Professional Documents
Culture Documents
SECONDARY SCHOOLS
BY
QUALITATIVE ANALYSIS.
W. P. I
PREFACE
MANY teachers of chemistry in attempting to furnish a satis-
factory course in Qualitative Analysis for secondary schools
have been confronted by the lack of a text-book sufficiently
simple, and at the same time sufficiently complete for their
purpose. The many excellent text-books on Qualitative Analy-
sisalready published have been specially adapted to the needs
of the more mature college student.
This work, therefore, has been made as simple as possible,
while providing a course of study adequate for secondary
schools. Methods of basic analysis in the presence of phos-
phates and oxalates have been omitted. The separation of
the members of the iron group has been greatly shortened and
simplified by the introduction of hydrogen peroxide to oxidize
the chromium to the acid state. Obscure and complicated
reactions have been omitted.
The first half of a one year's course in chemistry should be
devoted to a general introduction to the theory of the science,
and to a close study of the most common nonmetallic radicals.
The second half year should deal with the basic radicals and
should be combined with the study of Qualitative Analysis.
If descriptive chemistry of the basic radicals is studied by
237577
^4.\ i : PREFACE
...
.
Laboratory Directions . . . -. 12
Group I 24
III .... .
.... 48
Group IV 57
Group V . 64
Group VI 71
V. ACID ANALYSIS
Group I, Division
Division B
A ........88 88
89
Group .
......
I,
Group II . .91
Group III 93
radicals ;
NH SO NO
4, 2, 2, compound radicals.
A Basic Radical is a metal, or
any radical behaving like
a metal. Examples :
Ag, Cu, Ca, Na, and NH 4 the last
so classified because it behaves like such simple radicals
as Na, K, and Li.
An Acid Radical is a nonmetal, or any radical behaving
like a nonmetal. Examples :
Cl, Br, I, SO 2 NO 2
,
.
* The definitions of acids, bases, and salts, here given, are based on
the definitions given by Professor C. L. Jackson in his course in Descrip-
tive Chemistry at Harvard College.
7
8 METHODS OF NAMING
as hydroxides.
Examples :
* ~
from 2 HOH, Q~ (SO 2) sulphuric acid.
is bivalent.
The terminations -ous and -io are used in certain cases
with the first or specific name of a salt to distinguish
between two salts composed of the same elements in
different proportions. Examples Hg2 Cl 2 mercurous chlo-
:
QUESTIONS
1. What is valence or quantivalence?
2. What is qualitative analysis V
3. What is quantitative analysis?
4. Show by examples the difference between a basic and an acid
radical.
5. What is a base or basic hydroxide ? Give four examples.
6. What is an alkali ? Give four examples.
7. Give examples of at least two substances that are not alkalies
in constitution, but show an alkaline reaction with litmus paper.
Can you suggest a reason for this ?
8.- Name a salt that gives an acid reaction with litmus paper.
9. What is the difference between an acid salt and a normal salt?
10. Relying on the rules for naming already learned, give the
correct chemical names for the following acids: HC1, IIBr, III,
HF, H 2 S,
HN0 HC H
3, 2 3 2,
II 2 CO3 ILPO 4
, , II 3 AsO 4, HC1O 3 ,
II 2 S(> 4 ,
HNO H 2,
SO 3 HC1O 2
2 ,
.
cals, and give the names and symbols of the salts formed :
i i ii in
Ag, NII 4 Ca, ,
Bi.
14. What
an hydroxide ?
is
15. What
meant by neutralization ?
is
Berthollet's Law
When two substances can form a substance insoluble
or volatile under the conditions of the reaction, that in-
soluble or volatile substance will be formed till one of
the factors is exhausted.
LABORATORY DIRECTIONS
To each student should be assigned a locker in which
he can safely keep his apparatus, and he should be held
strictly responsible for all breakage and loss.
The reagents for each individual should include the
following :
DiluteH S0 HN0 2 4, 3,
HC1.
Concentrated H SO HNO 2 4, 3,
HC1.
HC H2 3 2,
NH OH, 4
NH 4 C1,
To be kept in Solution
Alcohol, Limewater,
Ammonic molybdate, Magnesic sulphate,
Ammonic oxalate, Mercuric chloride,
Baric chloride, Mercurous nitrate,
Baric hydroxide, Potassic ferricyanide,
Bromine water, Potassic ferrocyanide,
Calcic sulphate, Potassic sulphocyanide,
Chlorine water, Silver nitrate,
Cobaltous nitrate, Sodic chloride,
Disodic phosphate, Sodic hydroxide,
Hydrogen peroxide, Stannous chloride.
Lead acetate,
(For the preparation of solutions see the Appendix.)
14 LABORATORY DIRECTIONS
and his bulb tube by closing one end of such a tube and
blowing gently into the tube till the end is blown into a
bulb. Also, that he make a glass spatula by closing one
end of a glass tube, melting the other end in the flame,
and quickly flattening the melted end by pressing it with
the round end of the steel forceps.
TO THE STUDENT 15
laboratory work.
2. Provide yourself with a towel and also with a large
Abbreviations
Points to be Observed
Whether a precipitate is formed.
Whether the precipitate is soluble in an excess of the
reagent.
* dilute acids unless otherwise directed.
Always use
IR. QUAL. ANAL. 2 17
18 GROUPING THE BASES
these solutions.
2. Can HC1 be used to precipitate one of these bases ?
AgNO 3 + H 2 S =
Cu(N0 3 ) 2 + H 2 S =
AsCl 3 + H 2 S
Fe 2 CJ 6 + H 2 S
Co(N0 8 ) a + H 2 S =
Ba(N0 3 ) 2 +H 2 S =
NaCl + H 2 S
8. The following
bases behave like Cu: Hg, Pb, Bi, Cd,
and are classified with Cu as Gr. II, Div. A, or the Copper
Group.
