--

pi 32&C.3L :2 2
- "- . . _. ____-____ ____
'table !J
iteactions of Group i Cations

Cations
Reagents
K+
I
Na+
,
NHt
I
Mg++
NaHCiH,Oe White crystalline
precipitate
KHC(,H,Oe
- White crystalline
precipitate
NH"HC,H"Oe
-
Na
a
rCo(N0
2
)6) Yellow crystalline
precipitate
K2Na[ Co(N0
2
)s)
- Yellow crystall ine
precipi tate
(NH')2Na[Co(N02)6]
-
KH
2
SbO, White crystall ine
precipitate
NaH
2
Sb0
4
White amorphous
precipitate
HSbO
a
White crystalline
precipitate
Mg (H
2
Sb0
4
h
CHaCOOH+
+ (CHaCOOhZn +
+ (CH3COOhU02
-
*
Yellowish crystal-
line precipitate
CHaCOONa
(CH
a
COO)2Zn .
. 3(CH
a
COO)2U0
2

-9H
2
O
- -
-
KOH, NaOH
I
NHa evolved IWhite amorphous pre-
cipitate Mg (OHh
,
I
White amOl'pUOUil Hed-brown precipi-
Nessler'!! reagent
precipitate
tate
K2 [Hgld+KOH
Mg(OHh
[/Hg" ]
NH2 I
"Hg/
White crystalline
-
Na2HPO, + NH,OH
in
precipitate
presence of NH,CI
MgNH,PO,
Greenish yellow pre-
- -
8-Hydroxyquinoline
eipitate
.
Mg(C
9
HsNh
Dark blue precipi-
- - -
p-N i trobenzene-azo-re-
tate or colour
sorcinol
No precipitate
-
-
(NHil2COa+ NH,CI
Not volatile
Volatile
Not volatile
Not volntile
Action of heat on salts
-
Yellow
Violet
Flame colouration
\
* At high K+ concentrations CHaCOOK ,(CHSCOO)2UOS may he precipitated.
-- -
no
Chapter I I I. Cations of Group II
The precipitate is soluble in acids, including acetic.
5. Microcrystalloscopictest. Add a drop ofdilute H
2
S0
4
solutioll
to a drop of a calcium salt solution on a glass slide and evapo-
rate slightly until a rim appears
around the drop. Examine the
crystals of gypsum, CaS04.2H20,

under the microscope. Dependent
on the Ca++ concentration, their
form may be as shown in Fig. 23
or 24.
The reaction detects0.4 Ca++.
The dilution limit is 1:25,000. Itis

