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6 & 7 CLIFFORD STREET, LONDON WI
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">,\)"*'"''0'' 41>")\"""'i\,",,",,,,'N,",,,*"it>Wil.">~
Co
-book of
1937
1941
1942 (twice)
Reissue with Appendix
1943
New Impression
1944
Third Edition under the title 'A Textbook of
Qualitative Chemical Analysis including
1945
Semimicro Qualitative Analysis',
1946, 1947 (twice), 1948,
New Impressions
1951, 1952
Fourth Edition under Ihe lille 'A Text-book of
, M=~q, "l.wl. 'M:wimitt~q, "i,,.,ui.w.:'% r.WlT.1>"l....;.._
Analysis' .
1954
New Impression (with minor corrections) 1955
New Impressions
, 1957. 1959. 1960
Rs. 16.50
wtJoLUII
vi
Preface
Preface
The writer would be glad to hear from teachers, analytical
chemists and others of any errors which may have escaped his
notice; any suggestions whereby the book can be improved will
be welcomed.
A. I. VOGEL
Woolwich Polytechnic,
London, S.E.lS
September 1953
CONTENTS
DHAPTER I
THE THEORETIC " r
PAGE
I, 5
2
2
3
5
6
.ures
'nation of
~.
<q
degree of
12
~tion
~J.",
of ions
.lisation. Interiom,
nd Onsager
0 ...
)n .
Tah~?,'
..It
1,19.
1,20.
1,21.
1,22.
1,23.
1,24.
1,25.
1,26.
1,27.
1,28.
1,29.
1,30.
1,31.
1,32.
1,33.
1,34.
1,35.
1,36.
1,37.
1,38.
ry
17
l
1,1~
15
, X!l'..i.'
r(,v'l)i~tiilt!n
0
,2
26
28
29
31
38
l6
47
\9
:n
1'.'9
60
61
64
68
72
76
82
83
88
90
90
91
93
95
97
99
101
Oontents
PAGE
1,39.
1,40.
1,41.
1,42.
1,43.
1,44.
Buffer solutions
Hydrolysis of salts
.
.
.
.
Hydrolysis constant and degree of hydrolysis..
Hydrolysis and the proton theory of acids and bases.
The distribution or partition law
The colloidal state.
109
114
117
125
13l
1:14
CHAPTER II
EXPERIMENTAL TECHNIQUE OF QUALITATIVE
INORGANIC ANALYSIS
TECHNIQUE OF MACRO ANALYSIS
II, 1. Dry reactions
II, 2. Wet reactions
1>3
154
165
188
189
. 1',}'
CHAPTER III
REACTIONS OF THE METAL IONS OR CATIONS
III, 1. The analytical classification of the metals
III,
III,
III,
III,
206
208
211
21'
217
219
221
223
229
:!33
234:
235
237
2'0
2'2
Oontents
PAGE
111,14.
111,15.
,111,16.
111,17.
111,18.
247
249
252
254
256
257
258
260
262
267
272
277
278
279
283
288
292
297
298
111,29.
111,30.
111,31.
111,32.
299
302
303
307
308
309
111,33.
111,34.
111,35.
111,36.
111,37.
311
315
317
318
323
324
111,19.
UI,20.
111,21.
111,22.
111,23.
111,24.
111,25.
111,26.
111,27.
111,28.
CHAPTER IV
IV,
IV,
IV,
IV,
IV,
IV,
IV,
IV,
IV,
Oontents
xii
IV,10.
IV,ll.
IV,12.
IV,13.
IV,14.
IV,I5.
IV,16.
IV,17.
IV,lS.
IV,19.
IV,20.
IV,2t.
IV,22.
IV,23.
IV,24.
IV,25.
IV,26.
IV,27.
IV,28.
IV,29.
IV,30.
IV,3t.
IV,32.
IV,33.
IV,34.
IV,35.
IV,36.
IV,37.
IV,3S.
IV,39.
IV,40.
IV,4t.
IV,42.
IV,43.
IV,44.
IV,45.
Reactions of thiocyanates
Reactions of ferrocyanides
Reactions of ferricyanides
Reactions of hypochlorites
Reactions of chlorides.
Reactions of bromides.
Reactions of iodides
Reactions of fluorides .
Reactions of nitrates .
Reactions of chlorates .
Reactions of bromates .
Reactions of iodates
Reactions of perchlorates
Reactions of borates
Reactions of sulphates .
Reactions of persulphates
Reactions of silicates .
.
Reactions of silicofluorides (fluosilicates)
Reactions of orthophosphates
..
Reactions of pyrophosphates and of metaphosphates
Reactions of phosphites
Reactiolls of hypophosphites
Reactions of arsenites and of arserlates .
Reactions of chromates (and dichromates)
Reactions of permanganates .
Reactions of acetates .
Reactions of formates .
Reactions of oxalates .
Reactions of tartrates.
Reactions of citrates
Reactions of salicylates
Reactions of benzoates
Reactions of succinates
.
Reactions of hydrogen peroxide - .
Reactions of hydrosulphites (hyposulphites or dithionites)
Special tests for mixtures of acid radicals
3H'i
3~8
:)1)3
3(,6
3G9
:r,2
:li3
:r77
:;;9
3131
:H,4
:1s5
:;89
390
::01
:j92
:\03
:;\)5
:)tJ7
-100
401
404
407
.j09
410
,H2
413
n5
416
CHAPTER V
SYSTEMATIC MACRO QUALITATIVE INORGANIC
ANALYSIS FOR ELEMENTARY STUDENTS
1.
2.
3.
4.
V, 5.
V,
V,
V,
V,
V, 6.
V, 7.
V, 8.
V, 9.
V,10.
131
t3!
433
438
44.2
4"
<148
450
i54
455
Oontents
xiii
CHAPTER VI
INTRODUCTION TO SYSTEMATIC SEMIMICRO
QUALITATIVE INORGANIC ANALYSIS
PAGE
VI, 1.
VI, 2.
VI, 3.
VI, 4.
VI, 5.
VI, 6.
VI, 7.
VI, 8.
VI, 9.
VI,IO.
Preliminary discussion.
Abbreviated course of instruction.
Systematic analysis. General considerations .
Preliminary tests .
Examination for acid radicals (anions) in solution
Confinnatol'Y tests for acid radicals or anions.
Special tests for mixtures of acid radicals (anions)
Examination for metal ions (cations) in solution
Separation of cations into groups; Table SM.S
Modification of the analysis in the presence of phosphate,
etc.
VI,lI. Analysis of a liquid (solution)
./
457
458
460
460
467
471
475
479
482
486
487
CHAPTER VII
SYST~MATIC QUALITATIVE INORGANIC ANALYSIS
VII,
VII,
VII,
VII,
VII,
1.
2.
3.
4.
5.
VII, 6.
VII, 7.
VII, 8.
VII, 9.
VII,IO.
VII,l1.
VII,12.
VII,13.
VII,14.
VII,IS.
VII,16.
VII,17.
VII,IS.
VII,19.
VII,20.
489
490
496
502
503
505
511
512
513
515
517
519
521
523
524
527
529
532
533
534
549
553
15154
1566
xiv
Oontents
CHAPTER VIII
f)(,6
f,()7
CHAPTER IX
REACTIONS OF SOME OF THE .. RARER" ELEMENTS
IX, IA. Reactions ofthallous compounds
572
IX, lB. Reactions of thallic compounds.
573
IX, 2. Reactions of tungstates
.
.
. 5'74
IX, 3. Analysis of Group I (Silver Group) in the presence of Tl
and W; Table I
fi'76
IX, 4. Reactions of molybdates
r, i 7
IX, 5. Reactions of auric compounds
[,79
IX, 6. Reactions of chloroplatinates
5S1
IX, 7. Reactions of palladous compounds
583
IX, SA. Reactions of selenites
584
IX, SB. Reactions of selenatea
586
IX, 9A. Reactions of tellurites
587
IX, 9B. Reactions of tellurates
. . . . .~S8
IX,IO. Analysis of Group II (Copper and Arsenic Groups) in the
presence of Mo, Au, Pt, Pd, Se and Te; Table II.
589
590
Analysis of Group IIA (Copper Group); Table III
591
Analysis of Group lIB (Arsenic Group); Table IV
IX,H. Reactions of vanadates
59!
IX,12. Reactions of beryllium compounds
595
IX,13. Reactions of titanic compounds
.598
IX,14. Reactions of zirconium compounds
601
IX,15. Reactions of uranyl compounds
604
IX,16. Reactions of thorium compounds .
606
IX,17A. Reactions of cerous compounds .
607
IX,17B. Reactions of eerie compounds
r,O!}
IX,IS. Analysis of Group lIlA in the presence of Ti, Zr, Ce, Th,
U and V; Table V .
.- fill
IX,19. Notes on the precipitation and separation of Group IIIB
in the presence of "rarer" elements
612
IX,20. Reaotions of lithium oompounds
ti 13
IX,21. Borax bead tests; Table VI .
615
CHAPTER X
X,
X,
X,
X,
1.
2.
3.
4.
PAPER CHROMATOGRAPHY
Introduction. RF values
Apparatus and general technique
Some typical group separations
Miscellaneous separations
1:16
(;18
fi23
627
OO'ntents
xv
APPENDIX
PAGE
632
633
640
643
647
648
650
651
CHAPTER I
THE THEORETICAL BASIS OF QUALITATIVE
ANALYSIS
ELEMENTARY TREATMENT
Qualitative analysis has for its object the identification of
the constituents of a substance, of mixtures of sulmtances or
of solutions, and the manner in which the component elements
or groups of elements are combined with one another. Quantitative analysis is concerned with the methods of determining
the relative proportions of these constituents. It is evident
that rigid qualitative analysis must precede the quantitative
analysis; the former should give an approximate illdication of
the relative proportions of the constituents present and should
serve as a guide to the methods to be adopted in the latter.
In what follows, the principles underlying the separation of
the more commonly occurring elements will be considered. The
treatment will be an elementary one and is designed as an
introduction to the subject. By its aid it is hoped that the
student will be able to appreciate the significance of the operations commonly employed in qua.litative analysis. In addition,
a knowledge of the principal reactions of the elements and their
derivatives is necessary. Chapters III and IV deal with this
aspect of the subject. The molecular chemical equa.tions are
given throughout. The student should have no difficulty, after
studying Sections I, 24 and I, 25 in converting most of these
into "ionic equations."
The identification of a substance involves its conversion,
usually with the aid of another substance of known composition,
into a new compound which possesses characteristic properties.
This transformation is called a chemical reaction. The substance by means of which this transformation is brought about
is termed the reagent. One distinguishes between reactions in
the wet way (i.e. those in which a li.quid, usually water, is
present) and reactions in the dry way; the former are by far
the more important and will therefore be studied in greater
detail.
1+
[I,
It 2. Electrolysis and Ions.-Pure water is a very poor conductor of electricity but, as already stated, when acids, bases
or salts are dissolved in it, the resultant solution not (Jnly
conducts the electric current but is also simultaneously decomposed. The decomposition is called electrolysis. Thus, if
an electric current from, say, a battery is passed through hydrochloric acid, the hydrogen chloride is split up into hydrogen and
chlorine. The hydrogen is liberated at the electrode by which
the current leaves the solution (the negative electrod, or
cathode) whilst the chlorine is liberated at the electrod by
which the current enters the solution (the positive elect, ode
or anode). This behaviour is a general one for electrolyto.:sfor the present it is assumed that no secondary changes occur a.t
the electrodes-and it is obvious that the part of the electrolyte
i,
3]
---11[1[1[1[1---
-~---
[I,
Na+
Cl-;
R+ + Cl-;
Ca++
2Cr;
2Na+ + S04--
The ions carry positive and negative charges and, since the
solution is electrically neutral, the total number of positive
charges must be equal to the total number of negative charges.
The number of charges carried by an ion is equal to the valency
of the atom or radical.
The abnormal results referred to above now receive a si tIlple
explanation if it be assumed that the effect of each ion upon
the vapour pressure, freezing point or boiling point is equivalent
to that of a molecule of a non-electrolyte. Sodium chll,ride
yields two ions in aqueous solution, so that the nearly double
depression of freezing point obtained in dilute solution wl)uld
appear to indicate considerable dissociation. The resul1 for
sodium sulphate and calcium chloride are similarly accounted
for.
It is evident that precise measurements of this
"abnormality" may be employed to calculate the extent of
Ionisation or the degree of dissociation. Another metho, i for
determining this quantity, dependent upon the measurelllent
of electrical conductivity, will be discussed in a subseqllent
section.
The phenomena of electrolysis also receive a simple explanation on the basis of the theory of electrolytic dissociation.
The conducting power of aqueous solutions of electrolyt""s is
due to the ions which transport the current through the
solution. Returning to the example of hydrochloric acid
already considered, it is clear that if two inert electrodes. say
4]
40H- = 440
+ 2HzO + Oz
2 )-;
rl,
~H+
H+
+01-
+ NOa-
5]
or
H 2SO,
+ H20
~~
H+ + HSO,-,
HaO+ + HSO,-
or
H+
+ SO,--,
H+ + H 2 PO,H SP04 + H 2 0
H 2 PO, - + H 2 0
HPO,-- + H 2 0
H+ + HPO,-- ~ H+
~ HaO+ + H 2 PO, -,
~ HaO+ + HPO, --,
~ HaO+ + PO,--~
+ P04 - - - ;
(I,
+ H 20
+ OH-
+H 0
2
NH,+
+ OH-
~B+H+
5]
where A and B are termed a conjugate (or corresponding) acidbase pair. It is important to realise that the symbol H+
in this definition represents the bare proton or unsolvated
hydrogen ion, and hence the new definition is independent of
the solvent. The equation expresses a hypothetical scheme for
defining the acid and base, and not a reaction which can actually
take place. The dissociation of an acid to yield H+ is conditioned by the presence of a base, i.e. a substance capable of
accepting the liberated H+.
The Bronsted-Lowry definition of an acid includes:
(a) the uncharged molecules known as acids in the classical
dissociation theory, e.g. HCI, HN0 3, H 2 S04, CHa.COOH, etc.;
(b) anions like HS04-, H 2 P04- and HOOC.COO-, which
occur in acid salts;
(c) the ammonium ion by virtue of the tendency represented
by NH4+ ~ NH3 + H+, and the hydroxonium ion (HaO+ F
H 20 + H+)-these are examples of cation acids; and
(d) cations, like the hydrated aluminium and other metallic
ions
[Al(H 20)o]3+ <? [Al(H2 0)6(OH)]2+ + H+
For bases, the new definition is concerned with the ability of
accepting a proton and not with the production of the hydroxide
or some similar ion. The following are included:
(a) uncharged molecules (ammonia and the amines) by virtue
of the reaction RNH2 + H + <? RNHa +;
(b) metallic hydroxides, due to the production of the
hydroxide ion-OH- + H+ ~ H 2 0.
The hydroxide ion is one example of an anion base: other
examples are the anions of all weak acids. Thus the acetate
ion is a weak base:
CHa.COO- + H+ ~ CHa.COOH
It is important to note that the familiar strong bases according
to the classical definition, such as the alkali and alkaline earth
hydroxides, are invariably ionic in nature even in the solid
state. The basic nature of these strong bases is due to the
OH- ions which are always present in the solid state or in
aqueous solution, and interaction with the solvent is not an
essential preliminary as for weaker bases, such as those of the
ammonia (RNH 2) type:
RNH2 + H 20? RNHs + + OH
10
[I,
are called amphoteric electrolytes or ampholytes: H 20, Het)3and H 2P04- are examples.
As already pointed out, the equation A ~ B + H+ does "ot
represent a reaction which can actually take place: othenl ise
expressed, the free proton, because of its small size and the
intense electric field surrounding it, will have a great affillity
for other molecules, especially those with unshared electn)fis
and therefore cannot exist as such to any appreciable ext<'nt
in an aqueous or other basic solvent. The acceptor of a pro! <m
is a base. Thus if one writes the two equations A 1 ~ B 1 + I {+
and B2 + H+ ~ A 2 , one obtains:
Al + B'}, .p A2 + BI
Acid l
Base.
Acid.
Basel
+ H 20
HsO+
+ or
+ H 20
~ HaO+
+ 02H a0 2 -
...
5]
11
H 2SO4
H804CH 3COOH
CH 3COOH
H 2O
NH4+
H 2O
H 2O
HCI
Bases
+
+
Baf;A 1
Acids
__,..
H30 +
+ H 2O ..,__,..
..,H
O
H30 +
2
+
H30 +
+ H 2O ~
__,..
..,NH4+
NH3
+ CH 3. COO- ~ CH3. COOH
H30 +
H 2O
~
NH
~
NHs
4+
__,..
HP0
-H
P0
..,4
2
4+
__,.. C H OH +
+ C2H 5OH ..,- 2 5 2
+
+
+
+
+
+
+
+
+
mr
NH3
OHOH-
01-
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
12
[I,
6]
13
I, 6, 1.
! Concentration
Substance
G.
equiv./litre
cxfram
freezing
point
cxfrom
conductivity
No. of ions
for one
molecule, n
KCI
001
002
005
010
0946
0915
0890
0862
0943
0924
0891
0864
BaCl2
0001
001
010
0949
0,903
0798
0959
0886
0754
K 2S04
0001
001
010
0939
0887
0748
0957
0873
0716
0001
001
010
0946
0865
0715
0930
0822
It
Ka[Fe(CN)6]
or a
TABLE
1, 6, 2.
Conon.
KCl
00001
00002
00005
0001
0002
0005
001
0
1492 1253
EQUIVALENT CONDUCTANCES AT
NaCl
- - -- - -- - -
[J
14
1483
1475
1465
1442
1416
1501
1243
1235
1222
1198
1178
1262
4222
4211
4192
4149
4105
4237
2465
2447
2425
2388
2345
2609
2701
2682
2662
2621
2589
2839
250
Na.
C2 H s0 2
894
887
877
857
837
913
H.
C2 Hl
104;
64.;
48~
35'
22,'
16~
388,(
Acids
Hydrochloric (H+, Cr)
Nitric (H+, NO s-)
Sulphuric (H+, HSO.-)
Phosphoric (H+, HsPO.-)
Hydrofluoric (H+, F-)
Acetic (H +, CH s . COO-)
Carbonic (H+, HCO s-)
Hydrosulphuric (H +, HS-)
Hydrocyanic (H+, CW-)
Boric (H+, H,BO s-)
O'lN
SaUs
092
0'92
061
028
0085
0013
00017
00007
00001
00001
small
Basea
Sodium hydroxide (Na+, OIr)
Potassium hydroxide (K +, OIr)
Barium hydroxide (Ba + +, 20H-)
Ammonia (NR, +, OIr)
091
091
081
0013
7J
15
Ao =..\0.,
+ .\0.,
and
"0, =
-'or =
"Na+ =
130'1 = 646
16
TABLE
1, 7, 1.
180
H+
Na+
K+
Ag+
1/2
1/2
1/2
1/2
1/2
1/2
1/2
Ca++
Sr++
BaH
Pb H
Cd++
Zn++
Cu++
3170
435
646
544
522
517
550
616
465
460
459
OH-
180
AND
25(
250
1740
655
NO s618
Br677
r
661
F468
010 3 550
IO s340
C2H 3 0 2 325
1/280,,-- 683
1/202 0,-- 6J.l
01-
AT
[If
-H+-----3480 on21"
7(;
Na+ 498 or
K+
Ag+
4::~
4('
I, 7, 2.
DISSOCIATION OF ACIDS AT
250
Degree oj Dissociation
0-5N
OOOIN
Strong Acids
Hydrochloric acid
Sulphuric acid (primary ionisation)
Nitric acid
Trichloroacetic acid
0862
0536
0862
0760
0993
0-960
0-997
0994
Weak acids
Acetic acid
Oarbonic acid
Hydrocyanic acid
0006
00008
000005
0126
0017
O'OOll
I
I
It is evident that the degree of dissociation varies considerably both with the nature of the acid and with the concentration.
8]
17
I, 8. Theory of Complete Ionisation. Interionic Attraction Theory of Debye, Huckel and Onsager.-It has already
been pointed out that strong electrolytes, particularly salts and
bases, are completely dissociated in aqueous solution. How
then is one to explain the increasing equivalent conductance
with decreasing concentration? We have seen that Arrhenius
ascribed this to the increasing degree of dissociation, the
mobilities of the ions at all concentrations being assumed constant. This classical view can now no longer be held to possess
any significance for strong electrolytes. Debye and Huckel in
1923 and Onsager in 1925 accepted the complete dissociation
theory, and attributed the changes in conductance with dilution
(and also the associated changes in osmotic activity in dilute
solutions) to the electrical forces between the ions. Owing to
the interionic forces, each ion will build up an "atmosphere"
of ions of opposit,e sign. When an electromotive force is
applied, the ionic" atmosphere" will be unsymmetrical, for the
ion has to build up a new ionic "atmosphere" in front, whilst
the "atmosphere" behind the moving ion will be dispersed.
The dispersal of the ionic "atmosphere," however, requires a
certain amount of time ("time of relaxation"), and hence there
will always be, in the rear of the moving ion, an excess of ions
of opposite sign as a result of which the mobility will be
diminished. Further, the motion of, say, a positively charged
reference ion will be subject to a retardation by the movement
of the negative ions in the opposite direction, and the effect will
be that of a viscous electrical drag (" electrophoretic effect ").
In short, the speed of the ions will be diminished because of the
attractive forces exerted by the ions constituting the "atmosphere" of opposite sign. The attractive forces will dearly be
greater the more concentrated the solution, since the ions are
brought closer together. Consequently the mobility of the ions
will decrease with increasing concentration. At extreme dilutions the interionic forces will become negligibly small owing to
tee relatively great distance between the ions, and the mobilities
18
[I,
I, 9.
9J
19
or
[0] X [D]
[AJ X [B]
or
kl = K
k2
P2 A 2
+ PaAs ~ q1B l +
q2 B 2
+ qsBa,
where PI, P2, Pa and ql, q2, qa are the number of molecules of
the reacting substances, the condition for equilibrium is given
by the expression:
[Bl]"l X [B 2 2 X [Barl = K
[Al]Pl X [A 2 ]P2 X [As 3
is
20
[1
HsO+
+ C2H a0 2- *
21
10]
K.
K.}
I, 10, 1.
Concn. X 104
Ac
1873
5160
9-400
2478
3886
5674
6871
9216
1122
0
1025
6595
5060
3194
2578
2148
1958
1699
1541
3886
IX
0264
0170
0130
0080
0066
0055
0050
0044
0040
Ka
105
178
176
183
182
183
184
184
184
184
~NH3
(aq.) + H 2 0
( dissolved)
~NH40H ~NH.1+
+ OH-
22
[I,
+ H 20
Bases
Acid I
NH4+
Acids
+ OHBasel,'"
I, 10, 2.
Dilution (litres)
1000c
K6 X 10
8
16
32
34
48
67
95
135
190
252
135
191
266
377
536
754
23
23
23
23
24
24
64
128
256
CXJ
11]
23
24
[I,
Fig. 1,11, 1
Fig. I, 11, 2
25
11]
I, 11, 1.
Molar
Concentration
HCI
HBr
HNO.
HIO.
H.SO,
NaOH
KOH
Ba(OH).
AgNO.
Al(NO.).
BaCl,
Ba(NO.).
CaCl,
Ca(NO.).
CdCI,
CdSO,
CuCI.
CUSO,
FeCla
KF
KCI
KBr
KI
KCIO a
KCIO,
K.SO,
K,Fe(CN).
LiBr
Mg(NO.).
MgSO,
NH,Cl
NH,Br
NH,I
NH,NO.
(NH')2 S0 ,
NaF
NaCl
NaBr
NaI
NaNO.
Na 2SO,
NaCIO,
Pb(N0 3 ).
ZnCI.
ZnSO,
0001
0966
0966
0965
096
0830
-.
0'01
0904
0906
0902
086
0544
090
0'712
0'90
072
0'71
073
0'71
047
040
072
041
075
- 093
0965 0'901
0965 0'903
0965 0'905
0967 0907
0965 0895
089
0'71
088
088
089
088
076
073
089
0'74
089
0909
071
040
088
087
089
088
067
- 090
0966 0904
0966 0914
091
097
0966 090
071
089
090
097
069
088
088
0'71
039
070
0966
d88
096
096
096
096
087
005 I 01
02
05
V ABIOU8
10
20
- - - -- - - -- -- 0830
0838
0823
069
0340
082
082
0526
079
0796
0'805
0785
058
0265
080
0443
072
020
056
049
052
043
0'57
0'52
0154
048
028
021
021
017
0'58 , 0'52
021
016
062
0'58
0'88
085
0815 0'769
0'822 0'777
084
080
0813 0'755
0788
052
043
019
014
0842 0810
055
051
022
018
079
074
078
on
080
0'76
0'78
0'73
048
040
081
0'75
0'823 0'780
0844 0'800
0'86
083
0'82
0'77
053
045
082
0'77
046
0'37
056
0'50
015
0767
0782
0748
046
0209
073
0370
064
016
044
034
048
042
015
011
047
011
055
081
0719
0728
076
036
011
0784
046
013
069
068
071
066
032
069
0730
0740
081
070
036
072
027
0'45
011
0758
0790
0'715
029
0154
069
073
0809
0871
0720
019
0130
068
076
051
014
039
040
028
045
019
044
039
071
035
035
006
005
004
051
0'43
005
067
071
070
0606 0576
0625 0602
068
069
052
038
009
007
042
007
059
074
0651
0665
071
067
0783
044
009
062
062
065
0'56
022
062
068
0695
078
062
027
064
017
038
007
101
1-17
078
010
012
070
089
0848 106
050
069
005
006
057
0'57
060
0'47
016
066
067
06H6 0734
080
095
055
048
020
058
011
033
004
005
26
[I,
, I
12]
27
1.12, L
DISSOCIATION CONSTANTS AT
250
Monobasic Acids
-
Nitrous acid
Hydrocyanic acid
Formic acid
Acetic acid
46
724
177
182
176
134
58
Propionic acid
Boric acid
10-'
10- 10
1O- 4 t
10- 5
1O- 5t
10- 5
10- 10
X
X
X
X
X
X
X
Monochloroacetic
acid
Cyanoacetic acid
Phenylacetic acid
Benzoic acid
o-Chlorobenzoic
acid
o-Nitrobenzoic
acid
Hydrofluoric acid
Phenol
15
349
4'88
637
X 10-3
X 1O-3 t
X 1O- 5t
X 1O- 5t
120 X 1O- 3 t
600 X 1O-'t
69 X 10-'
1,3 X 10- 10
Dibasic Acid8
Hydrogen
sulphide
Sulphurous
acid
Sulphuric acid
Carbonic
acid
X 10{KK 9.1
12 X 10X 10{KK 1'7
1'0 X 10t
Ka 115 X 1O{KK 561
4'31 X 1O- t
X 1O- t
8
15
11
---
Oxalic acid
1O- t
{KK 5'9
1O- 5t
64
{KK 220
1'40 X 1O- t
X 1O- t
1O- 5t
{KK 2'54
6'63
1O- t
lo-at
{KKa 455
1'04
lO-'t
X
X
Malonic acid
Succinic acid
d-Tartaric
acid
X
X
X
X
Tribasic Acids
Phosphoric
acid
Arsenic acid
{KK 623
7'52 X 1O- t
X 1O- t
K35 XX 1O3t
10{KKa 40
5'0
10K 6'0 XX 108
13
{KKa 269
9'20 X 1O-'t
1O- 5t
Ka 134 1O- t
1
Citric acid
X
X
10
-Bases
Ammonia
Methylamine
Dimethylamine
Trimethylamine
Ethylamine
18
179
438
520
1)45
56
X
X
X
X
X
X
10- 5
1O- 5 t
1O- 4 t
1O- 5t
10-5t
10-'
Diethylamine
Triethylamine
Aniline
Pyridine
Quinoline
Piperidine
12
64
40
20
60
1,3
X 10-8
X 10-'
X 10- 10
X 10- 8
X 10- 10
X 10-8
t Figures marked with a dagger (tl are the true or thermodynamio dissooiation oonstants (see Section It 11).
28
[I,
For very weak or slightly dissociated electrolytes, the e:- Pression ('J.2j(1 - ('J.)V = K reduces to ('J.'J. = KV or ('J. = '\ [{V,
since oc may be neglected in comparison with unity. ] i mce
for any two weak acids or bases at any given dilution !' (in
litres), one has OCI = VKIV and OCll = VK 2 V, or IXI '2 =
VKljVK;. Expressed in words, for !;tny two weak or sli iltly
dissociated electrolytes at equal dilutions, the degrees or dissociation are proportional to the square roots of their dis" ,ciation constants. Some values for the clissociation constal;' , at
25 for weak acids and bases are collected in Table 1, j , l.
I, 13. Dissociation of Polybasic Adds.-When a poly i . lsic
acid is dissolved in water, the various hydrogen atoms Ull< rgo
dissociation to different extents. For a dibasic acid H2A the
primary and secondary dissociation can be represented b.) the
equations:
(1)
H2A ~ H+ + H.t\I I . (2)
HA- ~H+ +A~-
(1a)
(2a)
HsA
H2A-
H+
I? H+
+ H 2 A+ HA--
(3)
(4)
(5)
14]
29
I, 14. Common Ion Effect.-The concentration of a particular ion in an ionic reaction can be increased by the addition
of a compound which produces that ion upon dissociation.
The particular ion is thus derived from the compound already
in solution and from the added reagent, hence the name
common ion. We shall confine our attention to the case in
which the original compound is a weak electrolyte in order that
the law of mass action may be applicable. The result is usually
that there is a higher concentration of this ion in solution than
jhat derived from the original compound alone, and new equiibrium conditions will be produced. Examples of the calculajion of the common ion effect are given below. In general, it
nay be stated that if the total concentration of the common
on is only slightly larger than that which the original com)ound alone would furnish, the effect is small; if, however, the
For further examples the reader is referred to any of the numerous boob
on chemical calculations.
II
30
[I,
12 X 10-15 X [HS-]
[H+]
17 X 10-zZ
12 X 10-15 X 36 X 10- 8
025
~ = 1.82 X 10- 5
(I - 0:)
v'KfC =
0:),
Vl82 X 10 4=00135
15]
or
31
or
I, 15. Solubility Product.-It was found as a result of experiment that for sparingly soluble binary electrolytes (i.e. those
with solubilities less than 0001 gmm molecules per litre), the
product of the total molar concentrations of the ions is constant
at constant temperature. This product Se is termed the solubility product. For a binary electrolyte:
AB,.=A++B81. = [A+] X [B-1
32
A"Bq
r;p
pA +...
+ qB-...
f1.
B-
(ions in solution)
K'fVu,
Sln
S~.
Nowacth liy
15]
33
x 20
'<;-8
SaCI Z
- -. - _!_{_I_
O~~O~.O~2~O~'O~4~O'~06~~O'~08~O~'I~O~0'12---0'~14~O~'16
Normality of added salt
34
[I,
8or---------------__~
'"
~
l<
70
50,-- added
(Calc.)
AgN03
" . Ag+ add
10 0~--0~.~02~0-.0-4~0.....0-6-0....0-8---'0.10
(Calc.
Normality
0/ added salt
15]
35
Hence
[Ag+]
= 105
SA.Cl=[Ag+] X
= 105
X
10- 5
(105 X 10-5 )
X
+ Cr04--.
17
10-12
36
[I,
[P04 - - - ]
or
or
or
2x.
3.1 and
~~
15]
37
Substance
AgBr
Ag Br0 3
AgCNS
AgCI
Ag2C20 4
Ag 2Cr04
AgI
AgI0 3
Ag3P04
Ag 2S
Ag 2S04
AI(OH)3
BaCO a
BaC2O,
BaCr04
BaS04
BizS a
CaCOa
CaC 20 4
CaF 2
CaSO,
CdS
Co(OH}z
CO(OH)3
CoS
Cr(OH)a
CuBr
CuCI
CuI
CuS
CuSCN
Fe(OH)z
Fe(OH)3
I, 15, 1.
Solubility
product
77 X 10-13
50
12
15
50
24
09
20
18
16
77
85
81
17
16
92
16
48
26
32
23
14
16
25
3
29
16
10
50
1
16
48
38
10-5
X
X 10-12
X 10-10
X 10-12
X 10-12
X 10-16
X 10- 8
X 10-18
X 10-411
X 10-5
X 10-23
X 10-11
X 10-7
X 10-10
X 10-11
X 10-72
X 10-11
X 10-1)
X 10-11
X 10-4
X 10- 28
X 10-18
X 10-43
X 10- 26
X 10- 211
X 10- 11
X 10-6
X 10-12
X 10-44
X 10-11
X 10-16
X 1O-a8
Substance
FeS
Hg 2 Br2
Hg 2Cl 2
Hg 212
Hg2S
HgS
K2!_PtC~)
MgC0 3
MgC 2 0 4
MgF2
Mg(NH4)P04
Mg(OH)z
l\fu(OH)2
l\fuS
Ni(OH)2
NiS
PbBr2
PbCl 2
PbCO a
PbCrO,
PbF 2
PbI 2
Pb 3(P04 )2
PbS
PbS 0 4
SrC0 3
SrC 2 0 4
SrS04
TICI
TIl
Tl 2S
Zn(OH)2
ZnS
Solubility
product
40
52
35
12
1
4
11
10
86
70
25
34
40
14
87
14
79
24
33
18
37
87
15
0
22
16
00
28
15
28
1
1
1
X 10-19
X 10-23
X 10-18
X 10-28
X 10-45
X 10-54
X 10-"
X 10-5
X 10-5
X 10-11
X 10-13
X 10-11
X 10-14
X 10-15
X 10- 111
X 10-24
X 10-5
X 10-4
X 10-14
X 10-14
X 10- 8
X 10-1)
X 10-32
X 10- 211
X 10- 8
X 10-11
X 10- 8
X 10-7
X 10-4
X 10- 8
X 10-22
X 10- 17
X 10-28
38
[I,
I, 16. Applications of the Solubility Product Relation ,In spite of its limitations (as outlined in the previous Sect:, lll)
the solubility product relation is of great value in qualitat ,ve
analysis, since with its aid it is possible not only to explain i ,ut
also to predict precipitation reactions. The solubility prod llct
is in reality an ultimate value which is attained by the i( ;lic
product when equilibrium has been established between I he
solid phase of a slightly soluble salt and the solution. If conditions are such that the ionic product is different from t he
solubility product, the system will seek to adjust itself in Sli :h
a manner that the ionic product attains the value of the S(,jubility product. Thus if the ionic product is arbitrarily mil' Ie
greater than the solubility product, for example by the addit, 'n
of a small quantity of another salt with a common ion, l' ,e
adjustment of the system results in the precipitation of ilie
solid salt. Conversely, if the ionic product is made smaller
than the solubility product as, for instance, by diminishing the
concentration of one of the ions (see Section I, 17), equilibrium
in the system is attained by some of the solid salt passing into
solution.
As an example of the formation of a precipitate, let us consider the case of silver chloride. The solubility product for
silver chloride is:
S~rcl =
[Ag+]
[01-] = 15
10-10
39
16]
TABLE
I, [tJ, 1
[KOl]
000670
000833
001114
001669
003349
[CZ-]
x lOS
64
79
105
155
303
175
139
107
074
039
Agel
x 1010
112
110
1'12
114
117
40
(I,
pot
TABLlIl
I, 16, 2.
EJTECT OF
N aOl (molea/lit,.e)
0933
1433
2272
3000
4170
5039
NaCI
AgCI
Ag (molea/litre) X 105
86
184
570
1194
3335
6039
16]
4:1
"2-
42
[I,
16]
43
44
[I,
16]
45
+ 20H- ~ [Zn(OH)4r- + 2H zO
(vi)
46
[I,
Ca++
18]
47
initial value in a saturated solution of calcium oxalate by combination with hydrogen ions to form first H0 2 0, - and subsequently H 20 20,. Equilibrium (i) will thus be disturbed; in
order to maintain the solubility product equilibrium more calcium oxalate will pass into solution to restore that removed
by reactions (ii) and (iij). If sufficient mineral acid is present,
the process will continue until the whole of the calcium oxalate
has dissolved.
When acetic acid is added, no reaction occurs. The ionisation constant of acetic acid,
[H+]
+ 2H+ ~ 2HOr04-
Or207 --
+ H 20,
and consequently the substance passes into solution. (All dichromates are soluble in water.) Acetic acid, on the other
hand, introduces only a very small hydrogen ion concentration
and therefore has little effect. For this reason, tIle barium
carbonate precipitate in Group IV is dissolved in dilute acetic
acid, not in hydrochloric acid, before the addition of potassium
chromate solution.
(i)
(ii)
48
[I,
(1'5 X 10-10)1
24 X 10-12
= 11
X 108
(iii)
Silver chromate will therefore not precipitate until its COncentration, or more correctly the chromate ion concentration,
is in excess of that given by this equation. It is evident thll t
if the initial solution contains chloride and 8- chromate in equ i
valent proportions, and one adds a solution of silver nitrate
dropwise, silver chloride will be precipitated until [Oro, --] is
in excess of the ratio given in equation (iii); henceforth silver
chromate will be precipitated with traces of silver chloride, the
equilibrium ratio in (iii) being maintained in the supernatant
liquid. In actual practice, the chloride ion concentration j,.;
usually approximately 01 molar, the silver nitrate solutio!!
about 01 molar and the chromate ion concentration aboll:
2 X 10-3 molar (2 ml. of 01 molar potassium chromate solutio,
per 100 ml. of solution). It is clear, therefore, that precipitv
tion of silver chloride is almost complete before reaction occur
between the excess of silver ions and chromate ions to give th,
red silver chromate.
The following detailed calculations may prove instructive.
Example 12. A solution contains 01 gram mole 01- and 000:'
gram mole Oro,-- per litre. Deci-molar silver nitrate solution i
added gradually to this solution. Calculate: (i) whether AgCI (.c
Ag 2CrO, will be precipitated first, (ii) the concentration of chlorid
ion in solution when the Ag 2CrO, begins to precipitate, and (iii) tho
fraction of the orginal chloride ion concentration remaining ill
solution when Ag 2CrO, commences to precipitate.
o
(i)
or
10-~
19]
49
(ill) The initial 01- oonoentration is 01 gram mole per litre, henoe
[01-] when Ag 2CrO, preoipitates is 43 X 10-6/0.1 = 43 X 10-5 =
00043 per cent of original chloride ion concentration.
Another example of some practical interest is the precipitation of a solution containing Sr++ ions and Ba++ ions by S04-ions. Which will be precipitated first1
The solubility products are given by:
[8r++] X [804--] = 28 X 10-7
(iv)
[Ba++] X [804--] = 92 X 10-11
(v)
These two expressions and also the relation:
[8r++]
28 X 10-7
3000
(vi)
[Ba++] = 92 X 10-11 = 1
must be satisfied for equilibrium between the two precipitates.
It follows therefore:
(a) if [Sr++] > 3000 [Ba++], and SO.-- is added, SrS04 will
be precipitated until [Sr++] = 3000 [Ba++];
(b) if [Sr++] < 3000 [Ba++] , and S04-- is added, BaS04
will be precipitated until [Sr++] = 3000 [Ba++].
Further addition of S04-- in either (a) or (b) will result in
the precipitation of a mixture of SrS04 and BaS04 in the ratio
of 3000 to I, the equilibrium ratio (vi) in the supernatant liquid
being maintained.
The student should carry out a similar calculation for SrS04
and CaS04 (solubility product = 23 X 10-4): this has an
important bearing upon the separation of Group IV metals
(see Sections III, 32, and VII, 15).
As previously pointed out, the values of many solubility
products are not known with any great accuracy: for this
reason considerable caution must be exercised in predicting
whether or not a given ion can be separated from one or more
ions on the basis of solubility product equations, particularly
when there is some doubt as to the exact magnitude of the
solubility products.
60
[II
2H+
and
H+
+ 01-
+ 201- ~ Fe012
(J' )
(iii!
(iv)
is disturbed.
20]
51
of the weak base, ammonia. The presence of a high concentration of ammonium ions reduces the hydroxyl ion concentration to so Iowa value that the solubility products of the above
hydroxides cannot be attained (compare Example 4 in Section
I, 14) and they consequently pass into solution.
Numerous examples are available to illustrate method (b),
but only two will be mentioned now as the subject is treated
fully in Section I, 20. Silver chloride is soluble in ammonia
solution, due to the formation oUhe complex ion [Ag(NHa)2]+;
this yields so small a silver ion concentration, particularly in
the presence of excess of ammonia solution, that the solubility
product of silver chloride is not attained. In a similar manner
silver cyanide dissolves in potassium cyanide solution, the
complex ion [Ag(CNbr being formed.
In method (c), the product of the reaction is either another
insoluble substance or a substance which can be removed from
the system by virtue of some such property as ease of decomposition or volatility. This procedure is exemplified when an
insoluble salt is heated with a large excess of a saturated
solution of sodium carbonate. Partial decomposition ensues
with the formation of the insoluble carbonate of the cation
and a solution containing the anion, together with the excess
of carbonate ions. Mter filtration, the residue may be dissolved in dilute hydrochloric acid, and a solution, containing
the cations, obtained. A specific example is the preparation
of a solution of barium sulphate; the initial aqueous extract
contains the sulphate ions, and the hydrochloric acid extract
the barium ions.
Process (d) may be illustrated by the dissolution of cupric
sulphide in nitric acid. The sulphide ion S-- is oxidised to
free sulphur So, the sulphide ion concentration is thereby
reduced below the solubility product of CuS and hence the
latter passes into solution.
I, 20. Complex Ions.-Reference was made in the previous
section to the increase of solubility produced by the formation
of complex ions. A complex ion is formed by the union of a
simple ion with either other ions of opposite charge or with
neutral molecules. Let us now examine a few examples in
some detail.
When potassium cyanide solution is added to a solution of
silver nitrate, a white precipitate of silver cyanide is formed
because the solubility product of silver cyanide.
52
[I,
[Ag+] X [CN-P = K
[{ Ag(CN)2} ]
(iii)
The constant has a value of 10 X 10-21 at the ordinary temperature. By inspection of this expression, and bearing in
mind that an excess of cyanide ions is present, it should i 'e
evident that the silver ion concentration Jllust be very sm;, II,
so small, in fact, that the solubility product of silver cyanide
is not exceeded.
The process of solution of the silver cyanide in the potasshl III
cyanide solution may be pictured as follows. Equations I i)
and (iii) control the silver ion concentrations in AgCN and 1 he
complex [Ag(CNhr respectively, the former being very mu,h
greater than the latter. The concentration of silver iOllS
derived from the saturated solution of AgCN is much great or
than that permitted by equilibrium (ii); acoordingly, the excc'ss
of silver ions combine with cyanide ions to form the complex
[Ag(CN)2r. This will result in the low-ering of the ionic
product of AgCN, and more of the latter will pass into solutiun
in order to supply the silver ions removed in the formation I)f
the slightly dissociated complex ion. This process will contin ue
either until all the AgCN has dissolved or until practically the
It is usual to employ square brackets to include the whole of a complex
ion. In order to avoid confusion with concentrations for which square
brackets are also widely used, concentrations will be expressed in heavy type
and complex ions either in lighter type or between braces.
20]
53
Ag+
Ag+ + cr ~ AgCI;
CI- + 2NHs ~ [Ag(NHs )2]+
solid
(or AgCI
+ CI-,
+ 2NHs ~ [Ag(NHs)2]CI)
Ag+
+ 2NHs
(iv)
{v)
= [Ag+] X [Cr]
(vi)
54
[I.
(or Fe(CN)2
+ 4KCN ~ K 4[Fe(CN)6])
20]
55
is passed into the solution CdS is precipitated (solubility product 14 X 10-28 ) but no copper sulphide (solubility products,
CU2S 2 X 10-47 , CuS 10 X 10-44 ) in spite of the fact that the
,...
56
[I,
+
I
HC-OH
I
UOO-
Tartrate ion
20H- -
2H20
Hb-O-
HC-O-
COO-
Hb-O\
HC-of Cil
COO-Complex CUpl'<
tartrate ion
These complex ions are very stable and yield such low COl
centrations of the simple metal ions that they often fail to
respond to the simple tests of qualitative analysis. It is for
this reason that involatile organic matter is destroyed before
proceeding with the systematic detection of the metals.
Complex ions are formed by Cu++, Cd++, Ni++, Co+++ an':
Zn++ with NHa molecules, e.g.
00+++ + 6NHa ~ [Co(NHs)6]+++
Zn++ + 4NHa ~ [Zn(NHs),]++
II
Many halide complex ions are known.
These include
[HgCI4r-, [SnClar-, [SbClar--, [FeF6r--, [AlF6
[AUC4r and [PtClar-. These, and many others of different
types, will be referred to in connexion with the reactions of
the metallic ions.
The stability of complex ions varies within very wide limitiIt is quantitatively expressed by means of the dissociation or
instability constant. The more stable the complex, the smaUer
is the instability constant. When the complex ion is very
stable, the common ionic reactions of the components are not
shown. A few seleoted values of these oonstants at the
ordina.ry temperature, determined by methods involving
r--,
20]
57
1,20, 1.
+ 2NHs
+ 2S I 0 3 - + 2CN+ 4CN+4NH a
+ 4NHs
+ 4CN-
+4C
+4Cr
+4C
6'8
10
10
50
46
25
14
5
60
50
40
10
22
1'3
14
33
26
2
x
X
x
x
X
x
x
X
x
X
x
x
x
x
X
x
X
x
10- 8
10- 18
10- 11
10- 1S
10-1&
10-7
10- 17
10-7
10- 17
10-11
10-n
10- 11
10-14
10-'
10-1
10-10-10
10- 17
viz.
+
+
38
rT,
Example 14. Calculate the silver ion concentration in 01 mohr[Ag(NHa)2]+ solution in which (a) excess of NHs is absent alld
(b) the NHs concentration is 3 molar.
(a) The dissociation of the complex ion is:
[Ag(NHs)2]+ ~ Ag+ + 2NHs
Let [Ag+] = x, and hence [NHa] = 2x. Since the dissociation of
the complex ion is small, we may assume [Ag(NHsh]+ = 01. By
substituting these values in the instability constant equation, we
have:
x X (2x)2/01 = 68 X 10-8
or
= {"68
X 10-9/4
= 19
21]
59
= [Ou+]2
[8--] = 20
10-47
CHEMICAL EQUATIONS
The two fundamental laws of chemistry, the law of definite
proportions and the law of conservation of mo,ss, find their
chief expression in practice in the form of chemical formulae
and balanced equations. It is therefore of greo.t importance
that the student should be familiar with the methods of writing
formulae and balancing equations. If the atomic weights are
known, the percentage composition of a compound can be
calculated from its chemical formula; the ratio of the weights
in which substances interact and the relative weights of the
products can likewise be computed from the chemical equation
representing the reaction. These quantities find considerable
application in the calculations of both qualitative and quantitative analysis.
60
[It
23]
61
62
[I,
CU20 into CUO or of FeO into Fe20a. Oxygen was the typical
oxidising agent. Now CuCI and FeCl 2 bear the same relatiun
to CuCl 2 and FeCl a respectively as do the corresponding oxides
to one another; it is customary, therefore, to regard the c()nversion of CuCI and FeCl2 into CuCl 2 and :FeCla respectiv, ,y
as oxidations, i.e. in oxidation the positive valency of an elemellt
or radical is increased.
It may be noted that combination with a non-metaL,,)
element other than oxygen resembles combination with oxyg('!\.
Thus carbon burns in fluorine more vigorously than in oxyge'
2F2 = CF4 , Iron burns in fluorine and, when heak:,
C
combines with chlorine and also with sulphur: 2Fe
3F2
2FeF a ; 2Fe
3Cl2 = 2FeCla ; Fe
S = FeS. Owing to tLn
similarity of these reactions to combinations with oxygen, thl'v
may clearly be regarded as a generalised sort of oxidation.
Reduction was formerly considered to be the process by whi('; I
oxygen was removed from a compound. Hydrogen Wit'
regarded as the typical reducing agent. The definition call
be logically extended to the process resulting in the decrea~('
of the positive valency of an element or radical. Thus tIw
conversion of Fe20a into FeO, of FeCl a into FeCI 2 , of CuCI"
into Cuel, are examples of reduction. It is evident that th,'
processes of oxidation and reduction are complementary:
whenever one substance is oxidised, another substance must
be correspondingly reduced.
Let us write the simple equation representing the oxidation
of ferrous chloride by chlorine in aqueous solution:
2FeC12 + C1 2 = 2FeC13 ,
23]
63
In the actual oxidation-reduction process electrons are transferred from the reducing agent to the oxidising agent.
The following are more satisfactory definitions:
Oxidation is the increase in the positive valency of an element
or radical either by the addition of oxygen, or by the addition
of chlorine or some other atom or radical which can constitute
acid radicals or anions (electronegative radicals). Qualitative
analysis is largely concerned with reactions in solution. The
above definition may therefore be extended to ionic reactions
and expressed in the form: oxidation is the process which results
in the loss of one or more electrons by atoms or ions. An oxidisin~ a~ent is one that gains electrons and is reduced to a
lower valency condition. This electronic definition of oxidation will apply, of course, to electrovalent compounds in the
solid state. Thus sodium is oxidised when it burns in chlorine
to form sodium chloride:
2Na
+ C12 _
2Na+C1-
'"
64
[I,
+1
+1 (H) .
The only exceptions are the hydrides of very electropositive metals, slloh
as those of lithium and sodium: the oxidation number of the metal is t 1
+1 -1
24]
65
normally -2 (0).*
(4) The oxidation number of a metal in combination is
usually positive. t
(5) The oxidation number of a radical or an ion is that of
its electrovalency with the correct sign attached, i.e. is equal
to its electrical charge.
(6) The oxidation number of a compound is always zero,
and is determined by the sum of the oxidation numbers of the
individual atoms each multiplied by the number of atoms of
the element in one molecule.
Let us consider a few simple applications of these rules.
(i) Oxidation number of Ou in OuO. To convert Cuo into
CuO, the copper undergoes two units of oxidation, hence the
oxidation number of the copper is +2. Alternatively, by
+2-2
+2-2
oxygen is -1, e.g. HID. and NaIO I ; oxygen difluoride, in which the oxygen
is combined with the only more electronegative element,
t Exceptions are to
><3+
+2-2
fluo~OF .
-4+4
66
[I,
+2+6-8
+ 7i'O+ ~;or'by ;;
units of reduction.
The reductant FeSO, is oxidised to Fe2(SO,)a:
+2 -2
+6-6
O.N.
24]
67
+ KI + H z80,
=
Cr 2 (SO,ls
+ K s80 4 + 12 + H 20
(ineomplete)
+6-6
Cr z(80,)s
The change in O.N. of two atoms of chromium is from +12 to +6,
or by 6 units of reduction.
The reductant KI is oxidised to 12 :
K 2Cr l 0 7
+1-1
KI - I I
Crz(SO,la
+ 4K 280, + 31a + xH 20
+H
S = FeCl s
+ 8 + HCI (incomplete)
+2-2
FeCl a ~ FeCl s
H28~
+ HIS
= 2FeCl 2
+ 2HCI + 8
+ HCI
KCl
+ MnCl 2 + CIs + H 20
KMnO,
+2-2
~ MnCI"
(incomplete)
68
[I,
+ (10 + xl HCI =
2KCI
(a)
(b)
10.-
25]
69
-+
NO (incomplete)
70
[I,
+ 4H+ -
NO a-
NO
+ 2H 0
2
4H+
+ 3e
NO
2H 2 0
-+
So
+ Cd++,
So
+ Cd++ + 2e,
+ 4H+ + 3e =
3(CdS
3CdS
or
NO + 2H 2 0)
So + Cd++ + 2e)
+ 3S + 2NO + 4H 0 + 6(.
+ 3S + 2NO + 4H 0
2
2
-+
Mn++
+ 8H+ -
MnO, -
Mn++
+ iliaO;
+ 8H+ + 5e
Mn++
4HaO
-+
Fe+++
To balance this electrically one must add one electron to the righthand side (or subtract one electron from the left-hand side):
Fe++
Fe+++
+e
Now the gain and loss of electrons must be equal. One permaIlganate ion uses 5 electrons, and one ferrous ion liberates I electron;
hence the two partial reactions take place in the ratio of I : 5.
MnO,or
MoO, -
+ 8H+ + 5e
5(Fe++
+ 8H+ + 5Fe++ =
Mn++ + 4H zO
Fe+++ + e)
Mn++
5Fe+++
4H 2 0
Cr.0 7 - - -+ Cr+++;
+ 14H+ -+ 2Cr+++
7H30
pota~
25]
71
+ 14H+ + 6e
2Cr+++
+ 7HaO
r
2r
2r
-+ II;
-+
II;
II + 2e
One dichromate ion uses 6e, and two iodide ions liberate 2e; hence
the two partial reactions take place in the ratio of 1 : 3.
+ 14H+ + 6e .= 2Cr+++ + 7H sO
3(2r .= Is + 2e)
+ 14H+ + 6r = 2Cr+++ + 7HaO + 3Ia
Crlo,-or
Cr a0 7 - -
Fe++;
Fe++
So;
SO + 2H+;
So + 2H + + 2e
Thus one ferric ion liberates I electron, and one molecule of hydrogen
sulphide uses 2 electrons. The partial reactions will therefore take
place in the ratio of 2 : 1.
2(Fe+++ + e ~ Fe++)
HaS
So
--------------------~-----
2Fe+++
+ HIS =
+ 2H+ + 2e
+ S + 2H+
2Fe++
One permanganate ion utilises 5e, and two chloride ions liberate 2e,
hence the two partial reactions take place in the ratio of:.! : 5.