4. Sn and Sb behave like As, and this class is called
Gr. II, Div. B, or the Arsenic Group.
5. What is the general reagent for Gr. II ?
6. How may Div. B be separated from Div. A ?
20 GROUPING THE BASES
AgN0 3 +NH 4 OH =
Cu(NO 3 ) 2 + NH 4 OH =
AsCl 3 + NH 4 OH
Fe 2 Cl 6 + NH 4 OH
Co(N0 3 ) 2 + NH 4 OH =
Ba(N0 3 ) 2 + NH 4 OII =
NaCl + NH 4 OH
To the same solutions, add NH 4 C1 and then NH 4 OH.
1. Which of the above bases are precipitated by NH 4 OH ?
2. When NH 4 C1 is previously added, is the effect of
NH OH 4
modified in any way ?
3. The bases classified with Fe a are Fe, A1 2 and Cr2 , .
and these four bases form Gr. Ill, or the Iron Group.
AgN0 3 + NH 4 OH + (NH 4 ) 2 C0 3 =
Cu(N0 ) 2 + NH 4 OH +(NH 4 ) 2 C0 3 =
3
AsCl 3 + NH 4 OH + (NH 4 ) 2 CO 3
Fe 2 Cl 6 + NH 4 OH + (NH 4 ) 2 CO 3
Co(N0 3 ) 2 + NH 4 OH + (NH 4 ) 2 C0 3 =
Ba(NOg) 2 + NH 4 OH + (NH 4 ) 2 CO 3 =
NaCl + NH 4 OH +(NH 4 ) 2 CO 3
1. In separating the groups by use of the general re-
agents, the first group must be removed before attempting
to precipitate the next. ? Why
2. Which of the bases are precipitated by (NH 4 ) 2 CO 3 ?
3. Under what conditions ?
Perform
the following experiments in separations,
making use of the knowledge gained in the foregoing
experiments :
as before.
5. Mix AgNO 3 Cu(NO 3 ) 2
, , Fe 2 (NO 3 ) 6 , Co(NO 3 ) 2 and ,
Ha(NO 3 ) 2 .
Separate.
6. Mix AsCl 3 and Ba(NO 8 ) 2 .
Separate.
In what form was the Ag precipitated ? Cu ? Fe ?
Co ? Ba ? As ?
The methods used in the separation of the above elements
groups.
VI VI VI
O
II
(Fe), Fe 2 , A1 2 ,
2
.
Na, K, L'I, NH 4
.
Preliminary Experiments
Use about 2 any given solution for each experi-
c.c. of
ment. Keep and systematic record of results,
a careful
and whenever a change occurs on addition of reagent, ask
" "
yourself the question, What is it ?
a
Hg2 Mercury. Mercurous Compounds
To a solution of Hg2 (NO 3 ) 2 add :
precipitates :
Hg 2 (N0 3 ) 2
Hg2 (N0 3 ) 2
Hg2 (N0 3 ) 2 +H 2 S
Hg 2 Cl 2 + 2 NH 4 OH = Hg2 NH 2 Cl + NH 4 C1 + 2 H 2 O
QUESTIONS
On experiments.
1. What is the solubility of IIg 2 Cl 2 in H O?
2
2. In NH OH ?
4
3. In dilute acids?
Ag Silver
1. HC1 =
a. Filter and expose a portion of the precipitate to
sunlight.
b. Reduce another portion on charcoal in blowpipe
flame.
2. NaCl =
Filter and test solubility in hot H 2
O.
26 BASIC ANALYSIS
3. NH 4
C1 =
Filter and add NH 4 OH to pp., pouring the solution
through two or three times until pp. is all dis-
solved.
Now add HNO 3 to solution. What is the precipitate?
Filter and expose pp. to sunlight.
4. H 2
S =
5. Any soluble chloride =
precipitates :
AgN0 3 + HC1 =
AgN0 + H S =
3 2
QUESTIONS
1. In how many and what ways can you precipitate Ag as a
chloride ?
2. What is the solubility of AgCl in H O?
2
3. InNH OH? 4
12. Name any important uses of Ag and Ag compounds that you can.
GROUP I 27
II
Pb Lead
To a solution of Pb(NO 3 ) 2 or Pb(C 2 H 3 O 2 ) 2 add:
1. HC1 =
Filterand add hot H 2 O to pp. until it disappears.
Allow to cool. Does all the substance crystallize
out ? How can you determine this ?
precipitates :
Pb(N0 3 ) 2 + HC1
Pb(C 2 H 3 O 2 ) 2 + NaCl
Pb(NO 3 ) 2 + NaCl
Pb(N0 3 ) 2 + H 2 S
Pb(C 2 H 3 +(NH 4 )
2) 2 2
S =
Pb(N0 ) +
3
H 2
80 4 2
Pb(NO 3 ) 2 + K 2 Cr0 4
QUESTIONS
1. What is the solubility of PbCl 2 in cold H O? 2
2. In hot H O? 2
3. InHCl?"
4. InNH OH? 4
5. Name and describe three compounds of Pb that may be pre-
cipitated to prove the presence of Pb.
8. Lead pipes are much used for water pipes. What is the danger
of such use for drinking water?
Pb + O + H 2O = FbO H 2 2
.
Analysis. Gr. I
BiOCl. Add more HC1, and the last two substances will
redissolve if present. The filtrate contains Grs. II-VI,
and is marked and set aside. Wash the precipitate with
hot H 2 O, and test the wash water with H 2 SO 4 . A white
GROUP I 29
TABULATION, GR I
Reagent
Precipitate Filtrate
Precipitated by 2 S,
H
in acid solutions, as sulphides in-
soluble in (NH 4 ) 2 S (yellow).
Preliminary Experiments
ii
3. Cu =
foil
4. SnCl 2 =
precipitates :
HgCl 2 + H 2 S
HgCl 2 + (NH 4 ) 2 S =
HgCl 2 + SnCl 2 .
