4.

14 Chlorides, CI
most chlorides are soluble in water. Mercury(I) chloride, Hg2 Cl2,
Solubility soluble in cold
silver chloride, AgCI, lead chloride, PbCI2 (this sparingly
is
but readily soluble in boiling water), copper(I) chloride,
CuCl, bismuth
and mercury()
oxychloride, BiOCl, antimony oxychloride, SbOCl,
oxychloride, Hg2OClh, are insoluble in water.
CI reactions To study these reactions use a 0.1M solution of sodium chloride, NaCl.

cc H SO 1. Concentrated sulphuric acid considerable decomposition of the chloride

occurs in the cold, becoming complete on warming, with the evolution of
HCI gas hydrogen chloride,
CI+HSO4 HCI +HSO
of
The product is recognized (a) by its pungent odour and the production
white fumes, consisting of fine drops of hydrochloric acid, on blowing
across the mouth of the tube, (b) by the formation of white clouds of
ammonium chloride when a glass rod moistened with ammonia solution is
held near the mouth of the vessel, and (c) by its turning blue litmus paper red.

MnO(OH)2 + HzS04 2. Manganese dioxide and concentrated sulphuric acid if the solid chloride is
mixed with an equal quantity of precipitated manganese dioxide,' concen-
Clh gas trated sulphuric acid added and the mixture gently warmed, chlorine 1s

,The commercial substance (pyrolusite) usually contains considerable quantities of

chlorides.
202
 Chloride 4.14
evolved which is identified
by its suffocating odour,
colour, its
bleaching of moistened litmus paper, and
yellowish-green
iodide-starch paper blue. turning of potasSium
MnO(OH)2 +2H,S0, +2Cl Mn2t +Clh1 +230;
AgNO3 3. Silver nitrate solution
+ 3H;0
insoluble in water and white, curdy precipitate of silver chloride,
white AgCl in dilute nitric AgCl,
Solution, in potassium acid, but soluble in dilute ammonia
solutions (see under cyanide (POISON) and in sodium
silver, Section 3.6, reaction 1): thiosulphate
CI+Ag ^AgCl|
AgCI+2NH [Ag (NH,)]+CI
Ag(NH)lt +Cl+2H* AgCIL+ 2NH; »

The solution obtained after

quickly to avoid a serious explosion!dissolving in ammonia should be discarded
If the silver chloride (Cf. Section 3.6, reaction 1.)
and then shaken with
precipitate is filtered off, washed with distilled water,
sodium arsenite solution, it is converted into
silver arsenite (distinction from silver yellow
bromide and silver iodide, which are
unaffected by this treatment). This be used as
may a
confirmatory test for
a chloride.

3AgCl+AsOj» Ag, AsO+3CI

Pb CH3C00)2 4. Lead acetate solution white precipitate of lead chloride,
concentrated solutions (see under lead, Section 3.4, reaction PbCl2,
from
white PbCl2 1)
2C1 +Pb2* PbClh
Chromyl chloride test 5. Potassium dichromate and sulphuric acid (chromyl chloride test) assemble
a small, preferably all-glass, distillation apparatus as shown in 1
Selective for CI
Place 10 ml 2M sodium hydroxide in the recipient test-tube. The sample
which contains chloride must be in solid form. Mix the sample thoroughly
with about three times as much powdered potassium dichromate, and
place the mixture in the distillation flask. Add an equal volume ofconcen
trated sulphuric acid and warm the mixture gently." Deep-red vapours of
chromyl chloride, CrO2Clh, are formed. When reacting with the sodium
hydroxide in the recipient tube, chromyl chloride is converted to chromate

ions, resultingin a solution. The presence of chromate can be

yellow
verified by appropriate reactions (cf. Section 4.33).
ml of the solution in the test tube
One simple test is the following: acidify 2
followed by 1ml of 10%
with ml M sulphuric acid, add 1ml amyl alcohol
4 the organic layer turns blue (see
hydrogen peroxide. After gentle shaking
because of the danger
out in the presence of chlorates
This test must not be carried reaction 1).
chlorine dioxide (Section 4.19,
offorming explosive also be used, but owing to its highlyinflammablecharacter andit
ether may
Diethyl treatment),
removed by special
possible presence of peroxides
(unless previously acetate.
alcohol or, less efficiently, amyl
the
is preferable to employ amyl
203
4.15
Reactions of the anions
diphenylcarbazide
test (Sectio
the
Alternatively,
4.33, reaction 4).
Section
applied. that chloride was
9) may be
indicates
reaction distillate
the
4.33,
ofchromate in volatile liquid (b.p. 116.5°C
The
formation
chloride is a
as chromyl
the sample,
present in
2Cr0,C,1+3H20

4C1+Cr20; + 6H*
CrO+2C1
+2H,0
+40H
CrO,C% to the reaction:

be liberated, owing
also
Some chlorine may

3C1,1 +2Cr* +
7H20
+Cra0;+14Ht
6C1
of the test.
decreasesthe sensitivity which yield colourles
and this to the free
halogens,
give rise chloride exceeds
Bromides and iodides
ratio of iodide to
if the
solutions with sodium
hydroxide; and chlorine is
chloride formation
is largely prevented
1:15, the chromyl fluoride, CrO,F?.
rise to the volatile chromyl
evolved. Fluorides give be absent or removed.
and hence should
which is decomposed by
water, formed. Chlorates
chloride may be
interfere, as nitrosyl
Nitrites and nitrates

must, of course,
be absent. do not respond
of mercury, owing
to their slight ionization,
The chlorides with the chlorides of
to CrO;Clh occurs
conversion
to this test. Only partial
tin.
lead, silver, antimony, and 2.54 place a few
follows. Into the tube of Fig.
The spot-test technique is as of the test solution
evaporate a drop or two
milligrams of the solid sample (or dichromate and a drop of
in it), add a small quantity of powdered potassium
column about I mm long of a 1%
concentrated sulphuric acid. Place a
the capillary of the stopper
solution of diphenylcarbazide in alcohol into
chloride evolved
and heat the apparatus for a few minutes. The chromyl
causes the reagent to assume a violet
colour.
Sensitivity 1.5ug Cl.
Concentration limit 1 in 30 000.

