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STUDENTS' GUIDE
Quantitative Analysis.
IttTENDHXJ AS
AN AID TO
T>IK
STUDY OP
FRESENIUS' SYSTEM.
BY
H.
CARRINGTON BOLTON,
Ph.D.,
NEW
YORK:
JOHN WILEY
1899.
&
SONS
COPVRIG.'tT, iSSl,
Bv H. Carringtos Boltow.
B.irbcr,
Brooklyn. N. V.. U. S. A,
o
p5
to
&
40
"in
-J
< U
o
u
>
>
PREFACE.
A portion of
the following pages originally appeared In
Chemist,
under the
title:
^'Schemes of Analyses execrtted in the School of Mines, Cohimbia College." Numerous applications for copies in
para-
The system
Assistants,
of
the
Laboratory for
Dr.
Quantitative
Paul
The
practical
originally selected
by
Prof.
made
in this
i.
PREFACE.
The
plan oi
the Students'
Guide
is
similar to that
"Examples
details,
for
Practice
in
the needs o however, arc the result of observing five years' experience in teaching studeiUs during my
large classes.
The fragmentary
notes
is
character of
many
portions of
the
Kkesenius'
"
SysUm
of
(American litstmclion in Quantitative Chemical Analysis" New York, edition, by Profs. O.D. Allen and S. W. jolmson
;
S8i)
is
laboratory, but
many
though systematic, arrangement of this classic worli, and are at a loss to know how to begin work, ivhat io study, and
where
cases.
to
find the information appropriate to particular To aid the student in the study of Fresciiius' work,
it, is
one
STUnENTS.'
Guide.
It is
been made
however,
of
Frescmtis'
in
all
System; acknowl-
edgment
is,
made
cases.
By
occasional
is
the student's
attention
by
hope
of
in research," H, C. B.
Trinity College,
LIST OF ANALYSES.
List ot Aoilyteis.
i,
BarSc chloHdc,
iJa.
CI, 11,0.
3.
J.
Magnetic
siiSphate,
tiiilphate,
Amuwnio-ftfi-ic
yO^, Nil.,
by pre-
cipUiition
volmiK'lrically,
K, CI,
5. 6. J,
Hj'drodiscdic phosphate,
Silver coin,
direct weight.
Dolomite,
Bronze^
Coal,
CaO. MgO,
Cis,
HiO,, I'cj
),,
CO, by
los
and byUii-ect
S, Z.
volatile
wciglit.
S.
cy.
H,0,
Cu,
asli,
S.
10.
It.
12.
Coppfir
fiyrites,
ill
diipricat<3.
Alkalimetry,
Acuiimetryj
Chlorimctr;^,
13,
l.f.
Bkachingr powder.
Pb, Sa, Sb, Zn.
Type
Hiatal,
jj,
16.
;5ir(i;orc,
Zn.
ore,
Chromic iron
Pyrolusite,
Ct,0,.
17.
iS. 19.
MnO,.
SiO,,
Feldspar,
Slag,
SiO., AljOj,
;o.
St.
liijmatilia,
SiO,, Fc,
Complete analysis.
Fe.
13.
Pig iron.
?!icHol ore,
Mn,
S, Si.
graphite^ combined G, T\
I^, 2^.
Ni. Co.
Ar5cnopyrJt,
A.
vm
Ui(
ij.
oJ Aol]Fi>.
LIST OP ANALVSES.
Constituents IQ t* <l*nntiieA
Guano.
Superpliosphat* of lime,
!i,0
precipitated,
and
in-
s6.
27,
Water,
Specific gravity of a olid,
rrsattcr.
2S.
39,
*'
"
"
liquid,
By
the lla<k,
by hydrometer, and by
Sugar.
Potass ic ferrocyan!c!,
C, H, O.
N
C.
by Willand Varrentrapp's,
iJeSseos* ractliods,
II.
and
32. 33.
3+.
Oil of turpentine,
Urine,
Milk,
Qualit.itive
and quantitative.
sugar, ash.
Water,
sugar,
tjuttcr, casein,
3j.
K aw
cane
sugai
36. Petroleum,
Hy,
fire teat.
INTRODUCTORY NOTES.
By means
position of
o Chemical Analysis
we determine
the com-
any substance.
is
The
to determine the
The
is
to determine the
amount
Volumetric Analysis.
convert the lcno\vn cousrituIn Gravimetric Analysis we forms as will admit of their ents o a compound into such in by weight. This is done chiefly
exact determination
two ways
1st
By
fuch
{e.g.,
Cu by
the battery),
2nd,
By
new
AgN03+HCl = AgCl
+HNOj).
The forms must
1st
2nd,
fulfil
two conditions:
of
Must be capable
Must be
of
known
3j
INTKODUCTOKV NOTES.
The
eratian.'S,
The most
preferable
are
St,
Those most
in
2ml Those
to
be
which the proportion of the constituenti! determined is very smalt compared with the weight
(t'.j^,,
of the precipitate
In
BaSO,
is
cent.).
is
known
umetric Analysis,
p.
40).
Svcm
English
^^Z::^..
York, 1881
r^../..
edition.
;
"^JlZ
last
Quantitative
last
German.
New
.
York,
last
R,s^, //.
fans,
1850-62.
^...
//.,
and yy^/---.
Leipzig, 1S67.
Mr.
ode
^m...
Lehrbuch
der
cUemisch-analyt.schen
T^^tr^rmpthlUnrmcth
Braunschweig,
last edition.
Sy.ten.atic
last editiotx.
Handbook
of
Volumemc
quantUative
Analysis.
London,
J?a>m>.Me.s.
Analyse.
Crook^s.
last edition,
Leitfaden
ftlr
die
cbemische
Berlin, 1S63.
Seket Methods
in
Chemical Analysis.
,
London,
,
techn.sch-chemi.chen
Wshkr
,861.
Also
1871.
Van
Chem-
PrescoU.
NostTand,
New
York,
last edition.
Caldwell
ical Analysis,
New
York,
last edition.
Xli
Ar.alysis.
London,
Notes
on
;
Assaying
Nev.
York, Wiley
Sforer.
&
Sons
last edition.
First
Outlines
of
Dictionary
of
SoKibilUies of
Chemical Substances.
/lPP^
Cambridge, 1864.
Reactionen der
Stoffe.
Die Chemlsche
wichtigsten anor-
'Itihchrift fur
Wiesbaden,
1862 to date.
Giessen,
BuHeHn de
date.
la Soci6t^
Chimkiue de
Paris.
Paris,
1864 to
Chemical Nat^s.
Crookes.
London, 1S60
to date.
American ChevmL
Chandler.
New
American Journal of Sdaia and Art. New Haven, iSrg to date. Dana.
Journal of Analytical Chcmhtry,
1S87 to date.
D. and E. S.
Edward
Hart.
Easton,
THE
STUDENTS' GUIDE
irt
QUANTITATIVE ANALYSIS.
Amlysis No. I. Baric Chloride.
BaCU + 2H,0.
A, Determination of
See Fies, Quant, Anal., |
795.
141.
Chloriii.
a,
American
edition, tS8i.)
r\
grm. of powdered BaC^-f sH.O and slight excess of dissolve in cold water in a beaker add a and previously acidulated with HNO3; stir well,
Weigh
out 0,8 to
AgNOj
warm.
When
the precipitate of
and the supernatant liquid is slightly acidulated a No. 2 filter; then add boiling water stir, and. with HNO3, to the precipitate in the beaker; pour off through after the precipitate has settled again,
the
AgCl
washing by decantation three or filter by four times; then bring the precipitate on the
filter.
Continue
this
means
wash
it
down
into the
point of the filter; wash laistly with a little non-ackhfied water ; cover the funnel with paper ; label properly, and set Weigh a clean porcelain crucible; transtcr aside to dry.
j^
QUANTITATIVE ANALYSIS.
crucible, removing tlie AgCl from the precipitate to this Wrap a clean platipossible. the paper as completely as filter, forming a ^'cradle;" num wire around the rolled-up
burn the
cover
;
filter in
the
do not
let
the ashes
Moisten
HNO3
(one drop)
HCl; evaporate
cautiously,
until the
and heat
AgCI
is
temperature than partly fused, avoiding carefully a higher See Fres., 82, b. Wcish the crucible and necessary.
contents.
For
calculation, see
D.
Fres., 115,
;
1,
a,,'?-
grm,
BaCU
+ H,0
(free
dissolve in
warm
HNOj AgNOj in slight excess; cork When well settled, wash the
from chlorine); pour
flask
water,
glass, over a
Invert the flask, covered with a watchweighed porcelain crucible, placed in a large porcelain dish, and filled with water. Withdraw the watchwithout
filtering.
AgCl
flask.
of the crucible,
remove the
last portions
paper,
The
precipitate
settles best in
presence of an
excess of
AgNOj.
B. Determination
of Barimn.
See Frcs., 132,1, i, and loi, I, a. Dissolve i to 1.5 grm. substance in warm water acidulate with HCl dilute to about 250 cc; heat to boiling when boiling hard, add dilute HjSO,, in slight excess boil some minutes and then
; ;
;
CALCULATION OF ANALYSIS.
,
^
15
Test with a settles. keep warm while the precipitate by decantation dropof H^SO,; wash with boiliitg water dry filter wash well then bring the precipitate on a No. 2 crucible burn filter and ignite precipitate in a platinum contents of crucible. a cradle as above, and add ashes to
; ;
Sec
Frcs., 7
'?
precipitate with jVi,/tf._Wash until the filtrate gives no of A*NO When estimating barium in the presence
salts nitrates, chlorides, etc., these
down with
the BaSO^.
Since
it
is
impossible to remove
alone, treat the precipitate these by washing with water Cf. Crookes' acetate. with very dilute HCl. or ammonie
Watw
(by Ignition)
to 1.5 grms. substance; In a weighed crucible weigh out i small flame, and increase heat very gently at first over a finally, heat to low redness the temperature very gradually operation until the weight then cool, weigh, and repeat the liigh a temperature, remains constant. Caution avoid too substances contain large When else the CI will be expelled. magnesic sulphate, hydrodisodic percentages of water, as water at ioo- C. phosphate, alum, etc., begin to expel the
;
in
an
air-ba.th.
D. Calculation of Analysis-
79S,
^ilao
196-
Make two
state
to
of the desired
1
I
.
precipitate
1
\
Actual
weight of
precipitate
[
J
Actual | weight of \
constituent. J
1^
QUANTITATfVE ANALYSIS,
of
tjj
of
contituent
too
''<fffl<s of tl 1
theoretical pcrccntasfct
Ba 56.15
CI,
= 29.09
14.76
2H,0=
100.00
Use ofFrcscnius' Tables for the calculation of analyses Compare Tabic IH. I- res., page
854,
Examples:
Fe,0,
= 50,.
also
2Fe,
pages
%^,6, ei seq..
page J^a
'"',
of
eT-To
f^^
^'-
^'^^SSO,
yielded
we hav^r
'2
'
''"^^''' '^'''^^
^^
precipStaie
"-^^
^^-^
^*^
a3433S
c^o<SS67
*co
.007
^^^^^
* '
.0004
'^^<^ 0.00013
1.2074
041455=50^
0.41455
;^=32.7SpercentSO,
KEI'ORXJjNG
ANALYSES.
E. Reporting
Analyses.
let-
ter
Analyses may be reported on blank forms printed on paper 8" x lo", having following headings
:
, . .
Hakti'okd, !S8 Report of Analysis DliXEKMlNATJON OF GRAMMES TAKEN Metiiod of Analysis These headings are colimin in printed in vertical one horizontal line are placed following headings: Pkecii'ITATes, Actual
OF
Weights, Constituents, Calculated Weights, Percentages, Theoretical Percentages; under each a blank
space
is
left
of
2 1-2 inches.
Under "precipitates"
place
"
culated weights
in precipitates;
place the
"
amounts
of constituents existing
under
analyses.
The
last
be fdled only
in
room
for remarks on
Notes
Reactions. (I)
(2)
to the
BaCL
BaCI,
H,SO,
-AgNO^
The
the change,
however,
is
weight
is
appreciable.
(iLrANXri-ATIVE ANALYSI.-,,
iS
is thrown down as AgCJ [^ water, a slight bluish mllkiness maystiU 1,000,000 parts of This cloudiness disappears on adding an excess be seen.
When
of
HO.
Barium sulphate requires more than 400,000 parts of
''
water
for
solution.
The
solubility
is
KCIO,
ary of
Solubilities.)
Barium sulphate thrown down in a solution containing This becomes ferric salts is often contaminated with iron.
evident by the rcddisli
nition.
color of
ig-
be purified by washing with ammoniuni acetate, or hy solution in cone. HjSO^, and reprecipitation by pouring into water. BaSO^ dissolves In
precipitate
cone.