=
HgS + HN0 3
QUESTIONS
1. What is the solubility of HgS in HNO 3
?
15. Explain the use of the terminations -ous and -ic in naming
Hg 2 Cl 2 and HgCl 2 .
Hg - Cl - Cl
Hg
Hg - -
I
Cl Cl
Mercurous chloride Mercuric chloride
in
Bi Bismuth
To a solution of BiCl 3 or Bi(NO 3 ) 3 add :
1. NH 4 OH =
Filter, dissolve pp. in a few drops of cone. HC1, and
add the solution to a large quantity of H 2
O. The
oxychloride of bismuth is formed. What is its
?
symbol
GROUP II DIVISION A 83
2. H 2
S =
Filter and determine solubility of one portion of pp.
in hot HNO 3 and ,
of a second portion in HC1.
3. (NH 4 ) 2 S in excess =
To (NH 4 ) 2 S add HC1. What is deposited ?
precipitates :
BiCl 3 + NH 4 OH
Bi(N0 3 ) 3 + NH 4 OH =
BiO 3 H 3 + HC1
BiCl 3 + H 2
BiCl 3 + H 2 S
Bi(N0 3 ) 3 + H 2 S
(NH 4 ) 2 S 2 * + HC1 =
QUESTIONS
1. What is the solubility of Bi 2 S 3 in HNO 3
?
2. In (NH 4)2
S?
3. In H 0?2
muth?
7. For what is it used ?
8. How does Bi occur in nature?
9. What is fusible alloy and for what used ?
* See
page 13, note.
IR. QUAL. ANAL. 3
34 BASIC ANALYSIS
ii
Cu Copper
1. NH 4 OH = Salt of cupra-aniraonium
2. H2S =
a. Filter and test solubility of one portion in HNO 3
.
:
precipitates
*
Warning. KCN is a fatal poison, and care must be taken that it
does not come in contact with abrasions of the skin. KCN must not
be added to an acid solution, as cyanogen gas, which is a deadly poison,
may be liberated. All KCN solutions must be poured into the sink after
using.
GROUP II DIVISION A 35
QUESTIONS
1. Describe three different tests for Cu.
2. What is the solubility of CuS in HC1 ?
3. InHNO 3 ? 4. In(NH 4 ) 2 S? 5. In KCN?
Cd Cadmium
To a solution CdCl 2 CdSO 4 , , or Cd(NO 3 ) 2 add :
1. H 2
S =
Filter and pour on pp. HNO 3
.
2. (NH 4) 2 S =
Filter and pour on pp. sol. of KCN.
3. KCN in slight excess =
4. NH 4 OH =
5. NH OH 4
in excess =
Separation of Cd from Cu
Mix a few drops of CuSO 4 and CdSO 4 Add . NH OH4
in excess. What is formed? Add a solution of KCN
with constant stirring until blue color just disappears.
Any excess of KCN must be avoided. Now pass H 2 S
through the solution. A yellow precipitate of CdS is
formed. CuS is not precipitated in presence of KCN.
36 BASIC ANALYSIS
precipitates :
CdCl 2+ H2S
4 + (NH 4 ) 2 S
> =
Cd(NO 3 ) 2 + NH 4 OH =
CdCl 2 + KCN
QUESTIONS
1. What is the solubility of CdS in H 2O?
2. InHNO,? 3. In (NH 4 ) 2 S? 4. In KCN?
SnS 2 Sb 2 S 3 Sb 2 S 6 As 2 S 8 and As 2 S 5
, , ,
Make hole in filter,
,
.
Reject the wash water. This process should wash out all
free HC1. Make hole in filter and wash the precipitate
into a test tube with as little (NH 4 ) 2 S (yellow) as pos-
sible. Pour through the filter several times to remove all
Make a hole in the filter and wash pp. into beaker with
HNO 3
. Heat to boiling. All but HgS will be dissolved.
a solution of KCN
until the last drop causes the blue color
to disappear on stirring, and add
2 S,
when a yellow H
precipitate of CdS will indicate Cd.
* KC10 3 in the presence of H 2 S0 4 is dangerously explosive.
Warning. , ,
Take care that all solutions used with KC10 3 are free from H 2 SO 4 .
38 BASIC ANALYSIS
TABULATI
H. II, DIV. A
i(N0 3 ) 2 Cd(N0 3 ) 2
of H S0
2 4.
'
i(N0 8 ), Cd(N0 3 ),
light excess.
blue,
u pres.
doubt, test
rtion of sol.
HC,H 3 2 .
K 4 Fe(CN) 6 ;
n pp.,
u pres.
40 BASIC ANALYSIS
yellow pp., .-. Gr. II, Div. A, pres., but probably limited
to Cd and trace of Pb from Gr. I. Filtrate was rejected.
Pp. was washed by decantation. Pp. -f HNO 3
dis-
solved entirely, .-.
Hg abs. Partially evaporated with
a few drops H 2 SO 4 , w. pp. PbSO 4 , .-. Pb pres. Fil. -f
NH OH 4
in excess, no
pp., .-. Bi abs. No change in
color, .-. Cu probably abs. Small portion of sol. acidified
with HC 2 H 3 O 2 and K 4 Fe(CN) 6 added. No change,
.-. Cu abs. Remainder of sol. + H 2 S gave yellow pp.
ofCdS, .-. Cdpres.
Solution contains Pb and Cd.
QUESTIONS
1. What is the general reagent for Gr. II, Div. A?
2. Give the names, symbols, and colors of all precipitates pro-
duced by the general reagent for this group.
3. What is the reaction of HNO 3 on PbS?
4. OnCdS?
5. On Bi 2 S 3 ?
6. Reaction of HgCl 2 on SnCl 2 ?
7. How would you separate Cu from Cd?
8. Hgfrom Cu?
9. Bifrom Cu?
10. Pbfrom Cu?
Precipitated by H 2 S,
in acid solutions, as sulphides
soluble in (NH 4 ) 2 S (yellow).