4.15 Bromides, Br
Sohubility ,silver, mercury(), and copper(I) bromides are insoluble in water.
Lead bromide is sparingly soluble in cold, but more soluble in boiling water.
All other bromides are soluble.
Br reactions study these reactions use a 0.lM solution of potassium bromide KBr.

cc H2SO4 1. Concentrated sulphuric acid if concentrated sulphuric acid is poured on

some solid potassium bromide, first a reddish-brown solution is formeu
Br2 gas then reddish-brown bromine
vapour accompanies the hydrogen bromid

The iodine reacts with the chromic acid yielding iodic acid: the the
presenceof concentrated sulphuric acid and especially on warming, o r u
tes latter
chlorine from chlorides, regenerating iodide. This explains the failure to O1
chromyl chloride.
204
 Bromide 4.15

(fuming in moist air) which is evolved:

KBr +H2SO4 »
HBr + HSO +K*
2K Br+2H,SO4 Br21 +S01 +SO+2K* +2H,0
These reactions are accelerated by warming. If concentrated phosphoric acid
is substituted for the sulphuric acid and the mixture is warmed,
only
hydrogen bromide is formed:
KBr+HPO4 » HBr1 +H,PO4 +K*

The properties of hydrogen bromide are similar to those of hydrogen

chloride.

cc H2SO4+ MnO2 2. Manganese dioxide and concentrated sulphuric acid when a mixture of a
solid bromide, precipitated manganese dioxide, and concentrated sulphuric
Br2 gas acid is warmed, reddish-brown vapour of bromine is evolved. Bromine is
recognized (a) by its powerful irritating odour, (6) by i bleaching of
litmus paper, (c) by its staining of starch paper orange-red and (d) by the
red colouration produced upon filter paper impregnated with fluorescein

(see reaction 8 below):

2KBr +MnO2 +2H2SO4 Brat+2K* +Mn** +2S0+2H,0

3. Silver nitrate solution curdy, pale-yellow precipitate of silver bromide,
AgNO3 soluble in dilute, but readily soluble in concentrated
AgBr, sparingly
pale yellow AgBr ammonia solution. The precipitate is also soluble in potassium cyanide
but insoluble in dilute nitric acid.
and sodium thiosulphate solutions,

Br+Ag>AgBr|
in ammonia should be discarded
The solution obtained after dissolving
Section 3.6, reaction 1.)
quickly to avoid a serious explosion! (Cf.
4. Lead acetate solution white crystalline precipitate of lead bromide:
Pb(CH CO0)2
2Br+Pb* » PbBr2
white PbBr2

The precipitate is soluble in boiling water.

5. Chiorine water the addition of this reagent dropwise to a solution

Cl2 of a bromide liberates free bromine, which colours the solution orange
red: if chloroform (21ml) is added and the liquid shaken, the bromine
Br2
dissolves in the solvent and, after allowing to stand, forms a reddish-
brown solution below the colourless aqueous layer. With excess chlorine
water, the bromine is converted into yellow bromine monochloride

In practice, it is more convenient to use dilute sodium

acidified with dilute hydrochloric acid. hypochlorite solution,

205
 anions
4.15 Reactions of the

results (difference
from iodide).
solution
and a pale yellow
+Clh1 Br1 +2C1
2Br
Br21+Clh1 2BrCl1
acid on gently warming
Potassium dichrommate
and concentrated sulphuric
HSO4 + K2 Cr207
6. concentrated sulphuric acid, and potassium
cc
mixture of solid bromide,
a the evolved
a reaction 5) and passing
chlorides, Section 4.14,
dichromate (see free bromine but
Br2 gas solution, containing
a yellowish-brown
vapours into water, sometimes a pale yellow
colourless (or
no chromium,
is produced. A this
on treatment
with sodium hydroxide solution;
solution is obtained
dilute sulphuric acid, hydrogen per
the chromate reaction with
does not give carbazide reagent (distinction
alcohol, o r with the diphenyl
oxide and amyl
from chloride).
+2Cr*+8K*+7sOf+7H,o
3Br21
6KBr+K2Cr207 +7H,SO4
nitric acid oxidizes bromides to
Hot HNO3 7. Nitric acid hot, fairly concentrated (8M)
bromine:
Br2
6Br+8HNO 3Br2t +2NO1 +6NOg +4H,0
fluorescein (1)
converts the yellow dyestuff
Fluorescein test 8. Fluorescein test free bromine
or eosin (2). Filter paper impregnated
into the red tetrabromofluorescein bromine
therefore a valuable reagent for
red eosin with fluorescein solution is
a red colour.
vapour since the paper acquires
Br
HO
HO
Br 3r
COOH coOH

+4Br+4H*
+4Br
(1)
Chlorine tends to bleach the reagent. Iodine forms the red-violet coloured
iodoeosin and hence must be absent. If the bromide
is oxidized to free
no chlorine
bromine by heating with lead dioxide and acetic acid, practically
is simultaneously evolved from chlorides, and hence the test may be Con

ducted in the presence of chlorides.