The
may
H.SO^
and
in
Nord-
Analysis No.
2.
Magnesic
Sulphate.
MgS0.H-7H,0.
A, Determiuation of Sulphuric Acid.
See Fres.,
stance in
2,50 c.c.
;
132,
I,
i.
Dissolve
to
1.5
grm. of sub-
warm
boil
HCl,
dilute to about
hard
add
Bad,
BaSO,
filter, aiid
continue
as in Analysis
B,
B. Determination
.
of
Magnesium.
"^^' 104, 2. Dissolve abont 1.2 grm. of substance >n 150 ec. cold water, in a beaker; add 30 c.c. i\H,Cl,
I9
10
c.c.
NI^HO, and
(Should
add NH^Cl until it a precipitate form on adding NM4HO, Stir the contents of the beaker well, avoiding rcdissolvcs,) touching the sides with the glass rod. Cover, and set aside
for 12 hours, without
warming.
its
Filter
water,
to
whicli
one-fourth
been added, until the filtrate acidified with HNOj gives only a slight opalescence with AgNO,. Dry thoroughly on increasing the filter, ignite in a platinum crucible, gradually before the heat burn the filter on a cradle until quite white
;
adding the ashes to the contents of the crucible. If the preor two o cipitate or asli is not white, moisten with a drop (See Fres., cone. MNO3, evaporate, and ignite cautiously.
74, b
and
c.)
Weigh
C Determination
of "Water.
crucible,
Heat I to 1.5 grni. salt in a weighed platinum and proceed exactly as in Analysis I, C.
Analysis of Maguesic SulpJmte.
Notes
to
amraonio-magnesic phosphate in paragraphs water and saline solutions. Cf. Fres. page 816,
On
the
solubility of
35-35f
One
ammoniated
strong
sol.
^vater
"
of
NH.Cl.
"
"
water containing
NH^HO
andNH.Cl.
For
the ammonio-magnesic a discussion of the solubility of vol. phosphate, consult Cladding's letter in Chem. News,
47. P- 71 (!883).
QUANTITATIVE AKALYSIS.
2C
Rcactio>is.--l^y
precipitation
we have:
2MCSO.
On
we have
(NH,),Mg,P.O.
Theoretical Composition
16.26
MgO
sOj
32.52 5E-22
7H,0
100.00
Amlfsis No.
3.
Fe,(NHJ,(SOJ,+24H.O.
A- Determination of Sulphuric Acid.
Dissolve
I
gr.
to
1.5
c.c, dilute
HCl
in
to prevent ferric hydrate from precipitating ^Vl^^i ''be BaSO.p heat to boiling, add BaClj and proceed exsctlv ;s
Analysis
2,
A.
B. Determination
(Fres.,
(i.)
of
Ammonium,
99,
b, 2,
(-J.)
the salt, if necessary, before weighing, by press ing the powder between folds Diss'^lve of bibulous paper. about 1,5 grms. in a little cold water casserole, ac'd a in a
little
Dry
dilute
to dryness
HCl and
01
DETERMINATION OF IRON,
,o to 80
c.c.
21
while still warm; alcohol 10 the casserole The supernatant Uqmd hour.. nor sdr let stand several of PtCl,. should be colored by an excess alter in a small funnel, wash Swedish
;
"
do
(-.
with water thoroughly; dry uilh 'very dilute HCl, then watchthe ftUer and plaee it on the lunncl, then remove lot an air bath ,00^ C exactly-^ dasses with elip; dry in whole. glasses and we.gh the one hour precisely then elose crystalline precipitate on the (.) Brin^' the yellow w^h al means of a clean feather w^h
PI ux-
No
weighed
dry on funnel. Then tran^ ,h;i earefuUy, not too nrueh, Dry and before, and weigh. , ,n -lip, clvv at 100" C. as untU constant calculate results. .vei,h a,a>n, repeating
;
filter
by
composition (M-ija tt.1.,. Precipitate has the determinations, wash with a [In the case of potassium filtrate and ether; also concentrate n.ixture of alcohol and and add to the secondary precipitate wasliHv^".^, lUter from
,
the Lormer.]
)
weighed crucible, burn Transfer the precipitate to a (4 ignite gradually and strongly, a.hes the titer and add the on the first determ. Wei'h the Ft remaming as a check
;
lion, nation.
powadd a little oxalic acid rin the case of potassium, wash residue the crucible, ignite dor to the contents of (See water-bath, ignite, and weigh. with water, dry on
Fres,, 97.
3.
m
.
1-)]
For
p. 8
1
solubility
of
16.
2,
paragraph
U.
I
Detennination
of Iron.
e.)
By /^nhou.-(Ftes.,
in
U3,
i,
Expose
or
l.O
grm. of
the' salt
a weighed covered
Hflfi
platinum,
porcelain
22
crucible, to a
atiire
till all
QUANTITATIVE ANALYSIS.
moderate
is
the water
fore the
blast-lamp.
Weigh
heat
By Precipitation. -(Fres.,
I
about
NH.HO
i, a.) Dissolve' a large beaker with of water, acidify with HCl, heat nearly in excess; let settle after stirrin-
113,
NH
of
CI com'
the iron
volatilise as chloride.
One grm.
dry
filter
and
theXTtfnr"^""'^'^^'^
accordance with
6[(NHJ,S0,]
'^
31-1,0:
'^
oa- SefFr'"'" ^
distitied^iter
intoabottir'Fm
"P
to the zero
4" i:'^:r-'''''"=^^"*^'^''^^^"'S^^t'^n^J
r , ^'^^^"^^'^^
f
^'^-^
^'P^^"
"^
mark
and
sufficient
wat'^B:;;
'
^'"'^^^^d' ^ool suddenly "?' ^nder the faucet bui to avoid but ' collapse of flask wait
''Tr
'"'
''''^ ^^"^'
"^^o!
a few
DETERMINATION OF IRON.
23
fall
moments
upon
it.
The
valve.
flask should
This
is
be provided with a Kronig caoutchouc made by inserting a short <^lass tube through
neck of the flask, and fitting to the projecting the tube a piece of caoutchouc tubing about lo cm. end of slit 4 to 5 cm. long is cut lengthwi.'ic in the long.
a cork in the
caoutchouc tubing, and the open end stopped with a piece The valve is then complete, (Fig. i.) of glass rod.
Fig.
1.
Fio.
The
just
In place of the KrOnig valve, another form may be used. projecting end of the glass tube, fitted to the cork in
the neck of the flask,
is
even with
its
surface.
passed through another cork until Over the end of the cork and
tube a small piece of sheet caoutchouc is fastened by means of pins, the rubber acting as the valve, (Fig. 2.) I laving effected the complete solution of the iron wire in one of
24
QUANTITATIVE ANAI^YSIS,
these flasks, pour the solution into a large beaker contain, c,c. IIjO, placed upon a sheet of
Now
the burette, drop by drop, stininy continually, and continue until the pink hue
tiic
pour
solution of
K,Mn,Oa from
first permanently colors the whole liquid. and calculate a.s follows for the standard
Read the
:
burette
c.c.
used
c.c.
= grms.
Fe
x, or standard.
Repeat the
tained,
titration until
:
Correction
To
the
amount taken by
Reduction of the Ferric Solution. (2.) T:i'\s.%o\vz 4.0 grms, ammonia-iron-alum in water, dilute to exactly 500
c.c.
;
mix
well,
Place a piece of amalgamated zinc and a strip of platinum foil in each reduction bottle; pour in the solutions and washings; add a little cone. H,SO and cover the bottles with watch glasses. The reduction requires six to eight hours. If the platinum foils are new, scour them with sdica, rub them with
KHO solution,
then with
and wash
HNO.,
carefully.
Removal
of the polished
and possibly
greasy surface hastens the evolution of hydrogen and consequently the reduction.
Reaction
Fe,(SO,),+Zn+H,SO,=2(FeSO,)+ZnSO,+H,SO,.
(3-) Performance of the Anafysis.Wh^n the reduction ^complete, ascertained by testing a few drops with am^
monium
DETERMINATION OF
bottle into a large beaker,
IRON,
35
add ILSO4, and K^Mn^Oa from the burette until a permanent pink color is obtained, (See Tlie two determinations, one in eaeh Fres., 112, 2, a.) bottle, should not vary more than 0.2 per cent.
(4.)
No. of
c.c,
used V
100
per
i ct. 01
,
iron.
IV.
of
potassium
several ways.
t.4
Mohrs
Method.
iron.
V^
<i\g\\
out
grm. ammonio-
titrate as usual.
One-seventh
weight =:
Ammonio-ferrous sulphate
= FeSO^
is
+ (NHJ,S0., +
6H,0.
In both this and the preceding method the reaction the same.
Hempcfs Method,
acid,
Weigh
in
out 6.3
of
grms, pure,
dry oxalic
dissolve
-\
one
litre
water,
making
a decinormal
tion,
N
(
solution.
c.c.
Dilute 50
H^SO.,,
:
c.c,
of this solutitrate.
add 6
to
cone.
is
warm and
The
as follows
26
QUANTfTATIVE ANALYSIS.
D Determination of
Water may be determined by
Theoretical composition
Water,
difference.
(N?I,),0=
5.39
Fq^O 16.60
4SO3 33.20
24H,0=:44.8
100.00
Analysis No.
4. Potassium Chloride.
KCl.
imng
filling
A. -Determination of Chlorine.
^-^ actly as ^c^r.f-"f""r Analysis
^i,
^"
"^
^^=^^^^
No.
A.
of Potassium-
B.- Determination
JJissolve about Ssllvr^h ^f 0.1;
.,
1
^" ^'
j/rm in d t t.'"'-
'"^ ^"'^^^' -^^^^^^ ^-^^^-^^^ P-ge I. ^ * . UttU ^^1 JitHe cold water in a f-^c:cif
1
.
"
wtt. ^'
p.
"
"' '"'-
2'/
K
CI
5241
47S9
100.00
Analysis No.
5.
HYORODtsoDic
i2H,0.
Phosphate.
Na,HP0,+
A-
Deter minatiOLi
of Sodium.
about
grm.
salt in
200
water
in
a large beaker.
about 0.6 grm. clean piano-forte wire, place 10 (undei a flask, add cone. HCl witli some HNOj, boil hard boiling until excess a hood); when fully dissolved, continue
Weigh
off
of
HNO3
Add
is
removed, then
dilute, and,
if
necessary,
filtej
through a
filter
previously washed
with dilute
HCl
pure FeXl^ to that of the hydrodisoimmediately an excess of NH.HO, dic phosphate, and Heat and let the precipitate stand some hours wash by
this solution of
;
-decantation with
boiling water
very thoroughly.
until
Evap
HCl on
fumes
in
a water-bath
-of
to
dryness,
NH4CI
cease to
come
dissolve
the
residue
through a very small filter Add a few drops platinum preferred. dryness on a water-bath; of dilute HCl; evaporate to ignite very cautiously, not too long, and weigh the NaCL If the residue is not perfectly white and soluble in water
water;
filter
into a small
weighed
dish,
filter
weighed
dish.
Test residue.
2S
QUANTITATIVE ANALYSIS.
B.
Fres.,
salt
ill
Determination
134,
I,
of Phosphorio Aoid.
b. .
Dissolve
Atiafysis
about
1.2 grtms. of
the
excess and
NHJ-IO;
817.
continue exactly as
Consult Fres,
Exp, 32,
p.
C Determination
(r)
it
of Water.
place
an air-bath, until partially dehydrated; then heat cautiously over a Bunsen burner, ignite eventually to redness, and weigh. (2) By direct wei^hL WQigh. out about 0.7 gramme substance, and introduce it into the weighed ignition bulb by means of a very narrow piece of folded paper. Weigh CaCl, tube, and arrange apparatus, as shown 2*5, in
in a
Fig.
page 61, of Fres. Quani. Analysis (American edition, 188 1),' substituting aspirator for gasometer if more convenient.
Heat cautiously, aspirating continually, and raise the temperature to a low red heat for Three minutes. In driving' the water into the CaCI, tube be careful not to burn the cork Aspirate while cooling, not too rapidly. Weigh CaCl, tube after cooling and the ignition bulb as a check. Consult Fres., 36.
Theoretical Composition
:
When
water
caJculation
is determined by heating to redness, the must be based on two molecules of the salt.
2Na,0
17.33
SILVER com.
29
t
V
0-
yaANTlTATlVE ANALYSIS.
ANALYSIS OP DOLOMITK.