Preliminary Experiments
II IV
Anything else ?
42 BASIC ANALYSIS
Hg2 Cl 2 .
tact. When all action ceases, remove the Ft foil, and wash
the foil in warm H 2 O and HC1. The Sn will dissolve from
the Ft as SnCl 2 Four off solution and add HgCl 2
. .
:
precipitates
SnCl 2 + H 2S =
SnCl 4 + H 2 S =
SnS + (NH 4 ) 2 S 2 * = (NH 4 ) 2 SnS 3
(NH 4 ) 2 SnS 3 + 2 HC1 = SnS 2 + 2 NH 4 Cl + HS
2
Sn + HC1 =
SnCl 2 + HgCl 2 = Hg2 Cl2 +
SnCl 2 + Hg 2 Cl 2 = 2Hg +
QUESTIONS
1. What is the solubility of SnS in (NH 4 ) 2 S (yellow)?
2. How does the iron nail affect the SnCl 4 on boiling ? Explain
fully.
3. What is reduction ?
7. What is bronze ?
8. Britannia metal ?
9. Pewter?
10. Name one use for SnCl 2 .
in
Sb Antimony. Antimonious Compounds
3. Add H 2 S to SbClg =
Determine if careful dilution with H2O will aid the
precipitation. Filter aoid test solubility of one portion
in (NH 4 ) 2 CO 3 and second portion in 4) 2
S (yellow).
(NH
4. Add H 2 O to SbClg =
precipitates :
SbClg + H2S =
SbClg + H 2 =
Sb 2 S 3 + 3(NH 4 ) 2 S 2 = 2(NH 4 ) 3 SbS 4 + S
2(NH 4 ) 3 SbS 4 + 6 HC1 = Sb 2 S 6 + 6 NH 4 C1 + 3 H2S
QUESTIONS
1. What is the solubility of Sb 2 S3 in (NH 4) 2
S (yellow)?
2. In (NH 4 ) 2 C03 ?
3. Describe two tests for Sb.
:
precipitates
AsCl 3 + H2S =
+ 3(NH 4 ) 2 C0 8 =(NH 4 ) 8 As0 8
+ (NH 4 ) 2 S 2 =(NH 4 ) 2 As 2 S 5
+ 3H0
H2S
QUESTIONS
1. What is the solubility of As 2 S 3 in (NH 4) 2
S?
2. In (NH 4) 2
CO 3 ?
3. With
a knowledge of the solubilities of the sulphides of As, Sn,
and Sb, how the sulphides of As may be separated from the
state
other sulphides of this group.
4. Give a symbol for an arsenate.
5. For an arsenite.
6. On which side of a symbol is the acid radical, and on which
side is the basic radical?
Pp. (Sjc)
SnS SnS a Sb2 S 3 Sb 2 S 5 As 2 S 3 Fil.
Pp. SnS 2 Sb 2 S 5 ,
.
Wash, add KC10 3 Fil. = As S 2 3 and As 2 S 5 in
QUESTIONS
How is this group originally precipitated?
1.
(Fe), Fe 2 , A1 2 , Cr2
Preliminary Experiments
II VI
a. Potassic ferrocyanide =
b. Potassic ferricyanide =
c. Potassic sulphocyanide =
Boil B with HNO 3
. Dilute with H 2 O, divide into
three parts, and add :
a. Potassic ferrocyanide =
b. Potassic ferricyanide =
c. Potassic sulphocyanide =
Name a test for ferrous iron.
a. NH OH = 4
b. NH C1 + NH OH =
4 4
a. NH OH =4
b.
(NH 4) 2 S = FeS +
50 BASIC ANALYSIS
Cl /Cl
Ferrous chloride. Fe-Cl
n . Ferric chloride.
/Cl
Fe^-Cl
\C1
Ferrous compounds are converted to ferric by oxida-
tion, as with 3
HNO
acid reducing agents reverse the
,
change.
The simplest form of the reaction for converting a
ferrous to a ferric salt would be
2 FeCl 2 + 2 HCl-f O = Fe 2 Cl 6 + H 2 O,
or 2 FeSO 4 + H 2 SO 4 + O = Fe 2 (SO 4 ) 3 + H 2 O.
Fe 2 Cl 6 + H2 = 2 FeCl 2 4- 2 HC1.
forming HC1.
GROUP III 51
FeS0 4 +(NH 4) S = 2
Fe 2 (S0 4 ) 3 +(NH 4 ) 2 S =
Fe 2 (SO 4 ) 3 + NH 4 OH =
- Fe 2 (S0 4 ) 3 + 6 KCNS = Fe 2 (CNS) + 3 K 2 SO 4 6
QUESTIONS
1. What is the behavior of the iron solutions (both -ous and -ic)
with NH OH ?4
13. Steel?
14. Where and in what forms is iron found in nature ?
15. What are some of the physical properties of steel ?
16. Of wrought iron ?
1. NH OH =4
precipitates :
A1 2 (S0 4 ) 3 +NH OH =
4
A1 2 (S0 4 ) 8 + NaOH =
A1 2 6 H 6 + NaOH = Na 6 O 6 Al 2 +
Na6 6 Al 2 +NH 4 Cl =
A1 2 (S0 4 ) 3 + 3(NH 4 ) 2 S + 6 H 2 = A1 2 O 6 H 6
+ 3(NH 4 ) 2 SO 4 + 3H 2 S
(Problem. Make a solution of A1 2 C1 6 from alum.)
QUESTIONS
1. Does NH C1 affect the precipitation
4
of A1 2 O 6 H 6 by N H 4 OH ?
2. What form of A1 2 is precipitated by (NH 4 ) 2 S?
3. What is the effect of NH 4 C1 on Na 6 O 6 Al 2 ?
4. What is the solubility of A1 2 O 6 H 6 in NaOH ?
GROUP III 53
1. NH OH =
4
Filter and test solubility of precipitate in HC1.