usually possible by this test tode-

Fig. 24. Crystals of CaS04.
2H
zO tect Ca++ in the presence of BaH
formedfrom relativelyconcentrat-
and Sr++, because barium and
ed solutions
strontium sUlphates are precipitat-
ed in the form of small crystals,
,easily distinguished from the characteristic large gypsum crystals.
- 6. Flame test. Volatile calcium salts colour a colourless flame
brick-red.
38. Analysis of Mixtures of Group II Cations
The effects of the most important reagents on Group II
are compared in Table 1t.
The table shows that carbonates, phosphates, oxalates, and sul-
phates of Group II cations are sparingly soluble in water. Of the chro-
mates, BaCrO,and SrCr04are sparingly soluble and CaCrO, is readily
soluble. The sulphates areincreasinglymoresoluble in the sequence
Ba, Sr, Ca.
With the aid of these reactions several different methods of ana-
lyzingamixtureor'GroupIIcationscanbe devised; onlythesimplest
is considered here. It is discussed in the description given below.
Table 12 illustratesitschematically; it demonstrates theseparations
,during the variolls analytical operations and gives the student
a better picture of the course of the analysis as a whole.
Of course, the student must not work merely from the table, without
having read carefully the corresponding points in the description of
the analytical procedure. This would inevitably lead to errors, as
the table gives no indications regarding the conditions and tech-
niques for carrying out the individual operations. Moreover, the
individual operations are explained in the description; if they are
not understood, the work becomes mechanical.
The description of the analytical procedure and the table allow
.for the possible presence of Group I cations together with Group II
Table 11
Reactions of Group II Cations
NazCO
a
and K
2
co
3
1BaCO
a
SrCO
a
CaC0
3
.. - .......-
White precipitate Na2HPO, WhiteprecipitateIWhite precipitate
DaHPO, SrHPO, CaHPO.
Cations
Reagents
Ba++ Sr++ Ca++
(NH,hCOa White precipitate Whiteprecipitate White precipitate
BaCO
a
SreO
a
CaC0
3
Whiteprecipitate H
2
SO, andsoluble Whiteprecipitate White precipi-
sulphates BaSO,insoluble SrSO,insoluble tate* CaS04
in acids in acids
Whiteprecipitate White precipitate CaS04 -
(turbidity) (turbidity)
BaSO, formed SrSO, formed
at once after a delay
White precipitate White precipitate White preeipitate
BaC
2
0
4
(NH
4
hC
2
0
4
SrC
2
0
4
CaC
2
O.
Yellowprecipitate K
2
CrO, Yellowprecipitate -
SrCr04 BaCr04
Yellowprecipitate K2
Cr207+ -
BaCrO,
or K
2
CrO,+
+CHaCOOH
K
4
[Fe(CN)sl+
+CHaCOONa
White precipitate
+N,H,OH+
- **
Ca(NH,MFe(CN)sJ
+NH,CI
I<'lame colour IYellow-green ICrimson I
* PreCipitate forms only if the solution is not too dilute .
A precipitate may form athigh Ba++ concentrations.
------
Reactions of Group
(II Cations
Table 17
Reagents
-----
Al+++
Cations
Cr+++ Fe+++
Fe++ Mn++
Cations
Zn++ Co++ Ni++
~
White ppt. (NH,hS Grey-green or Black ppt.
Black ppt. Flesh-coloured White ppt. mack ppt. Black ppt.
AI(OHh grey-violet ppt. Fe2Sa
FcB ppt. MnS ZnS CoS NiS
Cr(OH)a
I-I
2
S in presenceof
HCOOH and
HCOON,H4
NaOH or KOH AI(OH)a
-
Cr(OHh
Reduction to
Fe++, S ppt.
Brown ppt.
Fe(OH)a
Greenish ppt.
turningbrown
:Fe(OHh
ZnS -
White ppt. White ppt.
turningbrown Zn(OHh
Mn(OHh
-
Blue ppt. of Greenish
basic salts ppt.
Ni(OH)2
KOH or NaOH in No ppt. (AlOii Cr(OHh :Fe(OHh No ppt. Pink ppt. Ni(OHh
Fe(OHh Mn(OH)2
excessonboiling formed) (ZnOi- Co(OHh
formed)
KOH or NaOH in
excess in pres-
ence of H
2
0
2
on
boiling
No ppt. (AlOi
formed)
No ppt. (CrOi-
formed, solution
yellow)
NH.OH Al(OHh Cr(OH)a
NH.OH, excess inIAl(OIlh
presence of am-
monium sal t8
Cr(OHh
CH
3
COONa on White ppt. INo ppt. ***
boiling CHaCOO(OH):"AI
K
2
CO
a
, Cr(OHh
(NH4)2C03
Fe(OH)a
Fe(OIIh
Fe(OH)a
Brown ppt.
CHaCOO(OHhFe
Fe(OH)a
Brown ppt. Brown ppt. No ppt.(ZnOii- Dark brown Ni(OHh
formed) MnO(OHh Fe(OHh ppt. Co(OHh
/
Fe(OHh Mn(OHh Zn(OHh Basic salts Basic salts
- ** -* -** **
*
-
-
White ppt. White ppt. Basic salts Basic salts Green ppt.
turningbrown MnC0
3
NiCO
a
---
---
---
--
300 Chapter IV. Cations o/Group //1
Cations
Reagents
A!+++ Fe+++ Cr+++
Yellowish
.****
AIPOq
Green ppt. White ppt.****
FeP0
4


- No ppt. Blue ppt. Kq(Fe(CN)I:l]

K
3
[Fe(CN)I:l] -
Formation of yel- - Oxidizing agents -
low (CrO;j-) or
orange (Cr20i-)
solution
Borax or Emerald green -