Note
$t
2. If
it is
clesimble to determine the SiOj, in the Ri'sid/w a" must be treated as follows
filter),
Dry and
about
heat.
ignite (with
mix
in a
six parts of
remove the fused mass with boiling water, add on a water-bath, an excess of HCl. evaporate to dryness
Coo!,
completely expelled heat in an air-bath until the HCl is and filter from again moisten with HCl, dissolve in water,
;
the residue.
The
residue which
is dried, ignited,
and weighed.
Examine
Fres., 140,
H,
A, a,
and
93, 9-
3. Heat the
" is
filtrate
a,"
add NH^Cl,
and
ted
NH.HO
if
in slight excess.
" is
the
Filtrate a
NH4HO
expelled, filter
105,
I,
(The NH.Cl may be omitHeat until excess of very acid.) quickly, and wash hot. SeeFres.,
partly washed,
dilute
^113, i,a,ad^
a.
" is
dissolved in a
is
little
warm
HCl on
and
the
solution
reprecipitated by
filter,
NH^HO
the precipitate
Weigh
*'
as
Fe^Oj-fAUO^.
The second
filtrate is
added
to
Filtrate d."
Note 5. Concentrate " Filtrate fi" add some NH^CI unconsiderable exless present already, add (NHJ, 0,0, in Let stand 12 hours in a warm cess, and some NH.HO, Wash partially and filter. Se^ Fres.,% IS4> ^t<^ place.
also ro3,
2, d, a,
>'
AWt'
in
6. Dissolve
HCl, reprecipitate with NH^HO and a little (NH,)AO,. Filter and wash hot, add filtrate and washings to " Filtrate c." Dry precipitate on funnel, transfer to crucible, burn filter, add ashes, add a few drops of cone. H,SO^ to contents of
32
QUANTITATIVE ANALYSIS.
low redness, and weigh
3, b, a.
as
CaSO,.
Note
7.
Compare
Fres., 103,
If
NH^Cl
in the
preceding steps,
the
thrown down
in "/^///w^^ 6-"
immediately.
:
add 3 grms. of
heat to boiling.
HNO3
for every
to be in the solution,
warm
grm. of
NH^Cl
Concentrate
''
Filtrate
c" add
2.
NM^HO
See
and NaJdPO^
and proceed as
% 7A-
in
Analysis
B.
tion.
Notes on the Decomposition of NH^Cl by IINO3 in soluComptes Rendus, October 13, 1851 (Maumene).
J.
Lawrence Smith
in
"The
place
is
was
first
supposed that equal volumes of CI, N,0, and N were given off, but it is shown that nearly all the NH,HO, with its
is converted into N,0, the liberated the excess of HNO3. little of the ISrH^Cl-}-HN03 does hot undergo the decomposition first supposed, and in this way only can the small amounts of N
equivalent of
HNO^,
and CI be accounted
little
for."
"
Some
nitrous or hyper-nitrous
if
whole process
cone.
HNO3
is
used
or none
if
dilute
HNO3."
on
The
folio Hows
action of
NH.NOj
NH.Cl
is
theoretically as
2{NH,N03;H-NH,C1=5N+C1+6H,0.
ANALYSIS OF DOLOMITE.'
33
The
8NlI,Cl
+ ioHNO,=9N,0+8Cl+2iHA
and
2HN03+NH,a=N,O+Cl + NO,+3H,0,
and
8.
d, bb,
By loss.
Frus..
39,
Weigh
in
the
Geis.sler
apparatus,
fill
the
witii
HCl
(dil.)
and with
li.SO.,
(cone.)
respectively.
tiously let the
eral,
till
warm
Cool
details
apparatus and
weigh.
p-or
Do
not
,-
p.^
By
direct weight.
II., c.
Arrange apparatus
loops on nails.
as in Fig. 4.
a contains soda-lime,
t
/
is
a flask of
about 300
c.c.
capacity.
contains cone. H.SO^. ^ contains pieces of pumice-stone saturated with HjSO^; avoid much liquid in the bend,
cone.
34
QUANTITATIVE ANALYSTS.
a strong hot solution of CuS0,,-t-.5H,0, add pieces of pumice-stone, boil hard, evaporate to dryness and The product should be nearly white. ignite well.
N.B.Make
g contains
in
in
inner tube,
{k\
Fig.
4.
Place i.o to
1.5
connect apparatus
Pour a little water through the funnel tube into c, then add gradually HCl, diluted one-half with water. Attach a, and aspirate
;
and
h,
and
gently.
this
Heat cautiously
to
incipient ebullition
let
maintain
continues.
Weigh
Note
9,
Calculation.
cool while
the aspiration
CaO.
47.8
21.8
"
CO.
MgO.
100.0
Having
estimated
these
constituents,
calculate
the
ANALYSIS OF URONZE.
35
amounts of CaCOj and MgCOj, and report under "Special Remarks," thus
found
CO,
:
MgO
required or M.
COj
Analysis N&t 8
BrOXze.
Ctt,
To
Zn,
A. Deterniinatioa
Dissolve about 0.6 grra. bronxe
of Tin.
filings, carefully freed
from accidental impurities, in moderately dilate HNO3, in a flask in the neck of which is placed a small glass funnel. After complete solution (except the SnO,), transfer contents to a porcelain dish, evaporate to dryness, moisten
with
HNOp
91.
filter
Dry
this
and weigh.
Fres., 126, L, a,
and
B.
DoterrQination
of Lead.
To filtrate from A add dilute H^SO^, evaporate until fumes of HjSO^ appear, or the residue is nearly dry, let the dish cool, then add water, and filter from the PbSO^. See Fres,, g 163, 2, and iiG, 3, a, X Dry, ignite, and weigh precipitate. See Frcs., 83, d.
0.
Determination
of Copper.
The
c.c.
fdtrate from E. should not measure more than 100 Place the solution in a large platinum dish, arran^'e
-5
QUANTITATIVE ANALVSIS.
element with the platinum dish, and the carbon elemen'. with a small piece of platinum foil which is immersed in
Let the battery run four or five hours. Take out a drop of the solution with a pipette, place on a watch Pour out the solution glass and test for Cu with H^S. when the precipitation is completed, and wash thrice with
the liquid.
Tlien wash the copper film the hand, over a Bunscn burner,
N.B.
It
is
Cu
before
proceeding further.
D. Determination of 2;inc.
Heat the filtrate and washings from C to boiling, add excess of Na^COj, boil a few minutes, wash by dccantation hot, then on filter. Dry, ignite, and weigh as ZnO. Fres,, 1 08, t,a, and 7j.
Analysis No.
9.
Coal.
(Pkoximate Analyses.)
To be determined. Moisture, Volatile and Combustible Matter, Fixed Carbon, Sulphur, and Ash.
A-
Determination
of Moisture.
ounce platinum crucible for fifteen minutes at IIS^C. a:r-bath, cool and weigh. Repeat this desiccation in the air-bath, weighing at intervals of ten minutes, until the
lialf
m an
weight
moisture.
It
constant or begins to rise. Loss of weight gives In reporting, give exact temperature at which was determined. N.B. The increase in weight is due
is
it
ANALYSIS OP COAL.
thirty to uincty
37
minutes in the air-bath. Anthracite coai News, Km. may be heated an hour or more. See Ckem.
Repr.,
Vol
V., p. 80.
B.
to
covered, Heat the same crucible with contents, closely three and bright redness over a Bunsen burner, exactly
allowing the crucible one-half minutes, and then without the blast-lamp, exactly three to cool, heat strongly before weigh. The loss and one-half minutes more. Cool and and includes half gives the volatile and combustible matter, See F below. the S in the FeS,.
C-
Determination
of Fixed Carbon.
Bunsen Heat crucible and contents, uncovered, over and the weight is burner, until all carbon is burned off from one to four hours or more. This talces constant.
Loss
in
weight
the S.
D Determination of
The
the ash.
the Ash.
difference between the weight last obtained and that Note color of of the crucible gives the weight of the ash.
E.
Determination
of Sulplmr.
Secure a sample of anhydrous NaXOj, shown to be absolutely free from S by the silver test. Weigh out about two grms. coal in fine powder, mix witli about ten grms. NaNOj and ten grms. NaXO, on glazed paper. The sodium salts need not be weighed accurately
;
KNOj may
be used
in place of
NaNO,.
Deflag-
3$
a
QUANTITATIVE ANALYSIS.
;
Bunsen burner add the mixed coal and sodium carbonate little by little, replacing the cover of the crucible quickly
expect to effect a perfect fusion. Place the crucible and contents in a casserole, add water, and digest until the mass is disintegrated, and the crucible can
each time.
Do not
be removed.
boiling,
If
Add cautiously an excess of HCl, heat to and throw down the ILSO^ with BaCl^ as usual. flocks of SiO, remain insoluble in HCl, evaporate to
water-bath,
dryness on
water,
filter,
heat until
HCl
is
expelled, add
and proceed as above. If the BaSO.^ is reddish after ignition, wash with solution NH^CJijO, and then with pure water, dry, ignite, and weigh again. The BaSO^ may also be purified by solution in cone. H.SO^ and
rcprccipitation with water.
Second Method for Determining SiUphur. VviX two to five grms. powdered coal in a flask holding a litre; add ]00 c.c. HNO, and five grms. powdered KCIO^, heat to boiling, adding more reagents as needed; continue until all
the carbon
is
oxidised.
dryness, add
HCl and
Hayes's
article in
Am.
Chem., Feb.,
Am.
P-
Calculations.
Theoretically we should deduct half S from the volatile combustible matter (because iron pyrites loses one-half its sulphur at a red heat), one-eighth S from the fixed carbon and three-eighths from the ash. (2FeS become Fe^O^, or 8 X 32 reduces to 8 X 3 4 24.)
Tractically half the amount of sulphur is deducted from the volatile combustible, and half from the fixed carbon; reports should be
39
G,
Estimation
lon^'.
coal with
PbCrO^
in
a hard glass
Pass the IIjO, CO, and MaSO^ formed through two U-tubes, one containing ignited CaC^, and the other a solution of Pb(N03) and through a potash
tube 0.25 metre
bulb,
The
first
IIjO, and
One part of carbon in Calculation of Calorific Power. burning yields S.oSo calorific units, and one part of hydrogen
in
COj,
burning 34,460
calorific units.
Hence
to calculate total
C by
8,080 and divide by 100; also multiply the percentage of by 34,460 and divide by ico. Add the quotients.
(A calorific
unit
is
the
amount
C.)
XXX [V.
p.
233.
1876.
Analysis No.
10.
Copper
Pyrites.
Determination cf Copper.
Pulverize very finely.
it
Weigh out
about 300 c.c. capacity and covered with a small funnel, the stem of which is slipped into the neck of Add 20 c.c. cone. HNO3, 5 c.c. cone. HCl, mixthe flask.
in a flask of
c.c.
cone.
H;SO^ and
filter
fumes
of
HjSO^ appear
and wash.
abundantly.
CaSO,,
Test residue for copper before the blow-pipe. Dilute filtrate to 200 c.c. exactly, mix well by pouring into a dry beaker and back agam three or four
etc.),
times
c.c.
with a pipette
<jO
QUANTrXATrVE AN'ALVSrS.
and place in a platinum dish previously weighed, (N.B, Volumotric apparatuii as sold is rarely reliable, therefore test pipette and ilasic before measuring as above) Arrange
battery, placing the " battery acid" (one part of H^SO., diluted with 8 to lo of water) in
two
cells of a
Bunsen
the
Connect the
zitic
and the carbon ( with a piece of platinum ) pole foil which is immersed in the liquid. Cover the platinum dish with two pieces of glass [)Iate, one each side
of the
platinum
foil,
to prevent loss
by spattering.
Or
use the
spiral described in C/iau. Nezvs, XIX, p. 222 (1869). See also Crookes Sckcl Methods, i>ages 187-200. It is best not to let the battery run all night prepare the solutions on one day and start the battery the next morning. Four hours or more usually suffice for complete
;
cone or
precipitation.
Test a few drop.? of the solution with II,S When precipitation is complete, pour off liquid, wash copper wuh distilled water three or four times (work rapK y) then with strongest alcohol twice; drain the alcohol oft, dry the copper at a very low heat, holding the platinum d:sh m the l^and over a small flame, which must not ouch the dtsh, and weigh immediately. Next treat the
tions should agree to about 0.2 per cent.
Amfyses No.
in
VOLUMETRIC ANALYSIS.
solutions of
4I
amount of the reacting substance being calculated from the volume of the liquid The first principles and method of procedure have used."
strength, the
known
been foreshadowed
of
in
Analysis No.