2.
3.
4. Pb(C 2 H 3 2) 2
=
To solution of Na 2 CrO 4 add Pb(C 2 H 3 O 2 ) 2 =
To solution of Cr 2 (NO 3 ) 6 add NH 4 OH =
Filter, wash pp. Make hole in filter, and wash into
beaker with NaOH. Add a few drops of H 2 O 2 ,
precipitates :
Cr 2 Cl 6 + NH OH = 4
Cr 2 Cl 6 + NH C1 + NH OH =
4 4
Cr 2 Cl 6 + NaOH =
= no change. Why ?
Cr a (NO 8 ) 6 + Pb(C 2 H 3 O 2 ) 2
Pb(C 2 H 3 2 ) 2 + Na 2 Cr0 4 =
Cr 2 (S0 4 ) 3 3(NH 4 ) 2 S + 6 H 2 O = Cr2 O 6 H 6 + 3(NH 4 ) 2 SO 4
-}-
3H 2 S
IR. QUAL. ANAL. 4
54 BASIC ANALYSIS
Pb(C 2 H 3 O 2 ) 2 , as PbCrO 4 .
QUESTIONS
1. What is the solubility of Cr 2O 6 H 6 in HC1?
2. In NH OH?
4
3. In NaOH?
4. In NaOH combined with HO2 2
?
the filter with NaOH as before, and boiled with a few c.c.
of H O2
2
. The precipitate is Fe 2 O 6 H 6 and may be
, dis-
Add NH C1 4 and NH OH
4
in excess.
Pp. Fe 2 6 H 6 Cr2 6 H 6 A1 2 6 H 6
Wash through paper with NaOH and boil.
56 BASIC ANALYSIS
Pp.
Wash
GROUP IV 57
NH 4
OH. The original solution must be tested to deter-
mine in what form the iron was present. If 2
S was H
added to remove Gr. any Fe 2 present will have been
II,
reduced to Fe, therefore Fe alone will be found on begin-
ning the analysis of Gr. III. FeO 2 H 2 is soluble in pres-
ence of NH 4
C1 and Fe 2 O 6 H 6
Fe must be is not, therefore
oxidized. Care must be taken not to carry the oxidation
far enough to oxidize manganous to manganic compounds,
as we should then precipitate Mn with Gr. III. H 2 O 2 in
presence of an alkali is used to oxidize Cr2 from the basic
to the acid state.
QUESTIONS
1. What is the general reagent for Gr. III?
2. Give the symbols and colors of the precipitates formed by the
group reagent.
3. What is the use of H 2 O 2 ? NH 4 C1? Why boil with HNO 3 ?
*
4. How separate A1 2 from Cr 2 ?
5. How separate Cr 2 from Fe 2 ?
6. Give symbols which illustrate Cr 2 behaving as an acid radical.
7. As a basic radical.
1. NH OH =4
2. NH OH in excess =
4
3. NH C1 and NH OH =
4 4
58 BASIC ANALYSIS
4. (NH 4 ) 2 S =
a. Filter. Make a colorless bead of Na 2 H 4 O 7 on Pt
wire in blowpipe flame, dip in precipitate, and
heat in the oxidizing flame.
b. Test the solubility of the remaining pp. in HC1.
5. NaOH =
Complete and balance the following, underlining all
precipitates :
Co(NO 3 ) 2 +NH 4 OH =
Co(N0 3 ) 2 +(NH 4 ) 2 S =
Co(NO 3 ) 2 + NaOH
QUESTIONS
1. What is the solubility of the hydroxide of cobalt in NII 4 O1I V
2. Jn NH ClandNH OH?
4 4
ii
1. NH OH =
4
2. NH OH in excess =
4
3. NH C1 + NH OH =
4 4
4. (NH 4 ) 2 S =
a. Filter and test precipitate with borax bead as in the
case of Co.
b. Test the solubility of the remaining precipitate in
HC1.
5. NaOH =
GROUP IV 59
precipitates :
NiS0 4 + NH 4 OH
+ (NH 4 ) 2 S
4
Ni(N0 3 ) 2 + (NH 4 ) 2
S =
NiS0 4 + NaOH
QUESTIONS
1. What is the solubility of MO H 2 2
in NH OH ? 4
2. In NH OH 4
and NH 4
C1?
3. InNaOH?
4. What is the solubility of NiS in HC1?
it
1. NH OH =4
2.
3. (NH 4 ) 2 S =
a. Filter, make bead, on Pt wire, of KNO + Na CO 3
3 2 ,
precipitates :
MnS0 4 + NH 4 OH =
MnS0 4 + NaOH =
Mn0 2 H 2 + HC1 =
MnS + HC1
QUESTIONS
1. What is the solubility of MnO H 2 2
in NH OH?
4
2. InNH ClandNH OH?
4 4
3. In NaOH?
4. What is the solubility of MnS in HC1?
Zn Zinc
To a solution of ZnSO 4 ZnCl 2 , or Zn(N0 3 ) 2 add :
1. NH OH =
4
2. NH C1 + NH OH =
4 4
3. NaOH cautiously =
4. NaOH in slight excess = Na 2 O 2 Zn -f
Compare with A1 2 .
5. (NH 4 ) 2 S =
Filter and test solubility of precipitate in HC1.
Make ZnS and test its solubility in HC H 3 O 2
2
.