2Br + Pb02 +4CH,COOH » Brat +Pb2+4CH,CO0 + 2H,0
of leaa
a of the test solution together with a few milligrams
drop
lace 2.53 and close the tube
and acetic acid in the apparatus of Fig.
1oxide which has bee
The funnel stopper carrying a piece of filter paper
n genuy.
impregnated with the reagent and dried. Warm the apparatus
circular red spot is formed on the yellow test paper.
206
 lodide4.16

Alternatively, the apparatus of Fig. 2.54 may be used; a column, about

1 mm long, of the reagent, is employed.
Sensitivity 2 pg Br2.
Concentration limit 1 in 25 000.

Fuchsin test
9. Fuschin (or Magenta) test the dyestuff fuschin

violet colour
HN
=NH, | a
H,N-
CH
bromine
forms acolourless addition compound with hydrogen sulphite. Free
violet brominated
converts the thus decolourized fuchsin into a blue or
the colourless fuchsin
dyestuff. Neither free chlorine nor free iodine affect
be employed for the
hydrogen sulphite compound, hence the reaction may
iodides.
detection of bromides in the presence of chlorides and
Place a drop of the test solution (or a few milligrams the test solid) in the
of
add 2-4 drops 25% chromic acid
tube of the apparatus shown in Fig. 2.54,
the 'head' which contains 1-2 drops of
solution and close the apparatus with
Warm the apparatus gently (do not
the reagent solution in the capillary.
the liquid in the capillary assumes a violet
allow it to boil). In a short time
colour.
Sensitivity 3 pg Br
Concentration limit 1 in 50 000.
The reagent is prepared from 0.1% fuchsin solution by just decolourizing
of 0.5M sodium hydrogen sulphite solution.
it with a few drops

4.16 lodides, I

Sohubility the solubilities of the iodides are similar to the chlorides and
hromides. Silver, mercury(), mercury(), copper(1), and lead iodides are
h e least soluble salts. These reactions can be studied with a 0.1lM solution
Ireactions KI.
of potassium iodide,
sulphuric acid with a solid iodide, iodine is liberated; on
1. Concentrated
cc H2SO4 warming, violet vapour 1s evolved, which turns starch paper blue. Some
drogen iodide is formed this can be seen by blowing across the mouth
Oxidized to brown l
of the vessel, when white fumes are produced - but most of it reduces the
Cllphuric acid to sulphur dioxide, hydrogen sulphide, and sulphur, the rela-
tive proportions of which depend upon the concentrations of the reagents.

31+2H2SO415t+SO +2H0 +SO1

I+H2SO4- HI+ HSO
91+4H2SO4 315 t+S+3SO+ 4H0
121+5H,SO4 415 t +H2St +4S0+4H,0
 the anions
4.16 Reactions o
phoe
warming with
concentrated
on
iodide is formed
Pure hydrogen
phoric acid:

I+HPO,
»
HIf +H,PO4 1odine is formed and
to the mixture, only
dioxide is added
If manganese reduced:
does not get
the sulphuric acid +2H,0
I5 1 +Mn +2S0í
31+MnO, +2H,S04 Agl
precipitate of silver iodide
solution yellow, curdy
2. Silver nitrate and in sodium thiosulphate
solutions.
AgNOs soluble in potassium cyanide
readily ammonia solution and
insoluble in
soluble in concentrated
yellow Agl very slightly
dilute nitric acid.

T+AgAgl
lead iodide, Pbl2, soluble in
3. Lead acetate solution yellow precipitate of
Pb(CHCO0)2 and yielding golden-yellow
a colourless solution,
much hot water forming
yeliow Pbl2 plates ('spangles) on cooling.
21+Pbt » Pbl2l
to a solution of
4. Chlorine water when this reagent is added dropwise
on shaking
which colours the solution brown;
an iodide, iodine is liberated, settles
a violet solution, which
brown coiour, I3 with 1-2ml chloroform it dissolves forming the
out below the aqueous layer.
The free iodine may also be identified by
characteristic blue colour it forms with
starch solution. If excess chlorine

water is added, the iodine is

oxidized to colourless iodic acid.

31+Clhf>I +2CI
I +8Cl21+9H,0 310g + 16C1+18H*
NaNO2 5. Potassium dichromate and concentrated sulphuric
acid only iodineis
K CraO7 or

(see chlorides, Section

liberated, and chromate is present in the distillate
no
brown colour, I3 4.14, reaction 5) (diference from chloride).
61+Cr20+7H,SO4 311 +2Cr +7S0 +7H,0
6. Potassium nitrite solution reagent is added
iodine is liberated when this
to an iodide solution acidified with dilute acetic or sulphuric acid (difier
from bromide and chloride). The iodine may be identified by colournin
starch paste blue, or chloroform violet.
31 +2NOz +4H* - j +2NOT +2H,O
bf
CuSO 7. Copper sulphate solution brown precipitate consisting of a mixtur
copper(I) iodide, Cul, and iodine. The iodine may be removed by t
white Cul| addition of sodium thiosulphate solution or sulphurous acid, and a nea
+
brown colour, I3 white precipitate of copper() iodide obtained.
SI+2Cu* 2Cul +lj
l +2S,0 31+S,0
ion
In practice it is more convenient to use dilute sodium hypochlorite sou
acidified with dilute hydrochloric acid.
 lodide 4.16
8.
HgCl2 Mercury (11) chloride solution
cury(TI) iodide: (POISON) scarlet precipitate of mer
Scarlet Hgl2