3,
III.,
Determination
eral
ion's
For explanation of genvolumetric methods, see P'rcs. 54, and consult StitHandbook of Volumetric Auulysis, also Mohr's Lchr-
Principles, use,
When
;
volumetric analysis
first
came
into
results in percentages
solution of acid was used for potash, another for soda, etc.
is
based on the
and
of their
;
so prepared that one litre contains one-half or the whole of the molecular weight of the reagent weighed in grms.
36.5
and
KHO
56.1, 36.5
grms. of
if
HCl
exactly neutralize
56.1 grms. of
KHO,
and
dissolved in one litre of water, the whole of one solution will not only neutralize the whole of the other, but any aliciuot part of one will exactly neutralize a similar aliquot
part of the other.
iettes,)the
And
amount
of reagent
volume of the siluuon. (Before employing burettes, pipettes, and graduated flasks, care should be taken to test
the accuracy of the graduation.)
Standard Solutions.
lar
weight
called
Solutions containing the molecureagent expressed in grms. per litre are normal solutions in the case of di-basic acids
of the
;
(H.SO^,
HoCA
etc.)
and of
(NajCOj)
^2
QUANTITATIVE ANALYSIS.
is
taken,
making
are
half
mrmal
solutions.
following
:
reagents
ALKALIMETRV.
I-LjSO^ of sp. gr. 1.840 with three or four times its
43
volume
of distilled water
cool
and
dilute to
is
Weigh off about 12 Sodium Carbonate Sijlution. heat in a porcelain dish grms. anhydrous C.P. Na^COj
;
to low
place in
a desiccator to cool.
this,
c.c.
Weigh
and dissolve
This
in distilled water.
shown by
this
simple calculation
Na,
--=
46
48
C
O.
Mol. wt. of
=12
==
Na.COs
106
=
-=
53
10.6 grms.
;
200
c.c.
c.c.
Take
of the
Na^COj
40 c.c, accurately measured, place in a wide-mouthed flask of about 300 c.c. capacity add litmus solution, and run in H^SO^ solution from a burette until a wine-red color is obtained boil hard to expel CO;,, and add more acid until the color is permanent. Read off the
;
;
c.c.
used.
Suppose 30
solution.
solution
(30
HjSO^
to every 25
c.c.
of the acid
solution
make
it
normal.
Measure,
therefore,
the
H,SO^
water.
and add the necessary amount of Suppose the HjSO^ solution measures 900 c.c., since 900:=: 25X36, then 36 X 5, or iSo c.c. water must be added. Add the water, mix well, and again determine
solution carefully
44
the Standard
:
QUANTITATIVE ANALYSIS,
one
c.c.
of the
ex-
In case oi actly Jiciitralize on of the acid should be deterdifficulties the exact standard
c.c. of the
ILSO^
solution.
mined gravimctrically by precipitating 10 or 20 c.c. with BaClj, and calculating from tlie BaSO^ obtained the
amount of HjSO^
in
one ex,
tion of cochineal is
Carminic acid being stronger than carbonic acid, a solusometimes substituted for litmus, in
The
dycstufi
tropaeoHne has recently been proposed as an indicator in alkalimetry. Cf. BiK d. chem. Ges. XI, 460 (1878).
Dcci'mrnml Sohtiion of Acid. Call the above normal "No. r;" take 100 c.c. of No. t, put into a litre flask, and dilute to one litre. Call this decUiormal soiution
solution
"
No.
2."
A. Valuation
of
Soda Ash.
{Determination of Na^CO,.)
Place about 12 grms. powdered sample in a platinum
crucible or porcelain dish heat moderately for utes over a Bunsen burner, until all
;
some minexpelled
;
moisture
is
weigh out exactly 10 grm, dissolve in water; dilute to one-hall litre and mix well. Take out 50 c.c, solution (which contains one grm, soda ash), and determine the amount of normal acid needed to neutralize, adding litmus s before, and boiling to expel COj. Suppose 50 c.c. solution soda ash
eool,
;
required 15
c.c.
ard acid
thpn ^^^"
^!f53
x
p.
stand-
',1
100
Tgrm,
Og^.
= 79-5
per cent,
results
Na^CO^.
are
See
Frcs.,
195,
These
appro.ximative and preliminary, and the operation be repeated, finishing with the deci-normal solution
2
only
.below
Take another 50
c.c.
must No.
c,c.
of
of .solution
"No.
and then
ACIDIMETRY.
" finish with solution
c,c.
45
in calculating, 10
No
2,"
Of course,
No.
I."
of
No,
2 equals
one
c.c. of "
B-~ Valuation
of Pearl Ash.
Proceed as before; weigh quickly the salt cooled in a In calculating, use desiccator, for it is very hydroscopic.
the factor 0.0691.
reaction being
much
increased by the
absence of
CO^.
ash
The process
is
as follows:
point assic hydrate (and decinorraal also) until the neutral is mentioned in the next normal (The is reached.
KHO
paragraph.)
one c.c. alkali, substract Since one c.c. acid the number of c.c. of standard alkali from the number c.c. of standard acid added in the first place, and then calculate
as usual.
ACIDIMETRY.
Generalities.
acids, especially
HCl,
HNO3, H,SO
is frequently deduced from the Sec tables in Gravity as determined by the hydrometer. percentages of acids in soluFres., pp. 690, O91, showing
Specific
tions of
different densities.
titration is desirable,
standard
KHO
solution
is
KHO,
dissolve in
litre of
down carbonates,
iiormal acid.
boil,
let settle,
of
46
QOANTITATIVI'. ANALVSfS.
A Valuation
Take
5
of HOI.
to 50 c.c. acid,
KHO
X
Ill
calculating
multiply
100,
the
number
this
of
c.c.
of
KHO
added by .0365
ber of
c.c. of
and divide
acid taken
Gravity
Example. Took
[.035
;
10
c.c.
i
HCI
c.c.
solution,
having a Specific
i
since
of
water weighs
grm the
weight
of acid
taken
10.35 grms. 8
c.c.
The
KHO,
whence
.0365
10.25
100
B.
Ajialysis
A.
using cochi-
"Witz
12), or use
Mohrs
Add
(in
to a
known
pure
is
excess) of
dry CaCO,.
After de-
composition
COj,
of CaCO^ in hot water. CaCOj in excess of normal HCI, and determine the HCI remaining by means of normal KHO, or NaHO and litmus solution. The results with dark
filter,
Dissolve the
CHLORIMETRV.
47
c.c. Determine akohol by neutralizing about 300 measured and distilling off some vine>^ar with CaCOj Then determine specific gravity by amount, say 150 c.c. the per cent, of alcohol. weighing, and from this calculate
D.
33-)
formed thus
2CaH,0,
The composition of bleaching powder The following are some of the formulse.
"
variously given.
+ H,0,. Watts, CaClO -f CaCl, Ca,0 + 2H,0. 4H.O. Bloxam, CaO C1,0 + CaCl, ^CaO +
Quelques Chimistes
"
CaCl,
Roscoe, CaCljO,.
Muspratt,
CaO
CI,
2H,0.
3H,0
Kolb, (2CaO,Cl,H,0), CaH,0..
Rose, (CaCL, Ca,0,) CaO,Cl,
Stahlschmidt's theory of
its
+ 4H,0.
formation:
Benefit D.
Chem.
Ges.,
1875:
3CaH,0,
-{-
CaH.O,
+ 2H,0.
Powder, by Dr. See paper on Constitution of Bleaching Lunge in American Chemist, Vol. V, page 454-
^g
QUANTITATIVE ANALYSIS.
allowed to stand in contact with air and light, it decomposes, CaCl, increasing, and the CaCIO dccreas-
When
uv.
Dry
C, decomposes
thus
(Thoki'K.)
3Ca3H,0,Cl,
By
thus
the action of
Ca^HoO.Cl,
The
value of
the CI in
The strongest contains 38.5 per cent available chlorine. One or two per cent, of this is present as calcium chlorate,
which
is
Action
of
hy
(CaCl,0,
CaCU)
2HCI
:
= 2CaCl, + 2(HC10).
(CaCUO,
CaSO,
ILORIDE OF LIME.
49
MetlmL
From
Frc.eniiis'
Qmnt.
Analysis,
As,0,
CaCUO,
= As.Gs +
CaCU.
The end
undetermined by KI and starch, turning this mixture blue. decom posed hypochlorite
reaction
is
(,
Prcpamtiou of
n.
^tich
fj.^^COj
250
aq.
c.c.
;
ddute
Starch P/.t.-Bo.1 three grms. one grm. water, add one grm. KI, Moisten paper with to 500 c.c.
Kl
this solution
and dry.
Solution of
..L-.t}^.
ib)
Prcpamtim of
- Dissolve
wah
25
ex
until
actly
grms
water.
^Bod
j;
Jissolved
and dilute
difficult to
to
one
Utre.
Make a
this
If
s^l^^'""'
Since
it is
amount, take
5.0^3 g^"^^-
then
4.95
:
1000=
c.c,
5 -Of
grms.
10127.
c.c.
Add
tion
then 12.7
to the litre.
One
of this solu-
0.00355 CI.
-^l\^ sample well; Process of the Determination. or 60 c.c. water weigh out 10 grms., rub in mortar with 50 Repeat. flask. decant turbid liquid into a litre
(c)
settle;
Fill
up
ro
Fill a burette,
into a beaker,
add the
QUANTITATIVE ANALYSIS.
;aon no longer gives Repeat on fresh amount
turbid liquid,
{iL)
a blue
mark on the KI
starch paper.
off
Cakulation.
Amoimt taken
represent the number of [French chlorimctrical degrees and 760 m.ra., which one kil. of sample jitrcs o CI at o.^C. Now one litre of CI weighs 3,177 grms.; should yield. Sec foot-note on 100 degrees. hence 31.77 per cent. Qumi. Anal] p. 700 of Fres. amount of ca/dum chloride present may be de-
The
termined by
estimating the hypochlorite as above, and c.c. a slight excess then adding to the second portion of 50
first
of
CaClA
AgNOj.
The amount
may be determined by
pure a third portion with ammonia, then acidulation with H,S04 and digesting with Zn.
Ca(ClOj).
12H
= CaCl, {- 6H,0.
Again determine the CI by AgNOj, and the increased amount over the second determination gives tjic 01 exist(Thorpe.) ing as chlorate.
TYPE METAL.
(0
51
^t
o " G
^t;
ti
J*
(S4
^ --Si
V
^j
2
3
O
c:
M
R"2
o
'It
.
"
fH
QyWtllTlTATIVE ANALYSIS.
^^f,
_Somc
titi,
H'
of
tho
till
may go
'^"^ '^'^^''^^'
into
solution
as
litratc of
tli*-^
"'^^'^^
'^^'^^
^"^^ ^'^"^
^J^^''''^''
;
in Precipitate c
mixed
witli tlie
sulphide of antimony
in
should be separated by F. W. Clarke's this case they on the solubility of the sulphide method which is based may he found in acid, and details of which
of tin in oxalic
I'O!-
another method
65, 7, a-
Note
->.
On
+
some
of the
antimony
dissolve and remain with Residue a, and lead may refuse to as follows after igniting and weighin which case proceed Sb ? fnse with Na,C03 and sulphur Pl> ? ing tlic SnO, Dissolve in warm water and filter in a porcelain crucible. which may be treated with HNOj from the residue of PbS, To the porcelain crucible and wci:j,hed as PbSO,.
:
in
alkaline solution
precipitate of
add
sliglit
excess of
HCl and
collect
SbSj
+ SnS, +
S on
filter;
to porcelain excess of S by washing with CS transfer dryness, fuse capsule, oxidi/x with UNO, evaporate to .silver dish, dissolve the mass in a mixture with NallO in a uf three
volumes
of alcohol
of
and one of water, and filter For details, see Fres., sodium.
To the solution containing stannatc of sodium, 165, 4, a UCl, saturate with ILS, and treat the precipitated
add SnSj as
usual.
See
Fres., 126,
I, c,
and
9E.
Consult article on the Estimation of Antimony, by E. M. Bartlcy, in American Chemist, Vol. V, page 436; also
fur
DETERMINATION OF
2IXC.
53
54
QUANTITATIVE ANALYSIS.
CHROMIC IRON
OHtC.
55
tf)
-I
-g
QUANTITATIVE ANALVSIS.
Amfysis No.
17.
Pyrolusite,
method
Determmation of MuOj.
Employ Fresenhis
arul Will's
as described in
edition of 1881, pages 705-709, Fres. Quafif. Analysis, Tiirirmci/iode 215, pp. 617203, A, See also Mohr's
(338 (cd. 1874).
Take
On
the Estimation
Manganese in Manganese Ores," by E. Scherer and G. Rnmpf, Chemical News, American RePeroxide of
print. Vol.