bead
* Oxidation products. Fe(OH)a or MnO(OHl2. gradually precipitated.
*'" Complex ions [Zn(NHs)a]++, [Co(NHa)6]++, [Ni(NHa)sJH tormed.
*** Cr+++ partially precipitated in the presence of Al+++ and FeH +.
**** AIPO, and FeP04 precipitates are insoluble in CHsCOOH. All the other
phosphates are soluble inacetic acid.
this makes analysis much easier and the results are more reliable.
For example, if anunknown solution iscolourless itcannot contain
any considerable amounts of the coloured ions mentioned above.
Similarly, if a white precipitate is formed with it may
be concluded that the unknown solution does not contain Fe+++,
Fe++, NiH or Co-+ ions, as their sulphides are black. If the colour
of the precipitate is pure white, the presence of AI+H or Zn
H
isto
be expected; Cr+
H
is probably present if the precipitate is grey-
green, andMn
H
if itispink. Ofcourse, different ions present togeth-
er may mask each other's colours, but often such masking does
not occur. Observation of colours makes analysis much easier. On
the other hand, errors are often revealed if the colours of the solu-
tions or precipitates are taken into consideration. For example, if
60. Analysis ot mixtures ot Group //I cations 301
Continued
Cations
Zn++ Co++ NIH
Fe++ Mn++
,
I I
Green ppt. Violet ppL White ppt.
Cos(P04h
White ppt. White ppt.
Ni
s
(P0
4
h
Zn3(PO,.h Mns(P04h Fes(P04)z
Pale green Green ppt. White ]lpt.
ppt.
White ppt. White ppt.

Fe2[Fe(CN)61
--. .
Dark red ppt.. Yellow-
Yellow ppL
brownppt.
Brown Blue ppt.
Fe3[Fe(CN)6b
Black ppt. Dark brown
Ni(OHh
- Fe+++ IPurpleviolet
ppt. Co(OHh
(MuO;!) or
brown ppt.
MnO(OHh
solution
Brown Blue
Violet or ame-
ish
Brownorgreen-
thyst
I
Fe+++, FeH , Co++ and NiH are not found during analysis of Group
III but the sulphide precipitate is black, it is obvious that some
kindof errorwasmade. Thisexampleshowstheimportanceof noting
the colours both of the unknown solution and of the precipitates
formed during analysis.
Valuable indications of the probable presence or absence of cer-
taincations insolution are also sometimes given by pH determina-
tions. For example, if a solution is strongly alkaline (pH>10)
and does not smell of ammonia, itcannotcontaiI} any cationswhich
do not form amphoteric hydroxides. Therefore in such cases only
aluminium, cromium and zinc of the Group III cations need be
tested for, as these are present in alkaline solutions in the form of
AlO;, CrO; (or and ZnO;- anions. If the alkalinity of the
solution is due to the presence of ammonia, or ammonia with an
ammonium salt, it may contain Fe
H
, Mn
H
, [Zn(NHs)6]++,
Table 22
Group IV Cations
Reactions of
Reagents
Ag+
Cations
Pb++ ' Hgt+
H
2
S in acid solu-
tion,or(NH,hS
Black ppt. Ag
2
S Black ppt. PbS Black ppt.
HgS+Hg
HCI and chlorides White ppt. of
AgCI, soluble
in NH!.OH
White ppt. of
PbCI
2
, soluble
in hot water
White ppt. of
Hg
z
C1
2
, black-
ened by
NH"OH
KOH or NaOH
NH,OH inexcess
Brown ppt. AgzO
-----------
Formation of
[Ag(NHah]+
ions
White ppt. of
Pb(OHh,
soluble in ex-
cess alkali
White ppt.
Pb(OHh
Black ppt. HgzO
Black ppt.
[NHzHgJNOa+
+Hg
H
2
O -
H
2
SO, - Whiteppt. PbSO, White ppt.
Hg
2
SO,
Whiteppt.,grad-
Black ppt. Ag SnCl
z
or Na2Sn02 -
ually black-
ens, HgzCl
z
-+

-
-"--
Cations
1-
Hg++ Cu++ Cd++ Bi+++
Black ppt. of Black ppt. CuS Yellow ppt. CdS Black ppt. Bi
2
S
a
HgS, insolu-
ble in HNO
a
I
-
- -
-
Yellowppt. HgO Blue ppt. of White ppt. of White ppt. of
Cu(OH)z Cd(OH}z....
Bi(OHh"
White ppt. Formation of Formation of White ppt. of
[NH2Hg]Cl deep blue
[Cd(NH
a
),J++ basic salts
[Cu(NHa)41 ++ ions
ions
/
- - -
White ppt. of
BiOCI,solublein
I1xcess acid
-
- -
-
Whiteppt.,grad- -
- Black ppt. Bi
ually black-
ens, Hg
z
C1
2
-+ .
-+Hg
Formation otcomplex [Ag(NHa)2]+ lons.
Formation of black mixture ot +Hg.
...Not formed In the presence of glycerol.
Fermed in the presence of glycerol.
24-584