21+HgClh Hgl,l +2C1

note that
The
mercury(II) chloride is practically undissociated in
precipitate dissolves in excess potassium iodide, forming solution).
mercurate(II) complex: a tetraiodo-

Hgl2l+21 - [Hglal
Starch 9. Starch test iodides
a number of
are readily oxidized in acid solution
to free iodineby
OxIdizing agent oxidizing
agents; the free iodine may then be identified
by the
deep-blue colouration produced with
starch solution. The best oxidizing
blue complex agent to employ in the
spot test reaction is acidified
solution (cf. reaction 6): potassium nitrite
31+2N02 +4H* I5 +2NO1 +2H,0
Cyanides interfere because of the formation of
therefore removed before the test either cyanogen iodide: they are
carbonate solution or by by heating with sodium hydrogen
acidifying and heating:
I +CN +ICN +21
Mixdrop of the acid test solution on a spot plate with a
a

reagent and add a drop of 50% potassium nitrite solution. drop of the
A blue
colouration is obtained.
Sensitivity 2.5 ug I2.
Concentration limit 1 in 20 000.
Ce(IV) + As(11) 10. Catalytic reduction of cerium(1V) salts test the reduction of
reaction salts in acid solution by arsenites takes place very slowly:
cerium(IV)
catalysed 2Ce4+AsOj+H,O -2Ce+ AsO+2H
Iodides accelerate this change, possibly owing to iodine liberated in the
instantaneous reaction (i):
2Ce +31 » 2Ce* +i
()
reacting further according to (ii):

AsO+l +H,0 - AsO+312H (ii)

the iodide ion reacting again as in (i). The completion of the reduction is
indicated by the disappearance of the yellow colour of the cerium([V) sola-
tion. Osmium and ruthenium salts have a similar catalytic effect. ate
amounts of chlorides, bromides, sulphates, and nitrates have no infiuence
but cyanides and also mercury(II), silver, and manganese salts interfere
solution with a drop each of neutral
together
of the test
e .

Place a drop sulnhut

solution and 0.1M cerium(IV)
slightly acid 0.1M sodium arsenite
s o o n disappears.
solution on a spot plate.The yellow colour

Sensitivity 0.03 ug I .
Concentration limit 1 in 1 000 000.

209
4.17 Reactions of the anions

4.17 Fluorides,F
alkali metals and of silver, mercury.
Solubility the fluorides of the common
aluminium, and nickel are readily soluble in water, those of lead, copper,
are slightly soluble, and those of the other
iron(II), barium, and lithium
alkaline earth metals are insoluble.
solution of sodium fluoride, NaF
F reactions To study these reactions use a 0.1M
1. Concentrated sulphuric acid with the solid fluoride, a colourless, corro-
cc HSO
sive gas, hydrogen fluoride, H2F2, is evolved on warming; the gas fumes in
moist air, and the test-tube acquires a greasy appearance as a result of
the corrosive action of the vapour on the silica in the glass, which liberates
the gas, silicon tetrafluoride, SiF4. By holding a moistened glass rod in the
vapour, gelatinous silicic acid H2Si03 is deposited on the rod; this is a
product of the decomposition of the silicon tetrafluoride.
2FHS04 HFat +SO
SiO +2H,F2 -SiF1 +2H20
38iFT+3H,O 2($iF+H^SiO31 +4H*
Note that at room temperature hydrogen fluoride gas is almost completely
dimerized, therefore its formula has been written as HF. At elevated
temperatures (say 90°C) it dissociates completely to monomer hydrogen
fuoride:

H2F22HF
The same result is more readily attained by mixing the solid fluoride with an
equal bulk of silica, making into a paste with concentrated sulphuric acid and
warming gently; silicon tetrafluoride is quickly evolved.

Etching glass 2. The etching test a clean watch glass is coated the
on convex side with
paraffin wax, and part of the glass is exposed by scratching a design on the
wax with a nail
wire. A mixture of about 0.3 g fluoride and 1 ml con-
or
centrated sulphuric acid is placed in a small lead or platinum crucible, and
the latter immediately covered with the
watch glass, convex side down. A
little water should be poured in the
upper (concave) side of the watch glass
to prevent the wax from
on a boiling water
melting. The crucible is very
gently warmed (best
bath). After 5-10 minutes, the hydrogen fluoride
have etched the glass. This is wI
readily seen after removing the paraffin wax
by holding above a flame or with hot
surface of the water, and then breathing upon tne
glass.
The test may also be
conducted in a small lead
close-fitting lid made from lead foil. A small hole capsule,
of about provided
with a
3 mm diameter
1s
pierced in the lid. About 0.1g
centrated sulphuric acid are suspected fluoride and a few drops cOn
Ot placed the clean capsule, and a smal pi
in
glass
(e.g. a microscope slide) is
waming very gently (best on a waterplaced it will hole
over the in the lid. Upon
spot appears on the bath) be found that an etcneu
210 glass where it covers the hole.
 Nitrate 4.18
Chlorates. silicates, and borates
absent. interfere and should therefore
be
3. Silver nitrate
solution no
precipitate, since silver fluoride is
water. soluble in
CaCl 4.Calcium chloride solution
white,
CaF2, sparingly soluble in acetic acid,slimy
but
precipitate of calcium fluoride.
whte CaF
hydrochloric acid. slightly
more soluble in dilute

2F +Ca** CaF2 »