+ SR+ + 5e .= Mn H + 4R zO)
5(2CI- ~ CI + 2e)
+ 16R+ + lOCI = 2Mn++ + 5CI, + SHzO
2(MnO,-
2Mn0 4 -
72
[I,
In neutral or alkaline solution, the manganese in the permanganate is generally reduced to MnO z, i.e. by 3 units of
~
26]
73
(formic acid)
74
[I,
+ H 20 + 2H+ = 2Fe+++ + 2H 20
2
REDUCING AGENTS
6r +
lOr
2r ~ 12 +
2r
2Fe+++ = 12
Cr2 0 7-14H+ = 312
2MnO,16H+ = 512
+
+
+
2e
+ 2Fe++
U
+ 2Cr+++ + 7H20
+ 2Mn++ + 8H 20
26J
1,26,
75
Radical or O.N.of
element "effective"
involved
element
Substance
KMnO, (acid)
KMnO,
(alkaline)
K.Cr.O,
HNO. (dil.)
HNO. (cone.)
CI.
Hr,
I.
3HCI: IHNO.
H 2O.
Na.O,
KCIO,
KBrO.
KIO.
NaOCI
MnO.MnO.-
+7
+7
Cr.O,-NO.NO.CI
Br
I
Cl
0
0
ClO.BrO.10 3-
+6
+5
+5
0
0
0
0
0
0
+5
+5
+5
+1
ocr
Reduetion
pTOduet
New
O.N.
Mn++
MuO. (or
Mn++++)
Cr+++
NO
NO.
cr
Br-
cr
0-0-CIBt-
Gain in
eleetrona
5
3
5
3
+3
+2
+4
-1
-1
-1
-1
-2
-2
-1
3
3
3
3
1
1
1
1
1
2
2
6
6
6
2
-1
I -1
CI-
I Decrea8e
inO.N.
+2
+4
-1
------
1
1
1
1
2
2
6
6
6
2
Substance
Radical or O.N. of
element " effective"
invoh'ed
element
H.SO. or
Na.SO.
H.S
HI
SnCI.
Metals, e.g. Zn
Hydrogen
FeSO, (or any
ferrous salt) I
Na.AsO.
H,C,O,
SO 3 -
S-
Sn++
Zn
H
Fe++
+4
SO.--
-2
-1
+2
0
So
AsO,---
New
O.N.
Increa86i
Loss in
in O.N . . electrona
+6
+2
Sn++++
Zn++
H+
Fe+++
0
0
+4
+2
+1
+3
'2
1
2
2
1
1
+3
+3
AsO.--CO.
+5
+4
2
1
I C.O.---
Oxida
tion
product
ro
2
2
1
2
2
1
1
2
+
+
Sn++
2Hg012 = Sn++++
Sn++
Hg2C1 2 = Sn++++
Sn++
01 2 = Sn++++
Sn++
2Fe+++ = Sn++++
76
[I,
27)
17
* Throughout this volume the terms equivalent weight and molecular weight
will be used synonymously with gram equivalent weight and gram molecular
w"}ght respectively.
78
[1,
- -
27]
79
+6-6
2(Fe804) -+ Fe2(S04)S
80
Qualitative Inorganic
An~lY8i8
[I,
TABLE I, 27, 1.
IONIO EQUATIONS FOR USE IN THE CALOULATION OF
THE EQUIVALENT WEIGHTS OF OXIDISING AND REDUOING AGENTS
Sub8tance
OXIDANTS
Potassium permanganate
(acid)
Potassium permanganate
(neutral)
Potassium dichromate
Ceric sulphate
Chlorine
Ferric chloride
Potassium iodate
Sodium hypochlorite
lIydrogenperoxide
Manganese dioxide
Sodium bismuthate
Nitric acid (conc.)
Nitric acid (dil.)
7-
REDUCTANTS
lIydrogen
Zinc
Hydrogen sulphide
Hydrogen iodide
Oxalic acid
Ferrous sulphate
Sulphurous acid
Stannous chloride
Stannous chloride (in pre.
Bence of hydrochloric
acid)
lIydrogen peroxide
Sodium thiosulphate
H.
Zn
H.S
2HI
C.O,Fe++
H.SO.
Sn++
+ H.O
26
2e
26
26
26
e
26
26
- 26
- 2e
- 26
~2H+
~Zn++
~ 2H+
+S
+ 2H+
~I.
~ 2CO.
~Fe+++
+ 4H+
~
~
SO,Sn++++
SnCl.2H+ + 0.
S,O.-
~
~
27)
81
82
1,28.
[I,
NaG/
Fig. I, 28, 1
obtain direct proof of the transfer of electrons in the oxidationreduction reaction under suitable experimental conditions.
This is clearly shown by the following experiment (Fig. I, 28, 1).
Solutions of stannous chloride and of ferric chloride, each
acidified with dilute hydrochloric acid to increase the cond>Jctivity, are placed in separate beakers A and B, and the
two solutions are connected by means of a "salt bridge" containing sodium chloride. The latter consists of an inverted
U-tube filled with a solution of a conducting electrolyte, such
as sodium chloride, and stoppered at each end with a plug of
... It follows from Faraday's law that each gram equivalent weight of an ion
is associated with a charge of one Faraday of electricity. A change of charge
of one thus corresponds to the gain or loss of one Faraday per formula weight
of the 8ubstance.
29]
83
84
All
na .
YSM
[I,
29]
85
00577
00591
86
[I
-=----:::_---=---=
29]
87
has an e.m.f. of 076 volt. The two reactions which take place
are:
Zn ~ Zn++ + 2e, and H2 -- 2e ~ 2H+
The zinc pole is negative and therefore the zinc electrode is
076 volt more negative than the hydrogen electrode, or the
potential of the molar zinc electrode is -0,76 volt (the molar
hydrogen electrode is arbitrarily taken as equal to zero).
Further, if one employs a copper electrode immersed in a molar
solution of cupric ions, and couples this with a molar hydrogen
electrode, the cell has an e.m.f. of 034 volt~ The copper pole
is now positive; the potential of the molar copper electrode is
accordingly +0'34 volt.
The standard or molar electrode potential of an element may
therefore be defined as the e.m.f. produced when a half cell
consisting of the element immersed in a molar solution of its
ions (more correctly in a solution of its ions possessing unit
activity) is coupled with a molar hydrogen electrode, the
potential of which is assumed equal to zero. Tabl@ I, 29, I
gives a list of standard electrode potentials at 25 0 0; the sign
of the potential here adopted is that of the charge on the
electrode.
TABLE
I, 29, 1.
LijLi+
KjK+
NaJNa+
BajBa++
Sr/Sr++
Ca/Ca++
Ce/Ce+++
MgjMg++
ThjTh++++
BejBe++
V/V+++
AljAl+++
MnjMn++
ZnjZn++
-3,045
-2925
-2714
-290
-289
-287
-248
-237
-190
-185
-180
-166
-118
-0763
I
I
CrjCr+++
Fe/Fe++
Cd/Cd++
Co/Co++
Ni/Ni++
SnjSn++
Pb/Pb++
Pt, (H 2)/H+
Cu/Cu++
2HgjHg2++
AgjAg+
PdjPd++
AujAu+++
250
-074
-0440
-0403
-0277
-0250
-0136
-0126
0000
+0337
+0789
+0799
+0'99
+1'5
..
88
[I,
RT
p
nF log. p
= RT
-n F
log' p
RT
- - log P
nF
e
!~ loge P
is a constant ff'
RT
E+ = nF log. p
+ constant
The gas laws may be written in the form p = RTc where '
is the concentration of the positive ions in the solution. Mor'
accurately, the expression should be p = RTa+ where a+ is th.
activity of the ions.
Thus
RT
E+ = -F
n log.
G+
+ constant (Eo)
(i)
n
Before the introduction of the activity concept, the concentration of the ions c!+ (in moles per litre) was used in place of the
activity:
00591
E+ = - - . log Ct+ + Eo
"
30]
89
= - 076
EOll = Eo
=
At equilibrium
E zn = Eeo
- 076 00295 log [Zn++] =
034 00295 log [Ou++],
[Zn++]
110
or
log [Cu++] = ().0295 = 3'73,
[Zn++] = () + 1037
[Cu++]
w
The equilibrium constant is given by:
[Zn++] X [CUO] = K
[ZnO] X [Cu++]
Now [Cu O] and [ZnO] refer to the solid metallic condition and can
therefore be regarded as constant quantities. The equation thus
reduces to:
[Zn++]
,
[Cu++] = K
or
90
[I,
I, 31. Concentration cells.-The electrode potential varif.with the concentration of the ions in solution. Hence b\
bringing two electrodes of the same metal but immersed i:;
solutions containing different concentrations of the ions of th.
metal into contact, a cell may be formed. Such a cell is terme,
a concentration cell. The e.m.f. of the cell will be the algebrai
difference of the two electrode potentials. It may be calculate"
as follows. At 25 0 :
00591
E = - - log
n
= 00591
-n-
Cl
+ Eo -
00591
- - log
Ct
log -, where
Cs
Cl
Cs -
> Cs
Eo,
Ag+ = O'043M
I Ag
El
II CuSO, aq. I Cu
33]
91
The chemical
Zn
Zn++
+ 2e,
+ 2e ~ CU
The net chemical reaction is:
Zn + Cu++ = Zn++ + Cu
The potential difference at each electrode may be calculated
by means of equation (i'), and the e.m.f. of the cell is the
algebraic difference of the two potentials, the correct sign being
applied to each.
As an example, we may calculate the e.m.f. of the Daniell cell
with molar concentrations of zinc ions and cupric ions.
E = Bo(ou) - EO(Znl = + 0344 - ( - 0762) = 1106 volts
The small potential difference produced at the contact between the
two solutions (the so-called liquid-junction potential) is neglected.
I, 33. Oxidation-reduction cells.-Redustion is accompanied
by a gain of electrons and oxidation by a loss of electrons. In
a system containing both an oxidising agent and its reduction
product, there will be an equilibrium between them and
electrons. If an inert electrode, such as platinum, is placed in
a redox system, for example one containing ferric and ferrous
ions, it will assume a definite potential indicative of the position
of equilibrium. If the oxidation tendency predominates, the
system will take .electrons from the platinum leaving the latter
positively charged; if, however, the system has reducing properties, electrons will be given up to the metal, which will then
acquire a negative charge. The magnitude of the potential
will thus be a measure of the oxidising or reducing power of
the system.
To obtain comparative values of the" strengths" of oxidising
agents it is necessary, as in the case of the electrode potentials
of the metals, to measure under standard experimental conditions the potential difference between the platinum and the
solution relative to a standard of reference. The primary
standard is the molar or normal or standard hydrogen electrode,
and its potential is taken as zero. The standard experimental
conditions for the redox system are those in which the ra.tio
of the concentrations of the oxidant to the reductant is unity.
_.
[I,
92
I~:::+ II I
H+ H 2(Pt) \
I, 33, 1.
Electrode
Co'+,Oo=+/Pt
Pb'+,Pb'+/Pt
MnO,-,MnO./Pt
MnO,-,Mn3+/Pt
Ce'+,Ce3+/Pt
BrO.-,Br./Pt
Cl.,2cr/Pt
Cr.0 7 i1-,2Cr3+/Pt
IO,-,I./Pt
Br.,2Br-/Pt
FeS+,FeH/Pt
HaAsO"HaAsO./Pt
1.,2r/pt
[Fe(CN)s]3-,
[Fe(CN).]'-fPt
CuI+,Cu/Pt
Sn'+,SnH/Pt
H+,H./Pt
Ti'+,TiS+/Pt
Cr3+,Cr2+IPt
SO,SO-/Pt
Znl+,Zn
I 003+
Electrode reaction
Pb'+
MnO,- + 4H+
MnO,- + 8H+
Ce'+
2BrOa- + 12H+
Cl,
Cr.0 7 i1- + 14H+
210,- + 12H+
Br.
FeH
HaAsO. + 2H+
II
e .= OoH
+
+ 2e .= Pb H
+ 36 .= MnO. + 2H.O
+ 56 <"Mn2+ + 4H.O
e .= Cel+
+
+ 10e .= Br. + 6H.O
+ 2e.= 2cr
+ 6e? 2Cr8+ + 7H.0
+ 10e .= I. + 6H.0
+ 2e.= 2Br6.= Fe H
+
+ 2e .= H aAs0 3 + H 2 O
+ 26.= 2r
Fe(CN).3Cul+
Sn H
2H+
TiH
Cr3+
So
Znl+
+
+
+
+
+
+
+
+
6 .= Fe(CN).'2e .= Cu
26 ?Sn H
26.= H t
e .= TiS+
e .= Cr'-t2e? SiI26 ?Zn
250
EO
+184
+175
+1-59
+151
+1-45
+1-45
+136
+1-36
+1-20
+107
+0'77
+056
+0'53
+0'36
+0'35
+015
000
-004
-041
-048
-076
I
34]
93
Oxidant
'----v----'
+ ne
'-----v--'
Red
Ox
E p-- EO
+ RT Iog.aoz.
-
nF
(i)
aR,d.
E p-- EO
+ RT
- o1 g .oz-.
C
nF
(i/)
CRedo
= EO
E
25'
+ O059! I
n
[Ox.]
og [Red.]
(i' )
94
[I,
00591
+ -1-
[Fe+++]
log [Fe++] ;
01
+ 075 + 0118 =
087 volt
Now
35]
95
+ qB + rC ...... + ne ~ sX + tY + uZ + ..... .
+ RT
_ Ioge.a'
n!!..
A' ~".
nF
acr
ax. ay.az
I"
......
00591 1 c~ .eI!_._:ccc__._._._._
+-og.
n
cA.CY,C
I
..
+ 00591
I [Mn0
X [H+]
5
og
[~In++]
4- ]
* ( t 250C)
a.
E = EO
+ 0.0591
[Mn04- ] + 0.0591 1 [H+] 8
5 1og [Mn++]
5
og
96
[I,
+ 2H+ + 2e ~ HsAsOs + H
HsAs04
or
2 0,
E = EO
+ 00591 I
E = EO
+ 00591 I
+ 00591 I
og
[HsAs 04]
og [HsAsOs]
og
[H+]2
MnO,-
Fe++
and
Fe+++
(i)
+e
(ii)
E = EO
+ 0059 I
1.51
og
+ 0059 I
5
[&0,-] X [H+]8
[Mn++]
og
[MnO,-] X [H+]8
[Mn++]
0059
= EO + -5=
077
[Fe+++]5
log [Fe++]Ii'
0059
+ -5- log
[Fe+++]5
l'Fe++15
36]
97
Combining the two electrodes into a cell, the e.m.f. will be zero when
equilibrium is attained:
1.51
J.e.
+ 0059
I [l\In0 4-] X [H+r
5
og
[Mn++]
_.
- 0 77
0059
+ ~5-
[Fe+++]5
log [Fe++]6
5(1,51 - 077)
[Mn++] X [Fe+++]6
log [MnO" ] X [Fe++]5 X [H+]8 =
0.059
= 627
or
[Mn++] X [Fe+++]6
62
K = [MnO" ] X [Fe++]5 X [H+]8 = 85 X 10
This result clearly indicates that the reaction proceeds to completion.
1,36. The Ionic Product of Water.-Kohlrausch and Heidweiller (1894) found that the most highly purified water that
can be obtained possesses a small but definite electrical conductivity. Water must therefore be slightly ionised in accordance with the equation:
HzO ?H+ + OH- *
Applying the law of mass action to this equation, one obtains,
for any fixed temperature:
ag+ X tJOH[H+] . [OH-]
fH+ foHta t
=
[H 0]
X -1-- = a cons D,
~20
Z
.
H20
where aX) [xl, and f. refer to the activity, <lOncentration and
activity coefficient respectively of the species x. Since water
is only slightly ionised, the ionic concentrations will be small
and their activity coefficients may be regarded as unity; the
activity coefficient of the unionised molecules may also be
taken as unity. The expression thus becomes:
[H +] X [OH-]
&
constant
[HzO]
+ OH-
H.O
+ nlo
? H.O+
Acldl
Bue2
Acid2
+ OHBasel
For the sake of simplicity, the more familiar symbol H+ will be retained,
particularly as in the subsequent discussion the term pH and not p{H.O) ia
employed.
4'4-
98
[,
[O~-]'
and [OR-] =
[~:l
37]
99
I, 36, 1.
IONIC PRODUCT OF
W A'l'ER
AT VARIOUS TEMPERATURES
Temp. (0)
K .. X 10-14
Temp. (0)
Ko. X 10-14
0
5
10
15
20
25
30
012
019
029
045
068
101
147
35
40
45
50
55
60
209
292
402
548
730
962
-lOglO [H+]
lO-
100
[I,
solution is one in which the hydrogen ion and hydroxyl ion
concentrations are equal. In an acid solution the hydrogen
ion concentration exceeds the hydroxyl ion concentration,
whilst in an alkaline or basic solution the hydroxyl ion ('oncentration is the greater.
Example8.-(i) Find the pH of a solution of which [H +]
10-6
Log 40 = 0602, hence log 40 X 10-5 is
40 X
11
5602 = 0602 - 5 = - 4398
(the decimal part or mantissa of the logarithm is always positiyo).
pH = - log [H+] = - ( - 4398)
4398
(ii) Find the hydrogen ion concentration corresponding to
pH = 5643.
pH = -log [H+] = 5643; .'. log [H+] = - 5643
This must be written in the usual form containing a negative charac
teristic and a positive mantissa:
log [H+] = - 5643 = 6357
Referring to a table of antilogarithms, the number corresponding
to the logarithm 0357 is 228; the number corresponding to the
logarithm 6357 is accordingly 228 X 10-6
[H+] is therefore 228 X 10- 6
(iii) Calculate the pH of a 001 molar solution of acetic acid I t he
degree of dissociation is 125 per cent).
The hydrogen ion concentration is 0125 X 001 -= 125 XIII 3.
Now log 125 = 0097;
:. pH = - ( - 3
+ 0097) =
2903
ill
= Kw =
10-14 ,
in the form:
log [H+]
This relationship should hold for all dilute solutions at ab. ,'It
25,
101
38]
1()4
165 10
10
10
lOB 10 16
12
10"10
13
10
14
10
14
13
12
11
10
[ow] 1014 10-13 1012 10" 1010 10 9 las 107 106 lc;& 104 163 102 101 1(10)
_ _ _t _ _
Acid
Alkaline
Neutral
Fig. I, 37, 1
-log K. = log
I of concentration [I]:
1
pI = -log [I] = log [1]
Thus for
[Na+] = 8 X 10-5 , pNa = 41
(iii) For a salt with solubility product S:
1
pS = -log S = log S
I, 38. Determination of the Hydrogen Ion Concentration.
-The hydrogen ion concentration of a solution is of great
importance both in pure and in applied chemistry. Two
methods are commonly employed for its estimation, (a) the
colorimetric method and (b) the electrometric method.
The Colorimetric Method. In this method one employs
what are known as indicators. An indicator is a Bubstance
102
[I,
which varies in colour according to the hydrogen ion con<' 'ntration. It is generally a weak organic acid or base all< I is
employed in very dilute solution. The change in colou! is
usually due either to the production of different tautoill' ic
forms of the original substance or to the formation of coloTI "d
ions; the formation of these takes place over a small I iIt
definite pH range. The hydrogen ion concentrations at wI; h
different indicators exhibit their colour change have b 'n
determined by direct electrometric methods; the pH ra ~e
over which the indicator is applicable is thus known. Ta le
I, 38, 1 summarises the pH values of a number of the ill' ~e
common indicators.
There are two methods for the determination of the pH (.: a
solution calorimetrically.
A. Buffer Solution Method. The approximate pH of : e
solution must be found first with the aid of a multiple-raj :fe
indicator solution (for example, the B.D.H. "universal" indi, l,tor*), by the systematic use of a number of indicators, or "y
the use of indicator test papers.t A "wide range" or "U.ilversal" test paper, covering pH 1-2 to 10, is marketed, as ",n
as anum ber of "narrow range" indicator test papers wh i 11
cover most of the pH range in steps of 1,5-2 pH units. Colo, 1matching charts are supplied by the manufacturers to show ti Ie
change in colour at 03 pH intervals. The test papers are b(,,,t
used, and their accuracy is greatest, by dipping the papers irl i <)
the fluid: if the test solution is "spotted" on the indicator paper
the colour shade of the spot produced may vary from tllC
centre outwards and some difficulty may be experienced in
deciding which shade to consider as showing the actual pH.
The test papers tend to deteriorate with storage. For tl,o
average observer, it is doubtful whether the test papers pern :'.
the determination of pH closer than to 0,5-1 pH unit, but tI, .
suffices for many purposes.
A series of buffer solutions (Sections I, 39 and A, 4) is selecte\,
differing successively in pH by about 02, covering the p t !
38J
103
I, 38, 1.
Ohemical
IColour in
f'I41'M
methyl diphenazonium
chloride
IX-Naphtholbenzein (acid)
Methyl violet Pentamethyl p-rosanilin"
hydrochloride
Cresol red
o-Cresolsulphone(acid)
phthalein
'rhymol blue
Thymol-suIphone(acid)
phthalein
Meta oresol
m-Cresolsulphonepurple
phthalein
Bromo-phenol Tetrabromophenolblue
sulphone phthalein
Methyl orange Dimethylamino-azobenzene-sodium
sulphonate
Congo red
Diphenyl-bis-azo-IXnaphthylamine-4sulphonic acid
Bromo-oresol
Tetrabromo-m-cresolsulphone-phthalein
green
Methyl red
o-Carboxybenzene-azodimethylaniline
Chloro-phenol Dichlorophenolred
sulphone-phthalein
Azolitmin
(litmUB)
Bromo-thymol Dibromo-thymolblue
sulphone-phthalein
Diphenol
o-Hydroxy-diphenylpurple
sulphone-phthalein
Cresol red
o-Cresol-sulphone(base)
phthalein
IX-Naphtholex-Naphthol-phthalein
phthalein
Thymol blue
Thymol-sulphone(base)
phthalein
IX-Naphtholbenzein (base)
PhenolPhenol-phthalein
phthalein
ThymolThymol-phthalein
phthalein
BrillilLD.t cresyl (See above)
blue (baBe)
L
pH
180~;!n
II'
RANGE OF SOME
Colour in
alkaline
8olution
pH
range
Redorange
Blue
O-()-l-Q
Colourless
Yellow
Yellow
01)-08
0-0..-1-8
Red
Bluegreen
Yellow
Red
Yellow
12-28
Red
Yellow
]-2-2'8
Yellow
Blue
Red
Yellow
31-44
Violet
Red
3()-50
Yellow
Blue
38-5-4
Red
Yellow
42-63
Yellow
Red
48-6'4
Red
Blue
5'()-8'0
Yellow
Blue
6()-76
Yellow
Violet
7()-86
Yellow
Red
72-88
Yellow
Blue
73-87
Yellow
Blue
8()-96
Yellow
BIuegreen
Red
82-100
Blue
9'3-10'5
Colourless
Colourloss
Blue
Yellow
1-2-2'8
83-100
108-120
104
[I,
-=
,~
38]
105
are fitted into a disc, and the latter is inserted into a comparator,
which is furnished with four compartments to receive small
test-tubes or rectangular glass cells, and is also provided with
an opal glass screen. The disc can revolve in the comparator,
and each colour standard passes in turn in front of an aperture
through which the solution in the cell (or cells) can be observed.
As the disc revolves, the pH value of the colour standard
visible in the aperture appears in a special recess. The Lovibond comparator* is shown in Fig. I, 38, 2: this may be used
with 135 mm. test-tubes or 135 mm. rectangular cells. The
comparator is employed with B.D.H. indicators. The colour
discs available include cresol red (acid and base range) thymol
blue (acid and base range), bromophenol blue, bromocresol
y,l!lltIm.Il1'dtJ'IJttll'io.'JH'" 1tti'IIlt.'1llJdf"UII.
~UIfIIJ' l];i'ftt,lJt}
I1.llrl/l1
H~
IItU1i1rllIHIl'
Fig. 1, 38, 2
blue, bromocresol green, methyl red, chlorophenol red, bromocresol purple, bromothymol blue, phenol red, diphenol purple,
cresol red, thymol blue and the B.D.H. "universal" indicator
-the pH ranges for these indicators are given in Table I, 38, 1.
A determination of the approximate pH of the solution is
first made with a "universal" or "wide range" indicator or
with indicator test papers (see under A), and then a suitable
disc is selected. Ten m}. of the unknown solution is placed
in the glass test-tube or cell, the appropriate quantity of
indicator (usually 0'5 m!.) is added, and the colour is matched
against the glass disc. Provision is made in the apparatus for
Manufactured by 'The Tintometer Ltd., Milford, Salisbury, England. A
similar apparatus is marketed by Hellige, Inc., of Long Island City 1, N.Y.,
U.S.A.: this utilises Merck's (U.S.A.) indicators. The glass discs in the two
instruments are not interchangeable.
-4*
I
I
106
[I,
n
C2
It a hydrogen electrode (Section I, 29) is immersed in til(~
solution the pH of which is to be measured, and this half c(11
coupled with a molar (or normal) hydrogen electrode by mea!
of a potassium chloride solution bridge in order to eliminat
liquid junction potential, the e.m.f. of the resulting cell:
Pt I H 2 , H+
a=1
II H 2 , H+ I Pt,
a=x
may be measured.
Here
00591
1
0
E = - 1 - log [H+] (at ca. 25 )
:. pH
=00591 pH
EjO0591
obI,
-E
. .I. (Ial.)
00591
38]
107
+ 2H+ + 2e ~ C(lH,(OH)z
108
fl,
E =EO +RT I
2F oge
aQ.~+
n_
-.tl2Q
a
RT
--EO + RT
2Flog. - +y log.~+,
Cht
Q
2Q
= 0699
+ 00591 log ~+
39]
109
To carry out the determination of the hydrogen ion concentration of a solution, about 1 gram of quinhydrone per
100 ml. of the solution is added, and the solution stirred. A
bright platinum electrode is immersed in the solution and the
quinhydrone electrode combined in a cell with a saturated
calomel electrode; a saturated solution of potassiulll chloride
m.1y be used as the salt bridge. The e.m.f. of the cell is
determined and the pH calculated. The e.m.f. is measured by
the potentiometer method based upon the Poggendorff compensation principle; details of this will be found in text-books
of physical chemistry*. It must be pointed out that the quinhydrone electrode cannot be employed in alkaline solutions
in which the pH is greater than 8, for the ra,tio of quinone to
hydro quinone is no longer unity"!".
Determinations of pH can be rapidly made with the aid of a
glass electrode and a pH meter: a description of these is outside
the scope of this volume. *
I, 39. Buffer Solutions.-A solution of OOOOIM hydrochloric
acid should give a pH equal to 4, but the solution is extremely
sensitive to traces of alkali from the glass of the containing
vessel and to ammonia from the air. Likewise a O'OOOIM
solution of sodium hydroxide, which should have a pH of 10,
is sensitive to traces of carbon dioxide from the atmosphere.
Aqueous solutions of potassiulll chloride and of ammonium
acetate have a pH of about 7. The addition of I mI. of molar
hydrochloric acid to 1 litre of the solution results in a change
of pH to 3 in the former case and in very little change in the
latter. The resistance of a solution to changes in hydrogen
ion concentration upon the addition of acid or alkali is termed
buffer action; a solution which possesses such properties is
known as a buffer solution. It is said to possess "reserve
acidity" and "reserve alkalinity. " Solutions of which the pH
values (determined by reference to the hydrogen electrode) are
known, which can be readily prepared and which are unaffected
by small additions of alkali or acid, are required for the colorimetric determination of hydrogen ion concentration and for
other purposes.
Buffer mixtures usually consist of solutions containing a
mixture of a weak acid or base and its salt. In order to
A detailed account is also given in the author's Terxt Book of Quantitative
buwganic AnalY8ia: Theory and Practice, Second Edition, 1951 (Longmans,
Green & Co. Ltd.).
t This is partly due to the facile oxidation of hydroquinono in alkaline
solution and partly to the ionisation of hydro quinone as a weak dibasic acid.
The effect of the latter is reduoed in buffered solutions.
<II
110
(I,
= K., or
ag+
= 1ZnA~'.
- X K. :t'. ' .
aA- " ' "
Il)
[A-] X K.
(ii)
[H+] - [Acid]
K
- [Salt] X
or
or pH = pKa
[Salt]
+ log [Acid]
(iv)
(v)
[ts:::l
p OH = p K b
X Kb
[Salt]
+ Iog [Base]
(vi
(vu I,
39]
HI
[I,
112
I, 39, 1.
pH
pH
10
20
30
40
500
60
70
800
90
372
405
427
445
463
480
499
523
557
90
80
70
60
50
40
30
20
100
-I
l
i
aru.
aA -
K = ----:rcJ. X K
(viii)
C"'A-
39]
113
or
[HCOOH]
[HCOO-]
00296
01480
02960
01776
00987
00100
00500
01000
00600
00300
[NaCl]
00400
00667
pH
0'01l
0050
0100
0100
0100
2'18
210
203
203
203
For- a more detailed discussion, see the author's Text Boole of Quantitative
Inorganic Analysis: Theory and Practice, Second Edition. 195]; R. P. Bell.
Acid8 and Basu. 1952 (Methuen).
"
114
rr,
1,40.
HYDROLYSIS OF SALTS
Salts may be divided into four main groups:
I, those derived from the strong acids and strong bases, e,g.
potassium chloride;
.
40]
ll5
II, those derived from weak acids and strong bases, e.g.
sodium acetate;
III, those derived from strong acids and weak bases, e.g.
ammonium chloride; and
IV, those derived from weak acids and weak buses, e.g.
ammonium formate or aluminium acetate.
When any of these is dissolved in water, the solution, as is
well known, is not always neutral in reaction. Interaction
occurs with the ions of water and the resultant solution may
be neutral, acid or alkaline according to the nature of the salt.
With an aqueous solution of a salt of group I, neither the
anions have any tendency to combine with hydrogen ions nor
the cations with the hydroxyl ions of water. The equilibrium
between the hydrogen and hydroxyl ions in water:
H 20
H+
+ OH-
(i)
~Mt
+A-
[I,
116
+ H 20
RNHs.OH
RNHs+
+ OH-
+ OH- ~ B + H 20
(= BR.OH)
(iv)
41]
117
BH+
+ H 20
+ H30+
(v)
+H
20
EH.OH
+ H+
For salts of group IV in which both the acid and the base
are weak, two reactions will occur simultaneously:
A-
+ H 20
HA
+ OH-
(vi)
(vii)
BH+ + H 2 0 ~B + HaO+
The acidic or basic reaction of the solution will clearly depend
upon the relative strengths or dissociation constants of the
acid and base. If they are equal in strength, the solution will
be neutral; if Ka> K b , it will be acidic; and if Ku > K a, it
will be basic or alkaline.
Having considered the possible cases, we are now in a
position to give a more general definition of hydrolysis.
Hydrolysis is the interaction between the ion (or ions) of a.
salt and the ions of water with the production of (a) a weak
acid or a weak base or (b) of both a weak acid and a weak base.
or by
+ A- + H 2 0
A- + H 20
+ OH- + HA,
M+
OH-
+ HA
(i)
lIS
[I,
(iv)
the free strong base and the unhydrolysed salt are completely
ionised and the acid is very little dissociated.
The degree of hydrolysis is the fraction of each gram molecule
hydrolysed at equilibrium. If c is the concentration of the
salt in gram moles per litre and x is the degree of hydrolysis,
then the concentrations of the various species in gram moles OJ"
gram ions per litre are:
[OH-] = xc; [HA] = xc; and [A -] = (I - x)c
The substitution of these values in (iii) gives:
Ij j
X = [OH-] X [HA] = xc X xc = ~
(v)
h
[A ]
(I - x)c
(I - x)
2c
+J
4c 2
(vii)
+H
2 0 ~HA
+ OH-
and
[H+] X [A-] / [HA] = K.,
must hold in the same solution as:
[OH-] X [HA] / [A-] = Xb
B t K .. = [H+] X [OH-] X [HA] _ [OH-] X [HA] = K
U
K.
[H+] X [A ]
[A ]
b,
therefore
K.,. / K. = Kb
{viii\
or
pKb = pK... - pK.
41]
119
[H+]
or
_ K _ Kw
-
K:
J~'K.Kw
(x)
(xi)
[OH-]
and
[Qlr-]~
:. pH = tpKw
+ ~pKa + t log c *
(xii)
Kb
Kw / K. = 10
10- 14 /1.82
10-5 = 55
is given by Kb = x 2c / (1 -
10- 10
-log c.
120
r I,
1 mole
i \
i)
1 mole
+
+
The contribution of the OH- ions from the second step is negligibJ \
small and hence only the primary hydrolysis need be considere( j
The HS- is effectively the weak acid in this reaction, hence tb
secondary ionisation constant (K2 = [S--] X [H+] / [H2S]) j
employed in the calculation of the hydrolysis constant.
Kh =K... / K. = 10 X 10-14 /12 X 10-15 = 8'~
Let x be the degree of hydrolysis, then: -
= 8.3 = [HS-]
K
h
i.e.
or
X [OH-]
=~
[S]
(1 - x)
x2
83x - 83 = 0
x = 099 or 99 per cent
0'lx 2
(1 - x)
41]
121
(a) The hydrolysis of the carbonate ion takes place in two stages
tHCOs -] X [OH-] = x 2 X 01
[COs ]
(1 - x)
x = 00414 or 414 per cent
Kb = 1.79 X 10-4 =
or
\I' Kh / C is 00423.
pH = IpK"
+ IpK, + ~ log c
i
.
-+- 513 + t( -
1) = 1162
(b) The hydrolysis of the bicarbonate ion may be written:
= 70
HCOs-
+ H 20
H 2 C03
+ OH-
(iii)
The ionisation of the bicarbonate ion itself must also be taken into
account:
HCOs- ~ CO a-- H+
(iv)
this is, in fact, th~ secondary ionisation of carbonic acid. Since the
equilibrium:
H+
+ OH- ~ H 2 0
(v)
[H+]2 X [COs--]
--[H 2 CO S] - -
Now [H 2 CO S]
or
The experimental value obtained by glass electrode measurements
is pH = 8'18, indicating that the cal culation is sUbstantially correct.
122
[I.
(xiv)
(xv',
(1 - x)
-'
.... },
Furthermore, since [B] and [HsO+] are equal {equation (xiii)
K _ [HsO+] X [B] _ [HsO+]2 _ [HsO+]2 _ K..,
h [BH+]
- (1 - x)c c
- Kb
(xvi)
[HsO+]
= JKK~C
pH = lpK.., - lpKb -
1 log c
(xvii)
(xviii)
temperature.
The hydrolysis may be written as :
NH, + + H 2 0 ~ NHs + HsO+
Kb = Kw / Kb = 10 X 10-14 /18 X 10- 6 = 56 X 10-10
Now Kb = x 2 c i (1 - x), where x is the degree of hydroly~i.'.
Substituting for Kb and c, and solving the quadratic equation for .c,
we find
x = 75
41]
123
Oase 3. Salt of a Weak Acid and a Weak Base. The hydrolytic equilibrium in a solution of a salt (BH)A, derived from a
weak organic base B and a weak acid HA, is expressed by the
equation:
BH+
+ A- + 2H2 0
H30+
+ OH- + B + HA
(xix)
+ A-
~~
+ HA
(xx)
(xxi)
= [HA] =
xc ; [BH+]
[A-] = (1 - x)c
(1 _ x)c X (1 - x)c
(1 - x)2
(xxiv)
124
[I.
42]
125
B2 ~ BI
Base.
Basel
A2,
Acid 2
(I,
126
lln30+ X a on -
(ii)
that is, the dissociation constant of an acid is inversely P")portional to' that of its conjugate base, and vice versa, in wa! r
(an amphiprotic medium). Otherwise expressed, if the acid is
strong, the conjugate base will be weak; if the acid is we: I.,
the conjugate base will be strong.
The question of strengths of bases is usually treat 1
separately from acids, but on the proton theory of acids alili
bases this is really unnecessary, since any protolytic reacti')l1
involving an acid must also involve its conjugate base. Tid)
older method of evaluating basic strength depended upon tf I)
OH- concentration produced in an aqueous solution of a ba- '.
Thus the basic dissociation constant of ammonia (NH3
HI)
~ NH4 +
OH-) was given by:
Kb = [NH4+] X [OH-:] / [NH a] *
The acid dissociation of the ammonium ion may be writt, i\
as:
(i v)
NH4+ ~ NHa + H+
this is an abbreviation of:
(v)
NH4+ + H 2 0 ~ NHa + HaO+
* The symbol [NH 31 represents the total concentration of undissociat. d
42]
127
Basel
Acid,
Basel
The products of such a reaction are the conjugate acid and the
conjugate base of the reactants. If the acid HA and a conventional strong base MOH are neutralised, we may write the
reaction:
HA + M+ + OH- = M+ + A- + H 20
Acid l
Basel
Basel
Acid l
Acid l
Basel
Acid.
Base,
Basel
Acid g
Base.
Basel
Acid g
128
strengths of the two acids concerned, but also upon the nat,., e
of the solvent. We are primarily concerned with water, ,n
amphiprotic solvent, which can act as an acid and a base !t
may interact with the neutralisation products in two ways:
(a)
BH+
and (b)
ABasel
H 20
Base.
Acid l
H 20
Acid.
Basel
~
HA
Acid l
HsOT
Acid.
OHBase.
Acid.
Acid I
Base.
42]
129
+ H 20
NHs
+ HsO+
(ix)
For the general case of the salt {BH+)A-, the equilibrium may
be written:
(x)
B.L. -
(xii)
[BH+]
B.L. -
[Base]
[Acid]
- [Unhydrolysed Salt]
(xiii)
+ H 20
+ H 20
HA
r? B
+ OH-
+ HsO+
(xiv)
(xv)
+ A- + 2H O ~ HsO+ + OH- + B + HA
j
(xvi)
130
[I,
BH+
A-
Unhydrolysed salt
Free base
HA
(xvii)
Free acid
[BH+] X [A ]
(x,iii)
Al+++
+ 30H-
+ H 20
[M(H 2 0)a:-l(OH)Jn-l)+
+ HsO+;
+ H 20
[Al(H ZO)5(OH)]2+
+ HsO+,
and this may serve as a basis for the following illustra t 1ve
calculation.
Example 26. Calculate the pH of a 01 molar solution of ,: iuminium chloride [Al(H 20)6]3+CI ss-.
Let y = [HsO+] = [Al(H ZO)5(OH)]2+
~~~"K = [HsO+] X [AI(H zO)5(OH)]2+ = y2 = 1'4
10-6
[Al(H 2 0)6]S+
0'1
X
(compare E;r,ample 3 in Section I, 14).
y2 =.: 14 X 10-6, Y = 118 X lO-s g. ions per litre,
or
pH =: 293
43]
131
Grams of iodine in
10 mI. of OS2 (0 2 )
Grams of iodine in
10 mI. of H 20 (0 1 )
K d = -2
176
129
066
0-41
00041
00032
00016
00010
420
400
410
410
132
43J
133
134
[I,
K = [KI] X [1 2]
[KIa]
is then computed.
A similar method has been used for the investigation of the
equilibrium between bromine and bromides:
Brz
+ KBr ~ KBra,
or Brz
+ Br- ~ Bra-
Cu++
+ 4NHa
I, 44. The Colloidal State.-It sometimes happens in qualitative analysis that a substance does not appear as a preoipitate
when the reactants are present in such concentrations that the
solubility product of the substance is greatly exceeded and
precautions are taken against supersaturation of the resulting
solution. Thus when hydrogen sulphide is passed into a
cooled solution of arsenious oxide, no precipitate is discernible when one looks through the resulting mixture. The
solution, however, has acquired a deep yellow colour and when
viewed by reflected light shows a marked opalescence. If a
powerful beam of light is passed through the solution and the
"J
135
136
[I,
44]
137
* For a more detailed account S66, for example, H. B. Weiser, A Text Book
of OoUow Ohemi8try, Second Edition, 1949 (J. Wiley), or the appropriate
sections in S. Glasston!!, TtUd Book oj Physteal Ohemi8try, Sscond Edition, 1946.
s:
138
[I,
HYDROPHILIC SOLS
..
44]
139
140
[I,
CHAPTER II
EXPERIMENTAL TECHNIQUE OF
QUALITATIVE INORGANIC ANALYSIS
BEFORE the student attempts to carry out the analytical
reactions of the various cations and anions detailed in Chapters
III and IV, he should be familiar with the operations commonly
employed in qualitative analysis, that is, with the lahoratory
technique involved. It is assumed that the student has had
some training in elementary practim11 chemistry, such as that
given in the author's manual*; he should be familiar with such
operations as solution, evaporation, crystallisation, distillation,
'precipitation, filtration, decantation, bending of gla8s tubes,
preparation of ignition tubes, boring of corks and con8truction
of a wash bottle. These will therefore be either very briefly discussed or not described at all in the following pages.
Qualitative analysis may be carried out on various scales.
In macro analysis the quantity of the substance employed is
05-1 gram and the volume of solution taken for the analysis
is about 20 ml. In what is usually termed semimicro analysis,
the quantity used for analysis is reduced by a factor of 01005, i.e. to about 005 gram and the volume of solution to.
about 1 ml. For micro analysis the factor is of the order of
001 or less. There is no sharp line of demarcation between
semimicro and micro analysis: the former has been called centigram analysis and the latter milligram analysis, but these
terms indicate only very approximately the amounts used in
the analysis. It will be noted that only the scale of the
operations has been reduced; the concentrations of the ions
remain unchanged. Special experimental techniques have
been developed for handling the smaller volumes and amounts
of precipitate, and these will be described in some detail.
For routine analysis by students, the choice lies between macro
and semimicro analysis. There are many advantages in adopting the semimicro technique; these include:
(i) Reduced consumption of ehemicals and the consequent
considerable saving in the laboratory budget.
(ii) The greater speed of the analysis, due to working with
smaller quantities of materials and the saving of time in
142
[II,
II, 1.
DRY REACTIONS
Fig. II, 1, 1
M3
144
[II,
*A
1)
145
!
I
146
[II,
1]
147
4. Spectroscopic tests. Flame spectra. The only trustworthy way to employ flame tests in analysis is to resolve the
light into its component tints and to identify the cations present
Fig. II, 1, 3
148
[II,
1]
149
Window
order to adjust the scale relative to the spectrum. The scale is'
calibrated directly into divisions of 100 angstroms and has also an
indication mark at the D-line: it is "calibrated" by means of a
sodium source, and the adjusting serew is locked into position by
means of a locking nut. The instrument can be mounted on a
special stand.
150
[II,
Sodium
Potassium
Lithium
Thallium
Calcium
Strontium
Barium
Description of line(s)
Double yellow
Double red
Double violet
Red
Orange (faint)
Green
Orange band
Yellowish. green
Violet (faint)
Red band
Orange
Blue
Green band
Blue (faint)
Wave-length in
'.
J.
5890,5896
7665, 7699
4044,4047
1
,
6708
6103
5350
6182-6203
5554
4227
6744, 6628
6060
4607
5536, 5347, 5243, 5137
- 4874
I
The spectra of the various elements are shown diagrammatically in Fig. II, 1,5; the positions of the lines have been drawn
to scale.
A more extended discussion is outside the scope of thi~
volume, and the reader is referred to the standard works on
the subject. *
........
_4 .. __
.... "
1]
RED
GREEN
I
:
151
VIOLET
BLUE
Nal - T-'~---r--r--,..u..-J'""'T"---r----r---'----:-l~
Kil
Li
III
~r
I--r--I
--.-----.-------r------ll
---l.;--r
Sr
~-,-uir......,.-----..glil----,--r--~~II
I I III I ~,~, 1 ~.
I
-t~
~~
,._
Bai"""""II",,,,,,,,,llF J,
000000
000000
~ ~
:8
o
0
'I0
0
0
0
i,
152
[IT.
1]
153
The reaction:
CuO + NaB0 2 = NaCuBOa (orthoborate),
probably also occurs. In the reducing flame (i.e. in the presence of carbon), two reactions may take place: (i) the coloured
cupric salt is reduced to colourless cuprous meta borate20u(B0 2)2 + 2NaB0 2 + 0 = 2CuB02 + Na2B,07 +00;
(ii) the cupric borate is reduced to metallic copper, so that the
bead appears red and opaque2Cu(B0 2b + 4NaB0 2 + 2C = 2Cu + 2Na2B407 + 200
With iron salts Fe(B02b and Fe(B0 2)a are formed in the
reducing and oxidising flames respectively.
Some authors assume that the metal metaborate may combine with sodium metaborate to give complex borates of the
type Na2[Cu(B02),], Na2[Ni(B02)4] and Na2[Co(B02)4]:
Cu(B0 2}2 + 2NaB0 2 = Na2[Cu(B02}4]
154
[II,
Redueing flame
Metal
Copper
Iron
Chromium
. Manganese
Cobalt
Nickel
Vanadium
Uranium
Tungsten
when cold.
Yellow when hot,
violet* when cold.
Titanium,
11,2.
WET REACTIONS
These tests are made with substances in solution. A reaction is known to take place (a) by the formation of a precipitate, (b) by the evolution of a gas or (c) by a change of
colour. The major number of the reactions of qualitative
analysis are carried out in the wet way and details of these are
given in later chapters. The following notes upon the methods
2]
155
These should be of
50, 100 and 250 m!. capacity, and are useful for decompositions
"r--,,-,
-T-r-):1--.r-T-JI-A-'-'-T-I,>
A-T
156
[II,
2]
157
(6) !
Fig. II, 2, I
158
[II,
2]
159
160
[II,
Fig. II, 2, 3
2)
161
placed inside the filter flask. The Jena "slit sieve" funnel, *
shown in c, is essentially a transparent Buchner funnel; its
great advantage over the porcelain Buchner funnel is that it
is easy to see whether the funnel is perfectly clean.
Strongly acidic or alkaline solutions cannot be filtered
through ordinary filter paper. They may be filtered through
a small pad of glass wool or of asbestos placed in the apex of
(0)
(b)
(0)
(d)
Fig. II, 2, 4:
6+
162
[II.
2]
163
164
[II,
3J
1&5
~~-+
1:2
Ii
~
E
""
:2
:2
<0
'""-
"-
4 mI.
(a)
j
omI.
(b)
20 mI.
3 mi.
(0)
(d)
Fig. 11, 3, I
166
[II,
(a)
(b)
Fig. II, 3, 2
1
1
i
~
""
1
(a)
(b)
Fig. II, 3, 3
3]
167
168
[II,
(0)
(b)
(c)
(d)
Fig. II, 3, 4
:j
3J
169
Bottles
5N
5N
5N
170
[IT,
r, =
2a Zg(dp
97]
--
dm }
(I')
Fig. 11,3,5
increase in the size of the particles a; (b) an increase in difference
between the density of the particles dp and that of the medium d m ;
(o) a decrease in the viscosity 7J of the medium; and (d) an increase in
the acceleration due to gravity g. Fine crystalline particles tend to
increase in size when allowed to stand in the liquid in which they are
precipitated, particularly when the solution is maintained at elevated
temperatures and shaken occasionally. The coagulation of colloidal
and gelatinous precipitates is also accelerated by high temperatures
and stirring, and also by the addition of certain electrolytes. Moreover,
an increase in temperature reduces the viscosity and also increases the
difference (dp - - dm)' This explains why centrifuge tubes or test-tubes
3J
171
F.
-mg-
* An excellent model is manufactured by Moseley Centrifuge and Engineering Co. of 119 Copenhagen Street, London, N.!.
t "Micro" centrifuge from Measurllig and Scientific Equipment Ltd.,
Spenser Street, London, S.W.I, or from International Equipment Company,
1284 Soldiers Field Road, Boston 35, Mass., U.S.A.
172
[II,
Fig. II, 3, 6
that at least one of these should be available in every laboratory
for demonstration purposes.
When using a hand-driven centrifuge, the following points
iti~ould be borne in mind:
bet'I) The two tubes should have approximately the same size
(0) a weight.
the aL
f
increas~he tube should not be filled beyond I cm. rom the top.
precipit~ may corrode the buckets and produce an unbalanced
temperat
and geiat,
and stirrin_' centrifuge from Measuring and Scientific Equipment Ltd.,
an increase inical model" centrifuge from International Equipment Com.
difference (d" Controlled speeds to a maximum of about 4000 r.p.m.
3)
173
174
[II,
""
Fig. 11,3,8
another vessel by merely compressing the rubber bulb. In difficult cases, a little cotton wool may be inserted in the tip of tL
dropper and allowed to protrude about 2 mm. below the glasc\
tip; any excess of cotton wool should be cut off with scissor..;,
6. Washing of precipitates. It is essential to wash HI!
precipitates in order to remove the small amount of soluti() I I
3]
175
(a)
(b)
Fig. II, 3,9
(c)
176
[II,
3]
177
Fig.
II,
3, 11
Fig. II, 3, 12
rubber band about 5 mm. from the top of the tube; this will
facilitate the removal of the hot tube from the water bath
without burning the fingers and, furthermore, the rubber band
can be used for attaching small pieces of folded paper containing notes of contents, etc.
A more elaborate arrangement which will, however, meet
the requirements of several students, is Barber's water bath
rack (Fig. II, 3, 13). The dimensions of a rack of suitable
size are given in Fig. II, 3, 14. This rack will accommodate
four centrifuge tubes and four semimicro test-tubes. The
apparatus is constructed of monel metal, stainless steel, a
plastic material which is unaffected by water at 100, or of
brass which is subsequently tinned. The brass may be tinned
by boiling with 20 per cent sodium hydroxide solution containing a few lumps of metallic tin.
I
~
178
"OBmm.
4mm.
Fig. II, 3, 14
Fig. II, 3, 13
'.
, .._,_.--~ ..
O~(b)O-
Fig. II, 3, 15
3]
179
(6)
(a)
Fig. II, 3. 16
intermittent heating with a micro burner of a crucible (supported on a nichrome or silica triangle) or of a semimicro
beaker (supported on a wire gauze). A little practice is
required in order to achieve regular boiling by intermittent
heating with a flame and also to avoid "bumping" and spattering: too hot a flame should not be used. In many cases
the flame may be removed whilst a little liquid remains: the
heat capacity of the vessel usually suffices to complete the
evaporation without further heating. If corrosive fumes are
evolved, the operation should be conducted in the fume cupboard.
11. Dissolving of precipitates. The reagent is added
and the suspension is warmed, if necessary, on the water bath
until the precipitate has dissolved. If only partial solution
occurs, the suspension may be centrifuged.
12. Precipitations with hydrogen sulphide. Various
automatic generators of the Kipp type are marketed, and may
be employed for groups of students. Owing to tho highly
poisonous and very obnoxious character of hydrogen mlphide,
these generators are always kept in a fume cupboard (draught
chamber or hood). A wash bottle containing water should
ISO
l'
f,
3]
181
(a)
Fig. II, 3, 18
(b)
(c)
Fig. II, 3, 19
182
(II.
(a)
(b)
I'i.
jt:
Fig. II, 3, 20
with about 1 cm. protruding over the upper edge. The chemical
reaction is started in the test-tube and a "filter tube" containing a tightly-packed plug of cotton wool is inserted through
the rubber collar, the filter plug again packed down with a
4 mm. glass rod, and 05-1 ml. of the reagent introduced. An
'" Test.tubes (75 x 10 mm. and 100 X 12 mm,) together with the matching
"filter tubes" (55 X 7 mm. and 80 X 9 mm.) are standard Pyrex products;
they are inexpensive and therefore eminently suitable for elementary and
other students. The smaller size is satisfactory for most purposes.
3J
183
184
[II.
3]
185
186
[II,
3]
187
* Semimicro test-tubes (Pyrex, 100 X 125 mm., S ml.) and the appropriate
"filter tubes" (Pyrex, SO X 9 rom.) are marketed, and these may lind application in analysis. The smaller 4 ml. te8ttubes will generally Bulnce: their
great advantage is that t.hey can be used dirently in a semimicro centrifuge
in the buckets provided for the 3 ml. centrifuge tubes.
188
5]
189
190
[II,
s:::=
11-:_ _ _
'(
Fig. II, 5, 2
until the entire solution is in the pipette and the tip is about I mIll.
above the precipitate. The pipette is removed and the liquid blo" ';
or drained out into a clean dry centrifuge tube.
Another useful method for transferring the centrifugate to, say.
another centrifuge tube will be evident upon reference to Fig. II, 5,~;
The siphon is made of thermometer capillary and is attached t"
the capillary pipette by means of a short length of rubber tubin'
5]
191
of 1 mm. bore. The small hole A in the side tube permits of perfect
control of the vacuum; the side arm of the small test-tube is situated
near the bottom so as to reduce spattering of the liquid in the centrifuge tube inside the teBt-tube when the vacuum is released. Only
~~~==~~==~~
pump
Fig. II, 5, 3
Il
UJZ
[II,
Fig. II, 6, 5
Fig. II, 6, 6
flubber stopper
t-
Clamp
Fig. II, 6, 7
Fig. II, 6, 8
Another valuable method for concentrating solutions or ev, 110rating to dryness directly in a centrifuge tube consists in condu( , ng
the operation on a water bath in a stream of filtered air sUPI ed
through a capillary tube fixed just above the surface of the liq [d.
The experimental details will be evident by reference to Fig. II, 7.
i
!,
5]
193
7+
194
[II,
6)
195
196
Ill,
Fig. II, 6, 2
Fig. II, 6, 3
Actual size
6]
197
198
flI,
'I
6]
199
~~.