Analysis No.
18, Feldspar.
A. Determination of Alkalies.
Prof.
[3]
I.
J.
See Am.
Set.
Also Frcs., 140, II, b, Weigh out one grni. Pulverize well in an agate mortar. Mix well in an agate mortar, Jirst, with of the silicate. about one grm of NH^Cl (pure enough to sublime without
269.
residue), and, sirondly, with about eight grms, C. P. precipitated CaCOj add the latter in three or four portions,
;
mixing well after each addition. Transfer the mixture by means of glazed paper to a platinum crucible. Apply the heat of a Bunscn burner to the upper portion of the crucible first and gradually carry the flame toward
the lower part, until the NII^Cl
is
completely decomposed,
DETERMINATION OF ALKALIES.
57
heat before
which ensues
utes.
Then
This operation
facilitated
is
greatly
by using a special
Prof.
pose by
Smith,
Fig5-
J.
Lawrence
in
and
stand
represented
The
its
supports on
rod-G a
cast-iron plate
is
held in
hook
to
N.
the
When
Fic. 5-
heat
of
is
applied
bottom
the crucible
by the
flattened burner F the decomone position proceeds regularly and is completed in about
hour.
it
in a porcelain casserole,
and
semi-fused mass with boiling water until thoroughly disintegrated. This may take some hours. Then Ai.O,, Un,0,{?}, filter from the residue (SiO Fe.Oj, of water. etc.), and wash well with about 200 c.c.
CaO,
and are now in the water solution. Add to this solution NH,HO and (NHJ^COj with a few drops of (NHJX.O,. about 50 Evajjorate without filtering, on a water-bath, to small filter a c.c. add a little NH.HO, and filter through platinum dish. Evaporate to dryinto a weighed (No,
2)
riWiUMWfll
Mill
QUANTITATIVE ANALYSIS.
g
ignite very gently to drive off a little ness on a water-bath, If the residue is not perfectly soluble CI and weigh.
NH
in watir
ignite,
filter off, evapor:ite, and quite white, dissolve, gives the weight of the This and weigh again.
by separating it with PtCl, Next determine the K. either manner, or by gravimetric or voland alcohol in the usual CI in the weighed chlorides. umetric estimation of the total page 841, 3. Consult also For calculation, see Fres., and 14. Crookes" Select Methods, pages 13
B.
KG +
NaCI.
.
.
Determination
six Fuse two grms. mineral with six grms. K^COj add excess o Moisten with water, digest, grms. Na^CU,.
HCl, evaporate
Analysis No.
to
dryness,
filter
expel
HCl
in
air-bath,
add
from SiO,.
Continue exactly as
SOLUBLE SILICATES.
59
6o
QUANTITATIVE ANALYSIS.
Analysis No.
19.
Iron
P.Os-
Slag.
Ta
be
ddermined:
SiO,
MgO,
Puiverizc
finely;
S,
weigh out exactly five grms. mix on glazed paper, by means o a horn spatula, with fifteen grms. anhydrous NajCOj and fifteen grms. K,COp
;
need not mixed slag and fluxes into a two-ounce platinum crucible, and heat over a Bunsen burner until by settling down room is made for more. Heat twenty minutes or more before
fluxes
NaNOj.
These
be accurately
weighed.
Put one-third
the
the
blast-lamp.
treat
Cool
boiling
suddenly,
crucible and
place
and
with
water until
grated.
little
Remove
little,
the
add
excess of
HCl
avoiding loss of liquid by violent effervescence; evaporate to dryness on water-bath, expel HCl
completely by drying (not above 115" C.) in an air-bath. Moisten with water, add HCl, digest, and proceed as pet
by
IRON SLAG.
11
.'
61
^, _>>
1
>
!J
JJ
1.
tV.2
rf
rt i<
"
3 ;^
-5
Vi r.
o 3 r^
c
S
rt
J^
<?.
o o.S
It:
,0
4
..o
u)
;.5
W)
.
ft
^ c5B
fi 'J
is
M6i
<5
r^ ;; J.
-1-
w
o
bo
^ :==...=
J-*
M
r:J
^^
y
>s
-^
to
r^
fTiri
u " d
<! "S
^
. "^
<i
*^
<y *^
.^
o
!ii
""^
3"
It
C:
,'i
h -~ c^
"^
f
aj
C e
^,
'-
^ F
.X
50
^ "O
>-H
J-.
p'
>
S S
>^
.5
"^
T3
c --^ ^o ~ P "
u - 5 M ^
1^
^
jC
i
c ^
rt iz
1
i"i
i-i-(
^
t
~i .
-C
^ br
CO
I
.s
"
V=;
^
'5
'^;,
6i
^^i
"
y O a ? n h "^
'J
w
'-e
^
'S i?
.*
>
m|. ^ a o
"
CJ
SIS
^^
'!
tc
8.
-a "
O
i;
ba
*'
^
'Jl
Q Oh
-v
JXl
Z ^ F
,3
'T^
ij
5 ^
o % S
'-
=
E?
*i
li
o
CO
tixi
"^
" s
" T3 r)
2 n u " "O K
a
"^
O
c
.)i
O-o > J; K -o ^
^
'^
^ "
t-
^^
,!J
cO
u s M " ^
J V
O
u
<^
> tU 3
^.
,
^
^
'J
y u
?>
8
o
8
P s o a "
;-!
i:
^."
';
~
a
e1
in
'>
'^
tfl
%
C/J
>-,"
>
" 'E
^ -a J3
^
U
-^^
o u
n
o
o
^^
02
.=
" o" I
O
T-j
"^
O O U o
U3
^ o ^ Cue.
"
r-
CA
Ct
.5
a
T
ii
c?
?
i;
3 u
4J
&
B
x;
-
d
aj
q>
S =
K ^
*;
Ui
c a
ft
a 5
xj
J
"
- "
to
"^
^3
c
5:0
ES
p
U "
C
u u
^
3
o ^
a*
rl
1)
- g
11
" s
+^ ^ ^u
4)
"
O
Si
>? -u
6^
V,
Q
c o S
in
^::
3 O <0 / s
&.9
S5
u *
63
64
QUANTITATIVE ANALYSIS.
^e13
c u
^
-u
if
.t^>.
O^
1
'^
^
L-
^Jj"
it
.
M ij^
>;
^^
<i '>5
'C
'Si
go
L^
(ii
Co
<,;/<
Si
1^
-a
s::
Q
8
"=
-f'ji
><
o
J3
D
U
CO
lU
jU
o c o * ^ o ^
'^^
flj
'
'~;
65
-3
- /,^
^,
' C (
r^
[jj
w
^
"^
^ ^
*--
^^"w^
^ -?.:,,
_^S:s
cl-^^-w.-i"!^
^-;.*:
-1
2d.
'P.,
e
-^ fl
..r->B^
*!Q^
""Pill > 5
:s-^,:
ty
'-
^ c=
G.S ^B^'-S
-- ^o^ w :i;.^ ^3
*-i-t
l-f^S ?
-*
E c-0 - o E
3
c!
"
^'-^
::
^>
"*
~
<^,^o
*J
S
C2
J^
'
^.X.'j:
14
t^^
'C
^ U V
0-(i,
0~
*
<i
S o
"
te
,
" T3
o o
-.^^ ri ~-^
-=^
j|pO^ e - -^ TJ Tj
p 'i - ?
i" p
LL<
^ ^ O: 111
G
.S =<
-:;
.; a:
J^;
**
iT
i^
"S *1
O .so
^^ > 5^-
'S "'^.^A -S
in
-_-,-?
= 3
9.
.1^-^
*^ it e,
S
*
^O
"
2.
n
I
I
'g -^ ^^
I
't?
66
QUANTITATIVE ANALYSIS,
in
an iron mortar
pounds into pieces that will pass through a tin forty or fifty Thoroughly raix the fine and holes. sieve with halHnch Break up about ten pounds of average quality, so
coarse.
that
through a tin sieve with quarter-inch holes, and pulverize in the iron mortai Mix well, take one pound, a brass sieve of 60 meshes to the until it will pass through Mix well, take out about 50 grammes, pul inch.
it'
will pass
linear
determinations.
yet
or a special portion of this required for as needed, in determination should be further pulverized,
powder. an agate mortar, to an impalpable fusion. Thoroughly mix the ore Note 2. Preliminary a third of the and its fluxes on glazed paper, put about the lower portion mixture in a two-ounce platinum crucible, been previously lined with a of whose interior surface has Na,CO and heat over a common Bunsen
thin layer of
violence of the burner with strong flame until the greatest Then add and treat the twoeffervescence has ceased. same precaution. thirds remaining successively and with the until the mass IS: Finally, heat strongly over the blast-lamp more NaXOj, in complete and quiet fusion, adding a little
should
for this not readily fuse. The time required fusion varies fron 30 to 50 minutes. resist this Certain highly aluminiferous ores obstinately known method of attack in such cases mix with the flux a pure precipiweight (two or three grammes) of chemically just before tated silica which has been strongly ignited
it
;
The amount of silica added is deducted from the total amount found in Residue
weighing.
afterwards
d.
6f
the crucible
below red heat, then chill it suddenly by plunging it into cold water contained in a porcelain caswith boiling serole, lay the crucible on its side and digest The fused mass will generally become detached water. from the crucible and come out in a cake. Then remove
cool until just
it,
HCl
to
and add this solution to that of the Insoluble Residue Should any portion of the fused mass, thicker than a {2). it ought to film, obstinately resist solution in the hot water,
be removed only by patience and long boiling; and no attempt should be made either to dig it out or to dissolve lest by the formation of Aqtia Regla or free CI it in IICl
;
(in the
presence of
NaNOj,
or
Mn^OJ
the crucible be
Sefakat!on of SiO^. In order to render the SiOj entirely insoluble, it must be perfectly dehydrated.
Note
5.
Tfce evaporation should be carried to dryness, the residue heated until odors of HCl can no longer be detected, and
the
mass
is
Precipitation of BaSO^. Avoid the addition of a large excess of BaCI^ solution. Add only 5 c.c. at first, and then after complete subsidence of precipitate, add a few drops to determine if any HjS04 remains unprecipitated, etc. Then proceed as in Fres., 132, I, i. After
Note
8.
These precautions are necessary to dissolve out any other salts of barium, which are always carried
Jown on the
s
first
precipitation.
If
the precipitate of
BaSO^
gg
QUANTITAXrVE ANALYSIS,
hot cone. H,SO,, pour into cold water, and collect the pre
cipitate as before.
Naie 9. Separation of SiO,. Evaporate as in Note 5. Then add HCI quite freely and warm for some time before adding any water, as the high heat may have produced
anhydrous Fe.Oj, forming an oxychloride which is very Should the acid slow to dissolve, especially in dilute acid. already added be too dilute, concentrate by evaporation,
add cone. HCI, and digest at a moderate heat. Note II. pRECtP[TATEON OF THE BASIC ACETATES. ^^iV-
combined with Solutions li and cV must be very carefully neutralized with sodium carbonate. (If ammonium carbonate were used, bromide of nitrogen might form in
//-(T/^/
Filtrate g.)
To
use crystallized sodium carbonate, and complete the neutralization with a very dilute solution of the carbonate, add-
ing
it
assumes a deep mahogany-red color. If a permanent precipitate forms, add a little hydrochloric acid, and repeat as above. Then dilute the solution to about i
until the liquid
each gramme of the sesquioxide present, add about 20 grammes sodium acetate dissolved in a small quantity of water, and heat the whole to boiling.
litre for
from ten to fifteen minutes for the complete precipitation of the acetates. The fdtcring should be done rapidly on a ribbed filter, keeping the fluid hot. and
It is sufficient to boil
precipitate
as
little
as
possible.
When
available the
advantage.
Bunsen pump may here be used with After the supernatant fluid has been poured
throw on the precipitate and wash
it
through the
filter,
with
boiling water containing a little sodium acetate. Should any basic acetate separate upon concentrating the filtrate,
add some sodium acetate, boil, filter, dissolve the prccip itate in HCI, and unite to the solution of the main body.