FeC 5.Iron(1ll) chloride solution white

crystalline precipitate of sodium
whte Nas FeFsl hexafluoroferrate(III)
soluble in water. The
from concentrated solutions of
fluorides, sparingly
with ammonium
precipitate does not give the reactions of iron
(e.g.
thiocyanate), except upon acidification.
6F+ Fes* +3Nat Naz[FeF6]! »

Zalizarin 6. Zirconium-alizarin lake

salts hydrochloric acid solutions of zirconium
test
coloured reddish-violet by alizarin red S or
are
ake decoiourizes
aluminium, Section 3.23, reactions 8 and 9 and under by alizarin (see under
6.18, reaction 12); upon adding a solution of a fluoride zirconium, Section
the colour of such
solutions changes immediately to a
pale yellow (that of the liberated alizarin
sulphonic acid or alizarin) because of the formation of the colourless
hexafluorozirconate(TV) ion ZrF6. The test may be performed on a
spot plate.
Mix
together on a spot plate 2 drops each (equal volumes) of a 0.1%
alizarin red S (sodium alizarin
sulphonate) and 0.1% zirconyl chloride
solution. Upon the addition of a drop or two of the fluoride
solution the
zirconium lake is decolourized to a clear yellow solution.

4.18 Nitrates, NO

Solubility all nitrates are soluble in water. The nitrates of mercury and
bismuth yield basic salts on treatment with water; these are soluble in
dilute nitric acid.
NOg reactions The reactions can be studied with a 0.IM solution of potassium nitrate
KNO.
cc H2SO4 1. Concentrated sulphuric acid reddish-brown vapour of nitrogen dioxide,
and pungent acid vapour of nitric acid which fumes in the air, are formed
red NO2 gas
the the reagent. Dilute sulphuric acid has r
on heating solid nitrate with
effect (difference from nitrite):

4NO + 2H,SO, 4N021 +Ot +2s0+2H,o

cc HSO4+Cu 2. Concentrated sulphuric acid and bright copper turnings on heating these
with the solid nitrate, reddish-brown fumes of nitrogen dioxide are
blue colour (Cu2*)
or
evolved, and the solution acquires a blue colour owing to the formation of
red fumes (NO2) copper(I1) ions. A solution of the nitrate may also be used; the sulphuric
211
4.18 Reactions oft the anions

then added very cautiously.

acid is

4H,SO, 3Cu 3Cu 2NO1 + 4SO4 + 4H20

2NO,
2NO + 0,12N0,1
sulphuric acid (brown ring
solution and concentrated
cc H,SO4 + FesO 3. Iron( 11) sulphate Add 3 ml freshly
either of two ways: (a)
Iest) this test is carried out in to 2 ml nitrate solution,
solution of iron(1I) sulphate
brown ing
prepared saturated acid slowly down the side of the
and pour 3 5ml concentrated sulphuric
beneath the mixture. A brown ring
test-tube so that the acid forms a layer
Add 4 ml concentrated sulphuric acid
will form where the liquids mect. (b) and cool the
2ml nitrate solution, mix the liquids thoroughly
slowly to
from the tap. Pour a saturated solution
mixture under a stream of cold water
of the tube so that it forms a layer
of iron(11) sulphate slowly down the side
on top of the liquid. A brown ring
will form at the zone of contact of the two
liquids.
The brown ring is due to the formation [Fe(NO)]*.On shaking and
of the
oxide is evolved,
warming the mixture the brown colour disappears, nitrogen
is unreliable in the
and a yellow solution of iron(III) ions remains. The test
and chromate (see Section
presence of bromide, iodide, nitrite, chlorate,
5.9, reactions 3 and 4).

2NO + 4H,S04 + 6Fe 6Fe* +2NOT + 4SO+4H,0

Fe2 +NO1 [Fe(NO)]*
Bromides and iodides interfere because of the liberated halogen; the test is
not trustworthy in the presence of chromates, sulphites, thiosulphates,
iodates, cyanides, thiocyanates, hexacyanoferrate(II) and (III) ions. All of
these anions may be removed by adding an excess of nitrate-free Ag,S04
to an aqueous solution (or sodium carbonate extract), shaking vigorously
for 3-4 minutes, and filtering the insoluble silver salts, etc.
Nitrites react similarly to nitrates. They are best removed by adding a little
sulphamic acid (compare Section 4.7, reaction 10). The following reaction
takes place in the cold:

H,N-HS03 +NO -N21 +SO+H*+ H,O

The spot-test technique is as follows. Place a
crystal of iron(I) sulphate
about as large as a pin head on a
spot plate. Adda drop of the test solution
and allow a drop of concentrated sulphuric acid to run in at the side of the
drop. A brown ring forms round the crystal of iron(II) sulphate.
Sensitivity 2.5 ug NOD.
Concentration limit 1 in 25 000.
Reduction of nitrates 4. Reduction of nitrates in alkaline medium ammonia is evolved (detected
by its odour; by its action
upon red litmus paper and upon mercury)
nitrate paper; or by the tannic
acid-silver nitrate test, Section 3.38, reaction
7) when a solution of a nitrate is boiled with zinc dust or gently warmed with
aluminium powder and sodium
obtained by the use of Devarda's
hydroxide solution. Excellent results are
alloy (45% 5% A1,50% C).
Zn,
212
 Nitrate 4.18

Ammonium ions must, of course, be removed

by boiling the solution with
sodium hydroxide solution (and,
preferably, evaporating almost to dry-
ness) before the addition of the metal.