'i)~
'/
--:r-~'
I
20mm.
C
Fig. II, 6, 5
The all-glass spray shown in Fig. II, 6, 5 (not drawn to scale) gives
excellent results. A rubber bulb is attached at C; the cork is fitted
into a boiling tube or small flask charged with the impregnating
solution. The paper is sprayed first on one side and then on the
other.
(ii) For reagents that are precipitated on the paper, the strips
are soaked rapidly and uniformly with the solution of one of the
reactants, dried and then immersed similarly in a solution of the
precipitant. The excess reagents are then removed by washing,
and the strips dried. The best conditions (concentration of solutions, order in which applied, etc.) must be determined by experiment. In preparing highly impregnated papers, the precipitation
should never be made with concentrated solutions as this m::ty lead
to an inhomogeneous precipitation and the reagent will tend to fall
200
[II,
6]
201
the flat ground surface of B, the tube F placed upon it and then
held in position by sliding the rubber tubing just far enough over
c::>E
eo
Fig. II, 6, 7
the paper to hold it when the tube F is removed. The filter pipette
may be used either by placing a drop of the solution on the filter
disc or by immersing the tube end B into the
crucible, test-tube or receptacle containing the
solution to be filtered. The bulb is squeezed
by the thumb and middle finger, and the dropper
point closed with the fore-fmger thus allowing
the solution to be drawn through the paper
when the bulb is released. To release the drops
of filtered liquid thus obtained, th6 filter pipette
is inverted over the spot plate, etc., in an inclined position with the bulb uppermost.
Manipulation of the bulb again forces the
liquid in the tip on to the spot plate, etc. The
precipitate on the paper can be withdrawn for
any further treatment by simply sliding the
rubber tubing D down over the arm B.
Another method involves the use of an Emich
filter stick fitted through a rubber stopper
into a thick-walled suction tube; the filtrate is
colleoted in a micro test-tube (Fig. II, 6, 8).
The filter stick has a small pad of purified
asbestos above the constriction.
Fig. II, 6, 8
The apparatus illustrated in Fig. II, 6, 9 may
be employed when the filter paper (or drop Two-thirds actual
reaction paper) must be heated in steam; the
size
filter paper is placed on the side arm support.
By charging the flask with hydrogen sulphide solution, ammonia
solution, chlorine or bromine water, the apparatus can be used for
treating the filter paper with the respective gases or vapours.
7
rH,
I
Fig. 11, 6, 10
7
Actual size
Fig. II, 6, 11
Actual size
Fig. II, 6, 12
Actual size
into a micro crucible and treated with the reagent. The appar, '!lS,
shown in Fig. II, 6, 11, which is closed by a rubber stopP(' is
sometimes preferable, particularly when minute quantities of ga, .re
6]
Experimental Techn{que
0.1 Inorganic
A nalY8i8
203
concerned; the glass tube, blown into a small bulb at the lower
end, may be raised or lowered at will, whilst the change of colour
and reaction products may be rendered more easily visible by filling
the bulb with gypsum or magnesia powder. In some reactions, e.g.
in testing for ammonia, it may be desirable to suspend a small strip
of reagent paper from a glass hook fused to the stopper as in Fig.
II, 6, 12. When a particular gas has to be identified in the pre.
sence of other gases, the apparatus shown in Fig. II, 6, 13 should
be used; here the stopper for the micro test-tube consists of a small
glass funnel on top of which the impregnated filter paper is laid in
order to absorb the gas. The impregnated filter paper permits the
passage of the indifferent gases and only retains the gas to be tested
by the formation of a non-volatile compound that can be identified
by means of a spot test. Another useful apparatus is shown in
Fig. II, 6, 13
Actual size
Fig. II, 6, 14
Actual size
Fig. II, 6, 15
Actual size
204:
[II,
UU
WOOtman paper
Drop-reaction paper, No. 120,
double thickness.
No.3 MM., 1st quality.
No. 42 or No. 542.
"i
CHAPTER III
REACTIONS OF THE METAL IONS OR CATIONS
III, 1. The Analytical Classification of the Metals.-The
common metallic ions may be divided, for purposes of qualitative analysis, into a number of groups which are distinguished
by the fact that the metals of any group are precipitated by
a particular group reagent. Thus by the addition of a slight
I
Group
Group
reagent
Formftla of
lona
I precipitate
Distinguishing
featureB
I
(Silver
group)
Dilute HCI
II
(Oopper
and
arsenic
groups)
H.S in presence of
dilute HCl
Hg++,
Pb++,
Bi+++,
Cu++,
Cd++,
Sn++,
As+++,
Sb+++,
Sn++++
HgS, PbS,
Bi.S., CuS,
CdS, SnS,
As.S.,
Sb 2 S., SnS.
IlIA
(Iron
group)
Aq. Nil a in
presence
ofNH,Cl
Al+++,
Cr+++,
Fe+++
Al(OH).,
Cr(OH).,
Fe(OH).
Hydroxides
pptd. by
aq. Nil. in
presence of
excess of
Nil,Cl.
lIIB
(Zinc
group)
H.S in presence of
aq. NHa
and
Nil,C!
N++
1
,
Co++,
l\fu++,
Zn++
NiS, CoS,
MnS, ZnS
Sulphides pptd_
by H.S in presence of aq.
NH. and
Nil,Cl.
IV
(Oalcium
group)
(NH,).CO a
in presence
ofaq. NBs
andNH.Cl
Ba++,
Sr++,
Ca++
BaCO.,
SrCO.,
CaCO.
Carbonates
pptd. by
(NH,).CO.
in presence of
NH,Cl.
V
(Alkali
group)
No particular reagent
206
[Ill,
1]
207
[III,
208
LEAD,Pb
Lead is a bluish-grey metal with a density of 1148.
dissolved by dilute nitric acid:
3Pb
+ SHNO a =
3Pb(NOsh
It is rea dily
+ 2NO + 4H 0
2
111,2.
-,
2]
209
208
[III,
LEAD,Pb
Lead is a bluish-grey metal with a density of 1148. It is re;lilily
dissolved by dilute nitric acid:
3Pb
+ 8HNO a =
3Pb(NO s)2
+ 2NO + maO
111,2.
2]
209
21-0
[III,
of lead, and why it can be detected in the filtrate from the separation of tha
sparingly soluble lead chloride in dilute hydrochloric acid.
t8.
Benzidine Reagent
2]
211
( (yN'lli
bH
,f'~~'-...o/
~"-..
):
N(CH')3' HCI
/NH.NHC.H,).
( SC"-..N=NC.H,
brick-red complex salt in neutral, ammoniacal, alkaline or alkali.
cyanide solution.
Place 1 mI. of the neutral or faintly alkaline solution in a micro
test-tube, introduce a few small crystals of potassium cyanide, and then
2 drops of the reagent. Shake for 30 seconds. The green colollr of the
reagent changes into red.
Sensitivity: 01 fLg. Pb (in neutral solution). Concentration limit:
1 in 1,250,000.
Heavy metals (Ag, Hg, Cu, Cd, Sb, Ni, Zn, etc.) interfere, but this
effect may be eliminated by conducting the reaction in the presence of
212
[III,
much alkali cyanide: excess of KOH solution is &lso required for Zn.
The reaction is extremely sensitive, but it is not very selective.
The rea~ent is prepared by dissolving 2-5 mg. of dithizone in 100 ITt i,
of carbon tetrachloride or chloroform. It does not keep well.
Dry Tests
(i) Blowpipe test.-When a lead salt is heated with alkali
carbonate upon charcoal, a malleable bead of lead (which 1,;
soft and will mark paper), surrounded with a yellow incrustH'
tion of lead monoxide, is obtained.
(ii) Flame test.-Pale blue (inconclusive).
MERCURY Hg
Mercury is a silvery-white, liquid metal at the ordinary temper!.
ture and has a density (d~:) of 13595. It is unaffected by treat
ment with dilute hydrochloric or dilute sulphuric acid, but react,
readily with nitric acid. Cold dilute nitric acid and excess (If
mercury yield mercurous nitrate, whilst with excess of the hOT
concentrated acid mercuric nitrate is produced:
6Hg
Hg
+ 8HNO a =
+ 4HNO s =
+ 2H aSO, =
+ 2H.SO, =
olear solution.
3]
Vf
Oationa
213
+ 2NHa =
Hg(NH2)Cl
+ Hg + NH,Cl
+ 2KI =
K 2[HgI4]
+ Hg
+ H 2S = 2HNOa + HgS + Hg
+ 2NaOH = Hg 20 + 2NaNO a + H 20
/'-.
NH . N0 3 + 2Hg + 3NH.NO.
'-./
Hg
7. Stannous Chloride Solution: grey, finely-divided mercury is obtained with excess of the reagent.
Hg2 (NO a)2
...
214
[III,
Dry Tests
See under Mercuric Ion, Section III, 6.
Ag
Silver is a white, malleable and duotile metal. It is insoluble
dilute hydrochlorio and sulphurio aoids, but dissolves readily
nitrio acid (2: 1) and in boiling ooncentrated sulphuric iLcid:
SILVER
Ag
2Ag
111,4.
+ 2HNO a =
+ 2H 2S04 =
AgNO a + NOg
Ag 2S0 4 + S02
in
! 11
+ H 20;
+ 2H 20
A~+
+
+
AgN0 3
HCI =
AgCI
2NH3 =
[Ag(NHa)2]CI + 2HN0 3 =
[Ag(NH a)2]Cl + KI =
AgCI
HNO a ;
[Ag(NHa)2]CI;
AgCI + 2NH4NO a ;
AgI
KCl
2NHa
+ KC}
2AgCI + 3Na2S20a = Na4[Ag2(S20a)a] + 2NaCI
AgCI
+ 2KCN =
K[Ag(CN)2]
+ Mn++ +
40H- = MoOg
2Ag
2H g O
4]
10M
or Catiom
215
+ 2KCN =
K[Ag(CN)2J
+ KI
+ K 2 Cr04 =
AgzCrO,
+ 2KNO s
Altematively, the reaction with the clear solution may be earned out
on a spot plate, when red silver chromate lli precipitated.
The reagent consllits of a 1 per cent solution of potassium chromate
in N -acetic acid.
+ 8HNO s =
6AgNO s
+ 2NO + 3S + 4H 20
+ 2NaOH =
Ag20
+ 2NaNOs + H 20
+ 4NHs + H 2 0
Ag2 0
t7.
= 2[Ag(NH s )2]OH
para-Dimethylamino-benzylidene-rhodanine Reagent
HN--CO
(
"
216
rIll,
Spot the test solu~ion upon drop reaction paper, add 1 drop "f N
nitric acid, followed by a drop of the reagent. A red- violet precipita' " or
stain is formed according to the silver content of the test solutio!!.
Alternatively, the test may be performed on a spot plate or 'I a
semimicro test-tube; in the latter case the excess of the reageI,t is
extracted with ether or amyl alcohol when violet specks of the f'. ver
complex will be visible under the yellow solvent layer.
Sensitivity: 0'02 p.g. Ag. (in 02N nitrio acid).
Concentration limit: 1 in 2,500,000.
If mercury is present, treat a drop of the test solution eithflr on
drop reaction paper or on a spot plate with a. drop of 5 per cent p' ; assium cyanide solution, followed by a drop of the reagent and a drql of
2N nitrio acid. The silver rhodanine complex is precipitated: the
mercury is held in solution as undissociated mercuric cyanide.
If gold, platinum and palladium are present (copper mw, be
absent since cuprous copper gives a violet precipitate in acid soluti!m),
mix on a spot plate 1 drop of the test solution with a drop of 10 per cent
potassium cyanide solution and a drop of the reagent. Stir and actrlify
with 3N nitric acid. A red colour is obtained in the presence of 2;", JLg,
of silver.
The reagent consists of a 003 per cent solution of p-dirnethylan 'lUObenzylidene-rhodanine in acetone or in alcohol.
To detect Ag in a mixture ofPbCl 1 , Hg1CI, and AgCl (Group I), Ghe
mixture is treated with 5 per cent potassium cyanide solution wher!)by
Hg(CN)2 + Hg as well as K[Ag(CN)s] are formed: after filtratiOl.l (or
centrifugation), a little of the clear filtrate is treated on a spot plate
with a drop of the reagent and 2 drops of 2N nitric acid. A red col.mJ,tion is formed in the presence of Ag in weakly acid solution.
Dry Tests
When the student has worked through the reactions of the mt"Lals
in this group, he should attempt to identify the members of the
group both singly and when present in a mixture in the solutions
supplied to him by the teacher. With the aid of the follo'wing
simplified table which is directly based upon the reactions already
studied, this should prove a comparatively simple task. A more
detailed table will be given when all the metals have been stud led.
It is important that the student should a.cquire the habit of
recording his results in tabular form.
5J
217
Centrifugate. May
contain PbC].. Add
2 drops of ammonium
acetate solution and
1 drop of K.CrO,
solution.
Yellow ppt. of
PbCrO,.
Lead present.
The symbol (T) refers to the point at which the group separation is
commenced in connexion with Table S (Section V. 8) and Table SM.S
(Section VI. 9) respectively.
218
[III,
6]
219
+ 2HNO + 6HCl =
g
3HgCl z
+ 2NO + 38 + 4HzO
HgO
+ 2NaCl + H 20
4. Ammonia Solution: white precipitate of amino mercuric chloride (NHz)HgCl, known as "infusible white precipitate" for it volatilises without molting.
HgCl 2
+ 2NHa =
Hg\NH 2 )CI
+ NH4CI
220
[111,
+ Cu =
Hg
+ CuCl2
t9.
Diphenylcarbazone Reagent
/N ... N.C.H5 )
( CO"NH.NH.C.H.
HI
221
,lue to violet inner complex salt. The sensitivity of the test depends
.pon the pH of the solution. decreasing with increasing acidity. In
2N nitric acid, the test is highly selective provided chromates and
:lOlybdates (which give coloured compounds) are absent. Chromates
lay be reduced with sulphurous acid or with hydrogen peroxide to
.on-reacting chromic salts: molybdates may be rendered inacdve by
dding 5 per cent oxalic acid solution when a Mo-oxalic acid complex
! produced.
Place a drop of the test solution and a drop of 02N nitric acid upon
rop reaction paper, which has been moistened with the reagent. A
iolet or blue coloration appears.
Sensitivity: 1 fLg. Hg. Concentration limit: 1 in 50,000.
The reagent consists of a I per cent solution of diphenylcarbazone
1 90-100 per cent ethyl alcohol.
tlO. Cobalt Acetate-Ammonium Thiocyanate Reagent.--When
solution of a mercuric salt is treated with a concentrated solution of
obalt acetate and a little solid ammonium thiocyanate, a dpep-blue
rystalline precipitate of cobaltous mercuri-thiocyanate Co[Hg(CNS)4]
! formed.
Crystallisation is sometimes slow, but may be accelerated
y scratching the interior of the vessel with a glass rod.
Place a drop of the test solution on a spot plate, add a small crystal
f ammonium thiocyanate followed by a little solid cobalt acetate. A
lue colour is produced.
Sensitivity: 0'5 (-tg. Hg. Concentration limit: I in lCO,OuO.
)ry Test
All compounds of mercury when heated with a large excess
7-8 times the bulk) of anhydrous sodium carbonate in a small
ry test-tube yield a grey mirror, consisting of fine drops of
2Bi
+ 8HNO s =
2Bi(NO a)a
4HaO
+ 2NO
The salts of bismuth may be regarded as derived from the sesquioxide Bi2 0 3. The hydroxide Bi(OH)3 is a weak base; the salts are
accordingly hydrolysed by much 'Water (see Hydrolysis of Salts,
Section I, 40) yielding insoluble basio (usually bismuthyl, i.e. containing the radical BiO-) BaIts.
BiCl.
+ RIO
"'" BiOCl
+ mOl.
222
I fIl,
III, 7.
7]
223
t The test is rendered more sensitive by making use of the f!lct that
the slow reaction between lead hydroxide or sodium plumbite and
sodium stannite is greatly accelerated by the separation of even minute
quantities of bismuth:
Pb(OH)2 + Nu 2[Sn0 2] = Pb + Na 2[SnO S] + HaO
Silver, copper and mercury interfere: copper is rendered innOCllOUS by
the addition of a little potassium cyanide.
On a spot plate, mix a drop of the test solution, a drop of saturated
lead chloride solution, a drop of 5 per cont potassium cyanide l'olution
and 2 drops of sodium stannite solution. A brown to black coloration
appears.
Sensitivity: 001 ftg. Bi.
Bi(NOa)a
H 20
2Bi(NOsh + 3H2 0
(BiO)NOa
2HNO s ;
(BiO)2(OH)NOs + 5HNO a (very
large excess of water);
+ H 20
(BiO)Cl
BiOla
+ 2HOl
224
[lIT ,
au
+ SHNO. =
+ 2H.SO, =
3Cu(NO a).
4H.0
2NO;
CuSO,
SO.
2H.0
+ 6H SO,
I
= 4:CuSO,
+ CutS + SO, + 6R 0
I
8]
225
+ 2NO + 3S
Cupric sulphide tends to form a colloidal solution and pass through filter
paper. This is avoided by carrying out the precipitation in the presence of
hydrochloric acid or some other electrolyte. It also tends to oxidise to the
soluble sulphate when exposed to the air in the moist state: this is prevented
by washing the precipitate with acidulated hydrogen sulphide water.
+ 2NaOH =
CU(OH)2
CU(OH)2
NazSO,
CuO + HllO
8+
226
[III,
8]
227
+ Fe = FeS04 + Cu
t9.
(CX:~NOH
),
""
S S
black precipitate of copper rubeanate Cur C( = NH)S}z from ammoniacal or weakly acid solution. The precipitate is formed in the
228
[Ill,
9J
229
Reaction (i) is fairly rapid; reaction (ii) is a slow one, but is enormously
accelerated by traces of copper salts. If the reaction is carried out in
the presence of a thiocyanate, which serves as an indicator for the
presence of ferric iron and also retards reaction (ii), then the reaction
velocity. which is proportional to the time taken for complete decolorisation, may be employed for detecting minute amounts of cupric ions.
Tungsten and, to a lesser extent, selenium cause a catalytic acceleration
similar to that of copper: they should therefore be absent.
Upon adjacent cavities of a spot plate place a drop of the test solution
and a drop of distilled water. Add to each 1 drop of the forric thiocyanate reagent and 3 drops of O'IN -sodimu thiosulphate solution. The
decolorisation of the copper-free solution is complete in 1'5-2 minutes:
if the test solution contains 1 I-'g. of copper, the decolorisation is
instantaneous. For smaller amounts of copper, the difference in times
between the two tests is still appreciable.
Sensitivity: 0'02 I-'g. Cu. Concentration limit: 1 in 2,500,000.
The "ferric thiocyanate" rea~ent is prepared by dissolving 15 g.
offerric chloride and 20 g. ofpotassiwn thiocyanate in 100 mI. of water.
Dry Tests
(i) Blowpipe test.-When copper compounds are heated with
alkali carbonate upon charcoal, red metallic copper is obtained,
but no oxide is visible.
(ii) Borax bead.-Green while hot and blue when cold after
heating in the oxidising flame; red in the reducing flame, best
obtained by the addition of a trace of tin or by moistening with
stannous chloride solution.
(iii) Flame test.-Green especially in the presence of halides,
e.g. by moistening with concentrated hydrochloric acid before
heating.
CADMIUM, Cd
Cadmium is a silver-white, malleable and ductile metal. It dissolves slowly in dilute hydrochloric and sulphuric acids with the
evolution of hydrogen. The best solvent for the metal is nitric acid.
Only one series of salts, derived from the oxide CdO, is of importance
in qualitative analysis.
III, 9.
230
[III,
+ H 2S ~ CdS + H 2SO,
CdSO,
2NHs
Cd(OH)2
(NH')2S0,
+ 2HzO =
+ 2NHs =
Cd(OH)z
(NH4)zS04;
[Cd(NHs ),]S04
2H20
to.
"
Dinitro-p-diphenylcarbazide Reagent
/NH.NH.C,H,.NO.(4)) .
( CO"NH.NH.C H . NO.(4) .
s
9]
231
colour produced in a. blank test with pure water when searehing for
minute amounts of cadmium.
Sensitivity: O'S fLg. Cd.
(O'NS N-N-NH-Q-N-N-Q )
Cadmium hydroxide forms a red-coloured lake with the reagent, which
contrasts with the blue tint of the latter.
Place a drop of the reagent upon drop reaction paper, add one drop
of the test solution (which should be slightly acidified with acetic acid
containing a little sodium potassium tartrate), and then onn drop of
2N potassium hydroxide. A bright pink spot, surrounded by a blue
circle, is produced.
Sensitivity: 0025 fLg. Cd.
The interference of Cu, Ni, Co, l!"e, Cr and Mg is prevented by adding
sodium potassium tartrate to the test solution: only Ag (removed as AgI
by the addition of a little KI solution) and Hg then interfere. Mercury
is best removed by adding a little sodium potassium tartrate, a few
crystals of hydroxylamine hydrochloride, followed by KOH solution
until alkaline; the mercury is precipitated as metal. Stannous chloride
is not suitable for this reduction since most of the cadmium is adsorbed
on the mercury precipitate.
The reagent is prepared by dissol ving 002 g. of "cadion 2B" in
100 ml. of ethyl alcohol to which 1 ml. of 2N-KOH is added. The
solution must not be warmed. It is destroyed by mineral acid.
Dry Tests
Blowpipe test.-All cadmium compounds when heated with
alkali carbonate on charcoal give a brown incrustation of
cadmium oxide CdO.
Ignition test.-Cadmium salts are reduced by sodium oxalate
to elementary cadmium, which is usually obtained as a metallic
mirror surrounded by a little brown cadmium oxide. Upon
heating with sulphur, the metal is converted into yellow cadmium sulphide.
Place a little of the cadmium salt mixed with an equal weight
of sodium oxalate in a small ignition tube, and heat. A mirror
232
(IIr,
[TABLES,
pp. 233-235.
.... v
III, 10.
The ppt. obtained with H 2S in the presence of dilute HCI (ca. 03N)
may contain the sulphides HgS, PbS, Bi.S., CuB, CdS and also SnS, SnS 2 ,
Sb.S, and As.S.. (T) Pierce the point of the filter with a small glass rod,
wash the ppt. into a beaker with a small quantity of water. Add 5 ml.
of yellow ammonium sulphide solution, heat to 50-60 for 2-3 minutes,
and filter. Wash the rt\sidue with a little dilute (1 : 100) (NH,)aS. solution.
Residue. May contain HgS, PbS, Bi.S., CdS and
CuS. Transfer the ppt. to a beaker or porcelain basin,
add ca. 5 ml. of dilute HNO" boil for a few minutes,
filter and wash with a little water.
Residue.
Black: HgS.
Warm the ppt.
with conc. HCl,
add bromine
water dropwise
until most or
all of ppt. dissolves. Boil off
any excess
of bromine.
Filter if necessary, dilute
with IIoIl equal
volume of
water, and add
SnCI. solution.
White ppt.,
turning grey or
black.
Hg present.
Alternatively,
dissolve the
ppt. in NaOCIHCl, etc., as
detailed in
Table IIA.
Filtrate. May
oontain metals
of Group lIB.
(See Table
III.)
Filtrate. May
contain
[Cu(NH.),]++
and
[Cd(NH.).]++.
If colourless, Cu
is absent; test
then directly for
Cd with H.S
(see below). If
blue, Cu present.
Divide the solution into two
unequal parts.
SmaUer portion
Add
K,[Fe(CN).J
solution and
acetio acid.
Reddish-brown
ppt.
Cu present.
(1).
Large,. portion.
Add KCN solution dropwise
until solution is
decolorised.
PIIM HIS for
10-20 IeOOnda.
YelloW' ppt. of
CdS.
Cd preHat (2).
III, 10.
The ppt. obtained with HaS in the presence of dilute HOI (ca. 031\
may contain the sulphides HgS, PbS, Bi.S., CuS, CdS and also As.S
Sb.S. and SnS. (1). (T) Pierce the point of the filter with a small glaE
rod, wash the ppt. into a beaker with a 8mall quantity of water. Ad"
10 mi. of 2N-potassium hydroxide and boil with constant 8tirring for 2-,
minutes (CAUTION,' see Note 2). Add 2 mi. offreshly-prepared saturate,
H.S water: stir and filter (preferably through a double filter). Wash tho
residue twice with a little water and collect the washings with the filtrat<'
Residue. May contain HgS, PbS, Bi.S., CdS and
CUS. Transfer the ppt. to a small beaker or porcelain
basin, add ca. 5 mi. of dilute RNO., boil gently for a few
minutes, filter and wash with a little water.
Filtrate.
May contain
metals of
Group lIB.
(See Table
III, Section
III,18.)
Residue.
Filtrate. May contain Pb(N0 3 ).,
Black: HgS.
Bi(NO.)., Ou(NO.). and Cd(NO.) . ~
Dissolve in a
Add excess of concentrated NH. solumixture of 25 tion until precipitation is complete.
mi. of 10%
Filter.
N aOOI solution
and 05 ml. of
Filtrate. May conResidue. May oontain
dilute ROI.
Add 1 mi. of Bi(OH). and Pb(OH) . Warm tain [Cu(NH 3 ),J ++
with 5 mi. of NaOH solution and [Od(NH 3 ).J++.
dilute HCl,
If colourless, Cu is
boil off excess and filter.
of CI. and cool. --------------~-----------I absent; test then
directly for Cd by
Add SnOI,
Residue. May
Filtrate.
passing H.S for 10solution.
be Bi(OH) .
May con20 seconds into the
White ppt.
Wash with a
tainsodium ammoniacal soluturning grey or little water. Pour plumbite
tion.
black.
sodium stannite Na.[PbO.].
Yellowppt.ofCdS.
Hg (ic)
solution over
Acidify
Cd present.
present.
filter.
with dilute If blue, Cu preBlackening of
acetic acid sent. Divide the
ppt.
and add
solution into two
Bi present.
KaCrO,
unequal parts.
Alternatively,
solution.
Smaller portion.
dissolve a little Yellowppt. Acidify with dilute
of the ppt. in 2-3 of PbCrO .
acetio acid and add
drops of dilute Pb present. K,[Fe(CN).J soluRNO.; place 1
tion.
drop of this soluReddish-brown ppt.
tion upon filter
Cu present (3).
paper moistened
Larger portion. Add
with cinchonineKCN solution droppotassium iodide
wise until solution
reagent.
is decolourised. Pass
Orange-red spot.
H.S for 10-20
Bi present.
seoonds.
Immediate yellow
ppt. of CdS.
Cd present (4).
10]
235
-------:----------------!
Residue.
Black: HgS.
Wash with 05
ml. of water
and discard the
washings.
Treat the ppt.
with 5 drops
of 10% NaOCI
solution and 1
drop of dilute
. HCI. Heat on
the water bath
for 1 minute.
To the clear
solution, add
1-2 drops of
SnCl, solution.
White ppt.,
turning grey or
black.
Residue. May
be Bi(OH) .
Wash with 05
mI. of water and
reject washings.
Add 1 mi. of
sodium stannite
reagent (3) to the
ppt.
Immediate black
Hg (ic) present. ening of ppt.
Bi present.
Alternatively,
dissolve a little
of the ppt. in 1-2
drops of dilute
HNO.. Place 1
drop of the solution upon filter
paper moistened
with cinchonine.
potassium iodide
reagent.
Orange-red spot.
Bi present.
Centrifugate.
May contain
metals of
Group HE.
(See Table
SMIIIA. Section III, 18.)
~
~
~
~
Centrifugate.
May contain
[Cu(NH.),](NO.).
and
[Cd(NH.),](N0 3 )
If colourless, Cu is
Centrifu- absent: test then
gate. May directly for Cd by
contain
passing HIS for 10
Na.(PbO I ] seconds into the
Acidify with ammoniacal solu.
dilute acetic tion. Yellow ppt.
acid, add 2 ofCdS.
drops of
Cd present.
If blue, Cu is pre.
K.CrO.
solution.
sent. Divide into
Yellowppt. two unequal parts.
of PbCrO,.
Smaller portion (4).
Ph present. Acidify with acetic
acid and add 1 drop
of K,[Fe(CN)8J
solution.
Reddish-bro\'ln ppt.
on standing for 2-3
minutes.
Cu present.
Larger portion. Add
KCN solution dropwise. with stirring,
until the blue colour
is discharged. Pass
H.S for 30-40
seconds.
Yellowppt.o[ CdS.
Cd present.
Confirm Cd by
ignition test with
Na.C,O., etc.
(Section III, 9).
236
[III,
II
Notea. (1) Alternatively, just acidify a few drops of the solution "ith
dilute sulphuric acid. Add one drop of the acid solution to a few drol ' of
zinc sulphate or acetate solution, and then add a little a.rnmonium me! tri.
thiocyanate reagent. A violet precipitate confirms Cu. If a little " llyl
alcohol is added, the precipitate collects in and colours the organic layer
(2) Cadmium may be confirmed, if desired, by the ignition test with SOdltlID
oxalate, etc. (see Section III, 9, Dry Tests).
NOTES TO TABLE
IIA
Notea. (1) Stannous sulphide SnS is not completely solubte in 2N K,' FI.
If tin is present in the stannous state, it is necessary to oxidise it with H ~ I j 2:
a limited amount of arsenious arsenic may be oxidised at the same time.
(2) Potassium and sodium hydroxides are extremely dangerous 8ubstal,' os
because of their destructive effects upon the eyes. Precipitates, when he,. :' ld
with KOH solution, tend to bump. To avoid any possibility of the mixl '; 1'e
spurting into the eyes with a consequent likely loss of sight, it is essell' 'al
(a) to conduct the operation in a fume chamber, (b) to stir the mixture ( "1
stantly and (c) to avoid bringing the face over the beaker. It is recommen, :,d
that goggles be worn during this and similar operations.
(3) Alternatively, just acidify a few drops of the solution with dilute;, I.
phuric acid. Add 1 drop of the acidic solution to a few drops of zinc sulpl, " e
or acetate solution, and then introduce a few drops of the a.rnmonium mere", i.
thiocyanate reagent. A violet precipitate confirms Cu. If a little 111","1
alcohol is added, the precipitate collects in and colours the organic lay"!,.
It is recommended that this test be performed even if the solution is aim"st
colourless. A blue solution indicates that copper is present in quantity.
(4) Cadmium may be confirmed, if desired, by the ignition test with sodium
oxalate, etc. (see Section III, 9, Dry Test8).
I
NOTES TO TABLE
SMIIA
llJ
10M
or Oations
237
3As,
+
+
238
[III,
= 3H zO
+ 3H20 =
+ 3NHs =
+ KgAsOg + KgAsSg
(potassium thioarsenit
(NH",)aAsO s + (NH,)aAsS a
2(NH4)aAsSs
2(NH4)aAsS4 + S;
As 2S5
6NH,CI
= 3H2S
+ 3AgNO a =
AgsAsOa
+ 3NaNOa
11]
]0nIJ
or OatioTUl
239
+ +
+ 13 + 2NaHCO a =
3NazCO s + 31. =
+ HsO
~"..--
240
_._" [III,
Evaporate slowly and finally heat until fuming ceases. Treat the
residue with 1-2 drops of a solution of stannous chloride in concentrated
hydrochloric acid, and warm slightly. A brown or black precipitate
or coloration is obtained.
Sensitivity: 1 p.g. As.
III, 12.
12)
241
+ R~SOa
= RsAsO s
+ RISO,
+ 21- + 2H+
.=AsO a---
+ I, + HIO,
and the iodine liberati:'d is converted into iodide ions by the hydrogen sulphide:
Is
+ HsS
.= 2HI
+S
+ MgCl2 + NHa =
Mg(NH.,)As04
+ 2N<~Cl
For some purposes (e.g. the detection of arsenate in the presence of phosphate), it is better to use the magnesium nitrate
reagent (a solution containing Mg(N0 3 b, NH4CI and a little
NH 3 )
Upon treating the white precipitate with silver nitmte solution containing a few drops of acetic acid, red silver arsenate
is formed (distinction from phosphate) :
Mg(NH 4 )As04
+ 3AgNOs =
Ag 3 As04
242
[III,
Reactions of the
13J
j}JetaZ
243
Ions or Oations
HaAs04
4AsH a = AS 1
4AsH a + 60
+ lONaOCl + 6H zO
As,
+ 12ZnSO, + 6H zO
+ 4ZnSO, + 4H 20
4AsHa
AsH a
+ 6H
= AS~06
(heat)
+ 6H aO
+ lONaCl
= 4H aAsO,
+ 3H 0 + AsHa
2
HaAsOa
+ 6Ag + 6HN0
244
[HI,
6AgNO.
+ 3H I O
= 6Ag
+ 6HNO. + HaAsO a
13]
245
+ AsH a + 3H zO
= 2Au
+ 6HCI + HaAsOa
The test may be performed on the semimicro scale with the aid of
the apparatus shown in Fig. III, 13, 3. Place 10 drops of the test
solution in the semimicro test-tube, add a few
granules of arsenic-free zinc and 1 m}. of dilute sulphuric acid. Insert a loose wad of pure cotton wool
moistened with lead nitrate solution in the funnel,
and on top of this place a disc of drop reaction
paper impregnated with 10 per cent silver nitrate
solution; the paper may be held in position by a
watch glass or microscope slide. Warm the testtube gently (if necessary) on a water bath to
accelerate the reaction, and allow to stand. Examine
the silver nitrate paper after about 5 minutes. A
grey spot will be obtained; this is occasionally yellow,
due to the complex Ag 3 As,3AgN0 3
For minute quantities of arsenic, it is convenient to
use the apparatus depicted in Fig. II, 6, 13. Mix a
drop of the test solution with a few grains of zinc and
a few drops of dilute sulphuric acid in the micro test- Fig. III, 13, 3
tube. Insert the funnel with a flat rim, and place a
small piece of drop-reaction paper moistened with 20 per cent silver
nitrate solution on the flat surface. A grey stain will be obtained.
Sensitivity: 1 fLg. As. Concentration limit: 1 in 50,000.
A more sensitive test is provided by drop reaction paper impregnated
with gold chloride reitgent (a 1 per cent solution of HAuCl,,2H zO).
Perform the test as described in the previous paragraph: It blue to
blue-red stain of metallic gold is obtained after standing for 10-15
minutes. It is essential to perform a blank test with the reagents to
confirm that they are arsenic-free.
Sensitivity: 0'05 lug. As. Concentration limit: 1 in 100,000.
246
[III.
Dry Tests
(i) Blowpipe test.-Arsenic compounds when heated up, 'Tl
charcoal with sodium carbonate give a white incrustation ,f
arsenious oxide, and an odour of garlic is apparent while hi'!'
(ii) When heated with excess of potassium cyanide and If
anhydrous sodium carbonate in a dry bulb tube, a black min'l,r
of arsenic, soluble in sodium hypochlorite solution, is produced
in the cooler part of the tube.
I
ANTIMONY,
Sb
Sb s(80,)a + 6H sO + 380 2
Sb,O, + 4NO + 2H,0
3Sb,06 + IONO + 5H,O
SbCI. + NO + 2H.Q
14]
247
+ 4KH.C,H,Os
= 4K(SbO).C,H,Os
+ 2H.O
III, 14.
+ 2HCl =
H 2 C,R,O.
+ SbO.Cl + KCl
REACTIONS OF ANTIMONIOUS
COMPOUNDS
248
[III,
This may
t7.
~~
C
CXo
15]
249
t8. Phosphomolybdic Acid Reagent (Hs[PMollO,o]aq.): "molybdenum blue" is produoed by antimonious salts. Of the ions in Group
II, only stannous tin interferes with the test. The test solution may
consist of the filtered solution obtained by treating the Group IIB
precipitate with hYdrochloric aoid: the antimony is present as SbCI s
and the tin as SnCI" which has no effeot upon the reagent.
Plaoe a drop of the test solution upon drop reaotion paper which has
been impregnated with the phosphomolybdic acid reagent and hold the
paper in steam. A blue ooloration appears within a few minutes.
Sensitivity: 02p.g. Sb. Conoentration limit: 1 in 250,000.
Alternatively, place 1 mI. of the test solution in a semimioro tf'st-tube,
add 0'5--1 mI. of the reagent, and heat for a short time. The reagent is
reduced to a blue oompound, which can be extracted with amyl aloohol.
Stannous ohloride reduces not only the reaotive phosphomolybdic
acid but also its relatively unreactive (e.g. ammonium or potassium)
salts to "molybdenum blue." However, antimonious salts do not
reduce ammonium phosphomolybdate: Sn + + may thus be detected in
the presenoe of Sb -I- + +.
Impregnate drop reaction paper with a solution of phosphomolybdic
acid and then hold it for a short time over ammonia. gas to form the
yellow, spa.ringly soluble ammonium salt; dry. Plaoe a drop of the
test solution on this paper: a blue spot appeal'S if stannous tin is present.
Sensitivity: 003p.g. Su. Concentration limit: 1 in 650,000.
The reagent consists of a 5 per cent aqueous solution of phosphomolybdic aoid. It does not keep well.
111,15. REACTIONS OF ANTIMONIC COMPOUNDS
Use a solution of antimony pentoxide in concentrated hydrochloric acid, or of potassium antimonate, KH 2SbO,.
Sh 20 5 + IORel = 2SbC15 + 5RzO
1. Hydrogen Sulphide: orange-red precipitate of antimony
pentasulpbide Sb 2S5 in moderately acid solutions. The pre-
'~-on,
cipitate is soluble in ammonium sulphide solution (yielding L
thio-antimonate), in alkali hydroxide solutions, and is a; )
dissolved by concentrated hydrochloric acid with the forni'tion of antimony trichloride and the separation of sulph l " .
The thio-salt is decomposed by acids, the pentasulphide hei' ~
precipitated.
250
2SbCl5
5H2S
Sb2 S5 + 6HCI
8b 2S5 + 3(NH4)28
2(NH4)sSbS4 + 6HCI
Sb 2S5
6KOH
KsSbSO s
K sSbS4 6HCl
+
+
= Sb 2S5
=
=
=
=
IOHCl;
2SbCla + 2S + 3H2S
2(NH4)a8b84 ;
Sb 2S5 + 6NH4Cl + 3H 2S
Ks8bSO s
K sSb84 3H zO;
Sb28 6
6KCI
3H 2 0
fr01U
COlll-
to'.
SbHs + 3AgNO s =
+ 12AgNO. + 6H,O =
AgaSb + 3HNO a ;
24Ag + Sb,O. + 12HNO a
15]
251
Sn + H 2S0 4 (dilute)
Sn + 4H 2SO, (cone.)
4Sn + lOHNO a (dilute)
3Sn + 4HNO s + (x - 2)H 2 0
3Sn + 4HNO s + 12HCl
= SnCl.
HI
= SnS04 + H2
= Sn(SO')2 2S0 2 4H 20
= 4Sn(NO a )2 + NH,NO a
3H 20
= 4NO
3Sn0 2,xH 2 0
= 4NO
3SnCl,
8H i O
+
+
Tin forms two oxides: stannous oxide SnO and stannic oxide
Sn02 from which the stannous and sbnnic salts respectively may be
regarded as derived. Both oxides are amphoteric, the stannic
compound to the greater degree.
252
III, 16.
[III,
16)
253
under antimony (Section III, 14, reaction 4), and the solution
is weakly acid, the tin is partially deposited upon the zinc in
a spongy form but does not stain the platinum. The precipitate should be dissolved in concentrated hydrochloric achl and
the mercuric chloride test applied.
254
[III,
t9.
(<(H}
SH
red precipitate when warmed with stannous salts in acid solution. The
following interfere: silver, lead, mercury, cadmium, arsenic and anti
mony (yellow precipitates); copper, nickel and cobalt (black precipitates); bismuth (red precipitate); colloidal organiC substances (starch.
etc.); phosphates and nitrites. The hydrochloric acid concentration oj
the solution should not exceed 15 per cent.
Place 2 drops of the test-solution, acidified with dilute hydrochloric
acid, in a micro crucible and add 3 drops of the reagent_ Warm (not
above 600): a red colour or precipitate develops.
Concentration limit: 1 in 500,000.
The reagent is prepared by dissolving 02 g. of 4-methyl-l : 2dimercapto-benzene in 100 ml. of 1 per cent sodium hydroxide solution
and adding 0,3-0'5 g. of thioglycollic acid. The use of the latter in
the reagent is not imperative, but it serves to facilitate the reduction
of any stannic salt present. The reagent is discarded if a white precipitate of the disulphidEl forms.
~ 2H+ + Sn++++
or of ammonium stannichloride, (NH4 MSnC4].
+ 6C1-),
17J
255
1. Hydrogen Sulphide: yellow precipitate of stannic sulphide SnS2 from dilute acid solutions (::}O3N). The precipitate
is soluble in concentrated hydrochloric acid (distinction from
arsenious and mercuric sulphides), in solutions of alkali
hydroxides, and also in colourless (NH4HS) and yellow
{(NH4)zS",} ammonium sulphide solutions. Yellow stannic
sulphide is precipitated upon acidification.
H z[SnC16 ] + 2H 2S
SnS2
NH4SH
NHs
(NH4)2SnSa
2HCI
3SnS2
6KOH
K2SnOa
2K2SnSs
6HCl
+
+
+
+
? SnS2
+ 6HCl
= (NH4}2SnSS (thiostannate);
= SnSz
+ 2NH4Cl + H 2S
+ 2K2SnSS + 3H 20;
= K2SnOa
= 3SnS2
+ 6KCI + 3H20
2. Sodium Hydroxide Solution: gelatinous white precipitate of stannic hydroxide Sn(OH)4, soluble in -excess of the
precipitant forming sodium stannate Na2[Sn03]'
+ Fe =
SnCII!
+ FeCl2 + 2HCI
Dry Tests
(i) Blowpipe test.-All tin compounds when heated with
sodium carbonate, preferably in the presence of potassium
cyanide, on charcoal give white, malleable and metallic globules
of tin which do not mark paper. Part of the metal is oxidised
to stannic oxide, especially on strong heating, which forms a
white incrustation upon the charcoa!.
...
256
[III,
(il) Borax bead test.-A borax bead which has been coloured
pale blue by a trace of copper salt becomes a clear ruby red in
the reducing flame if a minute quantity of tin is added.
DETECTIQN AND SEPARATION OF THE METALS ill THE ARSENIC GROUP
(GROUP IIB)
III, 18.
The filtrate from the Copper Group (Group lIA) may contain the
thio-salts (NH,)aAsS" (NH,hSbS, and (NH')2SnS.. Dilute with a little
water, add dilute HCI in slight exoess (i.e. until (l.cid to litmus), warm,
filter and wash with a little H 2S water. Reject the filtrate. The residue
upon the filter may contain As,S" As,S., SbIS" Sb,S., SuS. and S.'"
Boil the precipitate gently with 5-10 mi. of con()entrated hydroohlorio
acid, dilute with a little water, and filter.
ppt., and pour 1 mi. of AgNO s solution containing a few drops of dilute
acetio o.oid on to the residue on the
filter.
Brownish-red residue of Ag,AsO,.
Sb present.
Second portion.-Partially
neutralise the liquid, add about 15
cm. of clean iron wire, hoat for 5 ,
minutes to reduce the SnCI, to
SnCI., and filter into a solution of
HgCl .
White ppt. of Hg.Cl. or grey ppt. I
ofHg.
I
Sn present.
18]
III, 18.
257
The filtrate from the Copper Group (Group IIA) may contain KAsO.,
KAsS., KSbO., KSbS., K.SnO. or K.[Sn(OH).], and K.SnS., and a little
KHgS,. Add concentrated HCI cautiously (drop wise and with constant
stirring) until the solution is distinctly acid to litmus paper. Treat with
H.S for 2-3 minutes to ensure complete precipitation of the sulphides.
The formation of a precipitate indicates the possible presence of HgS,
As.S a, Sb.S. and SnS.. Filter, wash the precipitate with a little water,
and discard the filtrate and washings. * Transfer the precipitate to a small
conical flask, add 5-10 ml. of concentrated HCl, heat to boiling [FUME
OUPBOARD] and maintain the mixture near the boiling point over a
low flame with constant stirring for 5 minutes. Dilute with a little
water, and filter.
Residue. May contain HgS and AsIS .
If yellow, only As.S. present. Wash with
water. Pour 5 mI. of dilute NH. through
8+
208
III, 18.
LIll,
The centrifugate from the Copper Group (Group IIA) may contain
KAsO., KAsS., KSbO., KSbS., K.SnO. or K.[Sn(OH).], K,SnS. and a
little KHgS.. Transfer to a small conical flask, add concentrated HCI
dropwise and with stirring until the mixture is distinctly acid to litmus
paper. Treat with H.S for 30-60 seconds to ensure complete precipitation of the sulphides. The formation of a precipitate indicates the
possible presence of HgS, As,S., Sb.S. and SnS.. Centrifuge about
2'0 mi. of the mixture, remove the supernatant liquid with a dropper
pipette and discard it. Transfer the remainder of the mixture in the
flask to the centrifuge tube, centrifuge, remove the solution and discard
it: wash the residue with a little water, completely remove the washings
and reject them. * Treat the precipitate with 05-1 mi. of concentrated
HCI, place in the hot water bath for 2-3 minutes and stir frequently.
Centrifuge: remove the centrifugate to a 4 mi. test-tube; wash residue
with 03 m!. of dilute HCI and add washings to the contents of the
test-tube.
Hg
present.
Confirm
as in
Table
SMIIA,
if Hg not
found in
Copper
Group.
Centrifugate. Add
dilute HNO. until acid.
Yellow ppt. of As.S .
As present.
Centrifugate.
May contain
H[SbCI.] and H.[SbCI.].
Divide into two parts.
(i) Either-Render just alkaline
with concentrated NH. solution,
add 03 g. of oxalic acid, and pass
H.S for 20-30 seconds.
Orange ppt. of Sb.S 3
Sb present.
Sn present.
18]
ReactwnB oJ
u/,e .Metal
Ions or uations
259
Fe
Pure iron is a silver.white, tenacious and ductile metal. The
commercial metal is rarely pure and usually contains small quan tities
of the carbide, silicide, phosphide and sulphide of iron, and a little
graphite. Iron dissolves in dilute and concentrated hydrochloric
acid and in dilute sulphuric acid with the evolution of hydrogen
and the formation of ferrous salts; with hot concentrated sulphuric
acid, sulphur dioxide and ferric sulphate are produced. Ferrous
and ammonium nitrates are obtained with cold dilute nitric acid,
whilst a more concentrated acid yields a ferric salt and either nitrous
oxide or nitric oxide depending upon the experimental conditions.
Cold concentrated nitric acid renders iron passive; in this state it
does not react with dilute nitric acid nor does it displace copper
from an aqueous solution of a copper salt.
IRON,
Iron forms two important series of salts: the ferrous salts which
may be regarded as derived from ferrous oxide FeO in which the metal
is divalent, and the ferric salts, which may be regarded as derived
from ferric oxide Fe20s and containing trivalent iron.
,
260
[III.
n.r_
+ Na2S04;
FeS04
2NaOH = Fe(OH)2
2H 20
O2 = 4Fe(OH)s
4Fe(OH)2
+ NH4HS + NHs =
FeS + 2HCI =
+
+
FeS
(NH4)2S04;
FeCl2 H 2S
5. Potassium Cyanide Solutiont: yellowish-brown P'")oipitate of ferrous cyanide Fe(CNb, soluble in excess of 1 'le
Colourless ammonium sulphide should be used for this teat: it may ')e
readily prepared by P888ing H 2S into dilute Nfla solution.
t Very poiaonous; in acid solution the volatile and highly poisonous hydr.},
gen oyanide HCN is produced.
19]
261
+ 6H aO + 6H SO,
2
= FeSO(
202
'luat~tatwe lnorgan~c
AnalysUl
lUI,
Treat a drop of the faintly acidified test solution with 1 drop of th.,
reagent on a spot plate: a red coloration is obtained. Alternatively,
treat drop-reaction paper (Whatman No.3 MM., 1st quality) whicl
has been impregnated with the reagent and dried, with a drop of thE>
the test solution: a red or pink spot is produced.
Sensitivity: 03/Lg. Fe++. Concentration limit: 1 in 1,666,000.
If appreciable quantities of ferric salts are present and traces of ferrou,
salts are sought, it is best to carry out the reaction in a micro crucible
lined with paraffin wax and to fix the ferric iron as [FeFs]--- by the
addition of a few drops of potassium fluoride solution.
The rea~ent is prepared by dissolving 001 g. of cc cc' -dipyridyl in
0-5 ml. of alcohol or in 0-5 ml. of 0-IN -hydrochloric acid.
tiO. Dimethylglyoxime Reagent: soluble red ferrous dimethylglyoxime in ammoniacal solution. Ferric salts give no coloration, but
nickel, cobalt and large quantities of copper salts interfere and must be
absent. The test may be carried out in the presence of potassium
cyanide solution in which nickel dimethylglyoxime (compare Section
III, 25) dissolves.
Mix a drop of the test solution with a small crystal of tartaric acid;
introduce a drop of the reagent, followed by 2 drops of ammonia solution. A red coloration appears.
Sensitivity: 004/Lg. Fe++. Concentration limit: 1 in 125,000.
The coloration fades on standing owing to the oxidation of the ferrous
complex.
If it is desired to detect ferric iron by this test, it must first be reduced
by a little hydroxylamine hydrochloride.
The reagent consists of a 1 per cent solution of dimethylglyoxime in
alcohol.
tIl. o-Phenanthroline Reagent
20]
263
+ H 20
Fe(OH)++
+ H+).
1. Ammonia Solution: reddish-brown, gelatinous precipitate of ferric hydroxide Fe(OH)s, insoluble in excess of the
reagent, but soluble in acids.
The solubility product offerric hydroxide is so small (11 X 10 --36)
that complete precipitation takes place even in the presence of
ammonium salts (distinction from ferrous iron, nickel, cobalt,
manganese, zinc and magnesium). Precipitation does not occur in
the presence of certain organic acids (see reaction 8 below). Ferric
hydroxide is converted on strong heating into ferric oxide; the
ignited oxide is soluble with difficulty in dilute acids, but dissolves
on vigorous boiling with concentrated hydrochloric acid.
FeCl a
+ 3NH a + 3H I O
= Fe(OH)s + 3NH,CI;
2Fe(OH)a = FesO a + 3H aO
+ H 2S =
2FeCl2
+ 2HCl + S
+ 3NH4HS + 3NH3 =
Fe2Sa + 4HCI =
+ 6NH4Cl;
+ S + 2H2S
Fe2Sa
2FeCl2
5. Potassium Ferrocyanide Solution: intense blue precipitate of potassium ferric ferro cyanide (Prussian blue).
FeCl s
[III,
264
+ NazHP04 =
FeP04
+ HCI + 2NaOI
(i)
(ii)
(iii)
It is evident from the equations that for the complete precipitation of iron as phosphate it is necessary to use excess of the reagent
to react with the liberated hydrogen chloride. This is avoided by
the addition of excess of sodium acetate solution, since acetic acid
is produced {equation (iv)} in which ferric phosphate is insoluble,
and precipitation is quantitative.
Na.C.HaO.
+ HCI =
H.C.HaO.
+ NaCI
(iv)
+ Na.HPO, + Na.C.HaO. =
FePO,
+ H.C.HaO. + 3NaCl
+ 3Na.C2H sOz =
Fe(C2 H s Oz)s
+ 2H20
+ Fe(C2H s0 )s;
Fe(OH)2' C2H sOz + 2H .CzHaOz
3NaCI
Reaction.s 7 an.d 8 are combined for the removal of the phosphate radical
fro~ solutions in which it interferes with the normal course of analysis (see
SectIOn VIII, 2); they are also affected by the presence of organic acids
(tartario, citrio, sulphosalicylic and malic acids) and by polyhydric alcohols
(Il.g. glycerol, mannitol, various sugars), and special procedures must be
adopted in the ordinary oourse of analysis when these are present (see
Chapter VIII).
20)
265
these conditions, i.e. in strongly acid solution. The precipitate is soluble in ether, is insoluble in acids, and on treatment
with aqueous ammonia solution is converted into ferric hydroxide.
1I
FeCla
+ 3C6H 6N(NO)ONH4 =
3NH4 CI
+ [C6H6N(NO)O]aFe
10. Ammonium Thiocyanate Solution: deep red eoloration (difference from ferrous salts). The coloration was formerly
attributed to undissociated ferric thiocyanate, but is now
known to be due to the ferri-thiocyanate ion, [Fe(SCN)] ++.
The reaction is a reversible one and hence the sensitivity is
increased by the addition of excess of the reagent. The ferrithiocyanate ion is more soluble in ether and in amyl alcohol
than in water; accordingly upon shaking with either of these
solvents the red colour passes into the organic layer. Phosphates, arsenates, borates, iodates, 8ulphates, acetates, oxalates, tartrates, citrates and the corresponding free acids
interfere with the test.
The organic acids form complex ions of the type:
+ 3C,O,--
[Fe(C10,)a]---;
+ 3C,H,O.--
[Fe(C,H.O.l.r--
Fe + + +
Fe+++
r--
t The reaction is well adapted as a spot test and may be carried out
as follows. Place a drop of the test solution on a spot plate and add
1 drop of 1 per cent ammonium thiocyanate solution. A deep red
coloration appears.
Sensitivity: 025p.g. Fe+++.
Coloured salts, e.g. those of copper, chromium, cobalt and nickel, reduce
the sensitivity of the test.