To ZnSO 4 add H 2 S =
GROUP IV 61
precipitates :
ZnS0 4 + NH 4 OH =
ZnSO 4 + NaOH =
ZnO 2 H 2 + NaOH = Na2 O 2 Zn +
ZnS0 4 + (NH 4) 2 S =
ZnS0 4 + H 2
S
QUESTIONS
1. What is the solubility of ZnO 2 H 2 in NH OH?
4
2. InNH ClandNH OH?
4 4
3. InNaOH?
4. What is the solubility of ZnS in HC1?
5. InHC 2 H 3 O 2 ?
Analysis. Gr. IV
To the filtrate from the precipitate of Gr. Ill, or solu-
tion found not to contain Grs. I-III, heated to boiling,
add (NH 4 ) 2 S and keep warm for some time. The filtrate
contains Grs, V, VI and is set aside. The precipitate
is' CoS, NiS, MnS, and ZnS. Wash in hot H 2 O, allow
to cool, and add HC1 on filter. Pass solution through
62 BASIC ANALYSIS
solution.
TABULATION, GR. IV
Pp. CoS MS
Test with Bx. bead ;
blue indi-
cates Co pres.; brown indicates
Ni. If Co is pres., dissolve pp.
inaqua regia. Expel acid and
add NaOH in excess.
64 BASIC ANALYSIS
QUESTIONS
1. What is the group reagent?
2. Give the symbols and colors of all precipitates produced by the
group reagent.
3. If the precipitate with (NH 4 ) 2 S should not be black, what
inference ?
Preliminary Experiments
ii
Ba Barium
To any soluble Ba salt add :
1. NH OH = 4
2. (NH 4 ) 2 C0 3 =
a. Filter and test solubility of portion of pp. in HC1.
b. Test solubility of remainder in HC 2 H 3 O 2 .
3. NH 4 C1+(NH ) C0 = 4 2 3
4. CaS0 4 =
5. H 2 S0 4 =
6. K 2 Cr0 4 =
7. Na 2 HP0 4 =
8. (NH 4 ) 2 C 2 4
=
GROUP V 65
:
precipitates
BaCl 2 + NH 4 OH =
BaCl 2 + (NH 4 ) 2 CO 3 =
BaCl 2 + (NH 4 ) 2 C0 3 + NH 4C1 =
BaCl 2 + CaSO 4 =
BaCl 2 + H 2 S0 4 =
BaCl 2 + K 2 CrO 4 =
BaCl 2 +(NH 4 ) 2 C 2 4 =
BaCl 2 + Na 2 HP0 4 =
BaCO + HC 2 H 3 O 2 =
3
Ba(C 2 H 3 2 ) 2 + CaS0 4 =
ii
Sr Strontium
1. NH OH =
4
2. (NH 4 ) 2 C0 3 =
a. Filter and test solubility of portion of pp. in HC1.
b. Test solubility of remainder in HC 2 H 3 O 2 .
3. NH C1+(NH ) C0 =
4 4 2 3
precipitates :
Sr(N0 8 ) a + NH OH = 4
Sr(N0 3 ) 2 +(NH ) C0 = 4 2 3
Sr(N0 3 ) 2 4- NH C1 + (NH ) CO =
4 4 2 3
Sr(N0 3 ) 2 + CaS0 4 =
Sr(NO 8 ) 2 + H 2 SO 4 =
Sr(N0 3 ) 2 +K 2
Cr0 4 =
Sr(N0 3 ) 2 +Na 2 HP0 4 ==
Sr(N0 3 ) 2 -f (NH 4 ) 2 C 2 4
=
SrC0 3 + HC 2 H 3 2 =
Sr(C 2 H 3 2) 2 + CaS0 4 =
ii
Ca Calcium
1. NH 4 OH =
2. NH 4 C1 + (NH 4 ) 2 CO 3 =
3. (NH 4 ) 2 C0 3 =
a. Filter and
test solubility of portion of pp. in HC1.
b. Test solubilit}' of remainder in 2
H3 2 HC O .
6. K 2 Cr0 4 =
7. Na2 HPO 4 =
8. (NH 4 ) 2 C 2 4
=
Filter and test solubility in HC1.
GROUP V 67
precipitates :
CaCl 2 + NH 4 OH =
CaCl a +(NH 4 ) C0 8 = 2
CaCl 2 + NH 4 C1 + ( NH 4 ) 2 CO 3 =
CaCl 2 + CaSO 4 =
CaCl 2 + H 2 SO 4 =
CaCl 2 + K 2 CrO 4 =
CaCl 2 + Na 2 HP0 4 =
+(NH ) C 2 4 =
CaCl 2 4 2
CaCOg + HC H 2 = 2 3
a
Mg Magnesium
To any soluble Mg salt add :
1. NH 4 OH =
2. NH 4 C1 + NH 4 OH =
3. (NH 4 ) 2 C0 3 =
4. NH 4 C1+(NH 4)2
C0 3 =
5. CaSO 4 =
6. H 2 SO 4 =
7. K 2 CrO 4 =
8. NH 4 OH + Na 2 HPO 4 =
9. (NH 4 ) 2 C 2 4 =
10. BaO 2 H 2 =
Complete and balance the following, underlining all
precipitates :
MgCl 2 + NH 4 OH =
MgCl 2 +(NH 4 ) 2 C0 3 =
MgCl 2 +NH 4 C1 +(NH 4 ) 2 CO 3 = Solution
MgCl, +NH OH + Na HP0 = MgNH PO +
4 2 4 4 4
MgCl 2 +(NH 4 ) 2 C 2 4
=
MgCl 2 + BaO 2 H 2 =
68 BASIC ANALYSIS
QUESTIONS
1. What is the effect of NH 4OH on the members of this group?
2. What is the effect of NH 4OH in presence of NH 4 C1 ?
3. What is the effect of (NH 4 ) 2 CO 3 on members of this group ?
4. What is the effect of (NH 4 ) 2 CO 3 in the presence of NH 4 C1?
5. What is the effect of CaSO 4 on each member ?
6. H 2 S0 4 ?
7. K 2 CrO 4 ?
8. (NH 4 ) 2 C 2 4 ?
9. Na 2 HPO 4 ?
10. What is the solubility of the carbonates of this group in HC1 V
11. InHC 2 H 3 2 ?
12. How may Mg be separated from the other members of this
group ?