NOg +4Zn +7OH+6H,0 NH,1+4[Zn(OH)4

3NO +8Al + 5OH +18H,0 3NH1 +8[AI(OH)4|
Nitrites give a similar reaction and may be removed most simply with the
aid of sulphamic acid (see reaction 3). Another, but more expensive,
procedure involves the addition of sodium azide to the acid solution; the
solution is allowed to stand for a short time and then boiled in order to
complete the reaction and to expel the readily volatile hydrogen azide:

NO +N +2H N2t +N,O1 +H20

N +Ht HN31
Other nitrogen compounds which evolve ammonia under the above
conditions are cyanides, thiocyanates, hexacyanoferrate(I) and (1I) ions.
These may be removed by treating the aqueous solution (or a sodium
carbonate extract) with excess of nitrate-free silver sulphate, warming the
mixture to about 60°C, shaking vigorously for 3-4 minutes and filtering
from the silver salts of the interfering anions and excess of precipitant. The
excess silver ions are removed from the filtrate by adding an excess of
sodium hydroxide solution, and filtering from the precipitated silver ovide.
The filtrate is concentrated and tested with zinc, aluminium, or Devarda's
alloy.
Attention is directed to the fact that arsenites are reduced in alkaline
solution by aluminium, Devarda's alloy, etc., to arsine, which blackens
mercury() nitrate paper and also gives a positive tannic acid-silver nitrate
test. Hence neither the mercury(T) nitrate test nor the tannic acid-silver
nitrate test for ammonia is applicable if arsenites are present.

Diphenylamine 5. Diphenylamine reagent (CgHs NH CsHs) pour the nitrate solution

carefully down the side of the test-tube so that it forms a layer above the
blue ring solution of the reagent; a blue ring is formed at the zone of contact of the
two liquids. The test is a very sensitive one, but unfortunately is also given
by a number of oxidizing agents, such as nitrites, chlorates, bromates,.
iodates, permanganates, chromates, vanadates, molybdates, and iron(11
salts.
Nitron 6. Nitron reagent (diphenyl-endo-anilo-dihydrotriazole CoH16Na)
white ppt CH-N
CsHs
N
HC

C,H
with solutons
white crystalline precipitate of nitron nitrate C2oHN,HNO,
chlorates, perchlorates,
of nitrates. Bromides, iodides, nitrites, chromates,
213
4.19 Reactions of the anions

thiocyanates, oxalates, and picrates also yield insoluble compounds, and

hence the reaction is not very characteristic.

7. Action the result varies with the metal. The nitrates of sodium
Heating
and
of heat
potassium evolve oxygen (test with glowing splint) and leave solid
decomposition nitrites (brown fumes with dilute acid); ammonium nitrate yields dinitrogen
oxide and steam; the nitrates of the noble metals leave a residue of the metal,
and a mixture of nitrogen dioxide and oxygen is evolved; the nitrates of the
other metals, such as those of lead and copper, evolve oxygen and nitrogen
dioxide, and leave a residue of the oxide.

2NaNOg 2NaNO2 +O1

NHNO3» N,O1 + 2H,0
2AgNO2Ag+2NO,t+O2t
2Pb(NO3)2 ^ 2PbO + 4NO,1 +O,t
Zn 8. Reduction to nitrite test nitrates are reduced to nitrites by metallic zincin
acetic acid solution; the nitrite can be readily detected by means of the
reduction to NO
sulphanilic-acid-1-naphthylamine reagent (see under nitrites, Section 4.7,
reaction 11). Nitrites, of course, interfere and are best removed with
sulphamic acid (see reaction 3 above).
Mix on a spot plate a drop of the neutral or acetic acid test solution with
a drop of the sulphanilic acid reagent and a
drop of the 1-naphthylamine
reagent, and add a few milligrams of zinc dust. A red colouration
develops.
Sensitivity 0.05 Hg NOg.
Concentration limit 1 in 1000000.
 4.6 Reactions of the anions

4.6 Sulphides, S
of alkali metals are soluble
Solubility the acid, normal, and polysulphides
solutions exhibit an alkaline reaction because af
in water; their aqueous
hydrolysis.
S+H,02 SH +OH
SH+H0#H^S +OH
The normal sulphides of most other metals are insoluble; those of the
alkaline earths are sparingly soluble, but are gradually changed by contact
with water into soluble hydrogen sulphides:
CaS+H,O- Ca2t +SH" +OH
The sulphides of aluminium, chromium, and magnesium can only be
prepared under dry conditions, as they are completely hydrolysed by water.
AlS +6H20- 2A1(OH)3l + 3H,S
The characteristic colours and solubilities of
many metallic sulphides
ave already been discussed in connection with the reactions of the cations
in Chapter 3. The sulphides of iron,
zinc, and the alkali
manganese, metals
are decomposed by dilute hydrochloric acid with the evolution of hydrogen
sulphide; those of lead, cadmium, nickel, cobalt, antimony, and tin(TV)
require concentrated hydrochloric acid for decomposition; others, such as
mercury(II) sulphide, are insoluble in concentrated hydrochloric acid, but
dissolve in aqua regia with the
separation of
sulphide in insoluble sulphides may be detected sulphur. The presence of
by reduction with nascent
hydrogen (derived from zinc or tin and
and hydrogen hydrochloric acid) to the metal
sulphide, the latter being identified with lead acetate
(see reaction 1 below). An alternative method paper
is to fuse the sulphide with
anhydrous sodium carbonate, extract the mass with
the filtered solution with water, and to treat
when a purple colour will
freshly prepared sodium nitroprusside
solution,
be obtained; the
may also be treated with lead nitrate sodium carbonate solution
solution when black lead sulphide
precipitated. is