9*
[III,
tll
Rea~ent
2Fe013
,~ ~;
.'1
+ 3HOl + HN03 =
3FeCl3
+ lOFeSO, + 8H2SO,
= 5Fe2(S04)S
= 3"Fe2,SO,)s
+ 2H20 + NO;
21]
267
ReG{Jent
Ferrous salt
Ferric salt
Potassium ferro.
cyanide solution.
Potassium ferricyanide solution.
Ammonium thio.
cyanate solution.
White or pale-blue
precipitate.
Deep-blue precipitate.
No coloration in
complete absence of
ferric salts.
Ammonia solu.
tion.
White to greenish.
white precipitate.
Deep-blue precipita te
(Prussian blue).
No precipitate;
brown coloration.
Deep-red coloration,
discharged by mercuric chloride solu
tion.
Reddish-brown precipitate.
Dry Tests
(i) Blowpipe te8t.-When iron compounds are heated on
charcoal with sodium carbonate, grey metallic particles of iron
are produced; these are ordinarily difficult to see, but can be
separated from the charcoal by means of a magnet.
(ii) Borax bead test.-With a small quantity of iron, the bead
is yellowish-brown while hot and yellow when cold in the
oxidising flame, * and pale green in the reducing flame.
, ALUMINIUM, Al
Aluminium is a white, ductile and malleable metal; the powder
is grey. The metal is little affected by cold dilute sulphuric acid,
but dissolves readily in the hot concentrated acid with the evolution
of sulphur dioxide. Nitric acid renders the metal passive; this
may be due to the formation of a protective film of oxide. It is
readily soluble in hydrochloric acid (dilute and concentrated) with
the evolution of hydrogen. Very pure aluminium, however, dissolves slowly in concentrated hydrochloric acid, but solution can be
accelerated by adding a little mercuric chloride solution. With
caustic alkalis a solution of an aluminate is formed,
2Al + 4H aSO, = Al,(SO,)s + SO, + 2H 10;
2Al + 6HCl = 2AlCl a + 3H.;
2Al + 2NaOH + 2H zO = 2Na[AlO.J + aHa
Aluminium forms only one series of salts derived from the oxide
hl'l.()'1>'
ill
the oXIdismg
[III,
+ H = FeOl2 + HOI;
2FeCI s + S02 + 2H 20 = 2FeCl2 + H 2S04 + 2HOl",
i
2FeCls + SnCl2 = 2FeCl2 + SnCl4 ;
2FeCI s + 2HI = 2FeOl2 + I2 + 2HOI
FeOla
=
K 2Cr2 0 7
5Fe2(S04)s
+ 6FeS04 + 8H2SO.
= 3Fe2(S04)s
21]
267
Rea{/ent
Ferrous salt
Ferric salt
Potassium ferro
cyanide solution.
Potassium ferri
cyanide solution.
Ammonium thio
cyanate solution.
White or pale-blue
precipitate.
Deep-blue precipitate.
No coloration in
complete absence of
ferric salts.
Ammonia solu
tion.
Dry Tests
(i) Blowpipe test.-When iron compounds are heated on
charcoal with sodium carbonate, grey metallic particles of iron
are produced; these are ordinarily diffioult to see, but can be
separated from the charcoal by means of a magnet.
(ii) Borax bead test.-With a small quantity of iron, the bead
is yellowish-brown while hot and yellow when cold in the
oxidising flame, * and pale green in the reducing flame.
, ALUMINIUM, Al
Aluminium is a white, ductile and malleable metal; the powder
is grey. The metal is little affected by cold dilute sulphuric acid,
but dissolves readily in the hot concentrated acid with the evolution
of sulphur dioxide. Nitric acid renders the metal passive; this
may be due to the formation of a protective film of oxide. It is
readily soluble in hydrochloric acid (dilute and concentrated) with
the evolution of hydrogen. Very pure aluminium, however, dissolves slowly in concentrated hydrochloric acid, but solution can be
accelerated by adding a little mercuric chloride solution. With
caustic alkalis a solution of an aluminate is formed,
2AI
Aluminium forms only one series of salts derived from the oxide
Al 2 0 S '
268
[III.
+ 6NHa + 6H20
= 2Al(OH)a
+ 3(NH4hS04
Na[Al0 2]
NH401
Na[Al0 2]
lIOl
Al(OB)3
21]
269
+ 3NH4HS + 3NHs + 6H zO
= 2AI(OHh + 3HzS + 6NH4CI
AlzS s + 6H 0 = 2AI(OH)a + 3HzS
2
5. Sodium Phosphate Solution: white gelatinous precipitate of aluminium phosphate AIP0 4 , insoluble in acetic acid,
but soluble in mineral acids and in solutions of caustic alkalis.
2AIP04 + 2Na2S04 + H 2S04;
2NaH zP04 + Na2S04;
Al Z (S04)a + 4Na zHP04 = 2AlP04 + 3NazS04
2NaHzP04
AlP04 4NaOH = Na[AIOz] + Na aP04 + 2H zO
AI 2 (S04)s
H 2S04
+ 2NazHP04 =
+ 2NazHP04 =
A1 2 ( S04}a
3NazCOa = Alz(C0 3 )a + 3NazS04;
AI 2 (CO a)s
6H zO = 2Al(OH)s
3HzCOa
NazCOs = 2Na[AIO z]
CO 2 3H zO
2Al(OH)s
+
+
;:5
HOO"
- n=o
H,NOOC
'OH
"'=ZcOONH&
270
[III.
a
((yew ):
~/V
CO
21]
t9.
271
(CXX(.J'
red precipitate or lake in ammoniacal solution, which is fairly stable to
dilute acetic acid.
Place a drop of the test solution (which has been treated with just
sufficient of N sodium hydroxide solution to give the aluminate ion
[AlOaJ-) on a spot plate, add I drop of the reagent, then drops of acetic
acid until the violet colour just disappears and 1 drop in excess. A red
precipitate or coloration appears.
Sensitivity: 07 fLg. AI.
Dry Tests
(i) Blowpipe test.-Aluminium compounds when heated with
sodium carbonate upon charcoal in the blowpipe flame give a
white infusible solid, which glows when hot. If the residue be
moistened with one or two drops of cobalt nitrate solution and
272
[III,
+ 2Co(NO ah =
2COAl 20 4
+ 4N02 + O2
CHROMIUM, Cr
Chromium is a white crystalline metal and is not appreciably
ductile or malleable. The metal is soluble in hydrochloric acid
yielding the blue chromous chloride CrCl 2 if air is excluded, otherwise chromic chloride CrClg is formed; hydrogen is evolved. Dilute
sulphuric acid reacts similarly forming chromous sulphate CrS04 in
the absence of air, and chromic sulphate Cr 2(S04)a in the presence
of air. Concentrated sulphuric acid, dilute and concentrated nitrie
acid induce passivity.
The normal oxide of chromium is the green aeaquioxide Cr 2 0 S '
from which the chromic salts may be regarded as derived.
Chromous salts, corresponding to 'the oxide Cro, are extremely
readily oxidised in air to chromic salts; the former are rarely encountered in elementary qualitative analysis and will therefore not
be considered here. An acidic oxide, chromium trioxide CrOg,
forming red deliquescent crystals, is known: this gives rise to the
coloured chromates (e.g. K 2 Cr04 or K20,CrOs) and dichromates (e.g.
K 2Cr 20 7 or K 20,2Cr0 a), which are discussed in Section IV, 33.
22]
273
In the presence of acetate ions and the absence of other trivalent metal ions, chromic hydroxide is not precipitated. The
precipitation of chromic hydroxide is also prevented by tartrates and by citrates.
2. Sodium Hydroxide Solution: precipitate of chromic
hydroxide, readily soluble in acids and also in excess of the
precipitant in the cold forming a green solution containing
sodium chromite Na[Cr02]. Upon boiling the latter solution,
hydrolysis occurs and the chromium is almost quantitatively
re-precipitated as the hydroxide (distinction from aluminium).
Cr(OH)s + NaOH ~ Na[CrOz] + 2H zO
If hydrogen peroxide is added to the sodium chromite solution,
a yellow solution of sodium chromate is produced, which may
be identified by the" perchromic acid" reaction (Section IV, 33,
reaction 4; reaction 6 below) or by the diphenyl-carbazide
reagent (Section IV, 33, reaction 9).
2Na[Cr0 2 ] + 3Hz0 2 + 2NaOH = 2Na2[CrO,] + 4H2 0
274
[III,
2Cr+++
+ 30Br- + 100H-
= 2CrO,--
+ 3Br- + 5H,O
2Cr+++
+ 38 20 8- - + SHIO
= 2CrO,--
+ 16H+ + 6S0,-
22]
275
Dry'!ests
(i) Blowpipe test.-All chromium compounds when heated
with sodium carbonate on charcoal yield a green infusible mass
of chromium sesquioxide Cr20,.
276
~
[III.
+ 5Na2COa + 3KNOs
= 2Na2Cr04
TABLES,
23]
277
III, 23. Table IV. Analysis of the Iron Group (Group IlIA)
Add 1-15 graIDll of solid ammonium chloride for each 10 ml. of
solution, heat to boiling and add dilute NH. solution slowly until the
solution smells of ammonia, boil for 1-2 minutes, filter rapidly and wash
with a little 1 % NH,Cl solution.
------------------------------------------------~---------
Filtrate.
Reject.
278
III, 23.
Mn present.
Centrifu
gate.
Reject.
Cr present.
The blue colour does not last
long as the compound is unstable.
(ii) Acidify with dilute HCl
(litmus paper test) and then render
just basio with dilute aq. NH., and
add 1 drop in excess. Heat on a
water bath for 1 minute.
White gelatinous ppt. of AI(OH) .
Al present.
Confirm Al thus: centrifuge,
wash with a few drops of water,
dissolve the ppt. in dilute HOI,
add 03 ml. of ammoniwn acetate
solution and 1 drop of the" alwni
non" reagent. Mix, allow to stand
for 30 seconds, and render alkaline
with ammoniacal ammoniwn car.
bonate solution. A red ppt. con
firms AI.
24]
279
+ 6RCI =
+ SRCI =
2CoCI 2
300CI 2
+ CI + 3H 0;
+ 01. + 4RaO
B
Cobaltous hydroxide is slightly soluble in a large excess of concentrated sodium hydroxide solution, but cobaltic hydroxide is insoluble.
280
[III,
+ 28NHs + 6HzO + O2
=4[Co(NHs)o](OH)3
+ 4NH4NO;
The precipitation of cobaltous hydroxide does not take place in the presenc>
of certain organic acids and organic hydroxy compounds, as in the case oj
aluminium (Section III, 21, reaction 2).
+ NH4HS + NHs =
3CoS + 8HNOs =
CoS
2~N03
2NO
3Co(NOs)z
+ 3S + 4HzO
4. Potassium Cyanide Solution: reddish-brown precipitate of cobaltous cyanide Co(CNh, soluble in excess of the
reagent to form a brown solution containing potassium cobaltocyanide K,,[Co(CN)6], analogous to potassium ferrocyanide
~[Fe(CN)6]' When the cob alto cyanide solution is treated
in the cold with dilute hydrochloric acid, cobaltous cyanide is
precipitated.
On prolonged boiling of the brown solution, preferably after
the addition of a few drops of hydrogen peroxide or of sodium
hypochlorite or of sodium hypobromite solution, it assumes a
yellow colour, due to oxidation to potassium cobalticyanide
K3[CO(CN)6J, analogous to potassium ferricyanide K 3[Fe(CN)6]'
The cobalticyanide solution gives no precipitate with acids
(distinction from nickel) nor with ammonium sulphide.
+
+
Co(NOs)z
2KCN = Co(CN)z
2KNO s ;
CO(CN)2
4KCN = ~[CO(CN)6];
~[CO(CN)6]
2H20
O2 = 4Ks[Co(CN)6]
4KOH
K.[CO(CN)6]
4HCl = Co(CN)2
4HCN
4KCI
24]
IOn8
or Oatio'IUI
281
7. oc-Nitroso-,8-naphthol Reagent
reddish-brown precipitate of slightly impure cobalti-nitroso-,8naphthol CO(ClOH602N)a (an inner oomplex salt) in solutions
282
[III.
Co,;xX:.J,
deep red' coloration. The test is applicable in the presence
of nickel; tin and iron interfere and should be removed; the
coloration produced by iron is prevented by the addition of
an alkali fluoride.
t9.
II
II
S S
25]
283
Dry Tests
(i) Blowpipe test.-All cobalt compounds when ignited with
sodium carbonate on charcoal give grey, slightly metallic beads
of cobalt. If these are removed, placed upon filter paper and
dissolved by the addition of a few drops of dilute nitric acid, a
few drops of concentrated hydrochloric acid added and the
filter paper dried, the latter is coloured blue by the cobalt
chloride produced.
(ii) Borax bead test.-This gives a blue bead in both the
oxidising and reducing flames. Cobalt meta-borate Co(B0 2 h,
or the complex salt Na 2[Co(B0 2)4], is formed see (Section II, 1).
The presence of a large proportion of nickel does not interfere.
NICKEL, Ni
Nickel is a hard, silver-white metal; it is ductile, malleable and
very tenacious. Hydrochloric and sulphuric acids, both dilute and
concentrated, attack it slowly; dilute nitric acid dissolves it re:tdily,
but the concentrated acid induces passivity.
Only one stable series of salts, the nickelous salts, which may be
regarded as derived from the green nickelous oxide NiO, is known.
A brownish-black nickelic oxide Ni 2 0 3 exists, but this dissolves in
acids forming nickelous compounds.
Ni:aO a
+ 6HCl =
2NiCI I
+ 3H 10 + Cl.
__ ~ ___ 1 _ _ _ _
~_1
_1
,-
..,,1Ik\
J1
Qualitative I norganic
284
Ana~ysis
+ Na2S04;
NiS04
2NaOH = Ni(OH)2
4Ni(OH)2 + 2H20 + O2 = 4Ni(OH)s
+ H 20
+ H 20
= Ni(OH)Cl
+ NH4Cl;
+ NH4Cl
= [Ni(NHs )6](OH)2
NiC1 2
+ H 2S ~ NiS + 2HCI
25]
285
+ 2KCN =
Ni(CN12
+ 2KCI;
+ 2KCN = K 2[Ni(CN)4];
2K 2[Ni(CN)4] + 9NaOBr + 4NaOH + H 2 0
= 2Ni(OH)a + 4KCNO + 4NaCNO + 9N"aBr;
KCN + Brz = CNBr + KBr;
Ni(CNh
Kz[Ni(CN)4]
+ 2HCl =
Ni(CN)z
+ 2HCN + 2KCI
OH
CHsC=NOH
CHs.C=NOH
+ NiSO, + 2NH,OH =
CH . C=N'\,.
CHs.C=N
/N=C.CH s
/Ni,
'.
N=C.CH.
dH
+ (NH')2S0 ,+2H 0
2
[III,
286
+ 2H.CHO =
+ 2C,H sO aN a =
K 2[Ni(CN),)
Ni(CN)a
t9.
~-Furil-dioxime
Ni(CN)a
+ 2CH (CN)OK
+ 2HCN
2
Ni(C,H 70 aN 2)a
Reagent
C.H 3 0- =NOH) :
( C.H 0-C=NOH
3
25]
287
tlO. Rubeanic Acid Reagent {(CS.Nlis)s}: blue or violet precipitate or coloration in ammoniacal solution. Copper and cobalt. as well
as iron, salts interfere with the reaction and should be absent.
Place a drop of the test solution upon drop-reaction paper. hold it
over ammonia vapour, and add a. drop of the reagent. A blue or blueviolet spot is obtained.
Dry Tests
(i) Blowpipe test.-All nickel compounds when heated with
sodium carbonate on charcoal yield grey, slightly magnetic
scales of metallic nickel. If these are placed upon a strip of
filter paper, dissolved by mean" of a few drops of nitric acid,
a few drops of concentrated hydrochloric acid added and the
filter paper dried by moving it back and forth in the flame or
by placing it on the outside of a test-tube containing water
which is heated to the boiling point, the paper acquires a green
colour owing to the formation of nickelous chloride. On
moistening the filter paper with ammonia solution and adding
a few drops of the dimethylglyoxime reagent, a red colour is
produced.
(ii) Borax bead test.-This is coloured brown in the oxidising
flame, due to the formation of nickel meta-borate Ki(B02h
or of the complex meta-borate Na2[Ni(B02)4] (see Section
11,1), and grey, due to metallic nickel, in the reducing flame.
MANGANESE,
Mn
Qualitative
288
lnorgan~c Anaty~
Mn + 2HCI
MnO. + 4HCl
MnaO, + SHCI
2MnaOa + 4H aSO,
2Mn aO, + 6H aSO,
2MnO. + 2H.SO,
LJ.l.l,
1'1
= MnCI I + HI;
+ Cl. + 2H_0;
+ CIa + 4B t O;
4MnSO, + O. + 4IlaO;
6MnSO, + O. + 6Il.0;
2MnSO, + O. + 2I1aO
= MoCl.
= 3MnCI.
=
=
=
+ 2NaC) ,
MnCl 2
26]
289
L......... ,
ililllU
2MnS04 + 5KI04 + 3H 20
2HMn04 + 5KIOs
+ 2H2S04
t9.
Chlorides, bromides, iodides and other salts that precipitate sil" \)r
should be absent, as should also compounds which will react w, i h
permanganic acid_
Place a drop of the test solution in a micro-crucible, add 1 drop )f
ooncentrated sulphuric acid and 1 drop of O'lN -silver nitrate soluti, ,1,
26]
291
; Ii
Dry Tests
(i) Borax bead test.-The bead produced in the oxidising
flame by small amounts of manganese salts is violet whilst
hot and amethyst-red when cold; with larger amounts of
manganese the bead is almost brown and may be mistaken
for that of nickel. In the reducing flame the manganese bead
is colourless whilst that due to nickel is grey.
(ii) Fusion test.-Fusion of any manganese compound with
sodium carbonate and an oxidising agent (potassium chlorate
or potassium nitrate) gives a green mass of alkali manganate.
The test may be carried out either by heating upon a piece of
platinum foil with potassium nitrate and sodium carbonate (if
platinum foil is not available, a piece of broken porcelain may
be employed), or by fusing a bead of sodium carbonate with a
small quantity of the manganese compound in the oxidising
flame and dipping the fused mass while hot into a little
powdered potassium chlorate or nitrate and reheating (coml,are
Section II, 1).
Mn804 + 2KNO a + 2Na2COS
= Na2Mll04
3Mn804
2KClO g
6Na2COg
= 3Na2l\1n04
ZINC, Zn
292
[III,
= ZnSO,
Hz:
= 4Zn{NO a)1
NH,NO a
3HaO;
= 4Zn{NO a)z
NzO
5H IO:
=
=
=
+
+
+
+
3Zn(NO ah + 2NO + 4H 20:
ZnSO, + SOl + 2H zO;
Na2[Zn02] + HI
2NHs
Zn(OH)2
27]
293
+ NH4HS + NHa =
ZnS
+ (NH4)2S04
4. Hydrogen Sulphide: partial precipitation of zinc sulphide in neutral solutions; when the concentration of acid
produced is about 03 . M (pH about 06), the sulphide ion concentration derived from the hydrogen sulphide is depressed so
much by the hydrogen ion concentration from the acjd that
it is too low to exceed the solubility product of ZnS, and consequently precipitation ceases. Upon the addition of alkali
acetate to the solution, the hydrogen ion concentntion is
reduced because of the formation of the feebly dissociated acetic
acid, the sulphide ion concentration is correspondingly increased, and precipitation is almost complete (compare Section
I, 16). Zinc sulphide is precipitated from solutions of alkali
zincates by hydrogen sulphide.
ZnS04 + H 2S ~ ZnS + H 2S04
2Na.C 2H sOz + H 2S04 = 2H.C2Ha02 + Na2S04
Na2[Zn02] + H 2S ~ ZnS + 2NaOH
Zn(NH4)P04
294
[III,
+ 8NaOH =
2Na2[Zn02]
+ Na4[Fe(CN)6] + 4H2 0
Zn++
+ [Hg(SCN)4r- =
Zn[Hg(SCN)4]
27]
295
cent copper sulphate solution and I drop of the ammonium mercurithiocyanate reagent. A violet (or blackish-purple) precipitate appears.
The reaction may also be conducted in a semimicro test-tube: here
0'3-05 ml. of amyl alcohol is added. The violet precipitate collects at
the interface.
Concentration limit: 1 in 10,000.
r--
preferably with dilute sulphuric acid), a drop of 002 per cent cobalt
sulphate solution, and a drop of the ammonium mercuri-thiocyanate
reagent on a spot plate or in a micro crucible. A blue precipitate is
formed.
The reaction may also be carried out in a semimicro test-tube in the
presence of 0,3-0'5 ml. of amyl alcohol.
Sensitivity: 0'2-05 p.g. Zn. Concentration limit: 1 in 100,000.
tIl. Rinmann's Green Test.-The test depends upon the production of Rinmann's green (largely cobalt zincate CoZnO z) by heating the
salts or oxides of zinc and cobalt. An excess of cobaltous oxide must
be avoided for it leads to a red-brown coloration: oxidation to cobaltic
oxide produces a darkening of colour. Optimum experimental conditions are obtained by converting the zinc into the cobalticyanide:
Ka[Co(CN)6] + Zn++ = KZnrCo(CN).] + 2K+
296
-
[III,
Ignition of the latter leads to zino oxide and cobaltous oxide in the
correct proportion for the fOl'IIl8.tion of cobalt zincate, whilst ca,! )on
from the filter paper (see below) prevents the formation of cob, ltic
oxide. All other metals must be removed.
Place a few drops of the neutral (litmus) test solution upon POtasf: !lm
cobalticyanide (Rinmann'B green) test paper. Dry the paper ov, l' a
flame and ignite in a small crucible. Observe the colour of the ,sh
against a. white background: part of it will be green.
Sensitivity: 06 p,g. Zn. Concentration limit: 1 in 3,000.
The potassium cobalticyanide test paper is prepared by soa], I ng
drop reaction paper or quantitative filter paper in a solution contaiJ 'lg
4 grams of potassium cobalticyanide and 1 gram of potassium chIO! :te
in 100 ml. of water, and drying at room temperature or at 100. The
paper is yellow and keeps well.
Dry Tests
Blowpipe test.-Compounds of zinc when heated upon
charcoal with sodium carbonate give an incrustation of t1le
oxide, which is yellow when hot and white when cold. 'I,0
metal cannot be isolated owing to its volatility and subsequc' ,t
oxidation. If the incrustation is moistened with a drop ,f
cobalt nitrate solution and again heated, a green mass (Rillmann's green), consisting largely of cobalt zincate CoZn02 l:'l
obtained.
An alternative method is to soak a piece of ashless filtt "
paper in the zinc salt solution, add one drop of cobalt nitra! '
solution and to ignite in a crucible or in a coil of platinum wir! .
The residue is coloured green.
DETECTION AND SEPARATION OF THE METALS IN THE ZINC GROU"
(GROUPIDB) .
28)
297
Residue. If black,
may contain OoS and
NiS. Test residue with
borax bead.
Blue bead.
Co present.
Dissolve residue in a
mixture of 15 ml. of
10% NaOCI sol~ion
and 05 ml. of "dilute
HOI.
Add 1 mI. of
dilute HOI and boil
until Ols is expelled.
0001 and dilute to about
4 ml. Divide into 2
equal parts.
(i) Add 1 mI. of amyl
alcohol, 2 grams of solid
NH,SON, and shake.
Amyl alcohol layer
coloured blue.
Co present.
(ii) Add 0'5 mI. of
NH,CI solution, NH,
solution until faintly
alkaline, and then a
little dimethylglyoxime
reagent.
Red ppt.
Ni present.
10*
298
111,28.
[III,
Residue. If black,
may contain CoS and
NiS. Test residue with
borax bead.
Blue bead.
Co present.
Add 10-15 drops of
dilute HCl and 5 drops
of 10% NaOCI solution,
stir and place in a hot
water bath for 1-2
minutes. Transfer the
liquid with the aid of
1 ml. of water to a semimicro boiling tube and
boil gently to expel Cl .
Divide the solution into
2 parts.
(i) Add 05-1 ml. of
amyl alcohol and 50
mg. of solid NH,SCN,
and shake.
Blue coloration in the
alcohol layer.
Co present.
(ii) Add 1 drop of
NH.CI solution, render
fa.intly alkaline with
NHa solution, and add
3-5 drops of dimethylglyoxime reagent.
Red ppt.
Ni present.
Centrifugate. Me:
contain Na.[ZnO.J.
Divide into 2 parts.
(i) Pass H.S.
White ppt. of ZnS
Zn present.
Use either test (ii
or (iia).
(ii ) Just acidify with
dilute H.SO" add 5
drops of 01 % CuSO.
solution, and 5 drops
of ammonium mercuri-thiocyanate reagent, and stir.
Violet ppt.
Zn present.
(iia) Just acidify
with dilute H.SO,.
add a drop of dilute
cobalt acetate
or
nitrate solution, 05
mI. of ammonium
mercuri-thiocyanate
reagent, and stir.
Pale blue ppt.
Zn present.
I
I
I
I
29]
299
BARIUM, Ba
Barium is a silver-white, malleable and ductile metal, which is
stable in dry air. It reacts with water at the ordinary temperature
forming barium hydroxide and liberating hydrogen. The metal is
soluble in acids with the evolution of hydrogen.
+ (NH4)2C204 =
BaC20 4
+ 2NH4CI
300
[III,
If barium sulphate is boiled with a concentrated solution of sodium carbonate, partial transformation into the less soluble barium carbonate OCCU/'6
in accordance with the equation:
BaSO,
Na.CO s ~ BaCO s
Na.SO,
+ 2H+
2HCrO,-
Cr 20 7- -
+ HIO
29]
301
t7.
II
Dry Test
Flame coloration.-Barium salts, when heated in the nonluminous Bunsen flame, impart a yellowish-green colour to the
flame. Since most barium salts, with the exception of the
chloride, are non-volatile, the platinum wire is moistened with
concentrated hydrochloric acid before being dipped into the
302
fIll,
Its
4. Saturated Calcium Sulphate Solution: white precipitate of strontium sulphate, formed slowly in the cold but more
rapidly on boiling (distinction from barium).
5. Ammonium Oxalate Solution: white precipitate of
strontium oxalate, sparingly soluble in water (0'66 g. per litr\' ;
S.P. 14 X 10-7 ) and in acetic acid, but soluble in mineral acid,.
6. Potassium Chromate Solution: yellow precipitate of
strontium chromate SrCr04 from concentrated solutions; the
precipitate is appreciably soluble in water (12 grams per litre)
and in acetic acid. No precipitation therefore occurs in dilute
solutions nor from concentrated solutions containing acetic:
acid (distinction from barium; see Section III, 29, reaction 6).
31]
Of"
Oation8
303
Dry Test
Flame coloration.-Volatile strontium compounds, especially
the chloride, impart a characteristic carmine-red colour to the
non-luminous Bunsen flame (see remarks under Barium).
CALCIUM, Ca
+ H 20 + CO2 ~ Ca(HCOs )2
304
[III,
+ (NH4)2S04 =
(NH4 MCa(SO')2J
t8.
CaCl 2
K 4[Fe(CN)6] = CaK 2 [Fe(CN)6]
2KCI
Sodium Dihydroxytartrate Osazone Reagent
Ca H 6. NH - N =C-COONa) :
CaH6.NH-N=~-COONa
31)
305
The reagent is useful inter alia for the rapid differentiation between
tap and distilled water: a positive result is obtained with a mixture of
I part of tap water and 30 parts of distilled water.
t9. Picrolonic Acid (or I-p-Nitrophenyl-3-methyl-4-nitro-5pyrazolone) Reagent
Dry Test
Flame coloration.--Volati1e calcium compounds impart a
yellowish-red colour to the Bunsen flame (see remarks under
Barium).
306
[HI,
32]
111,32.
307
Add 1-2 mI. of NH,CI solution, NH3 solution until just basic, followed
by (NH.).CO. solution lmtil precipitation is complete. Heat on a water
bath, with stirring, at 60-70 0 G for 5 minutes. Filter, wash with a little
hot water and discard the filtrate and washings.
The residue may contain BaCO., 8rCO. and CaCO.. (T) Dissolve
the ppt. in 5 mi. of hot 2N acetic acid by pouring the acid replatedIy
through the filter paper. Test 1 mI. for barium by adding J".CrO,
solution dropwise to the nearly boiling solution. A yellow ppt. indicates
Ba.
Ba present.-Heat the remainder of the solution almost to boiling,
and add a slight excess of K.CrO. solution (i.e. until the solution assumes
a yellow tint). Filter and wash tho ppt. (G) with a little hot water.
Render the hot filtra.te and washings basic with NHs solution and add
an excess of (NH.l.Cv 3 solution or, better, a little solid Na.CO.. A
white ppt. indicates the presence of 8rC0 3 and/or CaC0 8 Wash the
ppt. with hot water, and dissolve it in 4 mI. of warm 2N.acetic acid:
boil to remove excess of CO. (solution A).
Ba absent.-Discard the portion used in testing for barium, and
employ the remainder of the solution (B), after boiling for 1 minute to
expel CO 2, to test for strontium and calcium.
Residue (G).
Solution A or Solution B. The volume
Yellow: BaCrO.
should be about 4 ml.
Wash well with hot
Either-To 2 ml. of the cold solution, add 2 ml.
water. Dissolve the
of saturated (NII,).SO. solution, followed by 02
ppt. in a little congram of sodimD thiosulphate, heat in a b ..aker of
centrated HCl, evapoboiling wster for 5 minutes, and allow to stand
rate almost to dry.
for a short time. Filter.
ness, and apply the
Or-To 2 ml. of the solution, add 2 mi. of trio
flame test.
ethanolamine, 2 ml. of saturated (NH,).SO,
Green (or yellowish. solution, heat on a boiling water bath with
green) flame.
vigorous stirring for 5 minutes, and allow to stand
Ba present.
for 1-2 minutes. Dilute with an equal volume
(Use spectroscope,
of water and filter.
- - - - - ----_._;------_._--if available.)
Residue. Largely
Filtrate.
May
81'80,. Wash with a little contain Ca complex.
(If 81' absent, use
water. Transfer ppt. and
filter paper to a small 2 ml. of solution A
crucible, heat until paper or E.) Add a little
has charred (or burn filter (NH')2C20, solution*
paper and ppt., held in a and warm on a water
Pt wire, over a crucible), bath.
White ppt. of
moisten ash with a few
drops of concentrated CaC 20,.
HCI and ap}'ly the flame
Ca present..
Confirm by flame
test.
test on ppt.-brickCrimson flame.
Sr present.
red flame.
(Use spectroscope, if
(Use spectroscope,
if available.)
available.)
* When triethanolamine has been employed in the separation of Sr and Ca,
the addition of a little acetic acid (i.e. until the solution is faintly acid) may
uasist the precipitation of the CaG.O,.
308
111,32.
[lIT,
Centrifugate.
May contain Ca com
plex. (If Sr absent,
use 1 ml. of solution
D.) Addafewdrops
of (NH.).C.O. solu
tion (2) and warm
on a water bath.
White ppt. of
CaC,O .
Ca present.
Confirm by flame
test-brickred
flame.
(Use spectroscope,
if available.)
II
I
I
I
32]
111,32.
309
Residue (0).
Yellow: BaOrO,.
Dissolve in a
few drops of concentrated ROI,
evaporate to dryness in a small
crucible and
apply the flame
test. Green (or
yellowish-green)
flame.
Ba present.
(Use spectroscope, if available.)
;uu
LI1J,
SMVI
SMVIA
.~
33]
~)'!:;
Pl_il_
311
2. Sodium Hydroxide Solution: white precipitate of magnesium hydroxide, insoluble in excess of the reagent, but
readily soluble in solutions of ammonium salts.
3. Ammonium Carbonate Solution: white precipitate of
basic magnesium carbonate, often only on boiling or on long
standing. No precipitate is obtained in the presence of ammonium salts of strong acids, since the high concentration of
ammonium ions will lower the C0 3 - - ion concentration of the
solution when ammonium carbonate is added to so low 11 value
that the solubility product of MgCO a (26 X lO-5) is not
attained:
NH,,+
+ C0 3- - ~ NHa + HCO s-
4. Sodium Carbonate Solution: white voluminous precipitate of basic carbonate 4MgCO a,Mg(OHh,5H 20 or
[Mg(MgCOa),,](OHh, insoluble in solutions of bases, but soluble
in acids and in solutions of ammonium salts.
5MgS04
+ 5NazCOs + H 20
= 4MgCO a,Mg(OH)2
+ 5NazSO, + CO
5. Sodium Phosphate Solution: white orystalline precipitate of magnesium ammonium phosphate Mg(NH,)P0 4 ,6H zO
in the presence of ammonium chloride (to prevent the precipitation of magnesium hydroxide) and ammonia solutions; the preoipitate is sparingly soluble in water, soluble in acetio acid and
312
Ct!ua~tatt.Ve
111J.,
7. 8-Hydroxy-quinoline or "Oxine"
Rea~ent
(W}
When a solution of a magnesium salt, containing a lltlile
ammonium chloride, is treated with 1-2 ml. of the rea~"nt
which has been rendered strongly ammoniacal by the addil, Ion
of 3-4 ml. of dilute ammonia solution and the mixture hell! ed
to the boiling point, a yellow precipitate of the complex ,alt
Mg(C 9 H 6N.Ob,4H 2 0 is obtained. All other metals, ex, "pt
sodium and potassium, must be absent.
The reagent is prepared by dissolving 2 grams of oxine in
100 ml. of 2N acetio acid.
33J
313
It yields the same colour changes as Magneson I, but has the advantage
that it is more sensitive (sensitivity: 0'2 p.g. Mg; concentration limit:
1 in 250,000) and its tinctorial power is less so that the blank test is not
so deeply coloured. Its mode of use and preparation are identical with
that described above for Magneson r.
.11
1
31<l
tIll,.
For formula, see under Aluminium, Section III, 21, reMtion 10.
34]
316
[III.
316
t6.
Rea~ent
OJ'ONH3=>-NO' ,
'NOs NO.
35]
317
Dry Test
Flame coloration.-Potassium compounds, preferably the
chloride, colour the non-luminous Bunsen flame violet (lilac).
The yellow flame produced by small quantities of sodium
obscures the violet colour, but by viewing the flame through
two thicknesses of cobalt blue glass, the yellow sodium rays
are absorbed and tbe reddisb-violet potassium flame becomes
visible. A solution of chrome alum (310 grams per litrp), 3 cm.
thick, also makes a good filter.
SODIUM, Na
Sodium is a silver-white, soft metal. It oxidises rapidly in moist
air and is therefore kept under solvent naphtha or xylene. The
metal reacts violently with water forming sodium hydroxide and
evolving hydrogen. The salts are derived from the monoxide Na20.
III, 35.
1. Uranyl Magnesium Acetate Solution: yellow, crystalline precipitate of sodium magnesium uranyl acetate
NaMg(U02h(C2H302)9,9H20 from concentrated solutions. The
addition of about one-third volume of alcohol helps the precipitation.
NaCI
= NaMg(UOz)a(CzH30Z)9 + HCI
The reagent is prepared as follows. Dissolve 10 grams of uranyl
acetate U02(CzH30Z)2,2H20 in 6 grams of glacial acetio aoid and
100 ml. of water (solution a). Dissolve 33 grams of magnesium
acetate Mg(C 2H 30 2)2,4H 20 in 10 grams of acetio acid and 100 ml.
of water (solution b). Mix the two solutions a and b, a,llow to
stand for 24 hours, and filter. Alternatively, a reagent of equivalent
concentration may be prepared by dissolving uranyl magnesium
acetate in the appropriate volume of water or of N aoetio acid.
2. Chloroplatinic Acid, Tartaric Acid or Sodium
Cobaltinitrite Solution: no preoipitate with solutions of
sodium salts.
3. Uranyl Zinc Acetate Reagent.-As a delicate test for
sodium, the uranyl zinc acetate reagent is sometimes pre1erred to
that employing uranyl magnesium acetate. The yellow crystalline sodium zinc uranyl acetate NaZn(U02)s(C2Ha02)9,9H20
is obtained. The reaction is fairly seleotive for sodium.
318
[III,
* Arsine,
be absent.
36]
319
2MnSO,
+ H 20 2 + 4NHs + 4H 0
2
black
= 2Mn(OH)s
+ 2(NH')2S04
t The spot-test technique is as follows. Mix a drop of the test solution with a drop of concentrated sodiwn hydroxide solution OIl a watoh
glass. Transfer a micro-drop of the resulting solution or suspension to
drop reaction paper and add a drop of Nessler's reagent. A yellow or
orange-red stain or ring is produced.
Sensitivity: 03p.g. NH. (in 0002 ml.).
A better procedure is to employ the technique described lwder the
manganous nitrate-silver nitrate reagent in reaction 9 below. A drop
[III,
320
3. Sodium Cobaltinitrite Solution (Na3[Co(N02)6]): yellow precipitate of ammonium cobaltinitrite (NH4 MCo(N0 2)a],
similar to that produced by potassium ions.
3NH4Cl
+ Nas[Co(N02)6] =
+ 3NaCI
4. Chloroplatinic Acid Solution (H 2[PtCla]): yellow, crystalline precipitate of ammonium chloroplatinate (NH4 MPtCla],
similar to that of the corresponding potassium salt, but
differing from it in being decomposed by warming with sodium
hydroxide solution with the evolution of ammonia gas.
2NH4Cl
+ H 2[PtC4] =
(NH4 MPtC4]
+ 2NaOH =
(NH,h[PtC4]
Na2[PtCle]
+ 2HCl;
+ 2NHs + 2H20
+ NH4Cl =
NH,.H.C,H,06
+ NaCl
36]
321
t8. para-Nitrobenzene-diazonium Chloride Reagent.-The reagent (I) yields a red coloration (due to IT) with an ammonium salt in
the presence of sodium hydroxide solution.
OzN-Q-NaCl+2NHs+H zO
(I)
OaN-Q-N
NONH.+NH.Cl
(II)
Place a drop of the neutral or i'lightly acid test solution on a spot plate,
followed by a drop of the reagent and a fine granule of calcium oxide
between the two drops. A red zone forms round the calcium oxide.
A blank test should be carried out on a drop of water.
Sensitivity: 07 ttg. Concentration limit: 1 in 75,000.
The reagent (sometimes known as Riegler's solution) is prepared as
follows. Dissolve 1 gram of pnitraniline in 2 m!. of concentrated hydrochloric acid and 20 ml. of distilled water (warming may be necessary)
and dilute with 160 ml. of water. Cool, add 20 ml. of 2-5 per <lent
sodium nitrite solution with vigorous shaking. Continue the shaking
until all dissolves. The reagent becomes turbid on keeping, but can
be employed again after filtering.
11+
3!J
[JII,
micro test-tube; also place a drop of the reagent on the glass knol )f
the ~pper and close the apparatus_ Heat at 400 for 5 minU' "s,
Wash'tihe drop of the reagent on to a piece of quantitative filter pa 'lr
when a'black or grey fleck will become apparent; this turns blue UJ 'n
treatment with a solution of benzidine (the latter is prepared by I
solving 0'05 gram of benzidine or its hydrochloride in 10 ml. of glal ,1
acetic acid, diluting to 100 ml. with water, and filtering).
j' ,-
Dry Test
All ammonium salts are either volatilised or decompmd
when heated to just below red heat. In some cases, wh. ! e
the acid is volatile, the vapours recombine on cooling to fOl '11
a sublimate of the salt, e.g. ammonium chloride.
DETECTION AND SEPARATION OF THE METALS OF THE ALKALI GRO' P
(GROUP v)
The metals of this group are not precipitated by the earlier gro d)
reagents. It is assumed that the elements of Groups I to IV ha ' e
been removed as already described, or that only metals of Group V
are present. The student should, as in previous groups, prepare 1 'r
himself or obtain from the teacher, a solution containing some or :1
of the simple salts of the metals of the group. The filtrate ff( .11
Group IV, if employed, should be evaporated to dryness and ,'I
ammonium salts eliminated. This is m'ost conveniently carried () ,t
by concentrating the solution in an evaporating dish (FU~! E
CUPBOARD!) until salts begin to crystallise out, allowing to co' ,
then adding a little concentrated nitric acid by means of a droP} "
pipette in such a manner as to wash down the solid from the sid .i
to the centre of the dish, then heating cautiously until dry a, ,I
finally more strongly until fuming ceases. The cold residue m \'
then be divided into two portions: one is used in testing for Mg wi 'l
the "oxine" reagent, and the other in testing for Na and K and al ,
for the confirmatory test for Mg,
The sodium phosphate test for Mg (see Section 111,33, reaction ,;)
is not altogether satisfactory, particularly in dilute solutions wh, 1
precipitation is comparatively slow, and also the magnesium amm '
nium phosphate has a tendency to form supersaturated solution
traces of alkaline earth metals tend to interfere with the test.
37J
323
324
[III,
Notes. (1) If it is desired to carry out the Na.HPO. test for comparil' I
with the "oxine" test for Mg, treat the acid solution with a little NH"
followed by dilute Nfl. solution until alkaline, and 5-6 drops of Na 2Hl' ,
solution. Shake or stir the mixture and allow to stand for 3-5 minut,
A white crystalline ppt. of Mg(NH.)PO.,6H.O indicates Mg. Centrifuge at
wash the ppt. with 03 ml. of water: discard the washings. Dissolve t i
ppt. in 5 drops of dilute HCI, warming if necessary. Add 1 drop of t
"magneson" reagent, and then NaOH solution until alkaline. A blue PI'
confirms Mg.
(2) See Note 2 in macro Table VII.
* If the residue dissolves completely (or almost completely) in water, dilu'"
the resulting solution (after centrifugation, if necessary) to about 15 ml. all '
divide it into three approximately equal parts:- (i) Use the major portion 1
test for Mg with the prepared "oxine" solution; confirm Mg by applying tl,
"magneson" test to 3-4 drops of the solution; (ii) and (iii) Test for Na an"
K respectively, as described in the Table.
CHAPTER IV
GLASS A
(i) Ga8es evolved with dilute hydrochloric acid or dilute .sul-
phuric acid.
Carbonate, bicarbonate, sulphite, thio8ulphate, sulphide,
nitrite, hypochlorite, cyanide and cyanate.
(ii) Gases or acid vapours evolved with concentrated sulphuric
acid.
326
326
[IV,
CLASS B
(i) Precipitation reactions.
Sulphate, persulphate, t phosphate, phosphite, hypophosp: ,te,
arsenate, arsenite, chromate, dichromate, silicate, silicofluo! Ide,
salicylate, benzoate and succinate.
(ii) Oxidation and reduction in 8olution.
Manganate, permanganate, chromate and dichromate,
The reactions of all these acid radicals or anions will be
systematically studied in the following pages. For ",nvenience the reactions of certain organic acids are grou 1,ed
together; these include acetates, formates, oxalat.es, tartra; I)S,
citrates, salicylates, benzoates and succinates, It may be
pointed out that acetates, formates, salicylates, benzoates : nd
succinates all belong to another group; all give a characteri : ic
coloration or precipitate upon the addition of ferric ch101l,1e
solution to a practically neutral solution.
IV, 2. REACTIONS OF CARBONATES, C0 3 - Solubility.-All normal carbonates, with the exception of those of the aL ,Ii
mat"Is and of ammonium, are insoluble in water. The acid carbonate, 'lr
bicarbonates of calcium, strontium, barium, magnesium and possibly of j n
exist in aqueous solution; they are formed by the action of excess of carb"" 'c
acid upon the normal carbonates either in aqueous solution or suspension" I ,d
are decomposed on boiling the solutions.
CaCO,
+H
20
+ CO a ~ Ca(HCO.).
The bicarbonates of the alkali metals are soluble in water, but are lesB solu! I')
than the corresponding normal carbonates.
(i),
2]
327
Fig. IV, 2, 1.
+ COa;
328
(IV,
in ammonia solution and in nitric acid. The precipita 1 " becomes yellow upon addition of excess of the reagent, I ltd is
partly decomposed on boiling with water into brown "ilver
oxide Ag 2 0 and carbon dioxide.
+
+
+
+
+
+
IV, 3. Tests for bicarbonates.-The following tests distinguish carbonates from bicarbonates.
(i) To a cold solution of a bicarbonate, e.g. sodium bicarbonate NaHCO a, add a solution of magnesium sulpl"Lte.
No precipitate is formed in the cold since magnesiuDi bicarbonate Mg(HCO a)2 is soluble in water. Boil the solUl ion:
a white precipitate of magnesium carbonate MgCO a, "ilich
4]
329
IV, 4.
11*
[IV,
4J
331
=
~
CaSOg + H 2 0
Ca(HSOg)2
332
[IV,
Place a drop of the test solution (or a little of the test solid) in the
tube of the apparatus shown in Fig. II, 6, 10, and place a little washed
nickelous hydroxide on the glass knob under the stopper. Add 1-2
drops of 5-6N hydrochloric acid, close the apparatus and warm gently.
The green hydroxide turns grey to black according to the amount of
sulphite present. For small amounts of sulphites, transfer the nickel
hydroxide to a quantitative filter paper and treat with a drop of the
benzidine reagent: a blue colour is formed.
An alternative technique is to warm (water bath) the test solution in
a semimicro test-tube with a little dilute hydrochloric acid, and expose
the evolved gas to filter paper upon which a stain of nickelous hydroxide
has been made. The stain acquires a black colour.
Sensitivity: 04 fLg. S02' Concentration limit: 1 in 125,000.
The nickelous hydroxide is prepared by precipitating nickelOll~
chloride solution with sodium hydroxide solution and washin"
thoroughly Lmtil free from alkali. It should be freshly prepared.
The benzidine reagent is prepared by dissolving 005 gram (.f
benzidine or of its hydrochloride in 10 ml. of glacial acetic acid, dilutirl ~
to 100 ml. with water and filtering.
t 12. Sodium Nitroprusside-Zinc Sulphate Test.--Sodium nitroprusside solution reacts with a solution of a zinc salt to yield a salmOl'coloured precipitate of zinc nitroprusside Zn(Fe(CN)oNO]. The latt<
reacts with moist sulphur dioxide to give a red compoLllid of unkno>\
composition; the test is rendered more sensitive when the reacti('i.
product is held over ammonia vapour which decolourises the unus(', I
zinc nitroprusside.
Place a drop of the test solution (or a grain of the solid test samph-l
in the tube of Fig. II, 6, 10 and coat the knob of the glass stopper wit It
a thin layer of the zinc nitrovrusside paste. Add a dr()~ ()t '1.N b..'J&
",,-.,,-<>~-,c <>< bU\.p'n\lllC amu anu close the apparatus.
After the sulphur
dlOxlde has been evolved, hold the stopper for a short time in ammonia
vapour. The paste is coloured more or less deep red.
Sensitivity: 35f-l-g. S02'
Hg++
Hg++ + S-- =
+ S203-- + H 0 =
2
HgS;
Hg8
+ 80,-- + 2H+
PI~e a drop Of. the test solution and 2 drops of saturated mercuri,'
c~lorIde so~u~lOn J? the same apparatus (Fig. II, 6, 10) and, after :'
5]
IV, 5.
Reactions of the
Ac~:d
Rwiieals or Anions
333
+ 2HCl =
+
+
H zS 2 0 a 2NaCI;
H 2S zOa = HzSO a S
Na2S20a
2HCl = S02
H 20
S
+ + 2NaCI
+ 12 =
Na2S406
+ 2NaI
+ BaC1 2 =
BaS20a
+ 2NaCl
Na2Sz0a
2AgN0 3 = Ag 2S zOa
2NaNOa ;
AgZS 20 S
H 2 0 = Ag 2S
H 2S04 ;
AgzSzOs
+ 3NszS20
= 2Nas[Ag(S20 S)2]
334
[IV,
5. Lead Acetate Solution: white precipitate of lead thiosulphate PbSzO a, soluble in excess of the precipitant; III
boiling the suspension, a black precipitate containing lciLd
sulphide PbS is obtained (distinction from sulphite).
PbS 20 s
+ H 20
= PbS
+ H 2S04
6. Potassium Cyanide Solution.-A thiocyanate is produced when a solution of a thiosulphate is boiled with solutions
of potassium cyanide and sodium hydroxide. On acidifying
with dilute hydrochloric acid and adding ferric chloride solution, the characteristic blood-red colour of the complex ferrithiocyanate ion [Fe(SCN)]++ is obtained (distinction from
sulphite).
Na2Sz0a
+ KCN =
KSCN
+ Na2S0S
+ Na2S20a =
[Ni ena]S203
+ 2NaNOa
6J
335
+ Is
= 2NaI
+ 3N I
IV, 6.
+ H 20 ~ NaHS + NaOH;
+ H 0 ~ R,S + NaOH;
2CaS + 2H.O ~ Ca(SH), + Ca(OH)>>
AI,Ss + 6H.O = 2Al(OH)3 + 3H t S
Na.S
NaHS
336
[IV,
+ 2HCl =
+ 2NaCl;
+ 2NaOH
Na2S
Pb(C 2H 30 2h
Pb(ONah
H 2S
PbS
H 2S = PbS
+ H 2S =
+ 2H. C2H a0 2
+ 5H2S + 6HCI =
+ 3H2S + SHCI =
H 2S
2KCI
2KCl
12 ~ 2H1
+ 2AgN03 =
Ag 2S
+ 2NaNOs
+ Na2[Fe(CN)5NO] =
Na4 [Fe(CN)5NOS]
6]
337
t7.
tS.
338
IV, 7.
[IV,
AU other
1, i:
rites
NaNO z HCl
3RN02
O2
2NO
=
=
=
RNO z NaCl;
HzO + RNO s + 2NO;
2N0 2
2NaNO z
2Na.C2 H a0 2 + 2HN0 2 ;
3HN02 = H 2 0
HNO a NO;
FeS04 + NO = [Fe,NO]S04
+ 2H.C2 H s0 2 =
+ NaN02 =
AgN0 2
+ NttNO a
7]
339
+ I2 + 2NO + 2H2 0
6. Acidified Potassium Permanganate Solution: decolourised by a solution of a nitrite, but no gas is evolved.
2KMn04
+ 3H2S04 + 5HN02
= K 2S04
+ NH4Cl =
NaCl
+ N2 + 2H 20
+ 2HN02 =
2N2
+ CO2 + 3H20
CS(NH 2)2
+ HN0 2 =
N2
+ HSCN + 2H 20.
+ HN0 2 =
Nz
+ H 2S04 + H 20
340
Qualitative Inorganic Analysis
rIV,
t 11. SulphaniUc Acid-Cl-Naphthylamine Reagent.-Thi~ test
depends upon the diazotisation of sulphanilic acid by nitrous acid,
followed by coupling with Cl-naphthylamine to form a red azo dy(';
o'H'C'H,O~ RNO.
O,K.o.
~O.H
~H
IC,HaO.
~OaH
I #
cp
QN=NQ:)
~,:?
NH.
+ 'H,O,
SOsH
,:?
NH.
+ H.C. lI aO
#
t 12.
Indole Reagent
IV, 8.
Solubility.-Only the cyanides of the alkali and alkaline earth metals ,"re
soluble in water; the solutions react alkaline owing to hydrolysis. Merc ., ric
cyanide Hg(CN), is also soluble in water, but is practically a non-electro,>te
and therefore does not exhibit the ionic reactions of cyanides. Many of I he
metallic cyanides dissolve in solutions of potassium cyanide to yield complex
salts (compare Section I, 20).
KCN
8]
341
342
flV,
8]
343
The test is applicable in the presence of sulphide or sulphite; if thiocyanate is originally present, the cyanide must be isolated tirst by
precipitation, e.g. as zinc cyanide.
344
IV, 9.
[IV,
Solubility.-The cyanates of the alkalis and of the alkaline earths are so) ,ble
in water. Those of silver, mercurous mercury, lead and copper are insolilble
in water. The free acid is a colourless liquid with an unpleasant odour; it is
very unstable.
10]
345
IV, 10.
+ 2H2S04 + H 20
= COS
+ NH,HS04 + KHS04,
+ AgNO s =
AgSCN
+ KNOs
Upon boiling with N sodium chloride solution, silver thiocyanate is converted into silver chloride (AgSCN
NaCI ~
AgCI
NaSCN-distinction and method of separation from
the silver halides); the aqueous solution may be acidified with
dilute hydrochloric acid and ferric chloride solutioll added
when the characteristic red coloration of the ferri-thiocyanate
ion will be obtained.
Silver thiocyanate also decomposes upon ignition or upon
fusion with sodium carbonate.
3. Copper Sulphate Solution: solution is coloured green;
with excess of the reagent, black cupric thiocyanate Cu(SCN)2
346
[IV,
10]
347
slightly with dilute hydrochloric acid and add a drop of ferric chloride
solution. A red coloration is obtained.
IV, 11.
[IV,
348
REACTIONS OF FERROCYANIDES,
[Fe(CN)6r---
+ 6H2SO, + 6H20
2FeSO,
;00;
K 4[Fe(CN)6]
3H2SO,
K 4[Fe(ON)6) + FeSO,
6HON + FeS04
2K2SO.
~ K2Fe[Fe(ON)6J + K 2 804
~
+ 4AgNO a =
Ag4[Fe(ON}6]
+ 4KN(j~
II]
itad~cal8
or Amona
349
4. Ferrous Sulphate Solution: white precipitate of potassium ferrous ferro cyanide K 2Fe[Fe(CN)6], rapidly turning blue
owing to oxidation (see under Iron, Section II, 19, reaction 6).