NOTliS
69
with KCIO3 to oxidize FeO. be In boilinc? Filtrate e heatthe whole of the chlorate by c^u-eful to decompose
incr
"Note
in
and ferric phosphate by decantaand redissolve in hot cone. HNO,. tion two or three times,
Solutkn
r'
Determination of P.O^.-To remove the HCl wash the pro add NHJIO in large excess,
small bulk ( 1 50 c.c. to 100 Evaporate this solution down to and add about 50 partially neutralize with NH.HO,
cc
c
c"
of solution of
is
the solution
above, otherwise add a small the partial neutralization as the solution, do not bod, aad quantity of the salt. more. Then filter from the yellow let stand 24 hours or
Warm
phospho-molybdate withgranular precipitate of ammonium and wash the precipitate out brin-ing it all on the filter, parts of the precipiwith a solution prepared by mixing 100 gr.=i.2) and 80 parts of tant with 20 parts of HNO, (sp. a small Dissolve the yellow precipitate by pouring water. filter into the through the quantity of dilute the determine the phosphoric acid original beaker, and c.c.) ammoniacal solution by means of mag:nesia mixture (5
NH.HO
in
Magnesia mixture
If
is
preferably
made
magnesium phosphate
sium hydrate, add
with
falls
HCl
until
dissolved and
reprecipitate
NHJ-IO.
precipiReserve the filtrate and washings of the yellow a little more tate, and test for phosphoric acid by adding and allowing of the ammonium molybdate solution, heating pour If a yellow precipitate forms, to stand 12 hours.
through a separate
filter,
dissolve in dilute
NH4HO
and
add
Tf
to the
ammoniacal solution.
yellow precipitate
first
the
70
ficiently
QUANTITATIVE ANALYSIS.
washed, a red residue of oxide of iron may remain on the filter, in which case pour dilute HNO3 upon it allow it to pass into the ammoniacal solution, acidulate
that with
diluted precipitant, then dissolve the precipitate on the filter and that adhering to the beaker in as little dilute
NH^HO
as possible.
precipitate of ammonium phosphonot sufficiently constant in composition to admit of directly weighing it in exact analysis it is there-
molybdate
and the phosphoric acid thrown down with magnesia mixture as just detailed. According
fore dissolved in
to
NH,HO
loo'^
C,
it
contains
NH^HO
P,Os
92.461
MoO,
100.000
Lipowitz says the precipitate dried at 20" to 30" C. contains 3.607 per cent, of P.Oj,
cent.
P,0,.
3
When
dried at 120''
about
also
per cent.
For properties
Consult also Finkener's 93, i, foot-note. paper in Bericht d. d. chem. Ges XI, p. 1638 (1878}, and Chem. News, X L VII p. 66 1 ( 88 3), Note II. Washing of Fe,0,3H,0. Wash this precipi,
Fres.,
tate
AgNOj.
boiling
Then
water.
transfer to
filter,
Note
16.
Determination of
Mn. (Gibbs'
process.
Am
7'
NI i-lO LceW.
HCl solution add solution of Na,HPO, m large in Lccss and ThenaddcUIutcH.SO,or HCl until the wh.te
XLIV,
p.
216.)
To
the
precipitcite redissolvcs,
heat to boilmg, and add point about an hour, when Lcess Digest near the boiling and gelatinous, becomes precipitate, at first white
the
NH.HO m
Filter and wash crystalline scales. rose-colored and forms the precipitate If tinged red, redissolve with hot water. On ignitwn the preHCl. aad repeat the process,
dilate
cipitato is
white powder. converted into Mn.P.O,, a nearly separated as in present, it must first be
Fe.
ut
completely free from the KClOj Solution k\ which must be a wide-mouthed reduction used to oxidize Filtrate k, into Carefully let down mto the bottle hoidmg about 250 c. c. a zinc, free from iron, and
bottle
a lump of amalgamated upon it, add about lO c. c. strip of platinum foil resting watch-glass and set aside over cone H SO,, cover with a test the To ascertain if the reduction is complete nio-ht sulpho^yanide. which should solution with ammonium color. e'ive only a trace of pink ^ about 200 c. c., and introduce into a flask holding
Then
fitted
forte
untd complete add dilute H.SO,, and heat and wash out the Cool the flask, pour solution of iron. beaker containing about contents of the flask into a large concentrated II.SO, and 400 c. c. cold water, add a little
wire,
titrate
gramme
iron piano-
with a solution of
its
K.Mn.Os
strength.
water) to determine
of the reduction'''now nour and wash out the contents cone. H.SO,. and tilmte bottle into a large beaker, add
K.Mn.O, as
before.
72
QUAlStTITAX/VE AJTALVSIS.
Solution
b"*
ferric chloride formed will interfere with the end reaction In such a case re precipitate with of the permanganate.
exactly the
aver-
Analysis No.
C. III.
For method
tion, see
Sundry Suggestion's.
of
i.
Solution a^
may be used
for
Fe
is
tests,
if
tion.s of
Ca and
b^,
Mg
can be made,
Fe can
be
made
Solution
b^
the
Fe can
in
mctrically by dissolving
In the
latter
TiOj
will
impair the
results.
The
^ may be
by heating with fluoride of ammonium and concentrated sulphuric acid in a platinum crucible, whereby all the SiO, is expelled and is determined by the
loss in weight, the residue
Fe,
4.
In fusing Residue
or Precipitate k, hydro-sodium
sulphate
may be
water
substituted for
KHSO+,
it
for-
of crystallization
should be heated
In
either case avoid expelling the whole of the H^SO^, or if the mass is heated to redness, partially cool, add cone.
II, SO^
at a
lower teaiperature.
In this
73
will
be held
iti
and the resulting acid sulphate will dissolve out readily. For Special Determinations see Notes to Scheme I
in
I,
pp.
323
et seq.
Reactions. A full discussion of the many and complex reactions which take place in the preceding scheme for the
analysis of iron ores
i.s
superfluous.
We add
A.
may
serve
to throw light
The action
upon some
points.
of potassium
permanganate on ferrous
in
connection with
This action, however, may be regarded as taking place in two stages, as follows
1st stage.
2KMnO,+PI,SO,=K,SO,+2HMnO,.
2HMnO,-f7l-LSO,+ ioFeSO,=2MnSO,. +5(Fe,(SO,)3)+SH,0.
\%
2d stage.
Sobdiofi If
NHJIO
and the
precipitate dissolved
H^SO^
Note
in
the results of
of
The presence
HCl
permanganate as shown
in the
equations following:
and
1^-
2lIMnO,4-l4Ha=2MnCl,+SH,0+loCl, 2FeSO,+H,SO,+2Cl=Fe,(SOj.,+2HCl
When
KClOj
is
employed
in acid solution
c),
as aa
o.xidizing
the reaction
which takes place depends upon the acid used and partly upon the strength of said add. Concentrated sulphuric
acid
is
6KC10,+3H,SO,=2HC10,+2CLO,+3K.SO,+2H,0
and
nitiic acid thus:
74
QUANTITATIVE ANALYSIS.
8KCIO3
The
Odling (2):
(
t
(2)
KClOj
evident.
Appendix
to
Aimlysis No.
21.
A. Method
fjrms.
if
for the
Bstimaticn cf Fe and Ti
i
only.
grms. NaFl-)-i2
Neutralize
KHSO^.
is
Dissolve
there
with
acid.
H^S
water.
gas,
boil
some
if
hours,
occa-
sionally adding
of
H^S
filtrate
Filter from
the precipitate
dark colored
re-
add a little KClOj, boil to oxidize Reduce the iron with amalgamated zinc and platlIjS. inum foil, and titrate with KiMn^Oj as usual. As a result
fuse, etc.
To
of the fusion
we have
4NaFl+SiO.+4H^SO^==4NaHSO^-fSiFl,+2fI,0.
PLIGHTS METHOD.
c
75
n
r-
t,
*-
SI
J ^
rf *-
^ ^
cs,
76
QUANTITATIVE
A>.AI,YSIS.
NOTES TO
Note
I.
TIIIC
PRKCEDING SCHEME.
in
77
HCI+KCIO,
dizcd.
once, nor
some of the iron may remain unoxiShould a small portion of ferrous chloride remain in the solution, the subsequent precipitation of the iron as basic acetate (as in Filtrate f. Analysis No. 21) will be imperfect; instead of an orange red flocculent precipitate
too rapidly, otherwise
will fall as
a brick-red
ferric oxide?)
fdters.
which
SiOj
and dried at
C, contains 6 per cent. H,0, which is expelled on ignition, and must be deducted from graphite after the
SiOj
has
been determined.
is
According
to
Allen
(see
p. 91, Feb,, 1874) the Si of converted by the action of dilute HCl into
3Si0.2HjO.
By fusing
graphite with
and both
may be
estimated directly,
AA. Determination
Second Method.
232.
of Graphite
Che^yi.
c.c.
and
Silicon.
(Eggektz,
Mix
10
c.c.
HjSO^
is
with 50
News, H^O,
XVI 1 1.,
cool,
p,
5
add
and cool
The
reaction
as follows
2Fe,C+8H,SO,^SFeSO,+C,H,+H.
This equation, however, but imperfectly formulates the reaction, the S forming H^S and the P forming PH3. A
large
number
addition to
H
;
are evolved in
according to Dr.
78
QUANTITATIVE ANALYSIS.
Vol. 129,
\y.
57,
C,H..
C,H,. C,H,.
CH^
etc.
-J
i Am/lene,
Q^^.
etc.
Next add 10
c. c.
HNO3
and
boil 15 minutes.
dFeSO,+8HNOj=2(Fe,(SOj3)+Fe,(NOj6+N,0.
-|-4H,0.
Evaporate on a water-bath until vapor ceases to
come
off
is
nearly dry.
Add
75
c, c.
M.O-f-ij
c.
c.
HCl and
boil
15
minutes;
add more
through a
first
HCl
filter
if any Fc,Oj remains undissolved. Miter washed with HCl, dried and weighed; wash
Dry
the
at
more iron appears in washwater containing 5 percent. HNOj. ioo C, and weigh the residue consisting of SiO,4Ignite
of graphite.
it
graphite.
amount
and weigh again; the loss in weight gives Lest the residue contain someis
by
NHjn
and
H,SO which
4NH,FI+SiO,+2H,SO,=SiFl,+2(NH,).SO,+2H,0.
The loss in weight gives the however, Nott 2 of A.
amount
of SiO,;
consult,
F.
A. Cair.
HCl,
boil, filter,
wash
with boiling
79
alcohol, {l>) ether and (c) hot water. water, then ^vith (a) determine as in B. Dry and transfer to flask and
volatile combined carbon goes off In this process the together with certain hydrocarbons, and graphite +SiO. remain. The SiO. is removed by the liquid hydrocarbons, out in the alcohol and the the hydrocarbons dissolve boiling water. is removed at last by ether, \vhUe the latter
KHO
B -Detsrmmatlon
of Total Carbon.
Roger's Process. See H. Elliott's modification of London, May, 1869; also Journal of Chemical Society,
Vol. 11, p. 140. Cairns* article in Am. Chem., of a neutral solution To 2.5 grms. of borings add 50 ex. one part of sulphate to S P^rts of of CuSO,! containing minutes; the iron dissolves; water; heat gently for 10 silica, graphite, and comcopper is precipitated, and the bined carbon remain
_
Fe+CuSO,=Cu+FeSO,.
The
order to
volatile
neutral as possible, in cupric sulphate should be as in the form of avoid loss of combined carbon,
hydrocarbons, as shown in
AA.
-o c c CuCl. (I with 50 c.c. strong HCl. boiling, until the copper dissolves
Add
water), part of chloride to 2 parts of and heat for some time nearly to
:
CuCU+Cu=Cu,Cl,.
follows: select a glass tube Prepare an asbestus filter as and 1 8 to 20 cm. in ength. of about 3 to 4 cm. diameter, and place broken Draw out this tube to taper at one end, packed, in the narrowed portion glass and asbestus, lightly Filter the (See^r.... 21S. \ ^' P- 7S90 of the tube. asbestus, wash thoroughly cuprous solution through the
30
QUANTITATIVE ANALYSIS.
with boiling water, and transfer contents of filter to a flask In making this transfer, the carbon, holdiiitr about 200 c.c.
asbestus,
may
little
too'ether, in
water as possible.
Add
about 3 grms. of CrOj, (or if this is not available, about 5 grras. KXr^Oj), and arrange apparatus as in the determination of COi by direct weight,
to the contents of the flask
Ami/sis No,
7,
note
8, II
(page
34}.
Add 30
time.
c.c. to
40
c.c.
concentrated H^SO^,
by
little,
more
CO^
3C+4Cr034-6H,SO,=:3CO,-h2Cr,(SO,),-|-6H,O.
Boil one minute, attach
aspirate
slowly, three
guard tube of soda lime, and bubbles per second. Weigh the
of CO^. absorbed,
amount
and calculate
amount
of carbon.
Note~~Tht carbon separated from cast-iron by treatment with .sulphate of copper contains H and O, and cannot therefore be determined by weighing directly. Schutzenbcrgcr and Bourgeois assig.T to it the composition
expressed by the formula C3H,0, and consider it related to graphitic acid. BulleHn de la SocUtk Ckimiqiie dc Paris, Vol, 23. No. 9.