Sreactions For the study of these reactions a 2M solution of sodium sulpn

NaS 9H20 can be used.
HCI 1.Dilute hydrochloric or
H2S gas which may be identified sulphuric acid hydrogen sulphide gas is evoiv
of filter by its characteristic odour, and the blackenuE
paper moistened with lead by
acetate solution:
S+2Ht »H,St
HaS+ Pb* PbS! + 2H*
»

Alternatively, a filter paper moistened

yellow: with cadmiun1 acetate
souuo
turns

186
HS+Cd* Cás. +2H*
-
 Sulphide 4.6
A more sensitive test is
by attained
use of the sodium
plumbate(tI) solution, prepared by adding sodium tetrahydroxo
until the initial hydroxide to lead acetate
precipitate of lead hydroxide has just dissolved:
Pb2+20H Pb(OH);
Pb(OH) +20H[Pb(OH)1"
Pb(OH)4+H,S PbS| + 20H+2H,0
Hydrogen sulphide is a good reducing agent. It reduces
potassium permanganate, (2) acidified (1) acidified
potassium triiodide potassium dichromate, and (3)
(iodine) solution:
2MnO+ 5H,S+6H* 2Mn* +5S| + 8H,O
(1)
Cr0+3H,S +8H* 2Cr3+ +3S +7H,O
(2)
I +H2S3I+2Ht +SI
(3)
In each case sulphur is precipitated. Small quantities of chlorine
produced in
(1) and (2) if the hydrochloric acid is other than may be
this is avoided by very dilute;
using dilute sulphuric acid.
AgNO 2. Silver nitrate solution black
in cold, but soluble in precipitate of silver sulphide AgS, insoluble
black Ag,S hot, dilute nitric acid:
s2-+2Ag* AgaS
3. Lead acetate solution black precipitate of lead
reaction 2). sulphide PbS (Section 3.4,
4. Barium chloride solution no
precipitate.
5. Silver when a solution of a
sulphide is
silver foil, a brown to black stain of silver brought is
into contact with a bright
black Ag S stain sulphide
obtained more expeditiously by the addition of aproduced.
The result is
few
hydrochloric acid. The stain may be removed by rubbingdrops
of dilute
the foil with
moist limne.

Na,Fe(CN)sNO 6. Sodium nitroprusside solution

(Naz/Fe(CN),NO]) transient with
colour in the presence of solutions of alkalis. No reaction occurspurple
purple colour
solutions of hydrogen sulphide or with the free
gas: if, however, filter
paper is moistened with a solution of the reagent made alkaline with
sodium hydroxide or ammonia
solution, a purple colouration is produced
with free hydrogen sulphide.

S+[Fe(CN),NO]2 - [Fe(CN)sNOS]*
The spot-test technique is as follows. Mix on a spot plate a drop of the
alkaline test solution with a drop of sodium nitroprusside. A violet colour

187
4.7 Reactions of the anions
impregnated
with an ammoniacal (sM)
Alternatively, filter paper
appears. be employed.
sodium nitroprusside may
solution of
Sensitivity 1 ug Na2S.
Concentration limit 1 in 50 000.
is converted hu
NN-Dimethyl-p-phenylenediamine
test
NN-Dimethyl- 7. Methylene blue in strongly acid solution into the
chloride and hydrogen sulphide
phenylenediamine iron(III)
water-soluble methylene blue:
dyestuff,
blue colour
N(CH)
(CH,)N +6Fe
+H,S+
NH HN

(CH,N NICH,
6Fe*+NH+4H*+

This is a sensitive test for soluble sulphides and hydrogen sulphide.

Place a drop of the test solution on a spot plate, add a drop of
concentrated hydrochloric acid, mix, then dissolve a few grains of NN-
dimethyl-p-phenylenediamine in the mixture (or add 1 drop 1% solution
of the chloride or sulphate) and add a drop of 0.5M iron(III) chloride
solution. A clear blue colouration appears after a short time (2-3
minutes).
Sensitivity 1 ug H2S.
Concentration limit 1 in 50 000.

NaN3+3 8. Catalysis of iodine-azide reaction test solutions of sodium azide,

reaction catalysed NaN3, and of iodine (as I5) do not react, but on the addition of a trace
of a sulphide, which acts as a catalyst, there is an immediate evolution
of nitrogen:
2N +I 31+3N1
Thiosulphates and thiocyanates act similarly and must therefore be absent.
The sulphide can, however, be separated by precipitation with zinc or
cadmium carbonate. The precipitated sulphide may then be
introduccu
say, at the end of a platinum wire into a semimicro test-tube or centrifuge
tube containing the iodine-azide reagent, when the evolution of nitrogen
will be seen.
Mix a drop of the test solution and a drop of the reagent on a watch glas
An immediate evolution of gas in the form of fine bubbles occurs.
Sensitivity 0-3ug Na2S.
Concentration limit 1 in 166000
4.24 Sulphates, SO
Soubility the sulphates of barium, strontium, and lead are practically
insoluble in water, those of calcium and mercury(1I) are slightly soluble,
and most of the remaining metallic sulphates are soluble. Some basic
sulphates such as those of mercury, bismuth, and chromium are also
insoluble in water, but these dissolve in dilute hydrochloric or nitric acid.

Of these three sulphates, that of strontium is the most soluble.