5. Copper Sulphate Solution: brown precipitate of copper
ferro cyanide CU2[Fe(CN)6], insoluble in dilute acetic acid, but
decomposed by solutions of caustic alkalis.
K 4[Fe(CN)6]
+ 2CUS04 =
CU2[Fe(CN)6]
+ 2K S04
2
+ K 4[Fe(CN)6] =
4KN0 3
+ Th[Fe(CN)61
7. Hydrochloric Acid.-Treatment of a concentrated solution of potassium ferro cyanide with hydrochloric acid results in
the formation of hydro ferro cyanic acid H 4 [Fe(CN)6J, which may
be isolated by extraction with ether, and obtained as a white
solid.
K 4[Fe(CN)6]
t 11. U rany! Acetate Solution: brown precipitate of uranyl ferrocyanide (U02)2[Fe(C~)6] in the presence of dilute acetic acid. Ferricyanides react only in concentrated solutions, and after long standing
or heating to give the dirty yellow uranyl ferricyanide. Ferricyanides
350
[IV,
are reduced by filter paper to ferrocyanides. hence the test should not
be carried out on filter paper.
Place a drop of the test solution on a spot plate and add a dro:, of
N uranyl acetate solution. A brown precipitate or spot is obtained
within 2 minutes.
Sensitivity: 1 fLg. K 4[Fe(CN)61. Concentration limit: 1 in 50,00 11 ,
REACTIONS OF FERRICYANIDES,
[Fe(CN)6r--
l;iJ
lteactwns
OJ
351
IV, 13.
= 6N2
2. Potassium Iodide-Starch Paper: assumes a bluishblack colour in weakly alkaline solution as a resu] t of the
separation of iodine.
2KI + NaOOI + H 2 0 = 12 + 2KOH + NaOl
Chloride is invariably present, and this will vitiate many ionic reactiOWI.
352
II Y t
IV, 14.
REACTIONS OF CHLORIDES,
cr
14]
353
* This test must not be carried out in the presence of chlorates because of
the danger of fOrInmg explosive chlorme dioxide (Section IV, 19, reaction 1).
t Diethyl ether may alae be used, but owing to its highly inflammable
character and the possible presence of peroxides (unless previously removed
by special treatment), it is preferable to employ amyl aloohol or, less efficiently,
amyl acetate.
12+
354
[IV,
test (Section IV, 33, reaction 10) may be applied. The forlllation of a chromate in the distillate indicates that a chloride xas
present in the solid substance, since chromyl chloride I'" a
readily volatile liquid (b.p. 11650).
K2Cr207
+ 4NaCI + 6H2S0
Cr02Cl2
2Cr0 2Cl 2
+ 4NaOH =
+ 2KHS04 + 4NaHS04 + 3H
Na2Cr04
0;
+ 2NaCI + 2H20
+ 6NaCI + 7H2S04
= 3C12
cr.
* The iodine reacts with the chromic acid yielding iodic acid: the latter,
in the presence of concentrated sulphuric acid and especially on warming,
liberates chlorine from chlorides, regenerating iodide. This explains the
failure to form chromyl chloride.
15]
355
IV, 15.
+ Mn0 2 + 3H2S04 =
Br2
+ 2KHS04 + MnS04 + 2H 20
+ 2NHa =
AgBl' + 2KCN =
AgBr
[Ag(NHa)2JBr;
K[ Ag(CN)2J
+ KEr
356
[IV,
+ Pb(C zH a0 2)2 =
PbBr2
+ 2K. C2H s0 2
5. Chlorine Water.*-The addition of this reagent dropwise to a solution of a bromide liberates free bromine, which
colours the solution orange-red; if carbon disulphide, chloroform or carbon tetrachloride (2 mI.) is added and the liquid
shaken, the bromine dissolves in the solvent (see The Distribution Law, Section I, 43) and, after allowing to stand, forms
a reddish-brown solution below the colourless aqueous layer.
With excess of chlorine water, the bromine is converted into
yellow bromine monochloride or into colourless hypobromous
or bromic acid, and a pale-yellow or colourless solution result8
(difference from iodide).
2KBr
C12 Br2
5012
Br2 +
2KBr
ROOl
Br2
5HOCI
+
+
+
+
+ C12 =
2KC1 + Br2;
2H 20 = 2HOBr
2HOl;
6HzO = 2HBrOa + IORC1
HCI = 2KCI
Br2
H 20;
H 20 = 2HBrOa
5HOI
+
+
+ 6KBr + 7H2S0
= 3Br2
'.
-----------..........._
15]
357
Br
HOVY 0(
HYyII~O
V~~~~
B)~'~lli
~COaH
U
(I)
(II)
9. Fuchsin (or
Ma~enta)
-HaN-c\
_
+
C=O=NHa CJ
HaND
I
CH,
(I)
colourless addition compound with a bisulphite. Free bromine converts the thus decolourised fuchsin into a blue or violet brominated
dyestuff. Neither free chlorine nor free iodine affect the colourless
fuchsin bisulphite compound, hence the reaction may be employed for
the detection of bromides in the presence of chlorides and iodides.
Place a drop of the test solution (or a few milligrams of the test solid)
in the tube of the apparatus shown in Fig. II, 6, 14, add 2-,1 drops of
25 per cent chromic acid solution and close the apparatus with the
"head" which contains 1-2 drops of the reagent solution in the capillary.
358
[IV,
Warm the apparatus gently (do not allow it to boil). In a shor1 time
the liquid in the capillary assumes a violet colour.
Sensitivity: 3p.g. Br-. Concentration limit: I in 15,000.
The fuchsin-bisulphite rea~ent consists of a 0'1 per cent fu hsin
solution just decolourised by sodium bisulphite.
IV, 16.
REACTION OF IODIDES,
Solubility.-The solubilities of the iodides are similar to those of the chI, ,ides
and bromides. Silver, mercurous, mercuric, cuprous and lead iodides afp the
least soluble salts.
16]
359
the solution brown; on shaking with 1-2 ml. of carbon disulphide, chloroform or carbon tetrachloride (see Section I, 43),
it dissolves forming a violet solution, which settles out below
the aqueous layer. The free iodine may also be identified by
the characteristic blue colour it forms with starch solution.
If excess of chlorine water is added, the iodine is oxidised to
colourless iodic acid.
2KI
01 2 =
5012 12 + 6H20 =
2KI
HOOI
HOI =
12 + 5HOOI + H 20 =
+
+
2KOI
12;
2HIOa + lOHOI
2KOl
12
H 20;
2HIO a + 5HOI
+ +
7. Copper Sulphate Solution: brown precipitate consisting of a mixture of cuprous iodide CuI and iodine. The iodine
may be removed by the addition of sodium thiosulphate solution or sulphurous acid, and a nearly white precipitate of
cuprous iodide obtained.
+ +
+
20US04
4KI = 2CuI
12
2K2S04
12 + 2Na2S20S = Na2S406
2NaI
+ 2KI =
+ 2KI =
HgI z 2KOI;
K 2[HgI41
360
[IV,
2Ce H H
+ 2r
= 2Ce+ H
+ I,
\i)
+ 2r + 2H+
(ii)
+ 12 + HIO
= AsO,---
the iodide ion reacting again as in (i). The completion of the reduc1 J' ,n
is indicated by the disappearance of the yellow colour of the c,' tC
solution. Osmium and ruthenium salts have a similar catalytic eff, . t.
Moderate amounts of chlorides, bromides, BulphawB and nitratBB hH \e
no llifluence, but cyanides and also mercuric, silver and mangan. "e
BaIts interfere.
Place a drop of the test solution together with a drop each of neutral
or slightly acid O'lN sodium arsenite solution and 0'05N ceric amn,
nium sulphate solution (in 2N sulphuric acid) on a spot plate. T 'l
yellow colour soon disappears.
Sensitivity: 003 p.g. l-.
IV, 17.
r.
REACTIONS OF FLUORIDES, F-
17]
361
362
IIV,
t6.
18J
363
The most sensitive method of carrying out the spot test is as follows.
Impregnate some quantitative filter paper or drop reaction pllper with
the zirconium-alizarin-S reagent, dry it and moisten with a drop of 50
per cent acetic acid. Place a drop of the neutral test solution upon the
moist red spot,; the spot will turn yellow.
Sensitivity: 1 /Lg. F-. Concentration limit: 1 in 50,OO!}.
Large amounts of sulphates, thiosul phates, nitrites, arsenates, phosphates and oxalates interfere with the test.
The zirconium-alizarin-S paper is prepared as follows. Immerse
quantitative filter paper (or drop-reaction paper) in a 5 per cent solution
of zirconium nitrate in 5 per cent hydrochloric acid, drain and place in
a 2 per cent aqueous solution of alizarin-So Wash the paper, which is
coloured red-violet by the zirconium lake, until the washings are nearly
colourless and then dry in air.
IV, 18.
REACTIONS OF NITRATES, N0 3 -
364
[IV,
beneath the mixture. A brown ring will form where the lie I' dds
meet. (b) Add 4 m!. of concentrated sulphuric acid slowl." to
2 m!. of the nitrate solution, mix the liquids thoroughly md
cool the mixture under a stream of cold water from the ; ap.
Pour a saturated solution of ferrous sulphate slowly down "he
side of the tube so that it forms a layer on top of the lie Ilid.
A brown ring will form at the zone of contact of the two liql;ids.
The brown ring is due to the formation of the comp<"!lld
[Fe(NO)]S04. On shaking and warming the mixture the bI ,wn
colour disappears, nitric oxide is evolved and a yellow solutio, of
ferric sulphate remains. The test is unreliable in the present of
bromide, iodide, nitrite, chlorate and chromate (see Section IV, 45,
3 and 4).
6FeSO,
+ NaNOs
= N2
+ NaHSO, + H 20
18)
365
366
[IV,
II NC6H,ll
HdOc
NC.H6
white crystalline precipitate of nitron nitrate C2oH16N4,}i ~03
with solutions of nitrates. Bromides, iodides, nitrites, ':lro
mates, chlorates, perchlorates, thiocyanates, oxalates :1nd
picrates also yield insoluble compounds, and hence the rea, ,t ion
is not very characteristic.
The reagent is prepared by dissolving 5 grams of nitron in 10" ml.
2NaNO z O2 ;
N 20 + 2H zO;
2Ag
2NO z O2 ;
2PbO
4N0 2
O2
+
+
+
+
IV, 19.
19]
367
+ 3H2S04 =
2CI0 2
+ HCI04 + 3KHSO, + H 2 0
+ 3NaNOs
+ 3HzS04
KOI + 3H.COOH
= KCl
= KOI
= KCI
= KCI
+ 3Na2[Zn02] + 3HzO
+ 2Na[Al0 2] + H:!O
... It is best to filter off the excess of metal before adding the silver nitrate
solution.
368
rIV,
4. Silver Nitrate Solution: no precipitate in neutral' ,lution or in the presence of dilute nitric acid. Upon the add,' ion
of a little pure (chloride-free) sodium nitrite to the dilute IJ, ~ ric
acid solution, a white precipitate of silver chloride is obta"led
because of the reduction of the chlorate to chloride, (sec reaction 3 above).
No precipitate is obtained with barium chloride solution.
5. Potassium Iodide Solution: iodine is liberated ira
mineral acid is present. If acetic acid is used, no io(' i ne
separates even on long standing (difference from iodate).
6. Ferrous Sulphate Solution: reduction to chloride U' 'dn
boiling in the presence of dilute mineral acid (difference fi ,m
perchlorate) .
KOl0 3 + 6FeS04 + 3H2S04 = KCl + 3Fc2(S04)s + 3H20
7. Indigo Test.-A dilute solution of indigo in concentra: "d
sulphuric acid is added to the chlorate solution until the lat; ,~r
has a pale-blue colour. Dilute sulphurous acid or sodh m
sulphite solution is then added drop by drop; the blue col(, lr
is discharged. The chlorate is reduced by the sulphurous a, .:1
to chlorine or to hypochlorite, and the latter bleaches 1 i ,e
indigo.
S. Aniline Sulphate Test {(C6H5 .NH2)2H2S04 }.-A sm,!!l
quantity of the solid chlorate (say, :j>O'05 gram) (DANGE I:)
is mixed with 1 m!. of concentrated sulphuric acid, and 2-3 1 .!.
of aqueous aniline sulphate solution added; a deep-blue colo r
is obtained (distinction from nitrate).
t9. Manganous Sulphate. Phosphoric Acid Test.-Mangano 1
sulphate in syrupy phosphoric acid solution reacts with chlorates
form the violet-coloured mangani-phosphate ion:
6Mn++ + 12PO,--- + 6H+ + ClO s= 6[Mn(PO')2r-- + Cl3H~ )
Persulphates, nitrites, bromates, iodates and also periodates rea"
similarly. The first-named may be decomposed by evaporating tJ
sulphuric acid solution with a little silver nitrate as catalyst:
2H 2S 20 S + 2H 20 = 4H 2SO, + O 2
Place a drop of the test solution in a micro crucible and add a dro:,
of the reagent. 'Warm rapidly over a micro burner and allow to coo
A violet coloration appears. Very pale colorations may be intensifie!
by adding a drop of 1 per cent alcoholic diphenylcarbazide solutio"
when a deep violet colour, due to an oxidation product of the dipheny:
carbazide, is obtained.
Sensitivity: 005/Lg. CIO a-. Concentration limit: 1 in 1,000,000.
The reagent is prepared by mixing equal volumes of saturated manganous sulphate solution and syrupy phosphoric acid.
20]
369
IV,20.
370
[IV,
4. Hydrobromic Acid.-Mix together solutions of P' ,tassium bromate and bromide, and acidify with dilute sulpLuric
acid; bromine is liberated as a result of interaction bet II een
the bromic and hydrobromic acids set free. The bromine may
be extracted by adding a little chloroform or carbon t\trachloride.
HBrOs
+ 5HBr =
3Br2
+ 3H20
t In the spot test technique, the reaction is combined with a sem l! ive
test for manganese (oxidation of benzidine by manganese dioxic, to
"benzidine blue"). Place a drop of the test solution in a semiI" ,ero
centrifuge tube, add a drop or two of 2 per cent manganous suII",,1te
solution acidified with dilute sulphuric acid and warm for 2-3 mil, Ites
in a boiling water bath. Cool, add a few drops ofthe benzidine reo_"mt
und a few small crystals of sodium acetate. A blue coloration re~'Jlts.
Sensitivity: 30 p,g. ErOa -. Concentration limit: I in 2500.
The benzidine reagent is prepared by dissolving 005 grall, of
benzidine in 10 m!. of acetic acid, diluting to 100 ml. with water Ind
filtering, if necessary.
IV, 21.
21]
371
372
[IV,
+ 5H1 =
312
+ 3H20
(i)
(ii)
(iii)
The first two stages are rapid and the third stage is a slow reacL 'll.
The iodine can be readily identified by the starch reaction. Chlor,,' 0S
and bromates do not react under these conditions.
Place a drop of the neutral test solution on a spot plate and mb it
with a drop of starch solution (for preparation, see under Iodilks,
Section IV, 16, reaction 9) and a drop of a dilute solution of hy!!ophosphorous acid. A transitory blue coloration is produced.
Sensitivity: 1 p.g. 10 3 - ,
t9. Potassium Thiocyanate Test.-Iodates react with thioc~ ilnates in acid solution with the liberation -of iodine:
610 3 5SCN6H+
2HaO = 31a
5HCN
5HSO,-
IV, 22.
23]
373
+ H 2S04 =
HCI04
+ NaHS04
IV, 23.
+ 202
REACTIONS OF BORATES,
BO s---' B 4 0 7 --, BO z-
The borates are derived from the three boric acids: ortho-boric acid H.BO
pyro-boric acid H2B(07 and meta-boric acid HBO I Ortho-boric acid is a
white crystalline solid, sparingly soluble in cold but more soluble in hot water;
very few salts of this acid are definitely known. On heating ortho-boric acid
at 100 0 , it is converted into meta-boric acid; at 140 0 pyro-boric add is produced. Most of the salts are derived from the meta- and pyro-acids. Owing
to the weakness of boric acid, the soluble salts are hydrolysed in solution and
therefore react alkaline.
Na 2B.0 7
3H 20 ~ 2NaB0 2
2H.BO.;
NaB0 2
2H.O ~ NaOH
HaBO.
Solubility.-The borates of the alkali metals are readily soluble in water.
The borates of the other metals are, in general, difficultly soluble in water, but
fairly soluble in acids and in ammonium chloride solution.
+
+
+
+
374
[IV
The methyl borate is distilled off and passed into an aqueous solution
containing potassium fluoride, manganous nitrate and silver nitrat~'.
The ester is hydrolysed by the water to boric acid:
+ 2Ag+ + 40H-
= MuO.
+ 2Ag + 2H,D
23]
375
+ 3HzO + 2AgNOs =
2AgB0 2 + 3H2 0 =
2AgB0 2 + 2HsBOs
Ag 2 0 + 2HsBOs
+ 2NaN0 3 ;
+ 3H20 + BaOIl! =
Ba(BO z)2
+ 2HllBOa + 2Na.Cl
tiuatUatwe lnorgamc
~7t>
"
L' V \
.Anaty8~s
OR
O,N-OM~
ROIS~OIR
-LOR
RO,
'B-OR
RO/
I
Alternative names are: p-nitrobenzene-azo.l : 8-dihydroxyn.e.phthalen., ..
3: 6-disulphonic acid and "Chromotrope 2B" (the latter is the sodium se.l~).
24J
377
IV, 24.
378
[IV,
The reader is warned that the above tests (depending \I! Ion
the formation of a sulphide) are not exclusive to sulphates Imt
are given by most sulphur compounds. If, however, the
barium sulphate precipitated in the presence of hydrochloric
acid is employed, then the reaction may be employed ft ~ a
confirmatory test for sulphates.
2. Lead Acetate Solution: white precipitate of lead flulphate PbSO" soluble in hot concentrated sulphuric acid, in
solutions of ammonium acetate and of ammonium tartrate ( f)e
under Lead, Section 111,2, reaction 3), and in sodium hydroxi' le
solution. In the last case sodium plum bite is formed, and'n
acidification with hydrochloric acid, the lead crystallises out ,IS
the chloride. If any of the aqueous solutions of the precipitil , e
are acidified with acetic acid and potassium chromate solutit n
added, yellow lead chromate is precipitated (see under Lea I,
loco cit.).
Pb(02Ha02)2
+ Na2S04 =
PbS04
+ 2Na.02H a0 2
+ 2AgNO a =
Ag 2SO,
+ 2NaNO a
25J
379
reaction 7). Sulphates and sulphuric acid cause immediate decolorisation because of the formation of insoluble barium sulphate. This test
is specific for sulphates.
Place a drop of barium chloride solution upon filter or drop reaction
paper, followed by a drop of a freshly prepared 0'1 per cent aqueous
solution of sodium rhodizonate. Treat the reddish-brown spot with a
drop of the acid or alkaline test solution. The coloured spot disi1ppears.
Sensitivity: 4 fLg. SO,--.
IV, 25. REACTIONS OF PERSULPHA TES, S208-Solubility.-The bestknown persulphates, those of sodium, potassium.
ammonium and barium, are soluble in water, the potassium salt being the
least soluble (17'7 grams per litre at 0).
+ 2H zO =
Os + 2KI + HliO =
2(NH4)zS20S
2(NH4)zS04
Is
+ 2HzSO~ + Oz
+ O2 + 2KOH
380
[IVI
= I2 + (NH,hS04 + K ZS04
6. Potassium Permanganate Solution: unaffected ((1;,,tinction from hydrogen peroxide). Persulphates are unaffected
by a solution of titanous sulphate.
________
,
26]
IV, 26.
381
The silicic acids may be represented by the general formula xSiO., yR.O.
Salts corresponding to ortho-silicic acid H.SiO, (SiO.,2H.O) roeta-sili"ic acid
R.SiO. (SiO.,H.O) and di-silicic acid H 2Si.O.(2SiO.,H.O) are d0finitely
known. The meta-silicates are sometimes designated simply as silicates.
Solubility.-Only the silicates of the alkali metals are soluble in water;
they are hydrolysed in aqueous solution and therefore react alkaline.
Na.SiO.
2R.O ~ 2NaOH
H.BiO.
+ 2HCI =
H 2SiO a
+ 2NaCI
+ 2NaCI + 2NHs
+ NazCOs + 2NH3
+ 2NH, + ~ H
Acid.
+ 2NHa
SiO a
Acid l
Base,
+ 2AgNO s =
AgzSiO a
+ 2NaNO a
+ BaClz =
BaSiOs
+ 2NaCl
382
[IV,
26]
383
Phosphoric and arsenic acids form compounds analogous to silicomolybdic acid which also react with benzidine with colour formation
hence these acids should be removed before applying the test. In the
presence of phosphoric acid, the test is carried out as follows. Mix
a drop of the test solution with 2 drops of the molybdate reagent in a
micro centrifuge tube and centrifuge the mixture. Transfer the supernatant liquid to a micro-crucible by means of a capillary tube, warm
gently, cool and add 2 drops of 1 per cent oxalic acid solution (the
latter decomposes the small quantity of residual phosphomolybdate
(NH 4 la[PMo 120 40 ] but has little action on the silico-molybdic acid
complex), then introduce a drop of the benzidine reagent and 2-3 drops
of saturated sodium acetate solution. A blue colour forms.
Sensitivity: 6/Lg. Si0 2 in the presence of 250 times the amountofP.0 5
Concentration limit: 1 in 8,000.
The ammonium molybdate reagent is prepared by dissolving 5
grams of ammonium molybdate in 100 ml. of cold water and pouring
into 35 ml. of nitric acid (sp. gr. 12).
The benzidine reagent is made by dissolving 005 gram of benzidine
or its hydrochloride in 10 m!. of glacial acetic acid and diluting with
water to 100 ml.
384
[1 V,
IV, 27.
REACTIONS OF SILICOFLUORIDES
(FLUOSILICATES), [SiF6
r-
SiO.
+ 6HF =
Hs[SiF.l
+ 2H.O
+ H 2S04 =
SiF4
+ 2HF + Na2S0.
2. Barium Chloride Solution: white, crystalline preci! >itate of barium silicofluoride Ba[SiF6], sparingly soluble in wal .r
(025 gram per litre at 25) and insoluble in dilute hydrochloi ,)
acid. The precipitate is distinguished from barium sulpha' d
by the evolution of hydrogen fluoride and silicon fiuoride,
28]
385
+ BaClz =
Bu,[SiF6]
+ 2NaCI
3. Potassium Chloride Solution: white, gelatinous precipitate of potassium silicofluoride K 2[SiF6] from concentrated
solutions. The precipitate is slightly soluble in water (1'77
grams per litre at 25), less soluble in excess of the reagent and
in 50 per cent alcohol.
4. Ammonia Solution: decomposition occurs with the
separation of gelatinous silicic acid.
Naz[SiF6]
+ 4NHs + 3HzO =
HzSiO a
+ 2NaF + 4NH,F
. o. Action of Heat: decomposition occurs into Si1iCOll tetrafluoride, which renders a drop of water turbid, and the metallic
fluoride, which can be tested for in the usual manner (see
under Fluorides, Section IV, 17).
Naz[SiF6]
SiF4
+ 2NaF
13+
[IV,
386
III
+ 3AgNOs =
+ 21\ t (4Cl
387
temperature not exceeding 40, and by the addition of ammonium nitrate solution.
The precipitate is soluble in ammonia solution and in solut ions of
caustic alkalis. Large quantities of hydrochloric acid interfere with
the test and should preferably be removed by evaporation to i1 small
volume with excess of concentrated nitric acid. Reducing agents, such
as sulphides, sulphites, ferrocyanides and tartrates, seriously aflect the
reaction, and should be destroyed before carrying out the test.
29]
389
the paper over a hot wire gauze (or over a sheet of asbestos heated on
a hot plate) to accelerate the reaction. Then add a drop of the benzidine
reagent and develop over ammonia vapour. A blue coloration results.
Sensitivity: 15/-tg. P a06 in the presence of 500 times the amount of
SiO a. Concentration limit: 1 in 50,000.
The tartaric acid-ammonium molybdate reagent is prepared by
dissolving 15 grams of crystallised tartaric acid in 100 ml. of the
ammonium molybdate reagent referred to above.
t 10. Ammonium MolYbdate-Quinine Sulphate Reagent.Phosphates give a yellow precipitate with this reagent: tho exact
composition appears to be unknown.
Reducing agents (sulphides, thiosulphates, etc.) interfere since they
yield "molybdenum blue"; ferrocyauides give a red col<Jration.
Arsenates (warming is usually required), arsenites, chromates, oxalates,
tartrates and silicates give a similar reaction with some variation in the
colour of the precipitate. All should be removed before applying the
test.
Place 1 mI. of the test solution in a semimicro test-tube and add 1 ml.
of the reagent. A yellow precipitate is produced within a few minutes:
gentle warming (water bath) is sometimes necessary.
Concentration limit: 1 in 20,000.
The reagent is prepared by dissolving 40 grams of finely powdered
ammonium molybdate {(NH4)6Mo70w4HaO} in 20 ml. of water and
adding, with stirring, a solution of 0,] gram of quinine sulphate in
80 mI. of concentrated nitric acid.
IV, 29. REACTIONS OF PYROPHOSPHATES, P 2 0 7 - - - AND OF METAPHOSPHATES, PO aSodium pyrophosphate is prepared by heating disodium hydrogen
phosphate:
2Na 2HPO, = Na,P 207 + HaO
This is the normal salt. Acid salts, e.g. Na 2H aP Z0 7, are known.
Sodium metaphosphate (polymeric) may be prepared by heating
microcosmic salt or sodium dihydrogen phosphate:
Na(NH,)HPO, = NaPO,
Na.HaPO, = NaPO.
+ NHa + HIO
+ HaO
390
[IV,
Meta-phosphate~
~-
Ortlwphosphate
Pyrophosphate
1. Silver
nitrate
solution.
White ppt. (E pa
rates Blo" y),
soluble in d, lte
HNO".ind,j'lte
NHa solut .,m
and in di:te
acetic acid.
2. Albumin
and dilute
acetic acid.
3. Copper
sulphate
solution.
4. Magnesia
mixture or
Mg(NO.)2
reagent.
No coagulation.
Very pale
ppt.
No ppt.
White ppt., in
soluble in dilute
acetic acid; sol.
uble in dilute
NH. solution,
yielding a white
ppt. on boiling.
White ppt.
II
warming; ~ ,I.
uble in dill i' ,}
acetic acid.
R6a(/ent
5. Cadmium
chloride
solution
and dilute
acetic acid.
6. Zinc
sulphate
solution.
No ppt.
blue
Coagulation.
No ppt.
IV, 30. REACTIONS OF PHOSPHITES, HP0 3- Solubility.-The phoephites of the alkali metals are soluble in water; ;ell
other metallic phosphites are insoluble in water.
+
+
31]
391
+ H 20
+ H 20
+ Hg2Cl 2 + 2N:1CI;
H SP04 + 2Hg + 2NaC!
= H SP04
=
20
HaPOa
+ Pb(CzHsOzb =
PbHPOa + 2NaC 2H sO l
IV, 31.
2PHs
REACTIONS OF HYPOPHOSPHITES,
H 2P0 2-
392
[IV,
+ 2H20
= 2Hg zC1 + HaPO, + 3HCI + ~ tCI:
+ 2HgC12 + 2H 0 = 2Hg + H aP0 + 3HCl + N ,01
2
NaH 2PO Z
3HaP0 2
+ HOI =
euOl
+ Hz
+ 2NaOH =
2Hz
+ NaaP04
8. Zinc and Dilute Sulphuric Acid: inflammable phi '.'1phine is evolved (see under Phosphites, Section IV, 30, reaction 6).
9. Ammonium Molybdate Solution: reduced to "moly!,.
denum blue" in solution acidified with dilute sulphuric aCid
(difference from phosphite).
+ 2PHa + HzO
33]
393
+
+
+
+
+
+
+
+
+
-=
-=
394
[IV,
nd
+ 4H20 2 ~ 2Cr05 + 5H zO
K2Cr207
+ SHCI +
aCIHI.OH
34]
395
-+ H 2S04 =
+ 8HCl =
K2Cr207 + 3H2SOS
K2Cr207 + 3H2SO S
Cr 2 (S04)s + K 2 S04 + 4H 20
2CrCIs 2KCl 3H2S04 + 4H 2 0
-+
-+
-+
-+
-+ 14HCl =
2KCl
396
[IV,
+ lOKI + 8H 2S04
+ Sl! ,0
+ 5HN02 + 3H2S04
= 2l\fuS04 + K 2S0 + 5HNOs + 3H :0
2KMn04 + 5H C20 4 + 3H S04
= 2MnS04 + K 2S04 + lOC0 2 + SH. 0
2KMn04
35J
397
IV,35.
REACTIONS OF ACETATES, C zH 3 0 z-
398
[IV,
o.
+ AgNOs =
Ag.C2H s0 2
+ NaNOs
35]
399
400
[IV,
IV,36.
37]
Of'
.Anions
401
7. Mercuric Chloride Solution: white precipitate of mercurous chloride Hg 2C1 2 is produced on warming; this passes
into grey, metallic mercury in presence of excess of the formate
solution (distinction from acetate).
2H.C0 2Na
2H.C02Na
2H. C0 2H
HgO = (H. CO2)2Hg + H 20;
2(H.C02)2Hg = (H.C02)2Hg2
H.C0 2H
(H. CO2)2Hg2 = 2Hg
H. C0 2H
CO 2
+ CO 2 ;
IV, 37.
Naz'C20"
+ H2
Solubility.-The oxalates of the alkali metals and of ferrous iron are soluble
in water; all other oxalate" are either insoluble or sparingly solublE' in water.
They are all soluble in dilute acids:
Ca.C.O, + 2HCl = H . C.O, + 2HCl
Some of the oxalates dissolve in a. concentrated solution of Oll:alic acid
by virtue of the formation of soluble acid or complex oxalat('s. Oxalic
acid (a dibasic acid) is a colourless, crystalline solid H.C.O,.2H.O (or
HO.C.CO.H,2H.O), and becomes anhydrous on heating to 110; it is readily
soluble in wa.ter (111 graIIlll per litre at 20).
402
or ammonium
OXll l
q,te,
37]
403
404
[IV,
IV, 38.
Solubility.-Tartaric acid, HO.C.CH(OH).CH(OH).CO.H or H . C.H.o"
is a crystalline solid, which is extremely soluble in water; it is a dibasic a(",1.
The potassium and ammonium acid salts are sparingly soluble in wat, ,';
those of the other alkali metals are readily soluble. The norm~l tartrates "f
the alkali metals are easily soluble, those of the other metals being sparini' i ".
soluble in water, but dissolve in solutions of alkali tartrates forming comp).,~
salts, which often do not give the typical reactions of the metals present.
The most important commercial salts are" tartar emetic" K(SbO). C.H.O. '
05 H 2 0, "Rochelle salt" KNa.C.H,O.,4H 2 0 and "cream of tartal
KH.C,H.O .
38]
405
406
[IV,
39]
407
IV, 39. REACTIONS OF CITRA TES, C6H 5 0 7 - - Solubility.-Citric acid, HO.C.CH . C(OH)CO.H.CH. CO.H,H.O or
Hs.C.H,;O"H.O, is a crystalline solid which is very soluble in w.cter; it
becomes anhydrous at 55 and melts at 160. It is a tribasic acid, and th'3refore gives rise to three series of saJ.ts. The normal citrates of th" alkali
metals dissolve readily in water; other metallic citrates are sparingly ~oluble.
The acid citrates are more soluble than the [wid tartrates.
408
~
[IV,
evolved (compare Tartrates, Section IV, 30, which char alm. ,St
immediately).
The first products of the reaction are carbon mon~ndde and ac.e~one, ,ii
carboxylic acid (1); the latter undergoes further partlal decompositlOn nto
acetone (II) and carbon dioxide.
HO.C.CH . C(OH)CO.H.CH . CO.H
= CO
H 20
HO.C.CH. CO.CH. CO.R i 1) ;
RO.C.CR . CO.CH . CO.H = CRa.CO.CHa (II)
2CO.
Use may be made of the intermediate formation of acetone dicarbox dic
acid and of the interaction of the latter with sodium nitroprusside solutio,; to
yield a red coloration as a test for citrates. When about 05 grams of a cit, ,te
or of citric acid is treated with 1 m!. of concentrated sulphuric acid f
I
minute, the mixture cooled, cautiously diluted with water, rendered alku, ne
with sodium hydroxide solution and then a few c.c. of a freshly prep" .. ,d
solution of sodium nitroprusside added, an intense red coloration results.
40]
409
is formed. Salts of the halogen acids interfere and must therefore be removed before carrying out the test.
The reagent (an acid solution of mercuric sulphate) is prepared
by adding 10 m!. of concentrated sulphuric acid slowly to 50 mL of
water, and dissolving 25 grams of mercuric oxide in the hot solution.
IV, 40.
REACTIONS OF SALICYLATES,
C6H 4 (OH)C0 2- OR C 7H 50 a-
410
[IV,
C6H 4 (OH)C0 2H
HNO s = C6H s(NO z)(OH)C0 2H
(I)
H 20
Poly-nitro salicylic acids are formed when the concentration oj
nitric acid exceeds 2-3N. It must be emphasised that nitrosalicylic acids rrw,y explode on strong heating, and this must be borne
in mind when removing salicylates by oxidation with nitric acid
and evaporating to dryness prior to the precipitation of Group IlIA.
If salicylate is suspected, it is probably best to remove it by acidifying the concentrated solution with dilute hydrochloric acid: most
of the salicylic acid will separate out upon cooling.
(I)
+ CO 2
41]
411
+ HCI =
C6Hs. C0 2 H
+ KCI
3. Concentrated Sulphuric Acid and Ethyl Alcohol.Heat 05 gram of a benzoate or of benzoic acid with a mixture
of 15 m!. of concentrated sulphuric acid and 3 mI. of ethyl
alcohol for a few minutes. Allow the mixture to cool, and
note tbe pleasant and cbaracteristic aromatic odour of the e~ter,
ethyl benzoate (I). The odour is more apparent if the mixt,ure
is poured into dilute sodium carbonate solution contained ill
an evaporating basin; oily drops of ethyl benzoate will sepaeate
out.
C6Hs. C0 2H
+ C2H
5 0H
(I)
+H
20
+ AgN0
C6H!). C0 2 Ag
+ KN03
+ 2FeCl 3 + 3H20
= (C6H5.C02)aFe.Fe(OH)a(II)
+ 3KCI + ;3HCI
+ 2NaOH =
C6H6
+ Na2COa + H 20
412
IV, 42.
[IV.
0:
(I)
+ BaCl2 =
C2H4(C02}2Ba
+ 2NaCl
43]
413
(IV)+ 2H
414
[IV.
44]
415
416
[IV,
7. Indigo Solution: reduced to the colourless leuco compound, known as indigo white.
Na2S204 + 2H zO = 2NaHSO a + 2H (nascent)
C16HlO02N2 + 2H = C16H1202N2
Indigo
Indigo white
The indi~o solution is prepared by digesting 2 grams of in<! igo
with 10 grams of fuming sulphuric acid (OAUTION), and tllen
pouring very slowly into 1 litre of 4 per cent sulphuric acid.
8. Potassium Ferrous Ferrocyanide Test.-Upon adding
potassium ferro cyanide solution to a solution of a ferrous ',Llt
containing a little sodium hydrosulphite, a white precipi' Lte
of potassium ferrous ferro cyanide K2Fe[Fe(CN)6J is prodll' 'cd
(compare Section III, 19, reaction 6).
9. Action of Heat.-Upon heating sodium hydrosulpl ite,
it suddenly evolves sulphur dioxide at about 190 0 (exotheI' ,lie
reaction). The residue has lost its reducing power to indigo
and methylene blue solution, being a mixture of sodium ,ulphite and sodium thiosulphate.
2Na2S204 = Na2S0S + Na2S20a + 80 2
45]
(Y1'
Anions
417
14+
LJ:.
'lUG
T ,
45]
419
Method B. Acidify the "Na2COa practically neutral solution" (see 20 below) of the halides with dilute nitric acid, add
excess of silver nitrate solution, filter and wash until the
washings no longer give the reactions of silver ions. Shake
the precipitate with ammonium carbonate solution, filter and
add a few drops of potassium bromide solution to the filtrate;
a yellowish-white precipitate of silver bromide is obtained if a
chloride is present.
The hydrolysis of the ammonium carbonate in aqueous
solution gives rise to free dilute ammonia solution in which
silver chloride, but not silver bromide or silver iodide, is
appreciably soluble. The addition of bromide ions to the
solution of silver chloride in ammonia results in the solubility
product of silver bromide being exceeded, and precipitation
occurs.
Alternatively, wash the precipitated halides until free from
excess of silver nitrate solution, and then treat the precipitate
with a cold, freshly prepared solution containing 4 per cent
formaldehyde in OIN sodium carbonate solution: pour a little
of the latter reagent through the filter several times. Test the
filtrate for chloride with silver nitrate solution and dilute nitric
acid. Silver bromide reacts slightly with the reagent yielding
a faint opalescence; silver iodide is unaffected.
6. Chloride in the presence of Bromide.-Warm the
solid mixture* with a little potassium dichromate and concentrated sulphuric acid in a small distilling flask (Fig. IV, 2, 1),
and pass the vapours, which contain chromyl chloride, into
sodium hydroxide solution. Test for chromate, which proves
the presence of a chloride, with hydrogen peroxide and amyl
alcohol or with the diphenylcarbazide reagent.
7. Chloride in the presence of Iodide.-Add excess of
silver nitrate solution to the "Na2COa practically neutral
solution" (see 20) and filter; reject the filtrate. Wash the
precipitate with dilute ammonia solution and filter again. Add
dilute nitric acid to the washings; a white precipitate of silver
chloride indicates the presence of chloride.
The separation is based upon the solubility of silver chloride
in dilute ammonia solution and the practical insolUbility of
silver iodide in this reagent.
8. Bromide and Iodide in the presence of each other
and of Chloride.-The presence of a chloride does not inter If a solution is being analysed, it should be evaporated to dryness before
applying the test. Chlorates must, of course, be absent.
420
[IV,
45]
421
10. Iodate and Iodide in the presence of each other.The addition of dilute acid to a mixture of iodate and iodide
results in the separation of free iodine, due to the interaction
between the liberated iodic and hydriodic acids.
HIO a + 5H1 = 312 + 3H2 0
Neither iodates nor iodides alone do this when acidified with
dilute hydrochloric, sulphuric or acetic acids in the cold.
Test for iodide in the "Na2C03 practically neutral solu tion"
or in a solution of the sodium salts by the addition of a few
drops of chlorine water (or acidified sodium hypochlorite solu~
tion) and 2-3 mI. of chloroform or carbon tetrachlorid,; the
latter is coloured violet. Add excess of silver sulphate solution
to another portion of the neutral solution and filter off the
silver iodide; remove the excess of silver sulphate with sodium
carbonate solution. Pass sulphur dioxide into the filtrate to
reduce iodate to iodide, boil off the excess of sulphur dioxide,
and add silver nitrate solution and dilute nitric acid. A yellow
precipitate of silver iodide confirms the presence of iodate in
the original substance.
422
rIV,
_ minutes). Filter off the arsenious sulphide, and boil off \;he
hydrogen sulphide from the filtrate. Add ammonia solll I :on
until alkaline and excess of the magnesium nitrate reaf nt.
A white precipitate indicates the presence of a phosphate.
AS 20 5 + 4H1 = As 2 0 S + 2H 2 0 + 21 2 ;
AS 2 0 3
212
+ 3H28 = As 28 a + 3H20;
+ 2H 8 ~ 4H1 + 28
2
45]
423
+ 6NHs =
[Zn(NH s)6](OH)2}
424
[IV,
45]
425
Filtrate. Add
Ea(NO.). sol ution and warm
gently. White
crystalline precipitate indicates Silicofluoride.
14*
"
426
[IV.
+H
0 2 = NaCNO
+ 2H2 0 =
+H
NaHCO a
0;
+ NH3
45]
427
428
[IV,
~----------------------------------------Add CaCI, solution to the cold "Na 2CO. practically neutral solution, '"
rub sides of vessel with a glass rod, allow to stand for 10 minutes wit],
occasional shaking; filter.
Residue.
Co. citrate.
White.
Citrate
Filtrate.
Residue.
present.
May conCaC.O,.
Divide
Dissolve in tain Co.
into 2
tartrate.
a little
parts.
dilute HCI, Test
(i) Conneutral
add NHs
firm by
solution
solution
Deniges'
with
in slight
test.
Fenton's
excess.
(ii) DisWhite ppt. reagent,
solve in
violet
insoluble
dilute
coloration
in dilute
HCI, conacetic acid. (see Note),
Oxalate
or by silver vert into
present.
mirror test neutral
Confirm by for tartrate. solution
resorcinol
Confirm
with
test, or by by copper NH. soludecolouri s- hydroxide tion, etc.,
test.
and add
ation of
a dilute
CdCI.
solution of
solution.
acidified
White
gelatinous
KMnO. at
60-70.
precipitate.
Filtrate. Coloured.
Dilute, boil and
filter.
suc~
Residue.
cinate.
Basic
Separate
ferric
by
formate
procedure and basic
A.
ferric
acetate.
Separate
by procedure B.
Filtrate.
Coloured.
(a) Violet-salicylate.
Confirm
by "oil
of wintergreen"
test.
(b) Deep
blue or
greenish
blackgallate
or tannatet
Procedure A
Separation of benzoate and succinate.-Boil the precipitated ferric salts with a little dilute ammonia solution, filter off
* It must be remembered that phosphates, fluorides. sulphatas. etc., are
precipitated by calcium chloride solution.
t Ga.llates and tannates are of rare occurrence in general qualitative anaIyllis.
45]
429
Procedure B
Formates and Acetates in the presence of each other.Formate. (i) In the absence oj tartrates, citrates and reducing
agents. Add silver nitrate solution to the "Na2COa practically
neutral solution"; a white precipitate, which is conve;ted into
a black deposit of silver on boiling, indicates formate. A little
of the solid substance may be treated with concentrated sulphuric acid, when carbon monoxide (burns with blue flame)
will be evolved in the cold.
(ii) In the presence oj tartrates, citrates and reducin,l agents.
Acidify the mixture with dilute sulphuric acid and distil. A
solution of formic and acetic acids will pass over. Neutralise
distillate with dilute ammonia solution, boil off excess of
ammonia (if necessary) and test as in (i).
Acetate. If other organic acids are present, obtain the
solution of mixed acids as in (ii); otherwise, use the "Na2COa
practically neutral solution. " Boil under reflux with an equal
volume of potassium dichromate solution and dilute mlphuric
acid; this will decompose the formic acid. Distil off the acetic
acid, neutralise and test with ferric chloride solution.
If the solid is available, the cacodyl test may be employed.
For other methods of separation and detection of selected
anions, see Section VII, 17, Tables A and O.
CHAPTER V
1]
431
432
V, 2. Systematic Analysis.
General Considerations.--
3]
4:33
V, 3.
PRELIMINARY TESTS
ObseTVatwTI
1. The substance decrepitates.
2. The substance deflagrates.
(b) Mix the substance (ca. 01 gram) with twice its bulk of
anhydrous sodium carbonate, place it in a cavity in a charcoal
block and heat in the reducing flame of the blowpipe.
Ob8ervation
1. Incrustation without metal:
White, yellow when hot.
White, garlic odour.
Brown.
2. Incrustation with metal:
'White incrustation; brittle metal.
Yellow incrustation; brittle metal.
Yellow incrustation; grey and soft
metal, marks paper.
3. Metal without incrustation:
Grey metallic particles, attracted by
magnet.
Malleable beads.
Inference
ZnO.
As.O .
CdO.
Sh.
Bi.
Ph.
Fe, Ni, Co.
Ag and Sn (white);
flakes).
eu
(red
I' ,
Observation
(a) A gas or vapour is evolved.
1. Water is evolved; test with Htmus
paper.
Inference
Compounds with water
crystallisation (often accon
panied by change of oolour
ammonium salts, acid sal;
and hydroxides.
Ammonium salts.
Readily decomposable salts (,:
strong acids.
Nitrates, chlorates and certai"
oxides.
Ammonium nitrate or nitrat,>
mixed with an ammoniUl"
salt.
Nitrates or nitrites of heBv\,
metals.
.
Carbonates or bicarbonates.
Ammonium salts.
Normal and acid sulphites
thiosulphates; certain su]
phates.
Hydrated sulphides or suI
phides in the presence 0 i
water.
Unstable chlorides, .e.g. of
copper; chlorides In the
presence of oxidising agents.
Sources similar to chlorine.
Free iodine and certain
iodides.
As.
S (melts on heating), As,S3'
HgI. (red when rubbed with
a glass rod).
* If a white sublimate forms, heat with four times the blllk of anhydrous
Na.C0 3 and a little KeN in an ignition tube. A grey mirror, convertible
into globules on rubbing with a glass rod, indicates Hg (Note: Hg vapour
is very poisonous); a brownish-black mirror, yielding a white sublimate
and an odour of garlic when heated in a wide tube, indicates As; ammonia
evolved (test with mercurous nitrate paper) indicates ammonium salts.
..
3]
,~..
--,.,_""
435
Observation
Persistent golden-yellow Hilme.
Violet (lilac) Hame (crimson through
cobaltblue glass).
Brick-red (yellowish-red) flame.
Crimson flame.
Yellowish-green flame.
Lividblue flame (wire slowly corroded).
Na.
I K.
Ca.
Sr.
Ba.
Pb, As, Sb, Bi, Cu.
3.
4.
5.
6.
Reducing flame
1Y1 ~tal
Cu.
Mn.
Co.
Ni.
Fe.
Cr.
436
lV,
,jJ
43'(
effect produced.
Ob8ervation
I
1------------------____________________
Inference
1_ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _;
poisonou8.
I CO. from
carbonate or
bicarbonate.
NO a from nitrite.
CIa from hypochlorite.
(0)
SO a from sulphite.
SO. and S from thio
Bulphate.
HoS from aulphide.*
cyanate.
Test (viii). Action of concentrated sulphuric acid.Treat about 02 gram of the substance with 2-3 ml. of concentrated sulphuric acid and warm the mixture gently, and
incline the mouth of the test-tube away from you. (H chlorate
is suspected from the preliminary charcoal reduction test to be
present, use a very small quantity (less than 005 gram) for
this test, as a dangerous explosion may result on warming.)
If the substance reacted with dilute sulphuric acid, the
addition of concentrated sulphuric acid may result in vigorous
reaction and rapid evolution of gas, which may be accompanied
by a very fine spray of acid. In such a case, it is best to add
dilute sulphuric acid drop wise (best with a clean dropper) to
another portion of the substance until action ceases, and then
to add 3-4 ml. of concentrated sulphuric acid.
* Many sulphides, espeoially native ones, are not affected by dilute HISO,;
some HIS is evolved upon warming with ooncentrated HCI alone or with a
little tin.
438
Observation
1. Colourless gas evolved with pungent odour
2.
3.
4.
5.
HBr
and
Br,
fr,
bro-rnide.
nitrate.
CIO. from chlorate.
HF from fluoride.
CO (:rom formate.
CO
and
CO.
fro'"
oxalate.
COS, SO 2 and S frol
thiocyanate.
4]
Systematic Macro
Qualitative,lnorgan~c
Analysis
439
440
[V,
4. Tests with silver nitrate solution.-Sulphide and >ulphite interfere in the tests with silver nitrate solution, hen '\ if
either of these anions was detected in the preliminary test \\ lth
dilute sulphuric acid, it must be removed first as foll., \VS.
Acidify 10 ml. of the "Na2C03 prepared solution" with di'llte
acetic acid (use litmus paper): boil gently in a conical flas! or
porcelain dish in the fume cupboard to expel hydrogen sulpl :de
or sulphur dioxide (3-5 minutes). It is important that 'he
solution be acid throughout. Filter, if necessary, and aUo\\ to
cool. If the volume has been reduced appreciably. add wu,ter
to restore the original volume (solution S).
.,
Filtrate.
Discard.
4]
441
iV,
of ammonia. Divide the solution into two equal parts; reserve i~,tlf
for test 6.
Add CaCl 2 solution (equal in volume to that of the ~olution). a,d a
little dilute acetic acid and allow to stand. A white preClpr . te
indicates the presence of oxalate and/or fluoride . . Filter off t~e ",,~
cipitate and dissolve it by pouring a little hot dIlute sulphurIC ;,. old
into the filter. Treat the hot filtrate with a few drops of potasE "m
permanganate solution. If the permanganate is reduced, oxala, is
present.
6. Test with ferric chloride solution. Treat the Oi Iler
portion of the "neutral" solution from test 5 with aqueous F. ! jla
solution.
Reddish-purple coloration indicates thiosulphate.
Reddish-brown coloration, yielding a brown precipitate on dilul ;on
and boiling, indicates acetate.
, Yellowish-white precipitate indicates phosphate.
Blood-red coloration, discharged by HgCl 2 solution, indicat.es
thiocyanate.
5]
443
Sulphate. The BaCl2 solutIOn and dilute HOI test is fairly conclusive. Further confirmation is obtained by reduction of [he ppt.
(BaS04) on charcoal to sulphide (test for latter with lead acetate
solution) (IV, 24, 1).
Carbonate. Action of dilute H zS04 on solid, and lime water test
(IV, 2, 1).
Hypochlorite. Action of dilute HOI and test for 01 2 evolved
(IV, 13, 4).
Chlorate. The AgNOs-NaNO z test (IV, 19. 3).
Chromate. Hydrogen peroxide test with amyl alcohol as organic
solvent (IV, 33, 4).
Arsenite. Immediate ppt. of As 2S a in dilute HOI solution (III,
11, 1) and absence of ppt. with Mg(NO a)2 reagent (III, 11, 3).
Arsenate. Action of HzS on acid solution (III, 12, 1), AgNO s
solution test in faintly acetic acid solution (III, 12, 2) and Mg(NO a)2
reagent test (III, 12, 3).
Phosphate. Ammonium molybdate test (temperature not above
40) (IV, 28, 4).
Cyanide. Prussian blue test (IV, 8, 4) or ammonium sulphide
test (IV, 8, 16).
Thiocyanate. Ferric chloride solution test: colour discharged by
HgCl 2 solution or by NaF solution, but not by HOI (IV, 10, 6).
Acetate. Action of ethyl or of n- butyl alcohol and concentrated
H 2S04 (IV, 35, 3) OR indigo test (IV, 35, 9) using ordin,try testtube or ignition tube.
Oxalate. The Oa012 test and decolourisation of acidified KMn0 4
solution at about 70 is sufficiently conclusive.
444
[V,
... Full experimental details of the various tests will be found in Chapter IV.
t T,.ocu of nitrate are always formed in this reaction.
6]
445
4,46
(V.
CH . C,H,.SO.NClNa
+ HIO
CH. C.H,.SO.NH,
+ NaOCl
6]
447
that arsenates are only slowly precipitated by hydrogen sulphide in dilute acid solution.
Acidify the "Na2C03 prepared solution" with dilute hydrochloric acid, pass in sulphur dioxide to reduce the arsenate to
arsenite, boil off the excess of sulphur dioxide (test with potassium dichromate paper), and pass hydrogen sulphide into the
solution to precipitate the arsenic as arsenious sulphide: continue the passage of hydrogen sulphide until no more precipitate
forms. Filter, boil off the hydrogen sulphide and test the
filtrate for phosphate by the ammonium molybdate test (Jr with
the magnesium nitrate reagent.
An alternative method for the elimination of arsenate is the
following. Acidify the "Na2C03 prepared solution" with dilute
hydrochloric acid and then add one-quarter of the volume of
concentrated hydrochloric acid (the total volume should be
about 10 mI.). Add 05 mI. of 5 per cent ammonium iodide
solution, heat to boiling and pass hydrogen sulphide into the
boiling solution until precipitation is complete (5-10 minutes).
Filter off the arsenious sulphide, and boil off the hydrogen
sulphide from the filtrate. Add dilute ammonia solution until
alkaline and excess of the magnesium nitrate reagent (or of
magnesia mixture). A white precipitate indicates the presence
of phosphate.
+ 2H~ ~ ill1 + 28
448
[V,
7]
449
This Table and the Notes which follow are intended for beginners
and in consequence the various operations are given in somewhat
greater detail than in Table I (Seotion VII, 6).
US+
460
[V,
8]
451
pH
7+
10
06
0'5
03
L'
8]
453
+ CO a--
... NHa
+ HCO a-;
[V,
~54
+ HNO a
NH4 N0 8
+ HCI
N sO
2HaO
+ HCI
+ COli + H
,9. Modification of the analysis in the presence of phoshate.-Certain anions, which include phosphate, fluoride,
)rate, silicate and also those derived from organic acids such
; acetate and oxalate, interfere with the cation analysis after
roup II. Thus the presence of phosphate, fluoride, borate
. oxalate ions will cause the metals of Groups IIIB and IV
ld also Mg to precipitate when the solution is made ammoacal in Group IlIA. The various interfering anions and their
moval or elimination are discussed in detail in Chapters VII
ld VIII. It is unlikely that the student will encounter any
, the interfering anions in elementary analysis with the pos)le exception of phosphate. The manner of removal of
lOsphate is therefore given in the following table (Table P)
an illustration of the procedure to be adopted in dealing
th an important interfering anion. The student will appreLte that the phosphate separation need not be made even if
)4 --- has been shown to be present (e.g. by the ammonium
)lybdate test) if no precipitate is obtained in Group IIIA.
ith NH4 CI and aqueous NH 3 ) and also when it is known that
'oup IV and Mg are absent.