-^
EB.-Other Methods
mJ^i.^Tl?"'^,^''
for
been devised for deter''"" ^ ^^"^'^h ^^ *i briefly outline, "' rcmarki ema kmg. .'' however, that the foregoing is entirely satii.
^ "'^^^^'^^ '^^^e
8i
V..
Method of Alvaroonzalez.
p_
4jjr.
Place
with a solution of cupric sulpliate (40 grms. CuSO^ in 200 Add di200 ^,.c. l"IiO), stirring until the reaction ceases.
lute
let
dis-
solved.
through one of
Rotli-
er's fialf filters (described in Chem. Neivs, Jan. 30, 1874, 100* C. p. 57), wash thoroughly, and dry on funnel at
Detach
ppt.
from
filter
carefully, place in a
weighed cru-
dry at 100 C, and weigh. Ignite and weigh again; the difference between two weighings
cible (thrONY
away
filter),
This method is not free from objections, but will answer when great accuracy is not indispensable, and speedy results
are desirable.
Method employed by \."Lo\\nw.PC(i.^^\A^. 'S^^ Chemical Phenomena of Iron Smelting, London, 1872. Digest 3 grins,
2.
CuSO^
in
the spongy
Cu+C+graphite on an
in
asbestos
in
CO,
KHO
3.
Cf. Analysis
No.
30.
Method of Regnault and Bromeis. See Crookes' Heat borings in a combustion tube Select Methods, p. 74, with a mixture of plumbic chromate and KClOj, collecting
the
4.
CO,
in
KHO.
also
BoussiNGAULT
a thin paste
with 15 to 20
make
Fe+2ligCl,=FeCU4-Hg,Cl,.
g2
QUANTITATIVE ANALVSrS,
dilute with
HCl and warm for an hour; wash and dry. Transfer to a SiO,+C, filter from the boat, and heat in a current of pure H, volatilizing platinum
Then
20(^250
c,c.
the
HgjCL,
Weigh
burning
(b)
off the C,
Weyl
a galvanic current.
under the influence of Attach a weighed piece of cast-iron to a Bunscn cell, and suspend it in dilute
being given
off at
HCl.
pole,
The
and
iron dissolves, il
the negative
tlie
carbon
also
is
separated,
Weyl has
devised another
following reaction
Fe,+K,Cr,0,+7(I-r,SO,)=Fe,(SO,)3+Cr,(SOj,
+7tL0+K,S0,.
See Crookes' Sclea Methods,
{c)
]>,
^6.
McCreate
March
s jJfet/iad.
Jottrnal,
of
17, 1877.
dissolve cut the iron, while the copper dissolves in excess of this reagent; he then oxidizes the carbon by means of CrO^ in an apparprecipitated
atus
somewhat similar
CO,
in a
Liebig potash-bulb.
S.
Methods, pp, 81 to 84; also Britton's paper in the Franklin Institute, Mzy, 1S70.
Journal
oj
C.
and Phosphorus.
See Chem.
I.
Eggertz's Method
News. Vol.
XVII.
p.
207.
83
place in a A. Dissolve 10 grms. KCIOj in 200 ex. grms. fine borings, boll and add 60 ex. 500 c.c. fiask, add 5
HA
HCl.
little
by
little,
Fe
dissolves
4KC10j+i2tIC1^4KCl+3C10,+9Cl+6H,0,
and
3Fe+C10.+Cl+4HCl=Fe,a6+2H,0.
of sulEvaporate, dry on water-bath to insure oxidation unnecessary, since SiO^ does Thorough dryness is phur.
not interfere in acid solution with BaSO^. Then add to ex. HCl+30
on water-bath
20
c.c.
FeXU
is
Then add
and wash thoroughly. Add 2 ex. of a the saturated solution of BaCL (enough to precipitate cooling add 5 c.c. NH.,HO, I-I,SO, from 0.1 grm. S); after Filter, and wash by decantastir and let stand 24 hours. and then thotion with cold water two or three times, ignite, and weigh. If the roughly with hot water. Dry, shows traces of iron after ignition, purify by so-
iW,
filter,
precipitate
lution in
HjSO^. the For the determination of phosphorus dissolve some 140"' C pig-iron in the same manner, and dry at water, anhydrous Fe,0, will remain with the SiO= add
B.
; ;
filter,
KHSO^,
soften with
H,SO
and determine and dissolve in water. Filter from the SiO Add fdtrate to mam it as a check on the main analysis.
one, and determine the
date, as in
2.
IV,
425.
5
Treat
the
ex. H,0) containing a solution of K,Mn,0,(i grm. to 200 ceases, Avoid a very rapid evolution of the gas when this
;
H,S
and pass grms. of borings in a flask with HCl, three bottles and PH, formed through a series oi
QUANTITATIVE ANALYSIS,
and then pour the content, ol the Jpirate for some time, with water, and add snfhuent Stleinto a beaker, rinse Filter the colorless sothe K.Mn.O,.
HCl
to
decompose
lution.
add BaCl.
to
H,bO and
proceed
as usual.
3
Method employed by
J.
Lowthian Bell.
and pass the gases through a
Dissolve in
HCl
as above,
(lead nitrate super-saturated solution of potassic pUunbate hour, or until the evolution of with KHO), Boil half an
gas has ceased.
Wash
the
PbS
formed, oxidize
it
with
BaSO^ by means of IINOj, and throw down the S as collect on a filter, dry, Ba(NOj),. Let stand 24 hours, This method is said to give higher ignite, and weigh. Compare Fres., p^ercentages of S than that of Eggertz.
I 218,
4.
3-
Client.,
Vol.
5.
page 376.
Method emfbyed by Y^om^cK 2siA Dietz. See Practical Manual oi Chemical Analysis and Assaying applied London, 1872. Translated by Robert Mallet. to Iron,
Dissolve 3 to 5 grms. borings in HCl in a flask connected with four bottles, the first a condenser, the three following containing solution of AgNOj( I part of nitrate to 20 parta
of water).
and when gas ceases to evolve, aspirate. Pour contents of flask on one filter, and wash the Ag^S, Wash out the flask and cleanse the ends of the tubes wltn bromine water, and expel excess of Br by heat the followBoil,
;
Ag.S+8Br+4H,0=H,SO,+2AgBr+6HBr.
The phosphide
Filter from
is
AgBr. and
H,SO,
8$
llous-nnGhXiiJT for deicnnination of PhosSee Annak's de Chimie et de Physique, June, phorus. in American Chemist, Vol. VI, p. 275. 1 8; 5, and abstract
Method of
7,
l^or additional
methods consult
Neivs,
also papers
Allen,
Chem.
XXIX,
p.
91.
p.
and
147-
by Alfred paper by
Hamilton, Qmn, Nnus, Vol. XXI. Crookes' Sdect Methods, pp. 84-89.
Compare
etc-
iron
may be determined by
difterence or
by Margue-
of pig-iron method, in which case dissolve 0.2 grms. It is advisable to use a as usual. in H.SO^, and proceed the close of the dilute solution of K.Mn.O^ towards
rather
oxidation.
Groups II, iU, For the determination of the bases of pig-iron in HCl, remove and IV, dissolve 10 or 20 grms of and proceed as in Analysts the SiO, by drying thoroughly,
No. 21.
in the filtrate,
r,^
trom
means of bromine, or in the the basic acetate of iron by by hydrodisodic phosabsence of calcium, magnesium, etc., 3i8, 6. For other methods phate. See Fres., 109, 3, also articles by Samuel Peters of estimating manganese see
and by William Gah Chem. News, Vol. XXXIII, p, 35, XXXIII, p, 47braith, in Chem. News, Vol, Charles H. Piesse in Chefu. News, See also paper by
Vol.XXIX., pp. 57and no. which silicon exists For testimony as to the condition in E. H, Morton, Cheni. News, in pig-iron, see paper by
Vol.
XXIX.,
p. 107.
86
^
"^
-a 'u
QUANTITATIVE ANALYSIS,
87.
'kJ
"
*<
_i
a'*s:
s; 73 (w jj to
- F w
o
^'-
y
"
It
.12
="
.&.
1-
-o
rf
- a
-^
^
u O
ii
rt
--<
o n (^
c
rt
'
-^
rt
'^
i;
GO'S- g
... tj TP
t:
fc.
" o QT! _ y E u C )j
a o
Ho a
<5
etts jr
^ ^ o y
i;
id
11
:=: to
o c
I.
1-
i-O
"
^
'
i;
Ji i)
w - ^
-^H
rt
-^
n
rt
-.b-O p;
O ^
o ^ n
B
1:
c ? 2
c M
,;
^g
QUANTITATIVE ANALYSIS.
Analysis No. 25. GUANO,
230 Consult Fres., Quont. Analysis, S2. I, p. A. Cairns, Am. Chcvi., Vol.
also article
by
CaO, MgO, Fe.Oj, ?,0 SO3, To be dettrniined: SiO and volatile matter. .H,0, NHj, total N, organic
A. Determination
Heat
1
of Moisture,
H,0[+(NIIJ.CO,].
where great accuracy is required, a correction for the (NHJ^COj counted as water must here be made. Heat the substance in a U tube in a water-bath and a.spirate,
In cases
collecting the
(NH^)jCOj
in
normal ILSO.,.
Titrate with
Subtract (NI-l^),COj found from H,0 determined by heating at 100" C. as above. [-}-(^NH^)iC03]
KHO
as usual.
CAmmonia.
Use Schlosings method, Fres., 99, 3, b. Mix the guano with milk of lime and place under bell-jar over a dish of
normal PIjSO^.
A large surface
is
of acid in proportion to
desirable.
Let stand,
cold,
48 hours
normal
KHO
as in acidimetry,
D,Total Nitrogen.
Use Varrentrapp and
Will's
Absorb the NH^ in a standard solution of H.SO^, aspirate and disconnect bulb. Add litmus and titrate with standard KHO.
H Sulphnric
Dissolve in hot HCl, loilow the Scheme F.
filter
GUANO.
89
2-i
B 1
a
> u o
<1
T3
u
j.^
<^
d
o
o
o".
3 +
o
S
o c w
a
S S
C S
]>
-o
o^U
-S
"' 3
g-
"
.-t:
-a '5,
^ 3
P-l
*( -o .S
-^
6
!*
o
rr-l
o
4>
o d
.2
o
K
c
19
*:.
QUANTITATIVE ANALYSIS.
90
Ana/p^s No.
To
26.
-Superphosphate of Lime.
Moisture,
be d^Urnnned'.
reduced
(or
reverted)
A. -Determination
Dry
grni. at
loC'and weigh-loss
weight^moisture.
Weigh
4
o-rms.
,
KNO, and
crucible, dissolve in Na.COj, fuse in platinum dryness (to dehydrate HNO evaporate in a casserole to Wash thoroughly and SiO,+aq.)> add water and filter.
dilute filtrate
to
c.c.
of
tliis
solution
l\Oj with (=0.1 grm. of superphosphate) and determine (NH^), MoO^ as usual. Consult Note 12, Analysis No. 21.
C Determination
Digest
I
of Insoluble P.Os.
grm. with about 400 ex. of water in 8 to 10 different portions successively, rubbing the superphosphate Filter and treat residue with water in a porcelain mortar.
(filter
c.c.
solution of
c.c. of
ammonium
water, and
yo^'C. for
citrate containing
carefully neutralized
acid.
Digest at about
40
minutes or longer,
exactly as in B.
filter
and wash.
Dry
manner using
100
c.c,
(500
c.c.) for
D.Determination
(omitting the use of
ammonium
of the
POTABLE WATER.
9I
E. Calculation.
The reduced PjO, is found by subtracting the PjO; in C from that in D. The soluble PjOs=:B-D and the available P,Oj B-C.
Note.
Potable Water,
CI; SO^; SiO,;
matter, total
To be delemimed:
volatile
collect in clean
A. Determination
Measure out 250
of Total Solids
c.c. of
and Lose by
of
Ig-aition-
on
a water bath, in a
lOO
c.c. ca-
pacity.
paper screen.
weigh.
Dry
an
air
bath
120"-! 30*
C,
and
Weight of residue gives "Total Solids," Ignite gently over a Bunsen burner, moisten with a solution of
CO,
in distilled
I20''-130''
C.
as
between
second and
first
weights gives organic and volatile matLoss by Ignition," For further treatment
11
of residue see F. Compare Chapter " Watir Analysis" 3rd edition, 1874.
of
Wanklyn'a
of
water
(according
to
the
ploron
^
h
Zh
SiO. and
dish, washing care^ transfer to platinum dryness, filter from dish, evaporate to the porcelain for Dolomite, Auafysts No, 7. follo^v scheme
of
total
solids)
to small
bulk in
porcelain-
Add HCl
0. Determination of HjSO^.
Take i litre (or less) drops of HCl ^nd determine SO, 200 cc with a few If the water contains usual manner. as BaSO, in the H,SO, (as sulphates) to give a feeble precipsufficient'
itate
of
the water,
boil
down
to
with
one^half or one-
D. Determination of
CI.