223
4.24 Reactions of the anionsS
and hygroscopic liquid, of specifs
colourless, oily,
Sulphuric acid
is a
concentrated acid is a constant boilin
ling
commercial,
gravity 1.838. The pure, c. 98% acid. It is miscibi
338°C and containing
mixture, boiling point considerable heat. on
point
proportions with the evolution of
with water in all in a thin stream into the
the acid should always be poured
mixing the two, heavier acid, steam may be suddenlu
is poured into the therefO
water (if the water
with it some of
the acid and may
generated which will carry
cause considerable damage). sulphate
a 0.]M solution of sodium
To study these reactions use
S0 reactions
Na2SO4 10H,O.
barium sulphate, BaSO
white precipitate of
BaCl2 1. Barium chloride solution
in warm dilute hydrochloric
under barium, Section 3.31), insoluble
(see soluble in boiling, concentrated
white BaSO acid and in dilute nitric acid, but moderately
hydrochloric acid:

SO+Bat BaSOL
to the solution acidified
The test is usually carried out by adding the reagent
and phosphates are not
with dilute hydrochloric acid; carbonates, sulphites,
Concentrated hydrochloric acid or
precipitated under these conditions.
of barium
concentrated nitric acid should not be used, as a precipitate
chloride or of barium nitrate may form; these dissolve, however, upon
filtered from
diution with water. The barium sulphate precipitate may be
when
the hot solution and fused on charcoal with sodium carbonate,
sodium sulphide will be formed. The latter may be extracted with water,
and the extract filtered into a freshly prepared solution of sodium nitroprus-
side, when a transient, purple colouration is obtained (see under sulphides,
Section 4.6, reaction 6). An alternative method is to add a few drops of
very dilute hydrochloric acid to the fused mass, and to cover the later
with lead acetate paper; a black stain of lead sulphide is produced on the
paper. The so-called Hepar reaction, which is less sensitive than the above
two tests, consists of placing the fusion product on silver foil and moistening
with a little water, a brownish-black stain of silver sulphide results.

BaSO4+4C+Na,CO NazS+BaCO +4COo

Na,S 2Nat +S2
2S+4Ag+O2 +2H,02AgaSI+40H
A more efficient method for decomposing most
sulphur compounds i
heat them with sodium or potassium, and then test the solution of the
product for sulphide. The test is rendered sensitive by heating the substance
with potassium in an ignition
tube, dissolving
the melt in water, ana t
for sulphide by the nitroprusside or methylene blue reactions (see under
sulphides, Section 4.6, reactions 6 and 7). Heating substances with potas
Sum metal is a DANGEROUS operation and must be carried out w
appropriate equipment under supervision. not
The above tests (depending upon the formation of a sulphide) are
exciusive to sulphates but are given by most sulphur compou
224
 Sulphate 4.24
however, the barium sulphate
acid is employed, then the precipitated in the
presence of hydrochloric
reaction may
be used as a
sulphates. confirmatory test for
Pb(CH3CO0)2 2. Lead acetate solution
white precipitate of lead
white PbSO
in hot concentrated sulphate, PbSO4, soluble
sulphuric acid, in solutions of ammonium
ammonium tartrate (see under lead, Section acetate and of
hydroxide solution. In the last case sodium 3.4, reaction 5), and in sodium
formed, and on acidification with
out as the chloride. If hydrochloric tetrahydroxoplumbate(11)
acid, the lead
is
any of the aqueous solutions of crystallizes
the precipitate are acid-
ified with acetic acid and
chromate is precipitated (seepotassium chromate solution added, yellow lead
under lead, Section 3.4, reaction
6).
so+Pb* »PbSO4
AgNO3 3. Silver nitrate
solution white, crystalline precipitate of silver
white Ag2 S04
AgSO4 (solubility 5.8 gl7' at 18°C), from concentrated solutions. sulphate,
so +2Ag- AgSO4
Sodium 4. Sodium rhodizonate test barium salts yield
rhodizonate test with sodium rhodizonate
reddish-brown precipitate
a
(see under
barium, Section 3.31, reaction 7).
removal of colour Sulphates and sulphuric acid cause immediate decolourization 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 0.5% aqueous solution of
sodium rhodizonate. Treat the reddish-brown spot with a drop of the acid
or alkaline test
solution. The coloured spot disappears.
Sensitivity 4 4g SO4
Concentration limit 1 in 10000.
KMnOA on BaSO4 5. Potassium permanganate-barium sulphate test if barium sulphate is
precipitated in a solution containing potassium permanganate, it is coloured
cannot be reduced
pink (violet) by adsorption of some of the permanganate. The permanganate
which has been adsorbed on the precipitate cannot be reduced by the
common reducing agents (including hydrogen peroxide); the excess of
potassium permanganate in the mother liquor reacts readily with reducing
agents, thus rendering the pink barium sulphate clearly visible in the colour
less solution.
Place 3 drops test solution in a semimicro centrifuge tube, add 2 drops
1 drop barium chloride
0.02M potassium permanganate solution and
solution. A pink precipitate is obtained. Add a few drops 3% hydrogen
acid solution (in the latter case it will be
peroxide solution or 0.5M oxalic
warm on a water bath
until decolourization is complete).
necessary to
is clearly visible.
Centrifuge. The coloured precipitate
Sensitivity 2.5 ug SO.
Concentration limit 1 in 20000.

solution (POISON) yellow precipitate of basic

Hg(NOg)2 6. Mercury (I1) nitrate
mercury(II) sulphate:
yellow ppt
SO+3Hg* +2H20- HgSO4 2HgO +4H*
225
4.25 Reactions of the anions

by suspensions of barium or lead

This is a sensitive test, given even

sulphates.