10]
V,9.
455
Boil the filtrate from Group II until free from H,S, add a few drops of
concentrated RNO. (or 1-2 mi. of bromine water) and boil gently for
I minute. Test a small portion for phosphate with ammonium molyb.
date and nitric acid, and a further portion for the presence of Groups
lIlA, IIIB, IV or Mg by the addition of NE.CI Hnd Nfl. solution. If
both tests are positive, proceed as follows.
Adjust the volume of the solution to 10 ml. (1). Add 0,5-1 gram of
solid NE.Cl, stir until dissolved, then add the zirconium nitrate reagent
slowly and with stirring until precipitation is complete (2): a large eXCfSB
of the reagent must be avoided. Heat the contents of the test tube or
small conical flask to boiling and stir with a glass rod to prevent bumping.
Filter through a Whatman No. 32 fIlter paper (3): wash the ppt. with a
little hot water and combine the washings with the filtrate.
Residue.
Zirconium
phosphate.
Reject.
Filtrate.
Examine for
Groups IIIB,
IV and V.
Notes. (1) It is essential that the acidity with respect to hydrochloric acid should not exceed N, otherwise a turbid supernatant
liquid is obtained and the removal of phosphate is not quite complete.
Test with methyl violet or any other suitable indicator (brilliant
cresyl blue, cresol red, etc.).
(2) It is important that the excess of the zirconium nitrate reagent should not exceed 25 per cent, otherwise a turbid supernatant
liquid will be obtained; this turbidity cannot be removed by filtration or centrifugation. It is best, therefore, to add the zirconium
nitrate solution slowly and with stirring until precipitation appears
complete, heat just to boiling, filter, and test the filtrate with the
reagent, etc.
(3) The addition of half a Whatman filtration accelerator (or a
little filter paper pulp) assists filtration; the precipitate must be
washed thoroughly with hot water.
(56
[V,
CHAPTER VI
INTRODUCTION TO SYSTEMATIC SEMIMICRO
QUALITATIVE INORGANIC ANALYSIS
VI, 1. Preliminary Discussion.-It is assumed that the
student is already familiar with the operations (ignition tests,
blowpipe tests, flame tests, borax bead tests, precipitation,
filtration, evaporation, etc.) described in Sections II, 1 and 11,2.
A detailed description of semimicro apparatus and of semimicro
analytical operations is given in Section II, 3. The student
should read this carefully and thus acquire a general knowledge
of semimicro technique. To secure the introductory practical
experience the following course of instruction may be followed.
Reactions are normally carried out in 4 mI. test-tubes or in
3 ml. centrifuge tubes, unless otherwise stated. The solutions
employed in testing for cations or anions contain 10 mg. of
cation or anion per ml. For purposes of calculation a drop of
solution may be assumed to have a volume of 0'05 wI.: this
will help in rough computations as to volumes required in
adding excess of reagents, etc.
For the cations, a limited number of preliminary reactions
should be studied first, followed by an analysis of a mixture or
solution containing a member or members of each group. This
will give practical experience in the routine operations of semimicro analysis and also provide practice from the very outset
in the use of Group Separation Tables. Particular attention
should be paid to:
(i) the exact experimental conditions of the reaction;
(ii) the colour and physical characteristics (e.g. whether
crystalline, amorphous or gelatinous) of each precipitate; and
(iii) the solubility of each precipitate in excess of precipitant,
or in solutions of other reagents.
The student should, as far as possible, represent the chemical
reactions by ionic equations and then check the equations
against the molecular equations given in Chapters III and IV.
In this way excellent practice will be obtained in writing and
balancing equations, and also help to impress the reactions
upon the memory.
15*
~7
458
[VI,
2]
460
[VI,
VI, 3. Systematic Analysis. General Considerations.The student must realise that the object of qualitative analysis
is not simply to detect the constituents of a given mixturf';
an equally important aim is to ascertain the approximatu
relative amounts of each component. For this purpose abom
02 gram of material is usually employed for the analysis: tl",
relative magnitudes of the various precipitates will provide 'I
rough guide as to the proportions of the constituents present.
Every analysis is divided into three parts:
(1) The preliminary examination. This includes preliminary
examination by dry tests, examination of the volatile products
with sodium hydroxide solution (for ammonium), and with
dilute and concentrated sulphuric acid (for i1cid radicals or
anions). A special preliminary test for nitrate and/or nitrite
is also made here.
(2) The examination for acid radicals (or anions) in solution
(3) The examination for metal ions (or cations) in solution.
VI, 4.
PRELIMINARY TESTS
Test (i). Heatin~ in a closed tube.-Place about 5 mg.
of the substance in a dry ignition tube (70 X 4:-5 mm.) so that
none of it remains adhering to the sides and heat cautiously
with a semimicro burner; the tube should be held in an almost
4]
InjMen.
* If a white sublimate forms, heat with four times the bulk of anhydrous
Na 2CO. and a little KeN in an ignition tube. A grey mirror, convertible
into globules on rubbing with a glass rod, indicates Hy (Note: Hg vapour
is very poi8onou8); a brownishblack mirror, yielding a white Hublimate
and an odour of garlic when heated in a wide tube, indicates As; ammonia
evolved (test with mercurous nitrate paper) indicates ammonium salt8.
462
[VI.
Inference
Crystalline salts, e.g. NaCI, KC!. '
Oxidising agents, e.g. nitrates,
nitrites and ohlorates.
Apply test (b) below.
(b) Mix the substance (3-5 mg.) with twice its bulk of anhydrous sodium carbonate, place it in a cavity in a charcoal
block, and heat in the reducing flame of the blowpipe.
Observation
Inference
ZnO.
As.O .
CdO.
Sb.
Bi.
Pb.
Fe, Ni, Co.
Ag and Sn (white); Cu (rod
flakes).
4)
Inference
Na.
K.
Ca.
Sr.
Ba.
Pb, As, Sb, Bi, Cu.
Reducing flame
Fe.
Cr.
Mn.
Co.
Ni.
.'lfetal
Cu.
.464
[VI,
4]
Inference
CO. from carbonate or
bicarbonate.
(0)
Cl 2 from hypochlorite.
SO 2 from sulphite.
H.C.H.O. fr l) m
acetate.
O. from peroxid68 or
per-salts of alkali and
alkaline earth metals.
HCN from cyan,ide or
from solublefe,-ri- and
ferro-cyanidBB.
SO" etc., from thiocyanate.
Test (viii). Action of concentrated sulphuric acid.Treat 5-10 mg. of the substance in a semimicro test-tube with
03-05 ml. of concentrated sulphuric acid. If no reaction
occurs in the cold, place the tube in the hot water rack. (If
* Many sulphides, especially native ones, are not affected by dilme H 2SO;
some H 2 S is evolved by warming with concentrated HCI alone or with a
little tin.
t If cyanide is suspected, gently warm (water bath) 5 mg. of tha mixture
with 5 drops of 2N H 2SO, in a semimicro test-tube carrying over the mouth
a piece of filter paper moistened at the centre with 1 drop of dilute NaOH
solution. After 2 minutes, treat the drop on the paper with 1 drop of FeSO,
solution, warm and add a drop or two of 6N HCI. A blue colour indioates
the presence of a cyanide. For another test, ;100 Section IV, 8, r~8Ction 1.
Merourio oyanide is attacked slowly.
466
[VI,
Inference
HCl from chloride.
co
and CO
oxalate.
from
* The burning splint should be introduced into the tube; the application
of a flame to the mouth of the tube frequently fails to ignite the ga.s owing
to its dilution with air in the tube.
5J
VI, 5.
The carbonate MCO s is insoluble and the sodium salt NaA will
pass into solution whether MA2 is soluble in water or not.
Preparation of solution for testing for anions.-Boil 200
mg. of the finely divided substance or mixture with 25 m!. of
a saturated solution of pure sodium carbonatet (prepared from
04 gram of anhydrous sodium carbonate and 25 mL of distilled
water) for 5-10 minutes in a 10 mL conical flask with a funnel
in the mouth to reduce the loss by evaporation.t Transfer,
with the aid of about 05 m!. of water, to a 4 m!. semimicro
test-tube and centrifuge. Remove the centrifugate to another
test-tube: add 1 mL of hot distilled water to the residue, stir
and add the clear washings to the original centrifugate; the
total volume should be 3-4 mL The sodium carbonate extract
will be termed the "N a 2 CO a prepared solution." r se the
solution to carry out the following tests.
1. Sulphate test.-To 5 drops of the "Na2C03 prepared
solution" in a 4 m!. test-tube add dilute hydrochloric acid until
acid (test with litmus paper) and then add 3 drops in excess.
Place in the hot water rack for 5 minutes to expel carbon di... Certain carbonates, initially formed, are converted into insoluble basic
carbonates or into hydroxides.
t It is essential to use pure sodium carbonate; the A.R. solid is satisfactory.
Some "pure" samples may contain traces of sulphate or chloride: th<3 absence
of these impurities should be confirmed by a bhtnk experiment.
t If no precipitate is ohtained, the substanco is virtually free from heavy
metals, and the sodium carbonat~ t.reatrrwnt may be omitwd if more of the
solution is required.
468
[VI,
5]
Centrifugate. Add NaOH solution dropwise and with vigorous stirring until the
solution is just neutral to litmus or, better,
barely alkaline to nitrazine yellow indicator
(1); then add 2-3 drops of dilute acetic acid
and 5 drops of AgNO. solution. Roat to
about 800 in the water bath (2). If a permanent ppt. forms, add more AgNO. solution
until precipitation is complete. Centrifuge,
and wash with a few drops of hot water.
Residue (3).
Ag.PO.-yellow.
Ag.AsO.-brownish.red.
Ag.AsO.-yellow.
Ag.C.O.-white.
Centrifu~ate.
Reject.
[VI,
Qualitative Inorganic Analysis
470
_ _" Na 2C0 3 prepared solution" as follows. Acidify 5 drops of ilia
solution with dilute HN0 3 and cool. Add 03 ml. of amyl alcoJ,ol
and 2 drops of 3 per cent H 2 0 2 solution. A blue coloration ("p"f'chromic acid") in the organic layer confirms chromate.
The separations described in the above table are based up()n
the following facts:
(i) AgN03 solution precipitates only AgCl, AgBr and AgI
from a dilute nitric acid solution, the other silver salts beillg
soluble.
(ii) NaN0 2 solution reduces chlorate to chloride, which is
precipitated as AgCl in the presence of AgN0 3 solution:
NaClOa
+ 3NaN02 =
NaCl
+ 3NaN03
6]
Add an equal volume of CaCI, solution and place in the hot water rack
for 5 minutes. Centrifuge and wash with a few drops of hot water.
Residue. May be calcium fluoride, oxalate, Phos-j Centrifugate.
phate and arsenate.
Reject.
Add 1 mI. of dilute acetic acid, heat in the hot water
rack for 2-3 minutes and centrifuge.
~
Residue. May be calcium
oxalate and calcium fluoride.
Extract with 1 mI. of hot dilute
H.SO, and centrifuge, if necessary.
Treat the hot centrifugate or solu
tion with 2 drops of O'02N KMnO,
solution. If the permanganate is
decolourised, oxalate is present.
If the ppt. is not completely
soluble in dilute H 2S0 4 , test the
original substance for fluoride by
the water.film test (Section VI, 6).
------
Add NaUH
Centrifugate.
solution dropwise until neutral (, Ise
litmus ornitrazine yellow indicator).
White ppt. (sometimes separating slowly).
Arsenate and/or phosphate
present.
Treat the suspension or neutral
solution with a few drops of AgKO B
solution. A yellow ppt. indicates
phosphate: a brownish-red ppt.
indicates arsenate or arsenate
phosphate.
VI,6.
* The bench reagent usually contains excess of free acid added during its
preparation in order to produce a clear solutiun; this may prevent tho precipi.
tation of the basic acetate on boiling. It is therefore recommended tLat dilute
NH. solution be added dropwise to 1 mI. of sidflshelf FeCl a solution until u
slight precipitate forms and the mixture centrifuged. The clear centrifugate
(t!ometimes termed "neutrai FeCI, solution") is employed in the tdllt.
6]
Fig. VI, 6, I
at the junction of the two liquids after 1-2 minutes. (ii) Dis
solve 10-20 mg. of the substance in 05 m!. of water and add
about 1 m!. of FeS04 solution. Incline the tube and allow
05-1 ml. of concentrated H 2S04 to run slowly down the side
of the tube to form a layer under the solution (Fig. VI, (/, 1),
and after 1-2 minutes observe the brown ring at the interface.
~"\).~.~'\\\.~~. "\_"t.~~\' \._\\-~\\ -m._~. ~\ ~~ ~'U..\)~\'~"'I..\.~ ~~ \\.~ -m._\..
()\ m\'U..~ l\_~~~. ~"\'G.~ \'n.~ \o'\')._"\)e \._n_ \_~~ ~~" VI-a.'\R.1: 1:"3.<2K. -a.n.<\.
472
[VI,
,.esult,
6]
Fig. VI, 6, 1
at the junction of the two liquids after 1-2 minutes. (ii) Dis
solve 10-20 mg. of the substance in 05 ml. of water and add
about 1 ml. of FeS04 solution. Incline the tube and allow
05-1 ml. of concentrated H 2S04 to run slowly down the side
of the tube to form a layer under the solution (Fig. VI, G, 1),
and after 1-2 minutes observe the brown l'ing at the interface.
474
[VI,
for S02 with K2Cr207 paper* (Fig. II, 3, 19, a) or with 02 m}.
of fuchsin solution (Fig. II, 3, 19, b) (IV, 4, 10).
Thiosulphate. Dilute H 2S04 on solid and liberation of SO:'
(K2Cr207 test-details under Sulphite) and sulphur (IV, 5, 1).
Sulphate. The BaCl 2 solution and dilute HCI test is fairly
conclusive.
Further confirmation is obtained as follows. Centrifuge the suspension and remove the supematant liquid. Add 1 mI. of water, stir.
centrifuge and discard the centrifugate. Add 3-4 drops of water, stir
thoroughly to produce a fairly uniform suspension, transfer the sus
pension to a small plug of cotton wool in a small ignition tube, introduct,
2-3 drops of Na 2 CO S solution and heat cautiously to redness. MaintaiI
the lower part of the tube at a red heat for 2-3 minutes and allow t,
cool. Break the tube, transfer the residue as completely as possible t(,
a semimicro test-tube, add 0'5 mI. of dilute HCI and introduce a Pyre},
filter tube carrying a strip of filter paper moistened with lead acetak
solution. Place the assembly in the hot water rack. A brown staiI,
on the paper confirms sulphate.
7]
and place the tube in the hot-water rack for a minute or two.
Yellow ppt. (IV, 28, 4).
Cyanide. Prussian blue test (IV, 8, 4) or ammonium sulphide test (IV, 8, 1, 6).
Thiocyanate. Ferric chloride solution test; colour discharged by HgC1 2 solution or by NaF solution, but not by HCI
(IV, 10, 6).
Borate. Flame test (IV, 23, 2); or turmeric paper test
(IV, 23, 3); or mannitol-bromothymol blue test (IV, 23, 8).
Acetate. Mix 20 mg. of the substance with 1 m!. of ethyl
or n-butyl alcohol and 5 drops of concentrated H 2S04 Heat
in the hot water rack for 10 minutes, and pour into 2 m!. of
Na2C03 solution-characteristic odour of ester (IV, 35, 3)
OR, better, indigo test (IV, 35,9). Mix 15 mg. of the subsiance
with 15 mg. of CaC0 3 in a semimicro test-tube, introduce a
pressure-filter tube carrying a strip of filter paper mois1,ened
with a solution of 5 mg. of o-nitrobenzaldehyde in 1 m!. of
NaOH solution. Heat the test-tube strongly. Blue or green
stain on paper confirms acetate.
Oxalate. Precipitate with CaCl2 solution in the presence
of dilute acetic acid, the precipitate decolourises a dilute acid
solution of KMn0 4 (IV, 37, 3, 4 and VI, 5, 5); resorcinol test
(IV, 37, 5).
VI, 7. SPECIAL TESTS FOR MIXTURES OF ACID
RADICALS (ANIONS)
The subject is treated fully in Section IV, 45, and again (for
elementary students) in Section V, 6, but on a macro scale.
The student should be able to adapt these to semimicro work.
Some typical semimicro separations of mixtures of anions are
given below. The quantities are for guidance only and can
be reduced, if desired. If the mixture is insoluble in water,
it is often convenient to employ the "Na2C03 propared
solution" (Section VI, 5) or the "Na2 C03 practically neutral
solution" (Section VI, 5, test 5). The special gas 1esting
apparatus of Fig. 11, 3, 19 will, of necessity, find application
here.
1. Carbonate in the presence of Sulphite.-Treat 20 mg.
of the mixture with 20 mg. of finely I,owdered K2Cr207 and
05 m!. of dilute H 2S04 ; place the apparatus (Fig. 11, 3, 19,
476
[VI,
HN0 2
+ HO.S0 2 .NH 2 =
N2
+ H 2S04 + H 2 0
3. Nitrate in the presence of Bromide and Iodide. Treat 10-15 mg. of the substance with 1 m!. of sodium hydrc\ide solution and 10-15 mg. of Devarda's alloy (or of aluminill m
as powder or as thin foil), place in the hot water rack, and tl-;t
for ammonia with red litmus paper or mercurous nitrate paJ"'r
(Fig. II, 3, 19, a).
Another procedure is to just acidify 5 drops of the "Na2C('a
prepared solution" with dilute acetic acid, and then add tlte
ammoniacal silver sulphate reagent (see Section IV, 45, .J)
dropwise until precipitation is complete. Centrifuge. Add
excess of concentrated H 2S04 cautiously to the centrifugate
and apply the brown ring test.
4. Nitrate in the presence of Chlorate.-Test for nitrate
as under 3: then acidify with dilute HNO a and test for chloride
with a few drops of AgNO a solution.
If chloride is originally present, it may be removed by the
addition of saturated sUver sulphate solution or of the ammoniacal silver sulphate reagent.
o. Chloride in the presence of Bromide and Iodide.Dissolve 10-20 mg. of the solid in 0,5-1 m!. of water in a
semimicro boiling tube (or use 5-10 drops of the "Na2COa
prepared solution" acidified with dilute HNO a), add 1-1,5 ml.
of concentrated HNO a, and boil gently until the bromine and
iodine are volatiIised. Dilute with 1 m!. of water, and test
for chloride by the addition of a few drops of AgNO a solution.
Alternatively, repeat the experiment but add 20 mg. of
precipitated PbO instead of the concentrated HNO a. After
7]
478
[VI,
the hot water rack for 3-5 minutes (this converts part of the
AgSCN into NaSCN). Centrifuge and add to the clear centrl'
fugate one drop of dilute HCI and one drop of FeCl a solutiOlI
A red coloration indicates thiocyanate present.
If thiocyanate is present, it must be destroyed since it inte!
feres with the tests for the halides. Dry the main precipital"
in the crucible by heating gently in an air bath (Fig. II, 3, Hi),
remove the air bath and heat directly to dull redness for Olle
minute or until all the thiocyanate is decomposed, i.e. until
blackening of the precipitate and/or burning of sulphur jU:!j
ceases. Prolonged heating should be avoided. Allow 1 d
cool.
Mixtures of halides may now be identified as indicated III
5-8 above: a systematic procedure, which covers the thr, '13
halides, is given below.
To the residue in the crucible (if thiocyanate is present) or to t: Ie
remainder of the precipitate transferred to a 5 or 10 ml. beaker ,if
thiocyanate is absent), add 100-150 mg. of zinc powder (20 mesh) fl .1
10-15 drops of dilute H 2 SO,. Allow the reduction to proceed for 5- i 0
minutes with intermittent stirring: gentle warming for a few secOl. is
may be necessary to start the reaction. Transfer the liquid, with 1 :.e
aid of a few drops of dilute H 2S0 4 , to a centrifuge tube, centrifuge a,:d
divide the clear centrifugate into three equal parts.
Iodide test. Add 4-5 drops of CCI, and 5 drops of 3 per cent H,' II
or 5 drops of 25 per cent Fe2(SO,)a solution. Agitate vigorously uild
allow to settle. Purple to violet colour of the CCI, layer. Iod ,le
present.
Bromide test. (a) If iodide is present, it must be removed Ily
treating one-third of the solution with 5 drops of dilute H 2SO, nl,d
2 drops of 30 per cent NaN0 2 solution (chloride-free). Boil do:'. n
gently to 3-4 drops and allow to cool; Transfer the solution t, a
centrifuge tube and test for bromide as under (b).
(b) If iodide is absent, use one-third of the solution directly. A, ld
an equal volume of concentrated HN0 3 , heat in the boiling water b,,:h
for 30 seconds, and cool to room temperature with cold water. Add
3-4 drops of CCI, and stir vigorously with a glass rod. A brown col"'lr
in the CCI, layer indicates bromide present.
Chloride test. (a) If iodide and/or bromide present, dilute ; lIe
remaining third of the solution to 05 mI., add 1 m!. of concentra: "d
HNO a and boil gently until evolution of bromine ceases. Cool, dil ite
and test for chloride as in (b) below with AgNOa solution only.
(b) If bromide and iodide are absent, add 2 drops each of dilute
HNO a and AgNO a solution. A white precipitate (AgCI) indicH'es
chloride present.
8]
Centrifugate. Transfer
to a small crucible, boil until
H.S is expelled and volume
is reduced to 2-3 drops.
Transfer, with the aid of a
few drops of water, to a
centrifuge tube, make alka
line with dilute NH. solution and add 5 drops in
excess. Add 10 drops of
Mg(NO.). reagent (or of
magnesia mixture), and
allow to stand, with frequent stirring, for 10
minutes.
White ppt. of Mg(NH,)PO,,6H t O.
Phosphate present.
480
[VI,
warming. If insoluble in water, the following reagents are inve:,,tigated as solvents in the order indicated: dilute hydrochlof ll )
acid, concentrated hydrochloric acid, dilute nitric acid, CO! J centrated nitric acid and aqua regia (3 volumes of concentrakd
HOI to 1 volume of concentrated HN0 3 ). Most substances cucountered in an elementary course will dissolve in either wai"f
or dilute hydrochloric acid. If concentrated hydrochloric aCid
has to be used, the solution must be considerably diluted befc" e
proceeding with the analysis, otherwise certain cations, such ;IS
cadmium and lead, will not be precipitated by hydrog' U
sulphide. When concentrated nitric acid or aqua regia IS
employed as the solvent, the solution must be evaporat, d
almost to dryness, a little hydrochloric acid added, the soluti 'u
evaporated again to small bulk and then diluted with water i 0
dissolve the soluble nitrates (or chlorides). This evaporatj, ,n
is necessary because the nitric acid may react with the hydrof' ,'n
sulphide subsequently employed in the Group analysis.
To discover the most suitable solvent, treat portions of abc" It
15 mg.* of the finely powdered substance successively Wi' h
0,3-0,5 ml. of (1) water, (2) dilute hydrochloric acid, (3) C.'Itcentrated hydrochloric acid, (4) dilute nitric acid, (5) conc('ntrated nitric acid and (6) aqua regia (3 volumes of concentral ,'d
HOI: 1 volume of concentrated liNDa) in the order giV"ll.
Try the solubility first in the cold and then at the temperatll re
of a boiling water bath for water and dilute hydrochloric a, (d
using a semimicro test-tube. For the other solvents, it will i)e
necessary to investigate the solubility in a semimicro boiL Ilg
tube; if solution does not take place in the cold, warm gently
with a semimicro burner. When all the substance has dissolved, transfer to a semimicro test-tube, rinse the boiling tu be
with a few drops of water, and add the "rinsings" to j he
solution. If you are in doubt as to whether the substance or
a portion of the substance has dissolved, evaporate a little of
the clear solution on a watch glass.
If the substance dissolves in water, proceed immediately to
the test for the metal ions. If the use of dilute hydrochlc,ric
acid results in the formation of a precipitate, this may conl,ist
of the metals of Group I; the precipitate may either be filte red
off and examined for this Group, or else the original Bubstance
may be dissolved in dilute nitric acid. If concentrated 80< ids
are employed for dissolution, the remarks in the first paragraph
must be borne in mind.
This is most simply estimated by weighing out 75 mg. and dividir>t,i ii
into 5 approximately equal parta.
_j
8J
Oxides, Hydroxides, Free Metals and Simple Alloys.If a solid substance is found to contain no anions, it may be an
oxide, or hydroxide, or a metal or a mixture of metals, or an
alloy. Metals and alloys have certain characteristic physical
properties; many metals evolve hydrogen on treatment with
dilute acids. As a rule, nitric acid must be employed as solvent,
and it will then be necessary to remove the excess of nitric acid
(as already described above) before proceeding to the Group
analysis.
When a suitable solvent has been found, prepare the solution
for analysis using about 50 mg. of the solid: the volume of the
final solution should be 1-1'5 ml. Use this solution for the
Separation of Cations into Groups according to Table SM.S
(Section VI, 9). The various precipitates are investigated by
means of the appropriate Group Separation Tables SM1SMVII, given in Chapter Ill.
NOTES ON TABLE SM.S (SrMPLIFIED GENERAL TABLE FOR
SEPARATION OF CATIONS INTO GROUPS)
16+
482
[VI;
'lJ
lnorgantc AnatYSM
4~3
Acid concentration
pH
Neutral or alkaline
7+
Violet.
O'lN Hel
10
Blue.
0'25N Hel
0'6
Blue-green.
0'33N Hel
0'5
Yellow-green.
0'50N Hel
0'3
Yellow.
Add 1 micro drop of methyl violet indicator solution and introduce
dilute NHs solution with constant stirring until the colour of the
solution is yellow-green. A blue-green colour is almost but not
quite acid enough, yet is acceptable for most analyses: stucients who
484
[VI,
9J
+ 00 3 - -
~NH3
+ HOO a-;
+ HNO.
NH,NO.
+ HOI
= N ,0
+ 2H.O + HOI
486
[VI,
--+
2NHs
+ COl + HzO
The digestion also improves the filtering properties ofthe precipita ".
(15) Owing to the slight solubility of CaCO s , SrOOs and BaCI '3
in solutions of ammonium salts, the centrifugate from Group ; V
will, when these metals are present, contain minute amounts of t. Ie
ions of the alkaline earth metals. Since the Group IV metals m '.7
interfere to a limited extent with the flame tests for Na and K a, ,l
also the Na2HP04 test for Mg (if employed), it has been reCOl mended that the filtrate from Group IV be heated on a water ba:!l
for 2-3 minutes with half a drop each of (NH4)2S04 solution a; 1
(NH4)2C204 solution; any precipita,te which forms is removed :, V
centrifugation and discarded. Owing to the comparatively sm I
concentration of ammonium salts, this is generally unnecessary ,f
the procedure described in Table SMVII (Section III, 37) is adopt! i.
10]
VI,10.
Analy8'i,~
487
Residue.
Zirconium
phosphate.
Reject.
Centrifu~ate.
Examine for
GroupK IIIB,
IV and V.
488
[VI,
CHAPTER VII
489
490
[VII,
VII,2.
This is really a wet test, but is inoluded here (or the sake of oonvenien'''J.
2]
491
Inference
As.
S (melts on heating), As.S.,
HgI. (red when rubbed with
a glass rod).
I.
HgS.
~as
or vapour is evolved.
492
[VII,
Ob8ervation
Inference
Inference
Sodium.
Potassium.
Lithium.
Calcium.
Strontium.
Barium [molybdenum).
Borates, copper [thallium].
Lead, arsenic, antimony. bismuth, copper.
2]
493
substance on a clean platinum wire into the base of the nonluminous Bunsen flame. An alternative method is to dip the
platinum wire into concentrated hydrochloric acid contained
in a watch glass and then into the substance; sufficient will
adhere to the platinum wire for the test to be carried oui.
The sodium flame masks that of other elements, e.g. that of
potassium. Mixtures can be readily detected with the direct
vision spectroscope (see Fig. 11, 1, 4). A less delicate method
is to view the flame through two thicknesses of cobalt blue
glass, whereby the yellow colour due to sodium is masked or
absorbed, and the other colours are modified as follows.
Flame coloration
tkrough cobalt glass
Flame coloration
Golden-yellow.
Violet.
Brick-red.
Crimson.
Yellowish-green.
Nil.
Crimson.
Light green.
Purple.
Bluish-green.
Inference
Sodium.
Potassium.
Calcium.
Strontium.
Barium.
Inference
Crystalline salts, e.g. NaCI,
KCl.
Nitrates, nitrites, clJorates,
perchlorates, iodates, permanganates.
Salts of the alkalis aJ ld some
salts of the alkaline earths.
Apply test (b) below.
(b) Mix the substance (3-4 mg.) with twice its bulk of anhydrous sodium carbonate, place the mixture in a cavity of a
piece of charcoal and heat in the reducing flame of the blowpipe.
The sodium carbonate converts a metallic salt into a carbonate or oxide on
heating, and thus reduction occurs more rapidly than with the charcoal
alone, as in (al. Further, the sodium carbonate acts as a flux nnd, in the
fused state, protects any metallic globules, whioh Illay have formed benea.th
it, from oxidation.
494
Inference
Ob8ervation
1. White, infusible
when hot.
and
[VII
incandescent
Inference
Al,O., phosphates, arsenates,
silicates, borates.
ZnO.
MgO.
I
I
2]
495
OxtdiMng flfWM
Rf)(/,ucing flame
Iron.
Chromium.
MangRllese.
Cobalt.
Nickel.
Melrd
Copper.
496
[VH,
3]
497
[VII,
Ob81l'1'vation
Test
Treat a
1-2 m!.
gently;
(vii). Action of concentrated sulphuric acid.small quantity (say, 01 gram) of the substance w;l,h
of concentrated sulphuric acid, and warm the mixtlll'e
incline the mouth of the test-tube away from the
* Magnesite, dolomite and a few other native carbonates give little 01' no
CO. in the cold; CO. is readily evolved upon warming.
t Many sulphides, especially native ones, are not affected by dilute H 2 SO.;
some H,S is evolved upon warming with concentrated HCI alone or witiJ a
little tin.
:j: If cyanide is suspected, gently warm (water bath) 5 mg. of the mix! lire
in a small test-tube (e.g. 75 X 10 mm.) with 5-10 drops of 2J1.- H 2SO.: place
a filter paper moistened at the centre with 1 drop of N aOH so lution over 1 he
mouth of the tube. After 2 minutes, treat the drop on the paper with 1 drop
of FeSO. solution, warm and add a drop or two of 6N HCI. A blue colUllr
indicates the presenCE! of a cyanide. For another test, see Section IV, 8,
_ .............. .: .........
.,
.... 1 .............1......
499
3]
2.
3.
4.
5.
6.
7.
8.
Inference
HCI from chloride.
HBr and
bromide.
Br 2
from
[Contin'ued (i1)erleaJ
500
[VII,
Observation
Inference
Benzoate.
H. C.H30~ from acetu
Gallate.
Tannate.
0. from peroxide
some per-salts ( "
chromate,
CO and anhydrol;',
CoSO, from cobalt,.
cyanidet
COS, SO. and S frolll
thiocyanate.
Br. and
bromate.
0. fro]
+ K.CO. =
5KCN
+ KONO + CO. + Fe
3]
501
Test (ix). Borate test.-Make a paste of the original substance with calcium fluoride and concentrated sulphuric acid.
Hold some of this in a platinum loop just outside the base of
the Bunsen flame. A green flame, due to boron trifluoride,
indicates borates. Barium and copper do not interfere when
the test is carried out in the above manner.
* It must be emphasised that the mercurous nitrate paper test for ammonia
is not applicable in the presence of arsenite. Arsenite is reduced by alkaline
reducing agents to arsine, which blackens mercurous nitrate paper. The
tannic acid-silver nitrate test (Section III, 36, reaction 7) may also be used;
this test is likewise not applicable in the presence of arsenite.
(VII,
Alternatively, the following test (which is strongly reci dn- mended) may be employed. Fit up the appara1us showy, in
Fig. VII, 3, 1, using rubber stoppers; the end )f the ri& ittangled bend should be drawn out into a capillary of not m"re
than 05 mm. bore and 3-4 cm. long. The empty test-tilbe
acts as a trap between the mOllth
and the test-tube cOLtaining : ~le
solution under test to prevent ; he
solution from reaching the mOilth
should the capillary become blod; d.
Place about 01 grarr of the S i! bstance in the test-tube, add 1-2 ;,11.
of concentrated sulphu::ic acid " 1th
the aid of a dropper or small pipe 1 0e,
followed by 5-6 ml. of methyl alc( :lol
in I ml. portions (caution!). In mduce the modified "wash-boM Ie"
'--"
~
tubes and connect by a short leI1:!th
Fig. VII, 3, 1
of rubber tubing to the trap. B'!I)W
gently through the liquid and din'ct
the vapours issuing from the capillary into a colourless Bun ,en
flame. If a borate is present, the flame will acquiro a charac ' oristic green colour due to the volatile methyl borate B(OCB :h.
Under these experimental conditions copper and barium, w); !ch
colour the flame green, do not interfere. *
EXAMINATION FOR METAL IONS (CATJONS) H,
SOLUTION
VII,4. PREPARATION OF A SOLUTION OF TdE
SOLID
Use small quantities (5-10 mg.) of the powdered solid ,Ind
examine the solubility in the following solvents in the or ler
given: (l) water, (2) dilute hydrochloric acid, (3) 'Joncentrfl' ed
hydrochloric acid, (4) dilute nitric acid, (5) concerctrated nj, !'ic
acid and (6) aqua regia. Try the solubility first in the c' ,ld
and then on warming; if in doubt whether the substance ( " a
portion of the substance has dissolved, evaporate a little of he
clear solution on a watch glass. If the substance dissolve, in
water, proceed immediately to test for the metal ions. If the
* This procedure is simpler than that of Section IV, 45, 15; the lalter.
however, is fool-proof and perfectly Wlambiguous.
5]
~03
504
[V: I,
It is most important therefore that one group should be COillpletely precipitated before precipitation of the noxt group is
attempted, otherwise the group precipitates will be contaminated by metals from the preceding groups, and misleading
results will be obtained.
(3) The conditions for precipitation and for solution mU:3t
be rigidly followed.
(4) All precipitates must be washed to remove adheriflg
solution in order to avoid contamination by the ml.:,tals rema: '1ing in the filtrate. The first washings should be added to i 11e
solution from which the precipitate has been filtered; later
washings may be discarded.
(5) If the volume of the solution at any stage of the analY:'is
becomes too large, it should be reduced by evaporation.
(6) All the apparatus employed in the analy-;is must be
scrupulously clean. The use of dirty appara1ius may be
sufficient to introduce impurities into the substance under
examination.
NOTES ON TABLE I (GENERAL TABLE FOR SEPARATION
OF CATIONS INTO GROUPS)
6]
.........o
~
505
606
[VII,
pH
7+
1'0
0'6
0'5
0'3
Blue-green.
Yellow-~<"""
Yellow.
6]
507
Heat the solution almost to boiling and pass in H 2S, whilst slowly
shaking the flask with a swirling motion, until precipit1~tion is
complete: the latter will be apparent when bubbling either stops
altogether or is reduced to a very slow rate of 1-2 bubbles per minute.
Saturation is normally reached in 2-5 minutes. The best method
of determining whether precipitation is complete is to filter off a
portion of the solution and to test the filtrate with H 2S. If only a
white precipitate or suspension of sulphur is obtained, the presence
of an oxidising agent is indicated.
If an oxidising agent is present (e.g. a permangan;tte, dichromate or ferric salt), as is shown by the gradual separat:on of a
fine white precipitate of sulphur and/or change in colour of the
solution, it is usual to pass 80 2 into the hot solution until reduction
is complete, then to boil off the excess of S02 (test with K2Cr207
paper) and finally to pass H 2S. Arsenates, in particular, are slowly
precipitated by H 2S: they are therefore generally reduced by S02
to arsenites and then precipitated as As 2Ss with H 2S, after prior
removal of the excess of S02 in order to avoid interaction of the
latter with H 28 and the consequent separation of S. Stannic
compounds may be very slightly reduced to the stannous Etate by
this treatment; the amount of reduction is, however, so small that
it may be neglected. The original solution or substance must be
tested for the valence state of the arsenic.
The objection to the use of S02 is that some sulphuric add may
be formed, especially upon boiling, and this may partially precipitate Pb, Sr and Ba as sulphates. Any precipitate formed in this
process should accordingly be examined for these cations: PbS04
is soluble in ammonium acetate solution.
An alternative procedure to be borne in mind when arsem~te, etc.,
is present, which does not possess the disadvantages associa~ed with
S02 and is perhaps more expeditious, is to add 2-3 m!. of concentrated HCI and 05 m!. of 10 per cent ammonium iodide solution.
The arsenate is thereby reduced to arsenite, and upon saturation of
the hot solution with H 2S under "pressure," the arsenic is completely precipitated as AszS s. This reduction can be carried out
after the sulphides of the other elements have been precipitated in
the presence of 0'3N HCI.
The precipitated sulphides may be washed with a wash liquid
prepared by dissolving 025 gram of NH4NO a in 5 ml. of water and
treating this solution with HzS. The H 2S must be present in the
wash liquid to prevent oxidation of some of the moist sulphides to
sulphates.
(5) Nitric acid is added to oxidise ferrous iron to the ferric state;
if ferric iron was originally present, it will have been reduced by the
H 2S. Alternatively, bromine water may be used for the o;xidation:
the excess of bromine must be removed by boiling. Ferrous iron
is incompletely precipitated by NHs solution in the pr(':ience of
NH,Cl.
508
[VII,
I.
6]
509
510
[VII,
+ 2NH,Cl
MCl a
+ (NH,)aCOa
CO 2 + Hp
7]
511
---------.----------------------------------------Residue.
Zirconium
phosphate.
Reject.
Filtrate. Exa.
mine for Groups
IIIB, IV and V as
detailed in C.meral
Table I (Sflction
VII,6).
,
increases the speed of filtration by retaining part of the precipitate
and thus preventing the clogging of the pores of the filter paper.
512
VII, 8.
[V't,
The ppt. may contain PbOI" AgOI and Hg 2Cl.. Wash the ppt. on tit
filter first with 2 ml. of 1-2N HOI, then 2-3 times with 1 ml, portions of
cold water and reject the washings with water. Transfer the ppt. to '.'
small beaker or to a boiling tube, and boil with 5-10 ml. of water. Filte,
hot.
A~
Filtrate.
May cant", I
PbCI .
0001 a portion of the so! ,
tion: a white crj stalline p!
of PbCI. is obtained if Pb
present in any ql.antity.
Divide the fil ;rate into :3
parts:
(i) Add K.CrJ. eoluti l.
Yellow ppt. of PhCrO"
soluble in dilute l.cetic aciL
(ii) Add KI sc lution. 1 [low ppt. of Ph1., soluble n
boiling water to a colour' ;8
solution, which ieposits 1, 1liant yellow Q) 'Ystals u; n
cooling.
(iii) Add dilute Hoi" .
White ppt. of PbSO., soh Ie
in ammonium acetate s, .1
tion.
Pb
present.
pre~ent.
(2) AgOI is solu ble in dilute NH3 solution, yielding the so (ble
complex salt [Ag(NH 3 )2]Ol. The solution of this comple:l. salt
is decomposed by both dilute HN0 3 and by KI Ilolution fith
the precipitation of the insoluble- salts AgOI and AgI re pectively.
9]
513
Aqua regia converts the black mixture into RgCl 2 (see under
Mercury (Section III, 3, reaction 1)}. The mercuric ion is then
detected with SnC1 2 solution.
2HgC12
Hg 2Cl 2
+ SnC12 =
+ SnC12 =
SnC~
SnCI,
+ Hg2C12 ;
+ 2Hg
17+
14
[VII,
+ 3(NH4 l2S2
= S + 2(NH,lsAsS, (ammonium thio-arsenate)
Sb 2S a + 3(NH4 )2S2
= S + 2(NH4 )aSbS4 (ammonium thio-antime,nate)
SnSz + (NH')2SZ = S + (NH4l2SnSa (ammonium thio-staDIlate)
As 2S S
9J
515
Filtrate.
May contain RAsO., KAsS,.
KSbO., KSbS 2 , K,[Sn(OH).], K 2SnS. and a
little K.[HgS.]. Transfer to a small conical flask
or beaker, add concentrated HCl dropwise and
with stirring until the mixture is distinctly add
to litmus paper. Treat with H.S for 2 minutes
to ensure complete precipitation of the sulphidos.
The formation of a ppt. indicates the possible
presence of Hg, As, Sb or Sn. Filter and wash
the ppt. with a little water. Reserve the residlle
for analysis by Table VIA.
Group lIB present.
+ 6KOH
= 3H 0 + KaAsOa + KsAsSa (potassium thio-arsenite)
2Sb 2S a + 4KOH = 2H 2 0 + KSb0 2 + 3KSbS z
Sb 2S5 + 6KOH = 3H 2 0 + K aSbS4 + KaSbSOa
3SnS2 + 6KOH
= 3H zO + KzSnOa + 2K2SnSa (potassium thio-stannate)
HgS + KzS = K 2[HgS z]
As 2S a
+
+
516
[VII,
The disadvantages attending the use of ammonium poly_ sulphide in the separation of Groups IIA and lIB Hre:
(i) Some CuS and HgS are dissolved.
(ii) In the presence of large quantities of the Copper Group,
small amounts of tin may escape detection.
(iii) Acidification of the ammonium polysulphide extJ"ct
leads to the precipitation of sulphur, which may obscure i he
presence of sulphides of Group lIB.
(iv) Ammonium polysulphide solution, unless freshly l't'epared, may contain sulphate and this will lead to jihe preci pitation of barium as BaS04, etc.
Explanation (Table V)
The residue insoluble in yellow ammonium sulphide solution
or in 2N KOH solution may contain HgS, PbS, Bi 2S 3, ells
and CdS. Their separation is based upon the following fact,,:
(1) HgS is insoluble in dilute HNO a ; the sulphidefc ofPb, 1:1,
Cu and Cd dissolve with the formation of nitrates.
3PbS
Bi28 a
+ 8HNO a =
+ 8HNOs =
3HgS
2HNO s
6HCl = 3HgCl2
38
2NO + 4H 2 0
(2) The filtrate from the nitric acid treatment contains t}l(~
+ H 2S04 =
PbS04
+ 2HNOs
10]
517
* For
t This is most easily effected by making a small hole in the Glter with B
pointed glass rod, and washing the ppt. into the beaker or basin with dilute
HNO a
:j: Sodium stannite is prepared by adding NaOH solution to 1 mI. of SnCI,
solution until the ppt. of Sn(OH). first formed redissolves.
Alternatively, just acidify a small portion with dilute H 2SO,. Add I
drop of this solution to a few drops of dilute znSo, solution, and then introduce a little ammonium mercuri.thiocyanate reagent.. A violet ppt. confirms
Cu. The ppt. can be rendered clearly visible by adding B little nmyl alcohol
and shaking: it collects in and colours the organic layer.
" If the solution is colourless, the addition of KCN solution may be omitted.
~ Cd may also be confirmed in the ppt. by the ignition taRt with NB,C,O.,
ete. (Section III, 9).
I
Qualitative Inorganic And,lysi8 -
518
I!
rVII
+ 3Na2[Sn02] =
2Bi(OH)s
2Bi
+ 3Na2[SnOa] + 3H20
(4) The addition of acetic acid to the blue solution decomposes the complex into CUS04 and NH4 .C 2H a0 2 ; K.[Fe(CN)GJ
solution yields reddish-brown CU2[Fe(CN)6].
[Cu(NH s)4]S04
K 4[Fe(CN)e]
tl,,~
+ lOKCN
= 2K 3[Cu(CN)4]
[Cd(NHs )4]804
+ 4KCN =
2K 2S04
(CNh
8N11 1
K 2[Cd(ON)4] + K 2S04
4NHs
-+
+ 2NHs + H
20
= NH4CNO
+ NH4CN
2K +
+ [Cu(CN)4r-- ?
+ [Cd(CN),r-
3K +
2K +
11]
519
Filtrate.
May contain H[SbCl,] and
H.[SnCI.]. Boil to expel HaS, and divide the
cold solution into three parts.
(i) Render just alkaline with dilate NBs
solution, disregard any slight ppt., add 1-2
grams of solid oxalic acid, boil and pass H.S
for ca. I minute into the hot filtrate.
Orange ppt. of Sb.S .
Sb present.
(ii) To 2 drops of the solution on a spot
plate, add a minute crystal of NaN0 2 and then
2 drops of RhodamineB reagent.
Violet solution or ppt.
Sb present.
(iii) Partially neutralise the liquid, add 10
em. of clean iron wire to 1 ml. of the solution.
(If much Sb is present, it is better to reduce
with Mg powder.) \Varm gently to reduce the
tin to the stannous state, and filter into a
solution of HgCI .
White ppt. of Hg.Cl 2 or grey ppt. of Hg.
Sn present.t
(iv) Treat 02-03 ml. of the solution with
5-10 mg. of Mg powder, add 2 drops of FeCl a
solution, 2-3 drops of 5% tartaric acid solu
tion, 1-2 drops of dimethylglyoxime reagent
and then dilute NHs solution until basic.
Red coloration.
Sn present. t
Explanation (Table V J)
The precipitate obtained upon acidifying the ammonium
sulphide (NH4)2S", extract may contain As 2S5 (and/or AS 2S 3 ),
520
[VII,
+ 6ilCl =
SnS2
+ 4HCI =
+ 3H2S + 2S
SuCl, + 2H2S
2SbCI s
+ 16NHs + 20H20 2
= 2(NH4)sAsO"
As 2S S
+ 12NHs + 14H20 2
=
+ 5(NH4)2S0" + 12H2()
2(NH4)sAs04
+ 3(NH4)2S04 + 8H20
+ Mg(NO a)2 =
Mg(NH4)As04 + 2NH4NO a
(3) The filtrate from the HCI treatment contains 81>C1 3 (OJ
H[8bCI4 ]) and 8nCl4 (or H 2[8nClt;]). Antimony is identified by
adding NH3 solution and a large excess of oxalic acid to the
mixture: a relatively stable tin-oxalate complex ion is formed.
The antimony-oxalate complex ion is less stable and an appreciabJe concentration of 8b + + + ions is present in solution.
Hence whei~., 1I 28 is passed into the solution, Sb 28 3 alone is
precipitated. -'-'Co;~tinued treatment with H 28 (beyond 3-5
minutes) may, howe~1:' ~es~t in t~e ~ecomposition of the t.inoxalate complex ion: tillS will be mdlCated by the darkenmg
of the orange 8b 8 pre{,ipitate. Antimony is also identified
by the characteri:ti~ reacti9n with Rhodamine-B (8ection III,
14, reaction 7).
.
-~_
(4) The addition of met~Pic iron to the diluted solution
reduces the 8nCl4 to 8nCl 2 a)~d the 8bC13 to. black 8b; upon
Illtration, the solution contajns 8nC1 2 a~d IS. free from Sb.
~he 8nC1 2 is identified by the'l,usual. reactIOn WIth H~CI!~ solu,IOn; the FeC1 2 produced has Ill:0 actIOn upon the HgC1 2
11]
521
Hg
present.
Confirm
as in Table
V, if Hg
not found
in Group
IIA.
17
LVU,
ASzS a
6NHs
3H2 0 = (NH4)aAsOa
(NH4hAsOa
(NH4hAsSs
6HNOa
= As 2S a
+ (NH4)aAsS s
+ 6NH4NO a + 3H20
+ H 20 = NaB0 2 + H 20 2
12]
523
Filtrate.
May contain Na.CrO,
(yellow) and/or NaAlO, (colourless).
If colourless, Cr is absent and need not
be considered further.
If the solution is yellow, Or is indicated.
Divide the liquid into three portions.
(i) Acidify with acetic acid and add
lead acetate solution.
Yellow ppt. of PbCrO,.
Cr present.
(ii) Acidify 2 mi. with dilute HNO"
cool thoroughly, add 1 mi. of amyl alcohol,
and 4 drops of 3% H.O, solution. Shake
well and allow the two layers to sephrate.
Blue upper layer (containing "perchromic acid"; it does not keep well).
Cr present.
(iii) Acidify with dilute HOI (test with
litmus paper), then add dilute NH. solution until just alkaline. Heat to boiling.
Filter.
White gelatinous ppt. of Al(OH),.
Al present.
Dissolve II small portion of the ppt. in
1 m!. of hot dilute HOI. Cool, add 1 mI.
of 10% ammonium acetate solution and
05 mI. of the "aluminon" reagent. Stir
the solution and render basic with ammonium carbonate solution. A red ppt.
confirms the presence of Al.
524
[VII,
Ni present.
Filtrate. May
contain Na.[ZnO.].
Divide into two
parts.
(1) AC!dify with
acetic acid and
pass HaS. White
ppt. of ZnS.
Zn present.
(ii) J Uf.t acidify
with dilute H 2SO.,
add 0'5 mI. 01
o . 1 % 'J 0 b a 1 t
acetate 30lution
and 05 m!. of
the ammonium
mercuri-thiocyanate reagent:
stir.
Pale blue ppt.
Zn pr("sent.
525
13)
O2
2H zO}, add 5 m!. of NH401 solution and about 5 ml. excess
of dilute aqueous NHs. Then add 1 gram of solid K 2S2 0 S , boil for
30 seconds, filter and wash. The 00 and Ni remain in solution as
[00(NHs)6]+++ and [Ni(NH3)6]++' The Mn0 2 may be filtered off,
dissolved in HNO s + H 20 2 , etc. This separation is not essential.
(2) Any Ni(OH)2 and Oo(OH)s present will dissolve in the
HNO s
H 2 0 2 to form Ni(NOs)z and OO(NOSJ2 respectively. They
dissolve less readily than Mn0 2 , so that if any difficulty is experienced in effecting complete solution of the precipitate, the
undissolved solid may be discarded and the clear solution used to
test for Mn.
+ 2HOI = ZnOl2 + H 28
r--
526
[VII,
+ H 2S =
2NaOH
+ znS
With
13]
527
VII, 13.
The ppt. may contain CoS, NiS, MnS and ZnS. Wash well with 1 %
NH.Cl solution to which 1 % by volume of yellow ammonium sulphide
solution has been added; reject the washings. Transfer the ppt. to a
porcelain basin, add 5 m!. of water and 5 mI. of concentrated HCl and
stir for 2-3 minutes. If a black residue is obtained, the presence of NiS
and OoS is indicated: if complete solution takes place, only small amounts
of Ni and Co are likely to be present. Evaporate the mixture to 2-3 ml.
in the FUME OUPBOARD, add 4 ml. of concentrated RNO. (1) and
concentrate to 2-3 ml. If the solution is not clear, dilute with 8-10 ml.
of water, filter off the sulphur and return the filtrate to the porcelain basin
in the fume cupboard. Boil down to 1-2 mI., taking great care not to
evaporate to dryness. Add 5 ml. of concentra.ted RNO. and evaporate
again to 1-2 ml. (2).
Remove about 02 ml. of the solution with the aid of a dropper to a.
small test tube, add 5 ml. of dilute RNO, and then O} gram of sodium
bismuthate: stir and allow to stand. A purple coloration, due to R]\[nO.,
indicates Mn present. If Mn is present, treat the remainder of the
solution in the porcelain basin in accordance with the procedure com
mencing at (A): if Mn is absent, continue the analysis from (B) onwards.
(A) Add 10-15 ml. of concentrated HNO" and heat just to boiling in
the fume cupboard. By means of a spatula (preferably of glass), add
finely-powdered KCIO. in 01 gram portions [GREAT OARE: DAAGER
OF EXPLOSION (3)]; after each addition boil gently until the greonishyellow vapours of chlorine dioxide are expelled. Continue the ad,lition
of 01 gram portions, boiling gently after each addition, until 1'5 grams
have been added. A brown or black ppt. of hydrated MnO. will form.
Dilute with 3 ml. of water. Filter the ppt. through a small sintered glass
funnel or crucible, and wash the ppt. with 2-3 ml. of water.
Residue.
MnO xH.O.
Notes. (1) The precipitate is first treated with dilute Hel alone,
partly to indicate the presence of Ni and Co in quantity but also
because much free sulphur and sulphate would be formE,d if an
oxidising agent were used with the HCI at this stage.
(2) The repeated evaporation with concentrated HN0 3 completely
removes chloride ion, which interferes with the subsequent precipitation of Mn0 2
(3) The action of KCIO a in concentrated HN0 3 is rapid and
vigorous, and one of the decomposition products is the explosive,
528
[VII,
greenish-yellow gas 010 2 , If the chlorate is added in small quantities as instructed and the solution is boiled gently between each
addition to prevent the accumulation of 010 2 , the procedure is
reasonably safe and the only evidence of explosion will be a gentle
puff of gas. Under no circumstances may more than 01 gram of
KOlOa be added at one time.
(4) The H 2 0 2 solution is added to ensure the complete precipitation of cobalt as cobaltic hydroxide Oo(OH)s, since cobaltous
hydroxide is slightly soluble in excess of NaOH solution.
3008
or
+ 2HNOa + 6HOl =
300S
+ SHNOs =
300012
+ 2NO + 3S + 4H 20
30o(NOs)2
+ 2NO + 38 +- 4H20
+ 2KOIO s =
Mn0 2
+ 2KNOa + 2010 2
14]
529
Filtrate.
May contain Ca complex.
