary to precipitate with and weigh the barium sulphate. the precipitate is weighed. Z. total amount determined in a third portion after ignition chloride. 1910 . manner of precipitating barium sulphate. Theoretically the gravimetric determination of sulphuric acid is extremely simple. AND HYDROFLUOSILICTC ACIDS. Chem. According to the Errors which /. of barium sulphate and barium chloride is weighed. anal. SULPHURIC.' If. SULPHURIC ACID. H.. negligible amount.SO Form: Barium Sulphate. In may Occur in the Precipitation of the Precipitation of Barium Chloride with Barium Sulphate. therefore. however. the invariably too low.09.GRAVIMETRIC DETERMINATION OF THE METALLOID*. 464 In one portion the chloride-chlorine is determined by precipitaIn a second sample the chlorate and tion with silver nitrate. and this is true even when the solution evaporated to dryness in order to recover the last traces of result is is The precipitate always contains barium chloride in a form which cannot be removed by washing. the result must be too low. the composition of the precipitate varies in such a w