15. OneforBaSO 4 .
31. Can you point out the changes that take place when mortar
hardens ?
GROUP V 69
Analysis. Gr. V
The filtrate from the Gr. IV precipitate may be concen-
trated by evaporation. If the solution is not colorless, boil
with a few drops of HC1 and filter. To the concentrated
colorless solution heated to boiling, add NH 4
C1 if not
already present, NH OH 4
until alkaline, and (NH 4 ) 2 CO 3 .
The filtrate isMg and Gr. VI, and is set aside. The pre-
cipitate is BaCO 3 SrCOg, and CaCO 3
,
This precipitate .
tion add 4
CaSO A tardy precipitate, showing only after
.
TABULATION, GR.
f
Pp. BaC03 SrC03 CaC0 3 Fil. = Mg and Gr. VI.
Wash, dissolve in HC H 3 2 2 .
Immediate pp., Ba pres. (Sr, Ca?) Tardy pp., Baabs. Sr pres. (Ca?)
No pp., Ba and Sr a Us. Ca pres.
If Ba is present, to B add K,Cr04 .
Reject
Pp. SrC03 CaC03 Wash,
dissolve in HC H 3 2 2. Divide sol. into A and B. To A add CaSO,.t
Pp. SrS0 4 ,
white. Fil. Ca(C 2 H 3 2) 2 . Add NH OH4 and (NH 4 )XA
Reject.
Srremoved as SrSO 4 by H 2 SO 4
is .
QUESTIONS
1. What is the general reagent for Gr. V?
2. Give names and colors of all precipitates formed by it.
presence of Ca?
6. How confirm the presence of Ca?
Na, K, Li, NH 4
cipitate of MgNH 4 PO 4
indicates the presence of Mg. If
to drive off 4
NH
and test in spectroscope for Na, K, and
,
Pp. Mg0 H 2 2 .
Reject.
74 BASIC ANALYSIS
18. Saleratus?
19. How is gunpowder made?
20. How is soft soap made?
21. What is lithia water?
22. What is salatnmoniac, and for what used?
23. What is the source of the ammonia compounds used in com-
merce ?
24. Referring to the table of solubilities shown on the last page
of this, book, note the solubilities of all the common salts of Na, K,
and NH 4
.
o
*
id nd
PQ
PQ OT 6
O
O
h II
Q N
>V
J w
qqq
RATION
^ Q <1
AGENTS
&
O *
i Sh
o ^
A
PH
PQ
OQ
P_i
d,
PH
76 BASIC ANALYSIS
Solution contains Gi
ind add H S.
2
~r
CdS (SnS. SnS 2 Sb 2 S 3 Sb 2 S 5 As 2 S 3 As 2 S5 ) Fil. = Grs. III-VI
ish through filter with (NH 4 ) 2 S and warm. (see page 78).
Cu(N0 3 ) 2 Cd(N0 3 ) 2
a few drops H2 S04 .
78 BASIC ANALYSIS
Q
ff a 5a
I
II
*
3
02 ^
I
- -
O '3
I o
111 O
^2 '
-M o
ISL '
+
oJ5 1 -i te I
-1
-1
l 8|
eS K
tJD
.-*-
'5
'i
2 c
*3
.5 1
ft -5
?,&
Q ^a f:
I
>FJ -^
ALL GROUPS 79
M I
o*
M - <2 B
.
'^18-9
H O
tz; -43
""*
fcJO*^ 05 .^4 CD
Jf 5*1
-a.aBi
(C
IS
,0
a:^
3
i" co ^r "
'.2
"i O
p
w
a-
PH
"
02 ^
PART IV SOLIDS
Preliminary Examination
If the substance is neither a metal nor an alloy, it must
be powdered in a porcelain mortar, and small portions
used for each test. (For metals and alloys, see page 86.)
Do not spend too much time on this preliminary exami-
nation, nor rely too much on results obtained from it until
your experience in this particular work has been somewhat
extended.
3. Color
Hot Cold
Yellow White Zn salts
Red to black Brownish red Fe or Fe 2 salts
Yellowish red Yellow -Pb salts
Pale yellow - Bi salts
Orange yellow
Blue indicates A1 2
Green indicates Zn
Rose color indicates Mg
III
IV
Flame Colorations
Moisten Clean Pt Wire in HC1 and ignite in Bunsen
Burner Flame.
Violet indicates K
Yellow indicates Na
Carmine red indicates Li
Yellowish red indicates Ca
Bright red indicates Sr
Green indicates Ba
Blue to green indicates Cu
VI
Ignite before the Spectroscope and examine for
Characteristic Lines.
VII
Treatment with Cone. H SO 4
2
84, 3). Observe color of any gases given off and note
odor with care. To examine the odor safely, hold test tube
at slight distance and fan fumes toward the nose so that
they will be diluted with air, and gradually bring test tube
nearer. If any particular acid indicated at this point,
is
II Acid Solution
The substance insoluble in H 2 O,
or the residue from the
substance partially dissolved in H 2 O, is treated with dil.
HC1, then Avith cone. HC1, first cold, then boiling. Treat
in the same way with dil. and then cone. HNO 3 and finally ,
BOIL WITH H 2
I. Preliminary examination.
II. A
study of the solubility of the substance.
III. any acids have been identified, an elimination
If
from consideration of any bases that must evidently be
absent from the conditions of solution. For example, CO 2
is found the preliminary examination, and the sub-
in
stance is soluble in H 2 O. Under these conditions, no bases
can be present except those of Gr. VI, as carbonates of Grs.
SYSTEMATIC EXAMINATION 87
H 3 AsO 4 , and
2 4
H CrO , as As and Cr2
(including Cr), if
GROUP I -DIVISION A
*
H 2 CrO 4 ,
H 3 As0 3,
H 3 AsO 4 , H 2 SO 3 ,
H 4 Si() 4 , II
2
C0 3
The first three of these acids will have been found in
the basic analysis (pages 47 and 55), as they are reduced
by 2
H
S in the presence of H'Cl.