(If Sr is absent, use 2
m!. of solution A or B.)
Add a little {NH.).C.O,
solution * and warm on a
water bath.
White ppt. of CaC.O,.
Ca present. t
Confirm by flame test
on ppt.-brick-red flame.
(Use spectroseope, if
available. )
530
[VII,
+ NH
+ ~NHa
+ HCO a-
14J
531
532
[VII,
~dding
15]
533
the sulphate CaS04,2H 20, and the latter identified under the
microscope.
The nitric acid procedure gives an excellent separation of
strontium from calcium.
Explanation (Table X)
The filtrate from Group IV may contain Mg, Na, K and
ammonium salts. It is evaporated to dryness and heated until
all the ammonium salts have been volatilised: a residue is
indicative of the presence of one or more of these metals. The
* If it is desired to carry out the less satisfactory NaaHPO. test for comparison with the oxine test for Mg, treat the acid solution with a littln NH.CI,
followed by dilute NH3 solution until basic and Na.HPO. solution. Shake
and stir vigorously. A white crystalline ppt. of Mg(NH.)PO.,6H aO indicates
Mg. This ppt. sometimes separates slowly. Dissolve the ppt. in a little
dilute Hel and apply the "magneson" test. A blue ppt. confirms Mg.
t It is advisable to test the cobalt glass with a potassium salt to be certain
that the glass is satisfactory: some samples of cobalt glass completely absorb
the red lines due to potassium. It is recommended that a hand spectroscope
be used, if available.
t If the residue dissolves completely (or almost completely) in water, dilut~
the resulting solution (after filtration, if necessary) to about 6 m!. and divide
it into three approximately equal parts:- (i) Use the major portion to test for
Mg with the prepared "oxine" solution: confirm Mg by applying the "mag.
neson" test to 3-4 drops of the solution; (ii) and (iii) Test for Na and K reo
spectively, as described in the Table.
lVU,
536
[VII,
16]
537
538
[VII.
r-
16]
539
540
(VII.
Use the filtrate from 2 or, if ferro cyanide and/or ferricyanide and other
interfering anions are absent, acidify 10 ml. of the "NazCO. prepared I
solution" cautiously with dilute RNO. (to litmus or other indicator paper). ,I
Add one tenth of the volume of concentrated RNO., stir for 30 seconds
and then add AgNO. solution with stirring until precipitation is complete.
Heat to the boiling point, allow the ppt. to settle, cool and filter. Wash.
the ppt. with 2-3 ml. of N nitric acid.
,I.
Residue (A).
Yellow or
white. May
contain:
AgOl,
AgBr,
AgI (or
AgIO,)
AgSON.
Use Table A.
1\
I
I
i
j
!~-------;------------------
Residue (B).
May contain
Agel and
AgBr derived
from AgCIO.
and AgBrO .
Use Table B.
Filtrate.
Discard.
~------------------------~--------------------~-------------'
Notes. (I) The sodium hydroxide solution should be added unj j
the first permanent precipitate of C or of brown silver oxide appear: ,
The solution must not be allowed to become alkaline to litmus for
this will produce a large preoipitate of silver oxide which redissolves
only slowly.
,.
16]
541
542
[VII,
16]
Dissolve the residue C (1), which may contain AgaPO., AgaAsO. and
AgaAsO a, by pouring 10-15 ml. of 3N HCI repeatedly through it. Filter
and wash with 5 ml. of O'IN HCI.
Residue.
AgCl.
Reject.
Yellow:
As,S .
Arsenate
present.
Filtrate.
Mg(NH,)AsO". Reject.
6H.O.
Arsenite
present.
544
[VII,
16]
545
Thiocyanate (aulphocyanide).
Thioaulphate.
Ferricyanide.
Salicylate.
GcUlate.
Tannate.
+ [Zn(NHs)6](OH)2 =
ZnSiOs
+ 2NaOH + 6NHs
18+
546
[VII,
16J
547
10. Test for chromate. If the "Na2C03 prepared solution" is colourless, chromate is absent. If yellow, chromate
may be present; ferro- and ferri-cyanides also impart a yellow
colour to the solution. The presence of chromate will have
been indicated by the precipitation of green chromic hydroxide
in the silver nitrate solution tests (Table 0) and also in the
analysis for cations.
To confirm chromate, acidify 2 ml. of the "Na2C03 prepared
solution" with dilute sulphuric acid, boil for one minute to
expel CO 2, etc., filter if necessary, add 1-2 ml. of amyl alcohol,
followed by 1-2 ml. 10-volume hydrogen peroxide and shake
gently (compare Section IV, 33, reaction 4). A blue coloration
of the amyl alcohol layer confirms chromate.
11. Test for iodate. This anion will give a positive test
for oxidising agents, but will not normally be detected in the
systematic analysis.
The presence of iodate in the "Na2C03 prepared solution"
can be readily detected as follows. Treat 2 m!. of the solution
with silver nitrate solution until precipitation ceases, heat to
boiling for 2-3 minutes and filter. Render the filtrate strongly
acid with hydrochloric acid, add 2 ml. of 10 per cent ferrous
sulphate solution (or 10 per cent sodium hisulphite solution)
and shake it with 2 ml. of carbon tetrachloride. A purple
coloration of the organic layer indicates iodate.
This test utilises the fact that silver iodide, but not silver
648
[VII,
12. Test for periodate (1). This aniop will give a positive
test for oxidising agents, but will not be detected in the
systematic analysis. It will be necessary to remo're first
iodide or iodate by precipitation with silver nitrate in acid
solution, and the excess of silver ions with sodium I:hloride
solution: the resulting solution is strongly acidified with hydrochloric acid and a ferrous salt is added. If a perie.date if'
present, it will be reduced to iodine, which can be identified
with carbon tetrachloride.
Acidify 3 mI. of the "Na2C03 prepared solution" with 6(1
per cent perchloric acid and add I mI. in excess (2); add silver
nitrate solution, slowly and with stirring, until precipii ation i~
complete. Filter and collect the filtrate in a grou 1d-glass
stoppered conical flask or test-tube. Add 5 per cent sodium
chloride solution, 05 ml. at a time, to the filtrate until ::10 mor!'
precipitate forms. Stopper the flask or test-tube an:l shake
the mixture vigorously after each addition. Filter off thf'
silver chloride (3), transfer the filtrate to the stoppere<l vesseJ
add an equal volume of concentrated hydrochloric add (if ;,
precipitate of sodium chloride forms, filter), cool, then add 1-:'
grams of solid ferrous ammonium sUlphate and 2 m!. o~ carbol!
tetrachloride. Shake the mixture intermittently for 5 JUinute~
A purple colour in the carbon tetrachloride indicates periodatl'
present.
1
Notes. (1) This anion is rarely encountered and need not be teste' i
for in general qualitative analysis. It is given here for thol sake
completeness as no reactions for periodates are included in Chapter n '
Four tests which distinguish periodates from iodates are:
(a) With mercuric nitrate solution an orange-red pree pitate ,,(
1 2 0 7 ,5HgO is obtained {oompare iodates which give whit,.,
Hg(IOa)a}
(b) Upon boiling with ~lO per cent nitrio acid and a little mal
ganous sulphate solution, a purple solution of pennanganio am,j
is produced (compare iodates, which do not yield permangan,,;
acid).
(,I
17J
549
chocolate-brown pn1cipitate
(Ag&I0 6 ) is obtained; this darkens on boiling and is soluble in
dilute nitric acid (compare silver iodate AgIO which is white
and sparingly soluble in dilute nitric acid).
(d) With barium chloride solution a white precipitate is produced.
which is soluble in dilute nitric acid (compare barium iodate,
which is sparingly soluble in dilute nitric acid).
(2) Nitric acid tends to oxidise ferrous iron, hence it is advisable to
maintain the nitrate ion concentration as low as possible and to keep
the solution cold.
(3) The excess of silver ions is removed as silver chloride because
they are reduced by ferrous salts to silver.
RADICALS OR ANIONS
In every case where the presence of any acid radical has
been indicated, it must be confirmed by at least one distinctive
confirmatory test. Conclusive tests for anions (halides, sulphate, oxy-halides, thiocyanate, phosphate, silicate, fluoride,
cyanide and chromate) have already been given in Section VII,
16, it will, of course, be unnecessary to confirm these further.
The following list, which, for the sake of completeness includes
those anions already referred to, will assist the student. in the
550
Ii
[VII,
17]
5tH
Hypochlorite. (i) Action of dilute HOI, and test for 012 evolved
(IV, 13, 1). (ii) Cobalt nitrate solution test (IV, 13, 4).
Chlorate. (i) Sodium nitrite test (IV, 19, 4; also test 4 in VII,
16). (ti) Ferrous sulphate test (IV, 19, 6).
Bromate. (i) Action of conceutrated H 2S04 ; Br:) and O2 evolved
(IV, 20, 1). (ii) Hydrobromic acid test (IV, 20, 4).
Iodate. (i) Potassium iodide test (IV, 21, 6).
oxide or hydrogen sulphide test (IV, 21, 5).
Perchlorate. (i) Action of heat and test for chloride (IV, 21, 7),
and non-reduction with NaN0 2 or FeS04 in acid solution (IV, 22, 5).
Borate. (il Flame test (IV, 23, 2; better, test (ix) in Section
VII, 3). (ii) Turmeric paper test (IV, 23, 3).
Silicate. (i) Microcosmic bead test (IV, 26, 5) and silicon tetrachloride test (IV, 26, 6). (ii) Ammonium molybdate solution and
SnCl 2 solution test (IV, 26, 8).
Silicofluoride. (i) Action of concentrated H 2S04 and BaCl 2
solution test (IV, 27, 1, 2).
Persulphate. (i) Action of boiling water (IV, 25, 1).
ganous sulphate solution test (IV, 25, 5).
(ii) Man-
Chromate. (i) Hydrogen peroxide test (IV, 33, 4). (ii) Lead
acetate solution test (IV, 33, 3). (iii) Action of hydrogen sulphide
or sulphur dioxide (IV, 35, 5, 6). (iv) Solid when warmed with a
solid chloride and concentrated H 2S04 evolves chromyl ehloride
(IV, 14, 5). (v) Diphenylcarbazide reagent test (IV, 33, 10).
Permanganate. (i) Hydrogen peroxide test, and identification
ofMn ++ ion (IV, 34, 1). (ii) Action of oxalie acid, and identiiication
of Mn ++ ion (IV, 37, 4). (iii) Action of hydrogen sulphide or
sulphur dioxide (IV, 34, 2).
Arsenite. (il Action of H 2 S upon acid solution (III, 11, 1).
(ii) Silver nitrate solution test (III, 11, 2), and absence of precipitate with magnesium nitrate reagent (III, 11,3) or on boiling with
ammonium molybdate solution and nitric acid. (iii) Bettendorff's
test (III, 11, 6).
Arsenate. (i) Action of H 2S on acid solution (III, 12, 1), and
silver nitrate solution test upon practically neutral solution (III,
12, 2). (ii) Magnesium nitrate reagent test (III, 12, 3). (iii) Ammonium molybdate test (III, 12, 4).
Orthophosphate. (i) Ammonium molybdate test (temperature
not above 40) (IV, 28, 4). (ii) Magnesium nitrate reagent test
(IV, 28, 3).
Phosphite. (i) Silver nitrate solution test (IV, 30, 1), and Zn
dilute H 2S04 test (IV, 30, 6).
[
552
(VII,
Hypophosphite. (i) Silver nitrate solution test (IV, 31, 1), cop
per sulphate solution test (IV, 31, 4), and ammonium molybdat.
test (IV, 31, 9).
Cyanate. (i) Dilute H 2S04 test (IV, 9, 1). (ii) Oobalt acetat"
solution test (IV, 9, 5). (iii) Copper sulphate-pyridine test (n
9, 6).
Ferrocyanide. (i) Ferric chloride solution test (IV, 11, 3). (il
Ferrous sulphate solution test (IV, 11, 4). (iii) Uranyl acetat
solution test (IV, 11, 11). (iv) Titanium tetrachloride test (IY,
11,9).
Ferricyanide. (i) Ferrous sulphate solution test (IV, 12, 3,
(ii) Ferric chloride solution test (IV, 12, 4).
Thiocyanate. (i) Ferric chloride solution test; colour dischargE'd
by HgC1 2 solution or by NaF solution, but not by dilute HCI (IY,
10, 6). (li) Cobalt nitrate solution test (IV, 10, 7). (iii) COpP'!
sulphate-p)Tidine test (IV, 10, 9).
Acetate. (i) Action of ethyl or of iso-amyl alcohol and concell'
trated H 2S04 (IV, 35, 3), AgNO g solution test (IV, 35, 4) and FeCI:
solution test (IV, 35, 6). (ii) Cacodyl oxide test (IV, 35, 7). '(iii i
Indigo test (IV, 35, 9).
Formate. (i) Mercuric chloride solution test (IV, 36, 7) ('I'
AgNO g solution test (IV, 36, 4), and FeOls solution test (IV, 36, ( .
(ii) Mercuric formate test (IV, 36, 8).
Oxalate. (i) Immediate precipitation with CaCl 2 solution !!l
neutral solution; precipitate decolourises a dilute solution "f
KMn04 (IV, 37, 3, 4). (li) Resorcinol test (IV, 37, 5).
Tartrate. (i) Resorcinol test (IV, 38; 6).
test (IV, 38, 7).
Citrate. (i) Deniges' test (IV, 39, 5). (li) Cadmium chloride
solution test (IV, 39, 4), and negative results with resorcinol and
copper hydroxide tests (IV, 38, 6, 7).
Salicylate. (i) Violet coloration with FeCl3 solution, discharged
by mineral acids (IV, 40, 5), and soda lime test (IV, 40, 7). (ii)
"Oil of winter-green" test (IV, 40, 2).
lienzoate. (i) Buff-coloured precipitate with FeCl a solution,
soluble in dilute HCI with precipitation of benzoic acid (IV, 41, 1).
(li) Dilute H 2S04 test (IV, 41, 2), and no precipitate with Ba( '12
solution in neutral solution.
Succinate. (i) Light brown precipitate with FeCls solution,
soluble in dilute HCI, but no precipitation of acid occurs (IV, 42, 3).
(il) Ifluorescein test (IV, 42, 6).
18]
553
IS
554
(VII,
(iii) Add a little ferric chloride and potassium ferricyanide solutions; Prussian blue precipitate.
(b) Hydroxides and carbonates. Boil to decompose
hydrogen peroxide, if present. Add a slight excess of
barium chloride solution; if the solution now reacts
alkaline, hydroxyl ions are present. Filter off the precipitate, and examine for carbonate with dilute acid
(Section IV, 2, reaction 1).
(5) If the original solution is acidic, render a known volume
(say, 5 ml.) alkaline with aqueous ammonia before evaporating
it on a water bath. This will prevent the loss of volatile acids,
such as hydrochloric and boric acids. Examine the residue.
VII,19. ANALYSIS OF A METAL OR AN ALLOY
The analysis of a metal or of an alloy is simplified by ~he
fact that no acid radicals or anions need be looked for. Many
alloys contain small amounts of P, Si, C and S; phosphorus is
converted by the usual solution process into phosphate, and
may be identified as such (Section IV, 28).
The alloy or metal should be in the form of borings, turnings
or filings. About 05 gram is treated with 10 m!. of concentrated nitric acid in a porcelain basin in the fume chamber.
warmed gently until the evolution of red fumes ceases, and
evaporated almost to dryness. * About 10 m!. of water are
then added, the mixture heated for a few minutes and filtered,
if necessary.
Three cases may arise:
1. The metal or alloy dissolves completely. Examine
solution (A) by Table I (Section VII, 6), remembering that
phosphate may be present and should be tested for.
2. The metal or alloy does not dissolve completely.
The solution (A) is examined as in case 1. If the residue is
black, it may be either carbon or gold and/or platinum. Test
for carbon by igniting on a crucible lid; carbon glows and burns.
Gold and platinum dissolve in aqua regia (compare Sections
IX, 5 and IX, 6).
If the residue is white, it may contain inter alia hydrated
stannic oxide or antimony pent{)xide, bismuth oxide, together
with traces of copper, lead and iron, and is best analysed as
outlined in the following table.
The nitric acid will oxidise the P to H,PO,. S to H.SO AB to H.ABO
Sb to Sb.O,.xH.O (converted by gentle heating into Sb.O.). Sn to SnO zH.O
and Si to gelatinous silicic acid.
19]
555
Filtrate.
May contain _K't 2 SnS
Na.SbS.,* Na3AsS., Na.PO. and. possibly.
Na,S. Acidify with dilute ROI (te'it with
litmus paper), and filter.
Residue. May contain SnS,. Sb,S.,
As,S. and S.
Examine by Tables
VI or VIA (Section
VII, 11) for As. Sb
and Sn.
2SnO.
2Sb,O.
Sb,O,
556
[VII,
CU,Zn,Sn,Pb
CU,Sn,Zn,Pb
CU,Sn,Pb,P
Sn, Pb, Bi
Sn,Sb,Pb,Cu
Pb,Sb,Sn
Cu, Ni, Zn
Ni, Cu
Cu, Ni
Ni, Fe, Cr
Cu, Mn, Ni
Bi, Pb, Sn, Cd
Bi, Pb, Sn
20]
557
+C =
CO 2
+ 2Cu
The silver salts, AgCI, AgBr and AgI, will melt without
further change; AgCN decomposes to give a residue of silver,
and cyanogen gas is evolved.
Antimony oxide Sb 20 4 melts to a yellow liquid.
55S
(VII.
20]
559
PbCr04
4NaOH = Na2Cr04
Na2[Pb02]
2H 20
(ii) Prussian blue yields ferric hydroxide and sodium ferrocyanide (see under Iron, Section III, 20, reaction 5).
(iii) Copper ferro cyanide yields copper oxide and sodium
ferrocyanide.
(iv) Zinc ferro cyanide yields sodium zincate and sodium
ferrocyanide, i.e. it dissolves completely. The zinc is readily
identified by passing hydrogen sulphide into the solution; the
ferro cyanide (see Section IV, 11) is detected in the filtrate after
acidifying and boiling off the hydrogen sulphide.
(v) Alumina and silica may dissolve, forming solutions of
sodium aluminate and sodium silicate respectively.
660
[VII,
20]
561
PREPARING A SOLUTION
The above preliminary tests may supply valuable information as to the composition of the insoluble substance. In every
case, the following methods of bringing the substance into
solution for systematic analysis should be used.
;62
[VII,
Filtrate.
May contain
Na.CrO., Na[AIO.J, Na.[SnO.J,
Na.AsO., NaF, Na.SO. and the
corresponding K salts, if fusion
mixture was employed. Acidify
with concentrated HCI and
evaporate to dryness in the
fume cupboard. Triturate the
dry mass with concentrated
HCI, add water, warm and filter.
Filtrate.
Evaporate
almost to dryness to remove
Residue.
HNO" add May contain
dilute HCI and SiO.t
examine for Confirm by
metal ions by microcosmic
Table I (Sec- bead test or
tion VII, 6).
by the SiF.
test in a lead
capsule.
Filtrate. Test
a portion for sulphate. Examine
for metals of
Groups II and
III.
* An alternative procedure is the Na.CO.-S fusion method already decribed under the analysis of metals and alloys (Table XII, Section VII, 19).
The original insoluble substance may also be subjected to the Na.COa-S
usion, and the extract, after acidifying with 1 : I HCI, filtered. Any preipitate is washed, dissolved in concentrated HCI and H.S removed by
,oiling: Sb may be detected with Rhodamine-B and Sn with HgCI. solution.
t This precipitate may also contain WO.,xH.O from mineral tungstates
Ilso1uble in aqua regia. Confirm W by digesting with dilute NH. solution
o dissolve WO.,xH.O and then apply the SnCII-HCI test.
20]
563
CUzSi
SiC
+ 3K2COS =
K 2SiOs
+ 2K2 0 + 4CO
CHAPTER VIII
565
566
[VIII,
VIII, 1. PROCEDURE FOR THE REMOVAL OF INTER FERING ACIDS IN SYSTEMATIC QUALITATIVl
ANALYSIS
The acids are removed in the follOwing order:
1. Organic acids. The filtrate from Group II is evap, ,rated to dryness, when some carbon may be liberated and tI,e
organic acids decomposed. By repeated evaporation with concentrated HNO a, the black residue is completely oxidise, l.
The residue must not be heated too strongly as Fe20a, Cr2( 13
and Al 2 0 a may be rendered very difficultly soluble in HCI.
2. Borates and fluorides. The residue from 1 is It'peatedly evaporated almost to dryness with concentrated H( 1;
the HF volatilises with the HOI and the HaBOa volatilises 'll
the steam.
If borate is present and fluoride is absent, the former m;,.v
be removed by repeated evaporation to dryness on a wat!,r
bath with a mixture of 5 ml. of methyl alcohol (inflammable!)
and 10 ml. of concentrated HOI. The borate slowly volatilises
as methyl borate, (OHa)aBO a (poisonous).
3. Silicates. The evaporation with concentrated Hel
converts silicates into an insoluble form of Si0 2 Hence hy
complete evaporation to dryness with a further quantity If
concentrated HOI, extraction with water or dilute HCI, alld
filtration, the silicate is completely eliminated.
I
2]
567
(a)
(b)
(c)
(d)
(e)
568
[VIII,
sary.
ReSidue.
Examine for
Al and Cr, if
not previously
tested for.
[In general,
no ppt. will
be obtained
here.]
Filtrate.
Examine fOl
Groups lIIB.
IV and for
Mg as detailed
in General
Table I (Section VII, 6).
!'i
VII,12).
2]
569
during its preparation to produce a clear solution; the free acid leads
to incomplete precipitation.
(3) If the colour cannot be seen because of the presence of a
precipitate or of coloured ions, filter a small portion of the mixture
and test the filtrate with dilute ammonia solution as in Note 1.
A large excess of FeCl s solution must be avoided since it exerts a
solvent action on ferric phosphate and the precipitation of the latter
will be incomplete.
(4) The addition of filter paper pulp or a Whatman filtration
accelerator will facilitate filtration.
Explanation (Table J)
,
570
[VIII,
CH.APTER IX
REACTIONS OF SOME OF THE "RARER" ELEMENTS
No reference has been made in the earlier chapters to the characteristic reactions of the so-called "rarer" elements. Many of these,
e.g. tungsten, molybdenum, titanium, uranium and beryllinm, have
important industrial applications, and it was felt that a brief account
of the analytical chemistry of a number of selected elements might
usefully be included in this volume.
The term "rarer" elements as originally employed in the sense
of their comparative rare occurrence and limited availability must
now, in a number of cases, be regarded as a misnomer. Large
quantities of some of these elements are utilised annually, and the
range of the application is slowly but surely widening. A few
examples may be mentioned: the use of molybdenum, ttmgsten,
titanium and beryllium in the steel industry, of tungsten in the
manufacture of incandescent lamps and of titanium and uranium
in the paint industry. The interpretation of the term "rarer"
elements, as applied to the elements described in this chapter, is
perhaps best accepted in the sense of their comparatively rare
occurrence in routine qualitative analysis.
No attempt has been made to give more than a short introduction
to the subject; to economise in space, most of the simple equations
have been omitted. The elements have been classified, in so far as
is possible, in the simple Groups with which the student is already
familiar, and methods of separation have been briefly indicated.
Thus thallium and tungsten are in Group I; molybdenum, gold,
platinum, selenium, tellurium and vanadium in Group II; and
beryllium, titanium, uranium, thorium and cerium in Group III.
The presence of vanadium will be revealed by the blue colour and
absence of precipitate produced by hydrogen sulphide in acid solution; its actual isolation as sulphide is effected by the addition of
acid to the ammonium sulphide solution in Group IIIll. It is
hoped that the subject-matter of this chapter will suffice to enable
the student to detect the presence of one or two of the compounds
of the "rarer" elements in a mixture.
TlIALLIUlIt, TI
Thallium forms two oxides Tl 20 and TIIO. which corresponds to the tha.lloUB
thallic and salts respectively. The tha.lloUB salts are the more stable and hence
572
[IX,
of greater interest from the analytical viewpoint. Thallic salts are compar"
tively unstable and readily hydrolyse in solution: thus, when an aqueo,,"
solution of thallic sulphate or nitrate is boiled thallic hydroxide is precipitate,'
Thallous salts are oxidised to thallic by potassium permanganate, potassiu",
ferricyanide, lead dioxide, bromine, chlorine and aqua regia (but not by COl,
centrated nitric acid). The reduction of thallic to thallous compounds is eas; i,
effected by stannous chloride, sulphurous acid, ferrous salts, or hydroxylamin.'
IX,IA.
REACTIONS OF THALLOUS COMPOUNDS
Use a solution of thallous nitrate, * TINO a or of thallous sulphak,
T1 2S04 [All compounds of thallium are highly poisonous.]
1. Dilute Hydrochloric Acid: white precipitate of thallou,,,;
chloride TICI, sparingly soluble in cold, but more soluble in hot
water (compare lead).
2. Potassium Iodide Solution: yellow precipitate of thallous
iodide TII, almost insoluble in water; it is also insoluble in cold
sodium thiosulphate solution (difference and method of separation
from lead).
IB]
573
+ 4Ks(Fe(CNJ6J + 6KOH
= TlzOs + 4K,(Fe(CN)6] + KzSO, + 3HaO
574
[IX,
IX, 2.
REACTIONS OF TUNGSTATES
Use a solution of sodium tungstate, Na2W04,2H20.
1. Dilute Hydrochloric Acid: white precipitate of hydrated
tungstic acid H 2W04.H2 0 in the cold; upon boiling the mixtur,.
this is converted into yellow tungstic acid H2 W0 4 , insoluble in
dilute acids. Similar results are obtained with dilute nitric aI,' I
sulphuric acids, but not with phosphoric acid. Tartrates, citrat, "
and oxalates inhibit the precipitation of tungstic acid. The ppt. ,
soluble in dilute ammonia solution (distinction from Si0 2 ,xH2 0).
2. Phosphoric Acid: white precipitate of phosphotungstic ac
H S[P04(W 120S6)],5H20, soluble in excess of the reagent.
3. Hydrogen Sulphide: no precipitate in acid solution.
4. Ammonium Sulphide Solution: no precipitate, but if the
solution is afterwards acidified with dilute hydrochloric acid, L
brown precipitate of tungsten trisulphide WS s is produced. T::e
precipitate dissolves in ammonium sulphide solution forming :L
thiotungstate (NH4 MWS4 ].
5. Zinc and Hydrochloric Acid.-If a solution of a tungstate
is treated with hydrochloric acid and then a little zinc added, a blue
coloration or precipitate is produced; this is probably due to W 2 ()s
or to wels.
6. Stannous Chloride Solution: yellow precipitate, which !.r.comes blue upon warming with concentrated hydrochloric acid.
2J
575
t Heat a few mg. of the solid unknown with 10-20 mg. of potassium
bisulphate and 2 drops of concentrated sulphuric acid in a small pore
celain crucible, allow to cool, and add a few mg. of solid phenol. A red
coloration is produced.
Dry Test
Microcosmic salt bead: oxidising flame-colourless or pale-yellow;
reducing flame-blue, changing to blood-red upon the addition of a
little ferrous sulphate.
Separation.-Tungsten is precipitated in Group I and is associated with Ag in the ammoniacal filtrate of the group separation.
The filtrate is almost neutralised with dilute HOI (any precipitate
formed being kept in solution by the addition of ammonia solution),
and the silver precipitated as AgI by the addition of KI solution.
The filtrate is concentrated, acidified with dilute HOI and reactions
5, 6 or 9 applied.
The following table contains a scheme for the identification of
thallous thallium and tungsten (as tungstate) in the presence of lead,
mercurous mercury and silver.
576
[IX,
Ag
present.
Residue.
If whiteconsists of
PbSO,.
This is
soluble in
ammonium
acetate
solution;
K.CrO,
Filtrate. May solution
contain a tungthen precistate. Evaporate pitates
to a small volume, yellow
acidify with dilute PbCrO.,
HCl, add 3 mI. of insoluble in
SnCl. solution, 2N acetic
boil, e.dd 3 ml. of acid.
concentrated HCl,
Pb
and heat again to
present.
boiling.
Blue ppt. or
coloration.
Filtrate. May
contain Tl.SO,.
Just neutralise
with dilute NEa
solution, and
add KI solution.
Yellow ppt. of
TlI, insoluble in
cold Na.S.O.
solution.
TI present.
Confirm by
flame test;
intense green
flame. (Use
spectroscope, if
available.)
,
W present.
Confirm by the
Defacqz reaction.
MOLYBDENUM, Mo
Molybdenum forms three basic oxides MoO, Mo.O. and MoO., and onf'
acidic oxide :MoO.. The last-named is the most important; it is sparingly
soluble in water, but dissolves readily in solutions of alkalis forming molybdates.
Compare Table III, Section VII, 8.
t A gelatinous precipitate may also be hydrated silica, which is partially
precipitated here from silicate8 decomposable by acids.
4]
577
IX, 4.
REACTIONS OF MOLYBDATES
Use a solution of ammonium molybdate (NH.)6M070z4,4HzO.
1. Dilute Hydrochloric Acid: white or yellow precipitate of
molybdic acid H 2Mo04 from concentrated solutions, soluble ill
excess of mineral acid.
2. Hydrogen Sulphide.-With a small quantity of the gas and
an acidified molybdate solution, a blue coloration is produced;
further passage of hydrogen sulphide yields a brown precipitate of
the trisulphide MoSs, soluble in ammonium sulphide solution to a
solution containing a thiomolybdate (NH 4 MMoS 4 ], from which
MoSs is reprecipitated by the addition of acids. The precipitation
in acid solution is incomplete in the cold; more extensive precipitation is obtained by the prolonged passage of the gas into the boiling
solution and under pressure. Precipitation is quantitative with
excess of hydrogen sulphide at 0 in the presence of formic acid.
3. Reducing Agents, e.y. zinc, stannous chloride solution: colour
a molybdate solution acidified with dilute hydrochloric acid blue
(probably due to MoCI 3 ), then green and finally brown.
4. Ammonium Thiocyanate Solution: yellow coloration in
solution acidified with dilute hydrochloric acid, becoming blood-red
upon the addition of zinc or of stannous chloride on account of the
formation of ammonium molybdo-thiocyanate (NH4 )s[Mo(CNS)6];
the latter is soluble in ether. The red coloration is produced in the
presence of phosphoric acid (difference from iron).
t The spot-test technique is as follows. Place a drop of the test
solution and a drop of 10 per cent potassium or ammonium thiocyanate
solution upon quantitative filter paper or upon drop-reaction paper.
Add a drop of stannous chloride solution (5 per cent in 3N HCI). A
red spot is obtained.
Sensitivity: 01 f-tg. Mo. Concentration limit: 1 in 500,000.
If iron is present, a red spot will appear initially but this disappears
upon the addition of the stannous chloride solution (or of sodium
thiosulphate solution). Tungstates reduce the sensitivity of the test
(compare Section IX, 2, reaction 6).
5. Sodium Phosphate Solution: yellow, crystalline precipitate
of ammonium phosphomolybdate in the presence of excess of nitric
acid (compare Phosphates, Section IV, 28, reaction 4).
6. Potassium Ferrocyanide Solution: reddish-brown precipitate of molybdenum ferrocyanide, insoluble in dilute mineral
acids, but readily soluble in solutions of caustic alkalis and ammonia
(difference from uranyl and cupric ferrocyanides).
7. ~-Benzoin Oxime Reagent (or "Cupron" Reagent)
{ C.H. CHOH.C ( =NOH)C8H D }.
578
~lX,
Elements
IX, 5.
REACTIONS OF AURIC COMPOUNDS
Use a solution of gold chloride (hydrogen aurichloride or auri
chloric acid), H[AuOI4],3H 2 0.
1. Hydrogen Sulphide: black precipitate of aurous sulphide
Au 2S (usually mixed with a little free gold) in the cold, insoluble in
dilute acids, but largely soluble in yellow ammonium sulphide solution, from which it is reprecipitated by dilute hydrochloric acid.
A brown precipitate of metallic gold, together with aurous sulphide
and sulphur, is obtained upon precipitation of a hot solution; this
is also largely dissolved by yellow ammonium sulphide solution.
2R[AuCI,]
+ 3R aS =
AuaS
+ 2S + SRCI
+ 3R a.C aO,
= 2Au
+ 8RCl + 6CO
Reduc-
580
fIX,
+ 3SnC1
2Au
+ 3SnCl, + 2HCl
+ 3H 0 t + 8NaOH =
2
2Au
Dry Test
All gold compounds when heated upon charcoal with sodium
carbonate yield yellow, malleable, metallic particles, which :Ire
insoluble in nitric acid, but soluble in aqua regia. The aqua rt ;.:;ia
solution should be evaporated to dryness, dissolved in water <lnd
tests 1, 3 or 4 applied.
Separation.-Gold is usually detected and determined by dry
methods. In the wet way, it is precipitated by H 2S in Group fl,
dissolved by yellow ammonium sulphide solution and reprecipitat od
from the latter by concentrated HOI along with AS 2S 3 and MC'-':3'
Separation from AS 2 S3 and MoS 3 is effected by concentrated HKu 3
in which the gold precipitate is insoluble. The gold may then be
dissolved in aqua regia and identified by reactions 1, 3 or 4. Soe
also Table II in Section IX, 10.
PLATINUM, Pt
* For formula,
6]
581
IX, 6.
REACTIONS OF CHLOROPLATINATES
Use a solution of chloroplatinic acid, H 2[PtCla],6H2 0.*
1. Hydrogen Sulphide: black (or dark brown) precipitate of the
disulphide PtS 2 (possibly containing a little elementary platinum),
slowly formed in the cold, but rapidly on warming. The precipitate
is insoluble in concentrated acids, but dissolves in aqua regia and also
in yellow ammonium sulphide solution; it is reprecipitated from the
last-named solution of thio salt by dilute acids.
Ha[PtClo] + 2HaS = PtS a + 6HCl
2. Potassium Chloride Solution: yellow precipitate of potassium chloroplatinate K 2[PtCI6 ] from concentrated solutions (difference from gold). A similar result is obtained with ammonium
chloride solution.
3. Oxalic Acid Solution: no precipitate of platinum (difference
from gold). Hydrogen peroxide and sodium hydroxide solution
likewise do not precipitate metallic platinum.
4. Formic Acid: black powder of metallic platinum from neutral
boiling solutions.
Naa[PtCle] + 2HCOOH = Pt + 2NaCI + 4HCI + 2CO a
5. Zinc, Cadmium, Magnesium or Aluminium: all these
metals precipitate finely divided platinum.
Ha[PtCl o] + 3Zn = 2Pt + 3ZnCl a + HI
6. Hydrazine Hydrochloride: ready reduction in ammoniacal
solution to metallic platinum, some of which is deposited as a mirror
upon the sides of the tube.
(NH,)s[PtCloJ + N aH,,2HCl + 6NH. = 8NH,CI + N a + Pt
7. Silver Nitrate Solution: yellow precipitate of silver chloroplatinate Ag 2[PtCla], sparingly soluble in ammonia solution but
soluble in solutions of alkali cyanides and of alkali thiosulphates.
8. Potassium Iodide Solution: intense brownish-red or red
coloration, due to [PtI6
ions. With excess of the reagent
K2[Pt~] may be precipitated as an unsta,ble brown solid. On
warming, black PtI4 may be precipitated.
9. Stannous Chloride Solution: red or yellow coloration, due
to colloidal platinum, soluble in ethyl acetate or in ether.
r-
582
[IX.
Dithio~oxamide)
HaN--C--C-NH2 )
(
II
II
S S
11
)
2
Dry Test
All platinum compounds when fused with sodium carbonate U lion
charcoal are reduced to the grey, spongy metal (distinction f' lm
gold). The residue is insoluble in concentrated mineral acids, ;!ut
dissolves in aqua regia. The solution is evaporated almost to <lry.
ness, dissolved in water and reactions 1, 2, 5, 9 or 10 applied.
Separation.-Platinum is precipitated in Group II as P: :-i 2
The Group lIB metals are extracted with yellow ammonium "d
phide solution and reprecipitated with HCI. The sulphides of IS,
Sb, Sn, Au, Pt and Mo are dissolved in aqua regia, the excem :)f
acid evaporated and NH4Cl solution added. A yellow precipit, , te
of (NH4 MPtC1 6 ] indicates the presence of Pt. The filtrate is treai I'd
with FeS04 solution; Au is precipitated and is removed. Tile
filtrate is again treated with H 2S to reprecipitate As, Sb, Sn nlld
Mo as sulphides, which are filtered off. These sulphides are tl"'n
separated as described under Molybdates (Section IX, 4).
See also Table II in Section IX, 10.
PALLADIUM, Pd
Palladium, unlike platinum, is slowly dissolved by concentrat ,1
nitric acid {forming a brown solution of palladous nitrate, Pd(N0 3 )
and by hot concentrated sulphuric acid (forming palladous sulpha;
PdS0 4 ; the latter is readily produced by fusing with potassium pyr
sulphate). The metal dissolves readily in aqua regia yielding a mixture
of palladous and palladic chlorides or, more probably, the complex
acids H 2[PdCl.] and H 2[PdCls]: upon evaporation to dryness, the latt"l"
loses chlorine so that on treating the residue with water a solution of
palladous chloride or of chloropalladous acid H.[PdCI,) is obtained.
7]
583
IX, 7.
584
[~X'
ll\atm\lID. d.()\~s not \n\,enett, b\lt ~()\d. 801ld. n.\c\te\ ~ve a. ~\m\\.M te&.etlon,
IX, SA.
REACTIONS OF SELENITES
Use a solution of selenious acid, H2Se03'* or of sodium selenite,
N a2Se03,5H20.
8A.!
.n,W\jHVIIiO
vJ
uV"V -J
----
+ HC1),
to. Thiourea Test {CS(NH 2}2}.-Solid or dissolved thiourea precipitates selenium as a red powder from cold dilute solutions of selenites.
Tellurium and bismuth give yellow precipitates, whilst large amounts
of nitrite and of copper interfere.
Place a little powdered thiourea on quantitative filter paper and
moisten it with a drop of the test solution. Orange-red selenium
separates out.
Sensitivity: 2 p.g. Se.
t6. Hydriodic Acid Test.-Selenites are reduced by hydriodic acid
(or by potassium iodide and hydrochloric acid):
H.SeO a
+ 4HI =
Se
+ 212 + 3H aO
r-,
( "-/
NH
Selenious acid oxidises pyrrole to a blue dyestuff of unknown composition ("pyrrole blue"). Iron salts accelerate the reaction when it is
carried out in phosphoric acid solution. Selenic, tellurous and telluric
acids do not react under the conditions given below: the test therefore
provides a method of distinguishing selenites and selenates.
Place a. drop of 5 per cent ferric chloride solution and 7 drops of
syrupy phosphoric acid (sp. gr. 1'75) on a. spot plate containing 1 drop
19*
[IX,
of the test solution and stir well. Add a drop of the pyrrole reagen I
and stir again. A greenish.blue coloration is obtained.
Sensitivity: 05 p.g. Se. Concentration limit: 1 in 100,000.
The reagent consists of a 1 per cent solution of pyrrole in aldehydt'free ethyl alcohol.
8. Ammonium Thiocyanate and Hydrochloric Acid.Selenites are reduced in acid solution to elementary selenium:
2H2SeOa
+ HSCN =
2Se
+ COa + NH,HSO,
IX, SB.
REACTIONS OF SELENATES
Use a solution of potassium selenate, K2Se04 or of sodiml.
selenate, Na2Se04,lOH20.
1. Hydrogen Sulphide: no precipitation occurs. If the solution
is boiled with concentrated hydrochloric acid, the selenic acid i.
reduced to selenious acid; hydrogen sulphide then precipitates
mixture of selenium and sulphur.
H 2SeO,
+ 2HCI =
H 2SeO a
+ CIa + HaO
+ 4HCl =
HaSeOs
Dry Tests
(i) All selenium compounds when mixed with sodium carbonatn
and heated upon charcoal emit the odour of rotten horseradislJ.
A foul odour, due to hydrogen selenide H 2Se, is obtained UpOIi
moistening the residue with a few drops of dilute hydrochloric acid.
A black stain (due to Ag 2 Se) is produced when the moistened residue
is placed in contact with a silver coin.
(ii) Elementary selenium dissolves in concentrated sulphuric acid
to yield a green solution, due to the presence of the compound SSeO:>
Upon dilution with water, red selenium is precipitated.
Separation.-See under tellurium (Section IX, 9).
8B]
587
TELLURIUM, Te
Tellurium is less widely distributed in nature than selenium; both elements
belong to Group VI of the periodic system. VVhen fused with potassium
cyanide, it is converted into potassium telluride K,Te, which dissolves in
water to yield a red solution. If air is passed through the solution, the
tellurium is precipitated as a black powder (difference and method of separation from selenium). Selenium under similar conditions yields the stable
potassium selenocyanide KSeCN; the selenium may be precipitated by the
addition of dilute hydrochloric acid to its aqueous solution.
2KCN + Te = KaTe + (CN).;
2KaTe + 2H.0 + O 2 = 2Te + 4KOH
KCN + Se = KSeCN
KSeCN + HCI = Se + KCl + HON
Tellurium is converted into the dioxide TeO. by nitric acid. Like sulphur
and selenium, it forms two series of salts, the tellurites RaTeO. and the
tellurates R.TeO,.
REACTIONS OF TELLURITES
IX,9A.
Use a solution of sodium or potassium tellurite, NazTeOa or
KzTeOa.
1. Hydrogen Sulphide: brown precipitate of the disulphide TeSs
from acid solutions. The sulphide decomposes easily into tellurium
and sulphur, and is readily soluble in ammonium sulphide solution
but insoluble in concentrated hydrochloric acid.
2. Sulphur Dioxide: complete precipitation of tellurium from
dilute (1-5N) hydrochloric acid solutions as a black powder. In
the presence of much concentrated hydrochloric acid, no precipitate
is formed (difference and method of separation from selenium).
3. Ferrous Sulphate Solution: no precipitation of tellurium
(difierence from selenium). A similar result is obtained with
hydriodic acid (KI + Hel).
4. Stannous Chloride or Hydrazine Hydrochloride Solution
or Zinc: black tellurium is precipitated.
5. Dilute Hydrochloric Acid: white precipitate of tellurous
acid H2Te03 (difference from selenite), soluble in excess of the
precipitant.
6. Barium Chloride Solution: white precipitate of barium
tellurite BaTeOa, soluble in dilute hydrochloric acid but insoluble
in 30 per cent acetic acid.
7. Potassium Iodide Solution: black precipitate of Tel, in
faintly acid solution, dissolving in excess of the reagent to form the
red potassium telluri-iodide K 2[TeI6 ] (difierence from selenite).
t8. Hypophosphorous Acid Test.-Both telluritea and telluratea
are reduced to tellurium upon evaporation with hypophosphorous acid
HaPO aTeOa-- = PO,--Te
R,O;
3H.PO.2TeO,-- = 3PO,--2Te
2H+
2H.O
+
+
+ +
+ +
[IX,
588
IX,9B.
REACTIONS OF TELLURATES
Use a solution of potassium tellurate, K2Te04'
+ 2HCI =
K 2TeO a + H 2 0
+ Cl
+ 4HCl =
HaTeOa
r-,
5. Reducin~ A~ents.-No precipitate is produced in cold solutions with hydrogen sulphide or sulphur dioxide: with hot solutions,
or with solutions that have been boiled with hydrochloric acid,
S) and of black Te respectively
precipitates of brown TeS (or Te
are formed. Stannous chloride, hydrazine or zinc in acid solution
give black tellurium upon warming.
Dry Tests
(i) Fusion of any tellurium compound with sodium carbonate
upon charcoal results in the formation of sodium telluride Naz'I'e,
which produces a black stain (due to Ag2Te) when placed in contact
with a moist silver coin.
10]
589
590
[IX,
cleta.ueo. oo\ow
10J
Transfer the ppt. to a Hmall conical flask, add 5 ml. of concentrated ~Cl,
and boil gently for 5 minutes (with funnel in mouth of flask). Dilute
with 2-3 ml. of water, and filter.
Residue. May contain As, Au, Pt, Mo, Se and Te as
Filtrate. May
sulphides. Dissolve in concentrated HOI
a little contain Sb and
solid KCIO a ; concentrate the solution to the crystallisa. Sn as chlorides
tion point (use a water bath to reduce loss of Se to a or complex
minimum). Filter.
chloro-acids.
Residue.
Filtrate. May contain As, Au, Mo, Se Examine by
in
Yellow
and Te as chlorides or acids. Render alka- Table VI
K.[PtCl.]. line with ammonia solution, add Mg(NO.la Section VII, 11.
Pt
reagent or magnesia mixture, allow to stand
present.
for 5 minutes with frequent stirring or ~
Confirm
shaking. Filter.
~
by disResidue.
Filtrate. May contain Au, Mo, Se and Te
solving in White
as chlorides or acids. Concentrate to remove
a little
crystalammonia, boil with several ml. of saturated
hot water line
oxalic acid solution, dilute, boil and filter.
and add- Mg(NH.)- Extract ppt. with HCI to remove coprecipiing KI
AsO.,tated tellurous acid.
solution.
6H.0.
I-=OR;"e':"s:"'i':"d":'u-'e::'.::":":"':::'~I<';;i;:lt::'r::'a-t-e-. -~C~o-n-c-e-n-t-r-a""'t-e~w-l'""t"'hRed or
As
Brownish- strong HCI on a water bath and,
brownish- present. black or
after removing the precipitated
red
coloration.
purplishKel, treat with a slight excess 0 f
black.
solid Na 2 SO.. Filter.
AlternaAu
Residue.
Filtrate. Dilute with
tively,
apply the
present. Red.
an equal volume of
rubeanic
Se
water, and add Emccesacid test
present. sively a little KI solu(Section
tion and excess of solid
IX, 6, reNa.SO a whereby the
action 10).
K.[TeI.] is reduced to
Te. Filter.
Filtrate.
Residue.
Boil with HCl
Black.
to
remove
Te
present. dissolved SO.
and treat successively with
10 per cent
NH.SCN solution and a
little SnOI I
solution.
Red coloration, soluble
in ether.
Mo present.
Confirm by
potassium
xanthate test
or by the 0:benzoin oxime
test.
592
[IX,
Filtrate. May
contain Sb and
Sn as chlorides
or complex
chloro acids.
Examine by
Table VI (Sec.
tion VII, 11).
The most important compounds of vanadium are derived from the oxides
V 20. and V.O., both of which exhibit acidic properties, but the latter to the
~eater degree. Vanadium pentoxide, the anhydride of vanadic acid, is only
llightly soluble in water, but dissolves readily in concentrated solutions of
)austic alkalis, forming vanadates. Vanadic acid, like phosphoric acid,
lxists in the form of meta, pyro and ortho.compounds (HVO a, H.V.0 7 and
EIsVO. respectively). Unlike the salts of phosphoric acid, the metavanadates
Lre the most stable and the ortho-vanadates the least stable. A solution of
ill orthovanadate passes on boiling into the metavanadate, the pyro.salt
:>eing formed intermediately.
[X,H.
REACTIONS OF VANADATES
Use a solution of ammonium (meta-) vanadate, NH\tVO s, or the
nore soluble sodium meta-vanadate, Na V0 3
1. Hydrogen Sulphide.-No precipitate is produced in acid
olution, but a blue solution (due to the production of a quadrivalent
11]
593
H20 2
+ 6II,O ~
2H s[V(O,)08J + 3H , SO.
H2S04
t The spot test technique is as follows. Mix a drop of 15-20 per cent
sulphuric acid and a drop of the test solution either on a spot plate or
in a porcelain micro crucible. Mter a few minutes add 1 drop of 1 per
cent hydrogen peroxide solution and then another drop, if necessary.
A red to pink coloration appears.
Sensitivity: 25 pg. V. Concentration limit: 1 in 20,000.
Molybdates, chromates, iodides, bromides, eerie salts and also large
amounts of coloured metallic salts reduce the sensitivity of the reaction.
5. Ammonium Chloride.-The addition of solid ammonium
chloride to a solution of an alkali vanadate results in the separation
of colourless, crystalline ammonium vanadate NH4VO a, sparingly
soluble in a concentrated solution of ammonium chloride.
6. Lead Acetate Solution: yellow precipitate of lead vanadate,
turning white or pale yellow on standing; the precipitate is insoluble
in dilute acetic acid but soluble in dilute nitric acid.
7. Barium Chloride Solution: yellow precipitate of barium
vanadate (distinction from arsenate and phosphate), soluble in dilute
hydrochloric acid.
594
[IX,
8. Copper Sulphate Solution: green precipitate with mHtavanadates. Pyro-vanadates give a yellow precipitate.
9. Mercurous Nitrate Solution: white precipitate ofmercur(,us
vanadate from neutral solutions.
10. Ammonia Solution.-When this reagent is added to a
solution of a salt containing quadrivalent vanadium (e.g. that produced by reduction of a vanadate with hydrogen sulphide), dark
grey hypovanadic acid H2 VOs is formed; the precipitation is )lot
complete unless excess of ferric chloride be present.
11. Ammonium Molybdate SoIution.-No precipitate is produced in the presence of ammonium nitrate and nitric acid, a soluLle
molybdo-vanadate being formed (compare phosphate). If 1 he
vanadate is mixed with a phosphate, much of the vanadium is ,0,)precipitated with the ammonium phospho-molybdate.
12. Potassium Chlorate-p-Phenetidine Test_-Vanadildu
catalyses the reaction between p- phenetidine (H 2N. 06H4' 00 211 5,
1 : 4) and potassium chlorate: potassium hydrogen tartrate has an
activating effect upon the reaction.
Treat 05 mI. of the test solution in a semimicro test-tube with
005 gram of potassium hydrogen tartrate, 1 ml. of the p- phenetidine
reagent, I mI. of saturated potassium chlorate solution and dilute
to 5 mI. with distilled water. Immerse the test-tube in a water bat:1 :
a violet colour appears within a few minutes.
Lead interferes but is rendered harmless with 100 mg. of Na 2SO ,;
ferric iron also interferes and is rendered innocuous by adding 50 m ','.
of NaNOs. A similar result is obtained by replacing KClO s with ;,
saturated solution of KBrO a, but iodide as well as lead and ferric ir. 011
interfere.
Sensitivity: 0-001 JLg. V.
t 14.
Ferric
Chloride-Dimethyl~lyoxime
yrv
Test.-The reaction:
+ Fe+++ .= VV + Fe++
12J
595
Dry Test
Borax bead: oxidising flame-colourless (yellow in the presence
of much vanadium); reducing flame--green.
Separation.-Vanadates are not precipitated by H::S in acid
solution; reduction to the quadrivalent state occurs. With ammonium sulphide solution, the soluble thio-salt is formed, from which
brown V2S5 is precipitated by pouring into 6N H 2S04 , The precipitate may be dissolved in concentrated HOI, and reactions 4 and
12 applied.
In general, however, the vanadyl salt present in the filtrate from
Group II will be largely re-oxidised to vanadate by the nitric acid
treatment before the precipitation of Group InA. If the solution
contains the cations of Group IlIA and certain members of later
groups, the vanadates of these metals may be precipitated. However, if no other member of Group IlIA is present, vanadium may
be incompletely precipitated as ammonium vanadate. It is therefore recommended where vanadium is suspected (pale-blue solution
left after the passage of hydrogen sulphide in Group IJ) that the
Group II filtrate be tested for iron with potassium ferrocyanide
solution. If iron is absent, some ferric chloride solution should be
added before precipitation of Group IlIA.
See also Table V in Section IX, 18.
BEBYIllUM (OB GLUCINUlII:),
Be
poisonous.
IX, 12.
REACTIONS OF BERYLLIUM COMPOUNDS
Use a solution of beryllium sulphate, BeS04,4H20.
1. Ammonia or Ammonium Sulphide Solution: white precipitate of beryllium hydroxide Be(OHh, similar in appearance to
aluminium hydroxide, insoluble in excess of the reagent, but readily
soluble in dilute hydrochloric acid, forming a colourless solution.
Precipitation is prevented by tartrates and citrates.
596
[IX,
+ 2NaOH
Na 2[Be0 2]
+ 2H 20
On the other hand, the precipitate is insoluble in aqueous eth.' \amine solution whereas aluminium hydroxide dissolves in a modern i I)
excess of the reagent. Precipitation is prevented by tartrates aJ ,\ l
citrates.
3. Ammonium Carbonate Solution: white precipitate of ba>I\)
beryllium carbonate, soluble in excess of the reagent (differen, 1\
from aluminium). On boiling the solution, the white basic carbons i <l
is re-precipitated_
4. Oxalic Acid or Ammonium Oxalate Solution: no precipitate (difference from thorium, zirconium and cerium).
5. Sodium Thiosulphate Solution: no precipitate (differen, (.
from aluminium).
6. Basic
Acetate-Chloroform
Test.-Upon
dissolvir,.:
beryllium hydroxide (reaction 1) in glacial acetic acid an I
evaporating to dryness with a little water, basic beryllium acetal,'
BeO,3Be(C2H a0 2 )2 is produced, which dissolves readily upo:,
extraction with chloroform. This forms the basis of a metho' 1
for separating beryllium from aluminium, since basic aluminiUl' 1
acetate is insoluble in chloroform. The mixed hydroxides aT,
treated as detailed above.
t7. Quinalizarin Reagent*: cornflower-blue coloration with faint]
alkaline solutions of beryllhun salts. The reagent alone gives a charac
teristic violet colour with dilute alkali; but this is quite distinct fron'
the blue of the beryllium complex: a blank test will render the difierenc"
clearly apparent.