The presence or absence of the last three acids will have
been proved in the preliminary examination (pages 83,
VII, and 86).
Special tests must now be applied to determine whether
Cr2 is present in the acid or basic form, and whether the
As is in the -ous or -ic form.
*
Although some of these acids never occur except in their salts, the
full symbol of the hypothetical acid is here given.
88
GROUP I 89
H 2
S from solutions of Sulphites.
H 4 SiO 4 Addition of
. HC1 separates H 4 SiO 4 in the form
of a gelatinous precipitate. Filter, wash, and dry, when
it is converted into SiO 2 and may be recognized by its
gritty feel. Silicates.
H CO 3
2
. Add cone. HC1. Quick and energetic effer-
GROUP I DIVISION B
H 3 P0 4 H 2 SO 4
, , HF, H 2
C 4H 4 6,
H BO
8 8
* For methods of
removing the bases more completely than here indi-
cated, the student is referred to Wm. A. Noyes's " Qualitative Analysis,"
H 3
AsO 3 and H 3 AsO 4
. To the filtrate add NH OH 4
in
BaSO 4 and H 2 SO 4
,
is proved present. If the precipitate
is soluble in HC1, H SO 4 is
2
absent. In either case, special
tests must be applied for other members of the group.
Sulphates.
HF. Treat the original solid with cone. H 8O 4 in Pb 2
dish. A gas evolved that will etch glass shows Fluorides.
H C 4 H O Treat the original solid with cone. H SO 4
2 4 6
.
2
.
phate =?
Sodic sulphate and baric chloride =?
Calcic fluoride and baric chloride =?
Calcic fluoride and sulphuric acid =?
Potassic tartrate and baric chloride =?
Sodic borate and sulphuric acid =?
GROUP II
H 2
S and HCN have been proved present or absent
will
with certainty in the preliminary analysis (page 83, VII).
Some indication as to the presence of HC1, HBr, and HI
will also have been afforded.
A solution of the original solid without removal of bases
will, in most cases, be suitable for the analysis of this group.
If the solid was originally dissolved in HC1, it is obvious
that some other means of solution, such as the use of
HNO 3 must be found before proceeding to the analysis
,
GROUP III
HN0 3,
HC10 3 ,
HC H2 3 2
few drops to run down the side of the inclined test tube.
Brown or black ring of NO 2 shows Nitrates.
A Second Test. Add Cu filings to a solution of the
original solid, and then cone. H 2 SO 4 Brownish red fumes
.
of NO show Nitrates.
94 ACID ANALYSIS
QUESTIONS
1. How do you prove the presence of a chromate ?
. PREPARATION OF SOLUTIONS
Acids
Other Reagents
place.
Lead Acetate. Dissolve 1 pt. of the salt in 10 pts. of
H 2 0.
Limewater. Make'a saturated solution of CaO 2 H 2 .
purpose as well.
Antimonious Chloride. May be bought in the form of
solution. This should be diluted with an equal volume
of water and cone. HC1 added to dissolve the basic salt
formed.
Arsenious Acid. Made by " white arsenic "
dissolving
in cone. HC1.
Baric Chloride. 1 pt. salt in 5 pts. H 2 O.
Baric Nitrate. 1 pt, C. P. salt in 10 pts. H 2 O.
98 APPENDIX
Li
K
X;
Mg
Ca. l-HO1O1OlrHOlrHrH^lrHrHrHCOT^rHrHTj<C'l^lOT-lrH
Sr 1-HOlOlOlrHOlrHrHT^rH .'
rH CO rH rH rH rH <N Ol CO rH ?1
Ba rH Ol 01 Ol rH Ol rH rH Ol T* ;T*COrHrHrHrH<NOi:OrHOl<N
Zn rH <N I 01 rH N rH rH rn 01 01 CO * 01 i-H rH 01 (N ="> rn M rH M
Mn rH ?1 IN IN rH M rn rH rH Ol :0 Ol Ol N rH rH <N IN Ol rH (M (M T*
Ni
Co
'> A1 2 rH Ol I Ol rH .'
rH rH ; [ ] \
rH C-1 rH rH CO -N CC rH <M (>1 <N
^Q Cr2 rH 01 : 01 10 N rH 10 W 01 : ;
rH (N rH rH -O 01 IN * CO rH rH
3 Fe '2
Fe
*
L
rg
Sb : 01 01 : rt ; ; ^ 01 : : : rn 01 ^ : <M ^ : <M M CN rn
Cd
CU
I
rH 01 O1
Bi
' '
Pb rH C^ Ol Ol O Ol rH O CO Ol ^f* Ol Ol Ol -^ rH (N Ol Ol CO Ol Ol Ol
Ag I
rHOlOIOICCOIr-IMOirrMCCrH : CO rH 01 01 : * 01 01 (N
rH cc 01 ; ; : : ; 01 rn 01 01 ; ^ c- 01 *#
** ^jjS
Jl*j|lSfll3B
*
-
'
'-2JS5R-*
* S
.t: =
g g aj
2 S
STORER AND LINDSAY'S
Copies of this book will be sent prepaid to any address, on receipt of the price^
by the Publishers :
Specimen copies of the above book will be sent prepaid to any address,
on receipt of the price\ by the Publishers :
BY
MARGARETTA BURNET
Teacher of ZoiJlogy, Woodward High School, Cincinnati, O.
Illustrated - -
Cloth, i2mo, 480 pages. Price, $1.30
R mnnth'i
6-month ^
loans may be
renewed b y calling 642-3405
recharged by bringing books
to Circulation Desk.
Renewals and recharges
may be made 4 days prior
to due date.
B0
7 DAYS
General Library
University of California
Berkeley
237577