Antimony, zinc and aluminium salts do not interfere; aluminiun,
should, however, be kept in solution by the addition of sufficient sodiun
hydroxide; the influence of copper, nickel and cobalt salts can b,
eliminated by the addition of potassium cyanide solution; iron salt
are "masked" by the addition of a tartrate but if aluminium salts ar.
also present a red colour is produced. Magnesium salts give a similal
blue colour, but beryllium can be detected in the presence of thi,
element by utilising the fact that in ammoniacal solution the magnesium colour alone is completely destroyed by bromine water.
In adjacent depressions of a spot plate place a drop of the test solution
and a drop of distilled water, and add a drop of the freshly prepared
quinalizarin reagent to each. A blue coloration or precipitate, quite
distinct from the violet colour of the reagent, is obtained.
Sensitivity: 015jg. Be. Concentration limit: 1 in 350,000.
See Iwder Alwninium, Seotion III, 21, reaction 10.
12]
597
t8.
para-Nitrobenzene-azo-orcinol Reagent
The reagent consists of a 0025 per cent solution of p-nitrobenzeneazo-orcinol in N sodium hydroxide.
Dry Test
Upon heating beryllium salts with a few drops of cobalt nitrate
solution upon charcoal, a grey mass is obtained (difference from
aluminium).
Separation.-Beryllium is precipitated in Group IlIA. It is
ultimately associated with aluminium in solution as sodium aluminate and sodium beryllate respectively. Upon diluting and
boiling, only the Be(OHh is precipitated. Alternatively, the
quinalizarin test 7 may be applied to the solution or the basic
acetate-chloroform test 6 to the mixed hydroxides. BeryUium may
598
[IX,
TITANIUM, Ti
The most important compounds of titanium are those corresponding to
the two oxides Ti.O. and TiO., and are termed titanous &nd titanic compounds respectively. The former usually yield violet aqueous eolutions.
and are powerful reducing agents; they behave like iron and aluminium compounds towards the common reagents. The latter are usually colourless, an<!
are more frequently encountered in analytical work.
13]
599
r-
600
[IX,
(RO&O~)\
eddishbrown coloration with titanium salts in the presence of hydrolhloric or sulphuric acid. Appreciable concentrations of nitric acid
nhibit the reaction.
Mix a drop of the test solution and a drop of the reagent on drop'eaction paper or upon a spot plate. A reddish-brown (or purplish)ink) spot or coloration results.
Sensitivity: 5 p,g. TiO a. Concentration limit: 1 in 10,000.
Uranyl and ferric salts interfere and yield brown and deep green
:olorations respectively; these colours are destroyed by the addition
,f stannous chloride, for uranous and ferrous salts do not react with
hromotropic acid. Mercury salts give a yellow and silver salts a black
tain on drop-reaction paper; the colour due to titanium is, however,
till perceptible.
In the presence of uranyl salts and/or ferric salts, proceed as
allows. Mix a large drop of the test solution on a watch glass with a
mall quantity of a solution of stannous chloride in hydrochloric acid
1. large excess is to be avoided) and warm gently (hot plate).
Place
drop of the reagent on some drop-reaction paper and then a drop of
he clear solution from the watch glass. A reddish-brown (or purplish,ink) spot appears.
The reagent consists of a 5 per cent aqueous solution of chromotropic
cid. The reagent does not keep well, hence it is preferable to impregate drop-reaction paper with the reagent solution and allow the paper
) dry in the air. The impregnated papers are stable for several months.
[l use, a drop of the test solution and a drop of N HaSO, are placed
pon the impregnated paper: a purplish-pink colour results.
t8.
Pyrocatechol Reagent
/":::---_______
~llow
14)
601
Dry Test
Microcosmic salt bead: oxidising flame--colourless; reducing flame
-yellow whilst hot and violet when cold (this result is obtained
more rapidly if a little stannous chloride is added). If the bead is
heated in the reducing flame with a trace of ferrous sulphate, it
acquires a blood-red colour.
Separation.-If sufficient acid is present in the earlier groups to
prevent its separation by hydrolysis, titanium is found in Group
lIlA. It can be readily detected in the precipitate obtained after
treatment with Na202 by means of the hydrogen peroxide test 6;
NH4F solution will discharge the colour. It is usually best to fuse
the precipitate with 10 times its weight of powdered K 2S20 7 or
KHS04; the melt, containing the metals as sulphates, is extracted
with cold water, and the extract boiled for about 30 minutes.
Meta-titanic acid separates out. This is filtered off, dissolved in
concentrated HCI and the H 2 0 2 test applied.
See also Table V in Section IX, 18.
ZmaoNIUM, Zr
Zirconium'" forms only one important oxide, zirconia ZrO a, which is
amphoteric in character. The normal zirconium salts, like ZrCl., are readily
hydrolysed in solution giving rise chiefly to zirconyl salts, containing the
bivalent radical ZrOrr. The zirconates, e.g. Na 2ZrO., are best produced from
ZrOa by fusion methods. Zirconium also readily forms complex salts, e.g.
potassium fluozirconate K 2[ZrF6 ], produced by fusing zirconia with potassium
hydrogen fluoride.
Ignited zirconium dioxide, or the mineral, is insoluble in all acids except
hydrofluoric acid. It is soluble in fused caustic alkalis and in sodium car.
bonate; the resulting alkali zirconate is practically insoluble in water, being
converted into zirconium hydroxide by this solvent.. It is therefore best
dissolved in hydrochloric acid, and the zirconium hydroxides precipitated by
ammonia solution, etc.
602
[IX,
14]
603
Acid
(
604
[IX,
15]
5. Cupferron
titanium).
Reagent:
no
precipitate
605
(distinction
from
+ 6NaOR =
Na,2U .0 7
+ Na,[Fe(CN)6] + 3R 0
2
Sensitivity: 09 p,g. U.
2Fe+++
2Cu++
+ 28 20 8- - = 2Fe++ + S,06--;
+ 28 0 = 2Cu+ + 8 0 6-2
--
Dry Test
Borax or microcosmic salt bead: oxidising flame-yellow; reducing
flame-green.
Separation.-Uranium is precipitated in Group IlIA as
(NH4 hU2 0,. It is most simply separated from Fe(OHb Cr(OH)a
and AI(OH)s by digestion in the cold with a large excess of
606
[IX,
IX, 16.
REACTIONS OF THORIUM COMPOUNDS
Use a solution of thorium nitrate, Th(N0 3 )4,4H 20.
17Al
607
IX, 17A.
4. Saturated Potassium Sulphate Solution: white, crystalline precipitate, having the composition Ce2(S04)s,3K2S04 in neutral
solution and Ce2(S04)s,2K2S04,2R20 from slightly acid solution
(difference from aluminium and beryllium).
5. Sodium Bismuthate.-This reagent, in the presence of dilute
nitric acid, converts cerous into ceric salts in the cold. A similar
608
[IX,
reagent reicts
with neutral solutions of cerous salts to form ceric hydroxide ,ad
metallic silver (difI'erence from C()ric cerium); the former is colo\'!'ed
black by the finely divided silver:
Ce(OH).
+ [Ag(NHa)a)+ + OH-
= Ce(OH),
+ Ag + 2NHa
Ferric, manganous and cobaltous salts also give the higher met!!lic
hydroxides and silver, and must therefore be absent.
Mix a drop of the neutral test solution and a drop of the reagent n a
watch glass or in a porcelain micro crucible, and warm gently. A L',lck
precipitate or brown coloration appears.
Sensitivity: 1 p.g. Ceo
17B]
609
Dry Test
Bo,.ax Bead: oxidising Bame-dark brown whilst hot and light
yellow to colourless when cold I reducing Bame--colourless.
20+
610
[IX,
18]
611
Filtrate.
May contain Na.CrO" NaAlO.,
Na aVO, and sodium peruranate (probably
Na.UO.).
Acidify with dilute HNO., add 3-4 ml. of 20%
Pb(NO.). solution, followed by 2 grams of solid
ammonium acetate. Stir well, filter and wash with
hot water.
Residue. May
Filtrate. May contain
contain PbCrO, Al(NO a )., UO.(NO.). and
and Pb.(VO.). (4). excess of Pb(NO.)2'
Pass
Dissolve in the H.S to remove all th" Pb as
minimwn volume PbS. Filter, wash and boil
of hot 3N HNO. the filtrate to expel H.S.
(ca. 5-6 ml.),
Almost neutralise with NH.
thoroughly cool
solution, cool and pour into
the resulting solu- an excess of concentrated
tion, and transfer (NH.).CO. solution. Warm
to a small separa- for 5 mi.p.utes. Allow to stand,
tory funnel. Add filter and 'Wash.
an equal volume
Residue.
of amyl alcohol,
Filtrate. May
contain U, proand a little 6% White:
H.O..
Shake Al(OH) .
bably as (NH,).well and allow the Al present. [UO.(CO.).].
Confirm by Evaporute to a
two layers to sepaThenard's
rate.
small volume (7),
A blue colora- blue test (6). acidify with HCl,
tion in the upper
and add K.[Felayer indicates Cr
(CN).] solution.
present, and a. red
Brown ppt. of
to brownish-red
(UO.).[Fe(CN).],
coloration (5) in
b,ecoming yellow
the lower layer
upon the addiindicates V pretion of NaOH
solution.
sent.
Confirm V by the
U present.
KClOs-p-phenetidine test (Section
IX, 11, reaction
12).
612
[IX,
20]
613
+ NazHPO, + NaOH =
Li.PO,
+ 3NaCI + HIO
614
[IX,
C0 3 - - ;= NHs
+ HCO s-
3. Ammonium Fluoride Solution: a white, gelatinous precipitate of lithium fluoride LiF is slowly formed in ammoniacal
solution (distinction from sodium and potassium).
LiCl
+ NH,F =
LiF
+ NH,Cl
21]
615
O(
"CH2.CH 2/
IX, 21
Reducing jlama
Metal
Hot
Cold
Hot
1. Green
Blue
Colourless
2. Yellowishbrown
3. Yellow
4. Violet
(amethyst)
5. Blue
6. Violet
Yellow
7. Yellow
8. Rose-violet
9. Yellow
10. Yellow
11. Yellow
12. Yellow
13. Orange-red
Cold
Green
Opaque red
or brown*
Green
Iron
Green
Amethyst
Green
Colourless
Green
Colourless
Chromium
Manganese
Blue
Reddishbrown
Colourless
Rose-violet
ColourleBB
Blue
Grey
Blue
Grey
Cobalt
Nickel
Brown
Red
Yellow
Brown
Violet
Yellowbrown
Bottlegreen
Emeraldgreen
I'ale-violet
Colourless
Molybdenum
Gold
Tungstent
Pale
yellow
Greenishyellow
Colourless
Colourless
Green
Brownish
Grey
Colourless
Copper
Uranium
Vanadium
Titanium:
Cerium
CHAPTER X
PAPER CHROMATOGRAPHY
X, 1. Introduction. RF Values.-In filter-paper chromat,)
graphy a small amount of material (say, an aqueous soluti, rt
containing a mixture of cations) is placed upon a limited ar, t
near the end of a strip of filter paper, and a solvent is allow, ,1
to diffuse from the end of the paper by capillary action: und r
suitable conditions and after some time (1-30 hours), the
mixture will be found to have migrated from its limited an'a.
of application and separated wholly or partially into its COl 1ponents as distinct zones. The zones in the form of spots ., r
bands may be located by the application of appropri:1: '3
chemical reagents to the paper or by ultra-violet fiuorescen< '1.
The diffusion of the solvent and the resulting separation it, i 0
spots or bands is sometimes termed the development of t I! e
chromatogram; this term is a little misleading and should 1, ,t
be confused when employed in the above sense with the Sli i>sequent identification process by means of which the zones I' 'e
rendered clearly visible by treatment of the paper with varic is
reagents. The author prefers to confine the phrase "devel< :1ment of the chromatogram" to signify the treatment of 1 e
chmroatogram after it has been formed, and it will have t: s
significance when employed in the present chapter.
To specify the position attained by a substance or ion iI, a
paper chromatogram, the term RF was introduced: this is 1 ie
ratio of the distance travelled by the substance or ion to tJ! It
of the solvent front, measured from the point of application i)f
the mixture. Fig. X, 1, 1 will help to make the definiti' ,n
of RF clear: in (a) the strip of filter paper is shown immen d
in the solvent and supported by a glass rod; in (b) AB indica's
where the spot of the solution was applied at the beginni i g
of the experiment; in (c) the position of two bands (rendered
visible, for example, by spraying with an appropriate chemj('al
reagent) C and D, and also of the solvent front E, are indicated.
The RF value for the substance or ion at C is xjz and the
substance or ion at D is y/z. It is found that under comparable
conditions many ions have characteristic RF values; separation
by paper chromatography is usually possible when the HF
values differ by about 01.
616
1]
Paper Ohromatography
.
_ . _ 617
Hdj;
.,
(a)
(b)
(c)
Fig. X, 1, 1
618
[X,
2]
Paper Chromatography
619
Fig. X, 2, I
Fig. X, 2, 2
' :' J
620
[X,
2]
Paper
ChromaJoflraph,ll
621
622
[X,
III
IV
VI
Vl1 I
Fig. X, 2, 3
As for acetone.
99-102.
Paper Chromatography
3]
623
Ph
Ag
Hg (ous)
RF values
Colour of band
008
016
085
Rose pink.
Orange.
Pink.
624
[X,
Reagent
Oolour of band
Pb
020
027
Purple-brown.
Bright blue.
Bi
Cd
Hg (ic)
059
077
081
Dithizone
Rhodizonic
acid
Dithizone
Dithizone
Dithizone
On
Purple.
Purple.
Pink.
""
Group IIB.-As, Sb and Sn. The separation of a mixture
of the three elements is a difficult operation. The metals are
present as their lower chlorides in dilute (2-4N) hydrochloric
acid. The solution is spotted on paper and allowed to dry in
air for 15 minutes. The solvent consists of 75 ml. of acet\ lacetone (b.p. 137-141) saturated with water and treated wi; h
005 ml. of concentrated hydrochlorio aoid and 25 ml. (,f
acetone (sufficient of the last-named to give a olear solutioll).
The separation is allowed to proceed for 1 hour in an atmosphere
saturated with respeot to a saturated solution of acetylaceto!le
in water; the solvent movement is about 15 cm. The oomplexes
formed are very stable, particularly that with tin (RF = 1).
The strip is removed from the extraction vessel, the solvent is
allowed to evaporate for several minutes, and the strip is
sprayed (before it is completely dry) with a chloroform solution
of dithizone (0,05 per cent wjv), and then allowed to dry
thoroughly. The tin is found in the solvent front.
As
Sb
Sn
RF values
Oolour of band
02
0'5
10
Yellow.
Red.
Purple.
3]
Paper Ohromatography
625
Ni
Mil
Co
Zn
RF values
Colour of band
007
03
06
09
Blue.
Brown.
Brown.
Purple.
826
[X,
RF values
Colour of band
Be
Mg
ea
Sr
Ba
0'86
0'76
0'68
0'55
0'43
Yellowish-green.
Yellowish-red.
Orange.
Reddish violet.
Pale red.
076
0'56
0'45
Reddish-violet.
Reddish-violet.
Violet.
Li
Na
K
4]
627
Paper Chromatography
Fluoride
Chloride
Bromide
Iodide
Pyridine-l0% H 2 0 Acetone-20% H 2 0
000
024
047
071
025
051
062
077
628
[X,
The Platinum Metals: Pt, Pd, Rh, Jr, Ru, Os aid Au.
The metals are present as their chlorides or sodium chlor i-salts.
The solvent used is methyl ethyl ketone containing 30 p r cent
(vjv) of hydrochloric acid (d 1'18); it is freshly prepared The
solution is spotted on the paper strip and allowed ,) dry
thoroughly in the air. The atmosphere in the separation
vessel is saturated with respect to the solvent. F, 'r the
detection of Pt, Pd, Au and Rh, 0'5N stannous chlo ide in
dilute hydrochloric acid is a suitable developing rear 'nt; a
mixture of stannous chloride and potassium iodide soh:, ion is
somewhat more sensitive. Iridium is reduced to the co] urless
iridium trichloride by the stannous chloride, but can 1)e reoxidised to the brown tetrachloride by chlorine water.
Ruthenium and osmium are detected by spraying with a s ,lution
of thiourea in 5N hydrochloric acid; warming is ne< ussary
to develop the colours fully.
4)
Paper Ohromatography
629
630
Th
So
Rare earths
RJ!
Colour of band
096
017
000
Violet-blue.
Violet.
Violet-blue.
[X,
4]
Paper Ohromatography
631
applied to the paper and, without drying, is immediately transferred to the extraction vessel. The chromatogram is allowed
to run for 18 hours; the solvent moves about 3 cm. per hour,
and drips from the end of the strip at the end of the period.
The wet strip is sprayed with a saturated solution of alizarin in
ethyl alcohol containing 5 per cent (v/v) of 2N hydrochloric
acid. The strip is then heated gently, care being taken that it
never becomes completely dry; it is resprayed with the reagent,
if necessary. The characteristic red lines of the zirconium and
hafnium lakes appear slowly against the yellow background of
the reagent. Narrow bands are obtained with RF values of
01 for Hf and 02 for Zr. It is possible to detect 2 I-'g. of each
metal, and also the presence of about 2 per cent of hafnium in
commercial zirconium nitrate.
APPENDIX
A, 1.
Aluminium, Al
Antimony, Sb
Argon, A
Arsenic, As
Barium, Ba
Beryllium, Be
Bismuth, Bi
Boron, B
Bromine, Br
Cadmium, Cd
Calcium, Ca
Carbon, C
Cerium, Ce
Chlorine, Cl
Chromium, Cr
Cobalt, Co
Copper, Cu
Fluorine, F
Germanium, Ge
Gold, Au
Hafnium, ill
Helium, He
Hydrogen, H
Iodine, I
Iridium, Ir
Iron, Fe
Lanthanum, La
Lead, Pb
Lithium, Li
Magnesium, Mg
Manganese, Mn
Mercury, Hg
(1952)
Molybdenum, Mo
Nickel, Ni
Niobium, Nb
Nitrogen, N
Osmium, Os
Oxygen, 0
Palladium, Pd
Phosphorus, P
Platinum, Pt
Potassium, K
Radium,Ra
Rhenium, Re
Rhodium, Rh
Ruthenium, Ru
Scandium, Sc
Selenium, Se
Silicon, Si
Silver, Ag
Sodium, Na
Strontium, Sr
Sulphur, S
Tantalum, Ta
Tellurium, Te
Thallium, Tl
Thorium, Th
Tin, Sn
Titanium, Ti
Tungsten, W
Uranium, U
Vanadium, V
Zinc, Zn
Zirconium, Zr
2698
12176
39944
7491
13736
9013
20900
1082
79916
11241
4008
12010
1~013
35457
5201
5894
6354
1900
7260
1972
1786
4003
1008
12691
1931
5585
13892
20721
6940
2432
5493
20061
632
9595
5869
9291
14008
1902
16000
1067
30975
19523
39100
22605
18631
10291
1017
4496
7896
2809
107880
22997
8763
32066
18088
12761
20439
23212
11870
4790
18392
23807
5095
6538
9122
2]
Appendix
A, 1.
REAGENTS
833
CONCENTRATED ACIDS
Specific
gravity
Per cent by
weight
Approximate
normality
105
149
H9
995
48
17N
9N
12N
27N
7N
16N
9N
45N
36N
170
142
154
169
184
38
48
57
70
60
85
96
DILUTED ACIDS
Approximate
normality
5N
5N
5N
5N
0'3N
BASES
Ammonia solution, concentrated.-The commercial product, sp. gr. 0-88, contains about 28 per
cent NHs
Ammonia solution, dilute.-Dilute 335 m!. of
the concentrated solution to 1 litre with water ...
Barium hydroxide solution.-Shake 70 grams
of crystallised barium hydroxide Ba(OHh,8H20
with 1 litre of water; filter or siphon off the liquid
(saturated solution) and protect from CO 2 of the
air
15N
5N
0-4N
634
[A,
Approximate
normality
0'04N
2N
5N
SALT SOLUTIONS*
Ammonium acetate, NH4.C 2 H 3 0 2 (M.W.
77).-Dissolve 231 grams of the salt in 1 litre of
water ...
3d'
Ammonium carbonate (the commercial salt
is a mixture of NH4 HC0 3 and NH4C0 2 NH 2).Dissolve 160 grams of the salt in a mixture of
140 ml. of concentrated ammonia solution and 860
ml. of water .. ,
4N
Ammonium chloride, NH 4CI (M.W. 53'5).Dissolve 270 grams of the salt in I litre of water...
5N
Ammonium nitrate, NH4N0 3 (M.W. 80).Dissolve 80 grams of the salt in 1 litre of water ...
N
Ammonium oxalate, (NH4)2C204,H20 (M.W.
142).-Dissolve 35 grams of the crystalline salt in
1 litre of water
05.N
Ammonium sulphate, (NH4)zS04 (M.W. 132).
-Dissolve 132 grams of the salt in 1 litre of water
2N
Ammonium thiocyanate, NH4SCN (M.W.
76).-Dissolve 38 grams of the salt in 1 litre of - water ...
05.N
Yellow ammonium sulphide solution,
(NH4hS",.-Use the solution available commercially. It may be prepared, if desired, as
follows. Saturate 150 ml. of concentrated ammonia solution with H 2 S, keeping the solution cold;
add 10 grams of flowers of sulphur and 250 ml. of
concentrated ammonia solution, shake until the
sulphur has dissolved and dilute to 1 litre
6N
The common reagents chlorine water, bromine water, iodine soluti
hydrogen sulphide water are included here.
2J
Appendix
635
Approximate
normality
6N
Barium chloride, BaCI 2,2H 20 (M.W. 244).Dissolve 61 grams of the salt in 1 litre of water ...
05N
05N
O'03N
03N
(as oxidant)
Ferric chloride, FeCI3 ,6H20 (M.W. 270).Dissolve 135 grams of the hydrated salt in 1 litre
of water containing 20 m!. of concentrated HOI ...
(as oxidant)
O5N
Of)N
Ferrous sulphate, FeS04,7H2 0 (M.W. 277).Dissolve 140 grams of the salt in 1 litre of water
O'5N
(as reductant)
containing 7 ml. of concentrated H 2S04 .
Hydrogen sulphide solution, H 2 S (M.W. 34).
-Saturate 250 ml. of water with HzS gas derived
from a Kipp's apparatus. The solution contains
approximately 42 grams of HzS per litre
0'05N
636 .
[At
Approximate
normality
O'IN
05N
0'5N
Mercuric chloride, HgCl 2 (M.W. 272).-Dissolve 27 grams of the salt in 1 litre of water
0'2N
Potassium chromate, K2Cr04 (M.W. 194).Dissolve 49 grams of the salt in 1 litre of water ...
futassium cywllide, KeN (AI. W. S5l.-lJissolve 325 grams of the salt in 1 litre of water
(POISONOUS)
05N
(as precipitant)
0'5N
0'5N
O'IN
(as oxidant)
Potassium thiocyanate, KSCN (M.W. 97).Dissolve 49 grams of the salt in 1 litre of water ...
0'5N
O'IN
Silver sulphate, Ag 2 S04 (M.W. 312).-Dissolve 8 grams of the salt in 1 litre of water. This
is nearly a saturated solution
0'05N
3N
2J
Appendix
637
A. pproximate
normality
3N
Disodium hydrogen phosphate Na2HP04>12H2 0 (M.W. 358).-Dissolve 120 grams of the salt
in 1 litre of water
O'5N
Zinc Nitrate, Zn{NOS)2,6H 2 0 (M.W. 297).Dissolve 150 grams of the salt in 1 litre of water
O5N
SPECIAL REAGENTS
Experimental details for the preparation of many of the
special, largely organic, reagents are given in the text; these
can be locater' by reference to the Index. Some reagents,
which are required for macro and semimicro analysis and which
are not described in detail in the text, are collected below.
Ammonium molybdate reagent.-Method A. Dissolve
45 grams of the commercial salt (NH4)6Mo7024,4H20 (a paramolybdate) or 40 grams of pure molybdenum trioxide Mo0 3 in
a mixture of 70 ml. of concentrated ammonia solution and 140
ml. of water; when solution is complete, add it very slowly
and with vigorous stirring to a mixture of 250 ml. of concen
trated nitric acid and 500 ml. of water; dilute to 1 litre. Allow
to stand 1-2 days and decant the clear solution.
Method B. Dissolve 45 grams of pere commercial ammonium
molybdate in a mixture of 40 ml. of concentrated ammonia
solution and 60 m!. of water, add 120 grams of ammonium
nitrate and dilute to 1 litre with water.
The alkaline solution of ammonium molybdate keeps better
than does the nitric acid solution; there is little tendency for
the separation of solid. Before using the alkaline solution, it
is important to ensure that the test solution contains a slight
excess of nitric acid.
Dimethylglyoxime reagent.-Dissolve 1 gram of dimethylglyoxime in 100 ml. of rectified spirit (95 per cent ethyl
alcohol).
640
[A,
SOLID REAGENTS
Aluminium (turnings or foil), Al
Ammonium chloride, NH,Cl
Ammonium nitrate, NH 4 NO a
Ammonium thiocyanate, NH,SCN
Asbestos fibre, for filters
Borax, Na 2B,07,lOH 2 0
Calcium chloride, CaCI.
Calcium fluoride, CaF 2
Copper (foil or turnings), Cu
Devarda's alloy (powder)
Ferrous sulphate, FeSO,,7H 20
Fusion mixture, NaaCO a + K 2CO a
Glass wool
Iron (wire or powder), Fe
Lead dioxide (Mn free), PbO.
Litmus paper (red and blue)
Manganese dioxide (precipitated),
MnO.
Methyl violet paper
Microcosmic salt,
Na(NH,)HPO,,~"t:::20
Potassium
Potassium
Potassium
Potassium
Potassium
Potassium
bisulphate, KHSO,
carbonate, KICO,
chlorate, KCIO a
cyanide, KCN
dichromate, K 2Cr,O,
nitrate, KNO a
A, 3.
TEST SOLUTIONS
3]
Appendix
CATIONS
Formula oj
dry sall
Cation
Grams oj
salt per
litre oj
solution
140
Special precautions in
preparation of the
solution
I Use
100
HNO .
ml. of dilute
Ag+
Pb++
158
160
183
Hg++ (ic)
Bi+++
135
232
00++
Cd++
OoSO,,5H,O
or CuCl.,2H.O
3CdSO,,8H.O
or Cd(NOs) .4H.O
As (ous)
As,O,
393
268
228
278
132
153
53'7
188
As (ic)
Sb (ous)
ISb (ic)
SbCI,
24'5
8n++ (ous)
SnCI . 2H.O
190
8n++++ (ic)
Fe++ (ou.'!)
Fe+++ (ic)
Cr+++
Al+++
00++
Ni++
Mn++
Zn++
Ba++
Sr++
C8++
21+
295
FeSO"(NH,).So,,.
6H.O
FeCl.,61l.0
CrOI.,61l.0
or K.SO,,Cr.(SO,).,241l.0
Al.(SO.).,18H.O
or K.SO"Al.(SO.>S,.
24HP
Oo(NO.).,6H.O
NiSO.,7H.O
or NiOl.,61l.0
MnSO.,4H.O
or MnOI.,4H.O
ZnSO.,7H.O
or Zn(NO.).,6H.O
BaCI.,2H.O
or Ba(NO.).
SrCI.,6H.O
or Sr(NO.).,4H,O
CaOI.,2H.O
or Oa(NO a),,4H.O
703
484
512
960
1235
1759
494
478
405
407
360
44'0
455
17'8
190
30'4
324
36'7
589
Use5ml. ofdiluteHNO .
Use 5 ml. of dilute
H.O.HaOa.
Dissolve salt in 100 ml.
of dilute H..,\O. and
dilute to I litre.
Use5ml.ofdiluteH 2SO,.
Use 5 ml. of dilute HCI.
Use 5ml. ofdiluteH.SO,.
U Be 5 ml. of dilute HNO s.
Dissolve in hot water containing 20 mi. of dilute
HOI and dilute to llitre.
As for arsenious compound.
Dissolve in fiOO mi. of
dilute HCI and dilute
to 1 litre.
As for antimonious compound.
Dissolve in 100 mI. of
concentrated HOI and
dilute to 1 litre.
Dissolve in 500 ml. of
dilute HOI and dilute
to I litre.
Use 20 mI. of dilute
H 2SO,.
Use 50 mI. of dilute HOI.
Use 50 ml. of dilute HOI.
Use 50 ml. of dilute
H 2 SO,.
Use 20 mI. of dilute
H 2 SO,.
Use 20 ml. of dilute
H.SO,.
642
Formula of
dry 8alt
CIBion
Grams of
salt per
litre oj
Bolution
[A,
..,-
---
Mg++
1014
Mg80,,7H,O or
1054
Mg(NO ala,6H,O
K+
KCl
191
259
or KNO,
Na+
254
NaCI
370
or NaNO,
NH,+
297
NH.Cl
444
,'","" ~
or NH,NO a
Note. If a slightly turbid solution is obtained with the catioIll' ,f Groups
HIB, IV and Mg, about 5 ml. per litre of the dilute acid, corres: Jnding to
the anion of the salt, should be added.
ANIONS
Anion
Formula of Balt
CO.SO.8,Oa-
Na.OO.,10H.O
Na,SO.,7H,O'"
Na.S,O,,5H.O
S-Na.S,9H,O
NO.NaNOs
ON'"'
KCN
CNOKCNO
SC~
KCNS
[Fe(CN).]K,[Fe(ON).],3H.O
[Fe(CN).]Ka[Fe(ON).J
CC
NaCI
BrKBr
r
KI
FNaF
AsO.- or AsO.- (arsenite) NaAs a
AsO,- (arsenate)
Na.HAsO,,7H aO
NO.NaNO,
ClO,KOIO.
BrO,KBrO,
10,KIO,
CIO,KOIO,
BO.- (borate)
Na.B,07,10H.O
80,Na,80"lOH,O
SiO aNa.8iO.
[8iF.]- (silicofluoride)
Na.[8iF.]
PO,-Na eHPO,,12H O
HPO.- (phosphite)
Na,HPO.,2H,
H.PO.- (hypophosphite)
NaH.PO"H,O
Cro,K,CrO,
MnO,- _
KMnO,
C,H,O, (aeetate)
Na. C,H aO,,3R.0
H.CO. (formate)
n.COaNa
C,O,- (oxalate)
Na,.C,O,
C,H,O.- (tartrate)
NaK.C,H,0.,4H,O
C,H,07- (citrate)
N aa' C.H.0 7 ,2H,O
C,H,O,- (salicylate)
C.H,(OH)CO,Na.
C,H,O.- (benzoate)
C,H,COIK
C,H,O,- (succinate)
O,H,(CO.Na)
14'
... Th_ IIOlutions do not keep well and should be freshly pre,.a.red.
643
Appendix
4]
A.4.
BUFFER SOLUTIONS
The following standards are suitable for the calibration of
pH meters and for other purposes which require an accurate
knowledge of pH.
pH at
Solution
250
380
148
207
150
208
357
4000 (150)
4005
4015
465
464
465
685
918
684
907
120
0'1M KHC204,H2C204,2H20
0'1M HCI
009M KCI
Y (mi.)
pH
X (ml.)
Y (mi.)
pH
489
372
27,4
190
166
1'1
12'8
22'6
31'0
33'4
140
150
160
170
180
132
100
76
44
368
400
424
456
190
200
210
220
644
'[A, -
X (ml.)
Y (ml.)
Na2HP04 Citric acid
040
124
218
317
411
494
570
644
710
771
828
882
935
986
1030
1960
1876
1782
1683
1589
1506
1430
1356
1290
1229
.1172
IH8
1065
1014
970
pH
22
24
26
28
30
32
34
36
38
40
42
44
46
48
50
X (ml.)
Y (ml.)
Na2HP04 Citric acid
1072
1115
1160
1209
1263
1322
1385
1455
1545
1647
1739
1817
1873
1915
1945
928
885
840
791
737
678
615
545
455
353
261
183
127
085
055
j,II
f.
;, !
it d
f)~
(d)
(\~
tl t
{) ! i
fH
7:1
7~
7 I
7 ,i
7'~
8"
~-
Appendix
4]
645
-+
-+
+
P mi. 02M
(A) pH 22-38. 50 MI. 021v] KHphthalate
HCl, diluted to 200 ml.
(B) pH 40-62. 50 MI. 02111 KHphthalate
Q mI. 02M
NaOH, diluted to 200 ml.
(C) pH 58-80. 50 j}ll. 02jl1 KH 2P04
R mi. 02M
NaOH, diluted to 200 ml.
(D) pH-rS-100. 50Ml. O2M H3B03and a'2M lWl* +Sml.
02M NaOH, diluted to 200 mi.
B
P (mt.) pH
HeI I
Q (mi.)
NaOH
4660
3960
3300
2650
2040
1480
995
600
265
040
365
735
1200
1750
2365
2975
3525
3970
4310
45,.40
4700
22
24
26
28
30
32
3-4
36
38
I pH
40
42
44
46
48
50
52
54
56
58
60
62
R (mi.)
NaOH
pli
S (ml.)
366
564
855
1260
1774
2360
2954
3490
3934
4274
4517
4685
5'8
6'0
6'2
6'4
6'6
6'8
7'0
7'2
7'4
7'6
7'8
8'0
265
400
590
855
1200
1640
2140
2670
3200
3685
4080
4390
NaOH
pH
78
80
82
84
86
88
90
92
94
96
98
100
* That is, a solution containing 12'369 h'l'ams of HaBO. and 14'911 grams
of KCI per litre.
646
CJuat~tatwe lnorgan~c
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pH
X (ml.)
pH
X (ml.)
pH
X (ml
26
28
30
32
3-4
36
20
43
64
83
101
118
137
155
176
199
224
248
271
295
318
342
58
.60
62
64
66
68
70
72
74
76
78
80
82
84
86
88
365
389
412
435
460
483
506
529
558
586
617
637
656
675
693
710
9'0
9'2
9'4
9'6
9'8
10'0
10'2
10'4
10'6
10'8
11'0
11'2
11'4
11'6
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12'0
727
740
749
776
793
808
820
829
839
849
860
877
897
920
950
996
38
40
42
44
46
48
50
52
54
56
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41
3
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5
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78
6
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64 7324 7332 7340 7348 7356 736! 7372 7380 7388 7396 1
55 7404 7412 7419 7427 7435 7443 7451 7459 7466 7474 1
56 7482 7490 7497 7505 7513 7520 7528 7536 7643 7<151 1
2
2
3
3
3
3
4
4
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6
6
6
6
7
7
7
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69 7709 7716 7723 7731 7738 7745 7752 7760 7767 7774 1
2
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6
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57 7559 7566 7674 7582 7689 7597 7604 7612 7619 7627 1
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62 7~24 7931 7938 7945 7952 79,'ln 7966
63 7993 80(JO 8007 8014 8021 S(c., 8035
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71 8513 8519 8525 8531 8537 8,13 8549 8555 8561 8567 1
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1500 1503 1507 1510
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28 1905
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11
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1288
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1355
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1327
1358
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1300
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1361
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1334
1365
1396
1626
1663
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1824
1866
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1954
1629
1667
1706
1746
1828
1871
1914
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1306
1337 1340 1343 1346
1368 1371 1374 1377
1400 1403 1406 1409
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22 1660
23 1698
24 1738
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1633
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'30 1995 2000 2004 2009 2014 2018 2023 2028 2032 2037 0
1
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2
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2
2
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3
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1879
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1968
2061
2109
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2208
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1972
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2113
2163
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2070
2118
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ANTILOGARITHMS
0
12 34
'1>1 3236 3243 32U S268 stSB 3273 3281 3289 3296 3304 1
'52 3311 3319 3321 8334 S342 3350 8357 3365 3873 3381 1
53 3388 3396 3404 5412 8420 3428 3436 8443 3451 3459 1
oM 3467 3475 3483 8491 3499 3508 3516 3524 3532 3540 1
3651
S7I5
3802
3890
3639
3724
8811
8899
8648
3733
3819
3908
S656
3741
3828
3917
3698
3784
3873
3963
40~5
3681
3767
3855
3945
--140i8 -- - --
8690
3776
3864
3954
3G73
3758
3846
3936
S664
5750
3837
3926
4093
4188
4285
4385
4102
4198
4295
4395
6 '1 8 9
4
4
4
4
6 6 8 7
6 6 6 7
2
2
2
2
2
2
2
3
3
3
'55 S648 3556 3565 S573 3581 3589 8597 3606 3614 3622 1
'56
'57
'58
'59
, , ,
50 3162 3170 BI17 8184 11911 8199 3206 3214 8221 3228 1 1
1
7
6
6
7 7
3 3
3 3
3 4
B 4
4
4
4
5
6
6
2
2
2
2
6
6
6
6
1 8
7 8
7 8
1 8
4064 1
3707
5793
3882
3972
1
1
1
4159
4256
4355
4457
);
1 2 S 4
1 :I S 4
5
5
5
5
6
6
6
6
1 8
7
7
7
9
9
9
9
1
1
8
8
2
2
S
S
4
4
I---65 4467 4477 4487 4498 4508 4519 4529 4539 4550 4560 1 2
'-----66 4571 4581 4592 460S 4613 ~624 4634 4645 4656 4667 1 2
4
4
5
5
6
6
6 7 9 10
7 8 9 10
7 8 9 10
1 8 9 10
9 II
----
-----
-67 4677 4688 4699,4710 4721 4732 4742 4753 4764 4775 1 2 3
68 4786 4797 4808 4819 4831 4842 4853 4864 4875 4887 1 2 & 41955 4966 4977 4989 5000 1 2 8 6'
r---f--- - -
----
----
70 5012 5023 5035 5047 5058 5070 5082 5093 5105 5117 1
40
2
2
8
40
6
6
6
6
''11
'72
'i3
'74
IH29
6248
6370
6495
5140
6260
5383
5508
'75 6623 6636 0649 6662 0675 5689 0702 5715 5728 5741 1
'76
'77
'78
'79
6754
5888
6026
6166
5768
5902
6039
6180
--
-- -- --
6781
5916
6053
6194
6194
6929
6067
6209
5821
5957
6095
6237
5808
5943
6081
6223
--
5834
5970
6109
6252
6848
5984
6124
6266
5861
5998
6138
6281
--- -80 163iO 6324 4339 6353 6368 6383 6397 6412 6421
--. - -- f--- --81 6457 6471 6486 6501 6516 6531 6546 6561 6577
4
4
4
5
5
5
5
5
6
6
2
2
8
8
--
91012
6442 1
6692
'82 6607 fl622 6637 6653 6668 6683 6699 6714 6730 6745
-83 ti761 6776 6792 6808 6823 6839 681)5 687l 6887 6902
-84 691S 6934 6950 6966 6982 6998 7015 7031 7047 7063
8
9
9
9
7
7
7
7
8
3
3
3
4
4
4
4
7
7
8
8
I
1
1
1
5815
6012
6152
6295
T g
S I; ~
3 5 6
3 6 6
B
8
9
8 10
8 10
9 10
1011
10 11
10 11
10 12
11
11
11
11
12
12
13
13
9 10 12 13
----9 II 12 U
9 11 12 14
9 11 13 14
10 11 13 16
'85 7079 7096 7112 1129 7145 7161 7178 7194 7211 7228 2 3
10 12 13 15
5
6
5
6
7
1
7
7
10
10
11
11
7311
7482
7656
7834
7328
7499
7674
7852
7345
7516
7Bn
7870
7362
7634
7709
7889
7379
7551
7727
7907
7396
75('8
7745
7925
2
:I
2
2
'110 7943 7962 7980 7998 B017 8035 BO:;4 8072 8091 BUO 2
-- - - -
-- - -
91 8128 8147 8166 81B5 8204 8222 8241 8260 8279 8299 2
'92 8318 8337 8MB 8375 8395 M14 8433 8453 8472 84~2 2
93 8511 8531 8551 8570 8590 8610 8630 8650 8670 8li90 :I
94 B710 8730 8750 8770 8790 8810 8831 8851 8872 8892 2
3
3
4
4
"
4
4
4
95 8913 8933 8954 8974 8995 9016 9036 9007 9078 9099 2
"
9162
'97 9338 9354 9376
'98 9550 9572 9594
99 9712 9795 9817
9183
9397
9616
9840
9204
9419
9638
9863
9226
9441
9661
9886
9247
9462
9683
9908
9268
9484
9705
9931
-9290
9506
9721
9954
9311
9528
9750
9977
:I
"
1I
2
2
"
4
5
9
9
9
6
6
6
6
8
8
8
8
9
10
10
10
10
6
7
1
7
8
9
9
9
11
11
11
11
12
12
12
IS
13
14
14
14
16
16
16
16
11 13 U 17
11
12
12
12
13
14
14
14
16
15
16
16
17
17
18
18
12 15 17 19
_---13 16 17 19
13 16 17 20
13 16 18 20
l4 16 18 20
INDEX
Acetate ions, effect upon ionisation
of acetic acid, 30.
Acetates, reactions of, 397.
Acetone, 399, 492, 615.
Acetylacetone test, 597.
Acetylene, 498.
Ammonium mercurithiocyanate
reagent, 228, 294, 295; prep.
of, 228, 294.
Ammonium
molybdate reagent,
Ammonium molybdate-quinine
sulphate reagent, 389; prep.
of, 389.
Ampholytes, 10.
Analysis, macro, 141; micro, 141;
semimicro, 141; of alloys, 449;
of liquids (solutions). 455
(elementary), 487 (semirnicro),
553: of insoluble substances,
556; of solid and non-metallic
substanees, 489; spot, 189;
technique of, macro, 143,
micro, 189, semimicro. 165.
Analytical operations, macro, 143;
micro, ]89; semimicro, 165.
Anions, see Acid radicals.
Anthranilic acid reagent, 609.
Antilogarithms, table of, 650.
Antimony, 246; antimonie, reactions of, 249; antimonious,
reactions of, 247: special tests
for small amounts of, 250.
Apparatus, for spot test analysis,
194; macro, 155; micro, 189;
semimiero, 165, 187.
/'
Aqua, 21; regia, 448.
Arsenate, reactions of, 392: reduc
tion of (in analysis), 4;,2, 484
(semimicro),507.
Arsenic, 237; arsenic, reactions of,
240: arsenious, reactions of,
237; special tests for small
amounts of, 241.
oJ'"
_/~
<:>or
'
_/.~
(,~ror::>"?;rZ2?~",,#''\C'''/_
~~..J;f.'?;-.
~\1\)I.)'t\m~\\1\\, \)~Il.
Cells, calculation of e.mJ. of
voltaic, 90; concentration, 90;
oxidation-reduction, 91.
\~\,~\\~\,t1\,
Index
Colloidal state, 134, 135.
Colloids, 135; lyophilic, 137; lyophobic, 137.
Colour, 'changes of, by heating,
491; reactions with cobalt
nitrate, 387, 494.
Coloured compounds, commonly
occurring, 490.
Common ion effect, 29.
Comparator, 105; Lovibond, 105.
Complex cyanides, decomposition
of, 500, 559.
Complex hydroxide ions, 55.
Complex ions, 51; calculations involving, 57; instability constants of, 52; table of
instability constants of, 57.
Concentration limit, 195.
Concentration of reagents, 633.
Conductance, 12; equivalent, 12;
equivalent, and dissociation
constant, 21, 22; limiting, 13;
specific, 12.
Conjugate acid-base pair, 9, 125.
Copper, 224; hydroxide test, 406;
reactions of cupric, 225; sulphide suspension, prep. of,
343.
Coprecipitation, 45, 140.
Counter ions, 137.
Course of instruction, abbreviated
for elementary students, 431,
459 (semimicro).
Cupferron reagent, 264, 599; prep.
of,265.
~~...
losl; f(~r~
9'sa :I.9..:!:
41'5~
408,.
546.
\~.~\~\~~~~
p-Dimethylaminobenzene-a
phenylarsonic acid reagl
603; prep. of, 603.
p-Dimethylaminobenzylide
rhodanine reagent, 215, 5
prep. of, 216, 580.
Dimethylgiyoxime reagent,
262, 285, 583, 594; prep.
253. 262, 286, 637.
,8,8-Dinaphthol reagent, 407; prep.
of, 407.
Dinitro-p-diphenylcarbazide reagent, 230; prep. of, 231.
Diphenylamine reagent, 365; prep.
of, :365.
Diphenylcarbazide reagent, 274,
312,395; prep. of, 275, 312.
Diphenylcarbazone reagent, 220;
prep. of, 221.
Diphenylthiocarbazone (or Dithizone) reagent, 211; prep. of,
212.
Dlatr:ibution 1~l1V~
.z?"
",-/_?~,.3Y.::";::
131;
/,~
npplioations
DJthlOxami~e
,
. reagent,
RubeaulC aCId reagent.
see
\\\~~\~I\~)',\~\.,\\\,\\\,\\\,
1)1.)l.
Dialysis, 136.
Dichromates, reactions of, 393.
Digestion, 140.
654
Arsenite, reactions of, 392.
Atomic weights, table of, 632.
Auric compounds, reactions of, 579.
Centrifugation,
170;
advanta
-0S
of, 170.
-'.
0,
169; electric,
hand, 171; theory of,
'I ;
use of, 172_
Centrifuge tubes, 165, 174; cle" ning of, micro, 193; heating: )f
solutions in, 192; micro, I - I.
Ceric compounds, reactions of, 6' "I.
Cerous compounds, reactions f,
607.
Charcoal block, 143; reducti, ,s
upon, 144, 433, 462 (sel"Imicro), 493.
Chemical equations, see Equatioll>!.
Chemical formulae, see Formulae.
Chloramine-T, 446.
Chlorates, reactions of, 366, 540_
Chlorides, reactions of, 352.
Chlorine water, 635; equivalent
solution, 358, 420.
Chloroplatinates, reactions of, 581.
Centrifuge,
of, 23l.
Cadmium, 229; dry test for, 231;
reactions of, 229.
Calcium, 303; reactions of, 303.
Carbide, 498.
Carbonate, reactions of, 326.
Carborundum, 562.
Cells, calculation of e.m.f. of
voltaic, 90; concentration, 90;
oxidation-reduction, 91.
(semimicro).
Co agel, 137.
Coagulation, 135; value, 138.
Cobalt, 279; reactions of, 279.
I ~2
Cobalticyanide, 500.
Index
Colloidal state, 134, 135.
Colloids, 135; lyophilic, 137; lyo.
phobic, 137.
Colour, .changes of, by heating,
491; reactions with cobalt
nitrate, 387, 494.
Coloured compounds, commonly
occurring, 490.
Common ion effect, 29.
Comparator, 105; Lovihond, 105.
Complex cyanides, decomposition
of, 500, 559.
Complex hydroxide ions, 55.
Complex ions, 51; calculations in
volving, 57; instability con
stants of, 52; table of
instability constants of, 57.
Concentration limit, 195.
Concentration of reagents, 633.
Conductance, 12; equivalent, 12;
equivalent, and dissociation
constant, 21, 22; limiting, 13;
specific, 12.
Conjugate acid-base pair, 9, 125.
Copper, 224; hydroxide test, 406;
reactions of cupric, 225; sul
phide suspension, prep. of,
343.
Dialysis, 136.
Dichromates, reactions of, 393.
Digestion, 140.
Index
ectro}ysis. 2.
ectrolytes, 2.
ectrolytic dissociation, theory of,
2,4, 17.
'
in micro
analysis, 193, 202; in 5emi
micro analysis, 181.
Gas reactions in spot analysis, 193,
202.
Gel, 137.
Gold, see Auric compounds.
Gram equivalent weight, see Equivalent weight.
Index
Group separation (advanced),
general scheme in presence
of phosphates, etc. (Table I),
505; (Table II), 511.
Group separation tables (advanced):
Group I (Table III), 512;
Group II, separation of subgroups (Table IV, Method A),
513 or (Table IVA, Method
B), 515; Group IIA (Table V),
517; Group lIB (Table VI),
519 or (Table VIA), 521;
Group IlIA (Table VIl), 523;
Group IIlB (Table VIII), 524
or (Table VIllA), 527; Group
IV (Table IX), 529 or
(Table IXA), 532; Group V
(Table X), 533.
Group separation tables (advanced,
including "rarer" elements):
Group I in presence of TI and
W (Table I), 576; Group II
in presence of Mo, Au, Pt,
Pd, Se and Te (Table II, III
and IV), 589, 590, 591 and
592; Group IlIA in presence
of Ti, Zr, Ce, Th, U and V
(Table V), 611; Group IIIB,
notes on precipitation in presence of TI, V and Mo, 612;
Group V, notes on detection
of Li in, 615.
Group separation (elementary),
general scheme (Table S), 450.
Group separation tables (elementary): Group I (Table I), 217;
Group IIA (Table II), 233 or
(Table IIA), 224; Group lIB
(Table III), 256 or (Table
IIIA), 257; Group IlIA
(Table IV), 277; Group IHB
(Table V), 297; Group IV
(Table VI), 307; Group V
(Table VII), 323.
Group separation (semimicro),
general scheme (Table SM.S),
482.
Group separation tables (semimicro): Group I (Table SM.I),
217; Group IIA (Table
SM.HA), 258; Group lIB
(Table SM.IIIA), 258; Group
IlIA (Table SM.IV), 278;
657
;8
Index
4~3,
micro), 490.
I Magnesium nitrate reagent, 239,
,
241, 386; prep. of, 638.
npregnated reagent paper, 198.
lCrustation, 144.
Magneson I reagent, 313; prep. of,
ldicator, 10 I; narrow range, 102;
313.
universal, 102; wide range, Magneson II reagent, 313.
102; table of colour changes Manganese, 287; manganous, reand pH ranges of, 103.
actions of, 288.
uIigo solution, prep. of, 416, 638; Manganous nitrate--sil\rer nitrate
test, 399.
reagent, 321; prep. of, 322.
ldole reagent, 340; prep. of, 340. Manganous sulphate~phosphoric
lfusible white precipitate, 212.
acid reagent, 368; prep. of,
lSoluble substances, analysis of,
369.
556; preparing a solution of, Mannitol-bromothymol blue test,
56!.
376; reagent, prep. of, 377.
lStability constants of complex Marsh's test, 242, 250.
ions, 52; table of, 57.
Mass action, law of, 18, 19; appli,dates, reactions of, 370, 539; test
cation to solutions of weak
for, 547.
electrolytes, 20, 21, 22.
lllides, reactions of, 358.
Mercuric chloride paper, prep. of,
,dine, distribution between water
245.
and an organic. solvent, ]31, Mercury. 212, 2J8; mercuric, re134; solution, prep. of, 636.
actions of, 219 ; mercurous,
,nic mobilities, 16; strength, 23,
reactions of, 212.
24.
Metal ions, analytical classification
,nic product of water, 97; at
of, 205.
various temperatures, 99.
Metallic hydroxides, as weak bases,
mis~tion. theory of complete, 17,
130.
>::.:~~T,-.:~;_.::
g;~~~~:.,~~.
_;:,-'.'
'1.;: _~-
::!:'r::_~,;;_~~,;:~t,:----.-
'_i_
:'_;_:_'~___;.;.~,~~t.~~~.t.~_-_;_.
____ -:-"_~~-:.t
- .. ___
-~~~_
.~
... _
f=~~_i~~~?~~:~::'9:~: 1~ ~::~n ~
Index
..
_..
.'
--ur--~7:--:
~
- ..... . 1;;:. .
~-
..
-'",,'J'- ~- ----
. :"_--_
r; :-;-T'<=~';:-~
~;_:~i,=:'::"t~
- ,--:---;"-,,~_,.-,,,,~
SIi~f(~!ti~~~~~I~~illr;i~~
."_1''''_
~"'
..~
OC-7.
659
'if.t
~E:)~~t~j
!=t:U~-= j_~:::,I_n-:J.-~"~_~:':i__ "i'>~'"
_
_)_~>""F'I"
:&~M_
I.-.
;0
Index
Index
Reinsch's test. 246, 251.
Resorcinol test. 406.
RF values. 616.
Rhodamine-B reagent. 248; prep.
of, 249.
661
662
Index
Sulphanilic acid-IX-naphthylamine
reagent, 340; prep. of, 340.
Sulphates, reactions of, 377.
f,
254; stannous, reactions f,
252.
Titan yellow reagent, 314; pr, p.
of, 314.
Titanic compounds, reactions "f,
598.
Titanic sulphate solution, prep. (Jf,
414, 598.
Titanium chloride reagent, 349;
prep. of, 349.
Transfer capillary pipette, 190.
Transport number. 15.
Triethanolamine, 307, 308, 52 '.
531.
Tungstates, reactions Df, 574.
663
lndez
Washing, by rre"cBniation, 158.
Wet reactions, 154.
Whatman filtration accelerator,
Ultra-filtration, 136.
Ultramicroscope, 135.
Uranyl compounds, reactions of,
604.
Zinc, 291; hy,iroxide, precipitation and solution of, 44; reactions of, 292.
Zirconium-alizarin lake test, 362.
Date'
; " (I.
1\1.
UhaARY
I0 6I '
-<63____...l
LI ~?:__..:.....
INDEX TO TABLES-continUtd
O. ADVANCED ANALYSIS
PA.GE
490
496
502
534
549
416
428
505
511
568
512
513
515
517
519
521
523
[Oontinued
INDEX TO TABLES-continued
PAGB
524
527
529
532
533
553
554
.556
j'. C