Test the water with AgNO, for CI, and if no cloud otherwise 25 small bulk is formed evaporate i litre to Add a slightly acid solution of AgNO,, to 50 cc. suffice.
;
See Fres.
E.Determination of
Evaporate 6
finishing on
tilled
Na and E.
the residue with
into
dis-
litres to
a water bath.
a platinum
dish
and wash.
Add Ba(HO),
a
little
to filtrate.
Evaporate
to dryness,
(NH,),COj and
filter,
add
HCl
to
filtrate,
and weigh.
Dissolve in
This
POTABLE WATEK.
residue of
93
NaCl+KCl must
weighed NaCl-t-KCl and calculate tlie Fres. page 841. Compare Waukfyu, zrd
Na
and
as in
edition,
page 63.
MgO
Consult Sutton's Volumetric Analysis. %Zz,l0: or WankWater Analysis, 3rd edition, page 125. lyn's Principle. \rl^x<l water, so called, destroys much soap
before a lather
uble salts,
viz.
is
:
insol-
and oleates
of cal-
No. !, Label this solution "No. i." Take of solution distilled water, !C0 c.c; of 56 per cent, alcohol, 65 c.c. of 2." Label this soap solution " No 75 c.c, and mix.
;
'Dis^o^^t Preparation of Standard Calcium Solution. evaporate until I grm. of precipitated CaCOj in HCl, c.c. c.c. neutral, take up with water and dilute to 1000 of this solution contains grm. O.ooi CaCOj. burette with SiandardiBation of Soap Solution. ViW a Place ro c.c. of calcium solution soap solution No. 2.
1
QUANTITATIVE ANALYSIS.
J uo(;t{e
Add
f,3^,,
it
in a glass st.<>PP^^'
::;r'arco:tLue
Lmed
of
sufficient
the burette and shake until a lather addi.^ soap solution consistence to renjajn for Bve
^^^^^i^^^
Read
,
burette and
Repeat.
In certain
amount
c.c.
of
allowance should
,,
destroys 0.8
c.c.
soap solution.
as above.
grains per gallon of CaCO,. ligrammes per Utre and of chloride of of the standard solution
" Example. -iocc.
Perfatmance of
Amfysis.-Same
Report
mil-
calcium required 23
c.c.
But 10
of
c.c.
of
CaCU
CaCOj, hence
used
,
c-c.
^^
_ -of
\:a
.00043 gnns
23
I )
if
water under examination require grms. 10 33 c.c. of CaCl, solution, we have 33X. 00043 X per litre of CaCOj. This gives .1419; and .1419X.058318 For the factor .05S318 consult gives grains per gallon.
And
100
c.c.
I,
Calculaiion of Results,
Permanganate
of
potassium in solution
oxi-
PreparaticH of solution
litre of
i
water, weighing
very accurately.
Of
this solution
POTABLE WATER,
geii.
95
c,c.
To
of
add 5 c.c. dilute H,SO^, heat nearly to boiling and run in lo c.c. of from a burette the permanganate solution. Caloxalic acid will require 12 to 15 c.c, permanganate. c.c. of latter in milligrammes of oxygen. value of culate
I
Testing waier,
Take
00
c.c.
add standardized permanganate, little by little in the cold, until the water retains a pink tinges after one-half Report amount of o.xygen required to hour's standing.
oxidize organic matter.
ExampL'.
10
of
c.c.
K^MnjOs
is
But 10
c.c.
HjQO^
solution
equivalent to o.ooi
used
\
14.
I,
c.c. ^
J
I.
mgm.
(I
= .0713 mgras. =
J
if
oxygen
100 CO. of water under examination required mgms. per 0.8 c.c. of ICMn.Os, we have 0.8 X. 071 3 X lO This matter. litre of oxygen required to oxidize organic gives .5704 milligrammes and .S704X. 058318 gives grains
And
of
See
I,
Calmlation of Results.
I. Calculation of Results,
grains in a gallon, multi ply the number of milligrammes of each constituent by 0.058318; or use Dr. Wallers Table, published in Am.
To
convert grms. in a
litre into
Report results in two ways: the grains per gallon of uncombined constituents, viz., SiOj, Fe.Oj, AUO3, CaO, MgO, Na,0, K,0, CI, SO,, together with" Loss by Ignition "and "Total Solids;" and secondly
C/wm.,
Vol V,
p.
27S.
QUANTITATIVE ANALYSIS.
96
combined with
IS *:r-/wi*.
Combine
he fonowing scheme.
K
K
as
'
K, SO^
excess of
POTABLE WATER.
0.152 grains
97
Na
NajO making
(2)
Na,0
SOj
"
=
Amount of Na,0
0.204
Amount
for the
of
SO,
needed
NajO.
62
80
X
hence 0.204
~{-
But the water contains 0.340 grains SOj hence we have 0.263 =: 0,077 grains SOj left over to combine 0.340
with CaO.
SO^ CaO
:
Amount of SOj ]
remaining.
J"
:
Amount
of
CaO
J
80
56=
0.077
CaO
remaining
is
regarded
and
since.
^
CaCO,
= 07501
1.34 grains
Ca CO,.
Collecting the results of the calculation we have (thus far) the following figures for the constituents combined:
NaCl
= 0.354
oaANXrrATtVE ANALVSfS.
98
The
manner
example of the
Analysis op Croton
Water
bv Dk. C. F. Chandler.
0.326
.
0.097
.
0.988
Magnesia
Chlorine
0.524
.
0.243
.
Sulphuric acid
Silica
0,322
.
0.621
Alumina
trace
2.604
.
0.532
0.670
6.927
.054
6.S73
Chloride of sodium
....
AND
LIQUIDS.
09
Analyses No. 28
and No.
29.
Si'ecific
Liquids.
Gkavitiks of
Solids and
A Sp.
gr. of
Weight
"
water
=w = w'
Sp. gr.
W
flask.
B. Sp.
Weight
" " " "
gr. of
a solid by the
of solid
flask
"
+ water
-'
"
Sp. gr.
=
(w
of "
+ W) w"
in air
O. Sp.
gr, of
Weight
"
body
"
oil
==
"
oil
Sp. gr. of
"
"
" water
=a =
i
=: W'
The
w
a:
w' ^ w"
then
I
Sp. gr.
= w" =
w"'
w
w'"
D.Sp.
gr. of
Weight
"
"
water
=w = w'
water ==
:uKi corii in
w"
lOO
OUANT[TATIVF. ANALYSIS, ^
Sp. gr.
a B. -Sp.gr, of
Body
lighter than
Weight
of
body
"
in air
"
naphtha
= =
w
w'
w w' = w"
Sp. gr. of naphtha
" "
"
water
:
=A =
I
:
A w"=
Sp. gr.
w"'
w w
///
ji.
_ Determination
of the Proportion of
Alloy.
two Metala
in an
= S =A Weight of the alloy = Sp. of one of the metals = s" Sp. gr. of the second metal w' Weight of one nietal Weight of the second metal = w"
Sp. gr. of the alloy
gr.
s'
w"
For proofs of
this
Clitmistrj/f p. 74,
= Aw
O.
Sp.
gr.
Weight
of
" "
aask
" "
and water
"
liquid
=F =w = w'
F
OROANIC ANALYSIS.
lOI
Sp. gr.
w'
;^;zje'
it.
H.-Bp.
gr.
Weight of substance
(
"
" in liquid
Sp. gr.
of the substance
:
^w = w' =A
gr.
w
or
bp. gr.
(w W) = A sp. = (ww')A
:
1^
Amfysis No.
30. 3
^^^^ 32.
C?^^^V ^wa^j/orir.
of orgamc bodies Introductory Notes. The analysis Proximate Analysis which deals comprises two branches
;
which and Ultimate Analysis, by composing the of the dements the nature and quantity
organic bodies are determined, analysis is possible No systematic course of proximate animal chemistry is in of the science in the present state for a course o more advanced than vegetable
^
;
this respect
by Gomp-Besam-
the
Chanie, I. 55^Nenes Handworterbuch der ^f f'^P^f der See also HehUz Lchrhnch maionary, I, 249. Watt's tor Physiological Chemzstry. Zoodicmic and Lehmmis consut organic analysis, general principles of proximate Proximate Organtc Ontlincs
Dr
Albert B. Prescotfs
<'
of
Analysis:
kind.
^^0^
special
useful
of its
For
" ^^^^^^^ /^^^t^ Unt^rsuchungcn of which Technisdt-chennschcn buck der Kopp is most vahiable. the second edition by Emii
02
QUANTITATIVE ANALYSIS,
of conducting
in
The method
ciently
an ultimate analysis
System,
171-189,
in calling
is suffi.
detailed
Fresenitis*
yet the
following
summary may be
of service
attention
A. Determination of C, H,
and O,
in Sugar.
candy
better.
will
do,
Dry
at loo*^ C, in
watch
glass.
The
in
(2) Combustion tube of hard glass drawn out as shown Fres. 174, cleaned and carefully dried.
filled
filled
KHO
solution of
by Thorpe
(4) Chloride of Calcium tube; that of the form described in his Quant. Chcm. Analysis page 347, fig. 80 is
advantageous.
(5) Small U-tube containing potash-pumice in and CaCl3 in the other.
one limb
(8) Good corks, free from holes, rolled and pressed. (9) Cupric oxide, granulated preferred, chemically pure, freshly ignited to remove organic matter and moisture, and contained in a corked holder.
platinum boat to contain the substance, (10) or another process be followed, a mixing wire.
(it) Combustion furnace,
if
(12) If oxygen is to be employed, a cylinder of this gas and a system of drying U-tubcs must be provided.
OKGANIC ANALYSIS.
I03
(13) Sundry articles, such as glazed paper, agate mortar, towel, asbestus, a ramrod for cleaning combustion tube. etc.
Weigh
KIIO
bulb to-
Dry
the substance
may be
to be
the
it
combustion
is
must be
in
the agate mortar and transferred by the glazed paper to the combustion tube. Stir also with the iron mixer. Avoid
introducing moisture,
Connect the apparatus, arranging it as shown in the Test the joints by cut on page 433 of Fresenias' System. apparatus which that bulb of the heating the air in and the combustion tube drive is between the solution
(f)
KHO
if
an unequal level
tiglit.
is
Conduct the ignition, heating gradually, and beginning at the end next to the CaClj tube do not apply heat
;
CuO
if
that
method
em-
178.
The combustion
of sugar
may be
completed in about half an hour, other substances require more time, especially those rich in Carbon.
(/) Aspirate air, or pass
slowly.
weighed tubes, cool and weigh. From the CO2 and the H,0 found, calculate the C and the H respectively. The O is found by dilTerencc.
(/) Disconnect the
jQ,
QUANTlTA'rJVK ANAf.VSlS.
Theoretical Composit'wii of
Cii
Cane
Stigar.
BKTKRMINA'I'ION OF NITROGEN.
los
I06
article
;
qUANTITATIVK ANALYSIS.
it
should be heated in a porcelain dish to expel water and ammonia before using.
Operation
of
Fill
ful)
warm
soda-lime and
cool
an
tube
fi!l
and introduce the mixture again into the and then the tube with the same nearly to the open end. Insert
;
by a
well-fitting cork,
and
Begin
to heat
The gas
when
it
tail-
Detach the absorption tube, empty its contents into a beaker, rinse well, add a little litmus, or cochineal solution, and determine, by means of normal KHO, the amount of acid remaining imneutralized by the ammonia. For details of this process see Analysis No. 12,
Theoretical Camposition of Potassitim Ferrocyanide,
*
N
f;::
T.
,^
'7-^
-^^-^
^3-3
37.0
3H.O
J^^
100.0
DETERMINATION OF NITROGEN.
D.
107
Determinatioa
of
Duvias' method modified by Melseiis, Cf. AVfj. 1S4. See also Watts' Dictionary, I. 342.
When
<jr
nitrogen exists
e.
in
an organic substance
in
the form
an oxide,
g. nitro-benzol
CJU
(NO2), Varrentrapp
&
of
Will's
into ammonia on Dumas' method consists in heating the substance with oxide of copper, and measuring the
The
process
pump
to exhaust the
by following Melsens, who introduces hydrosodium carbonate into the tube which gives up carbonic anhydride on heating, and drives out the nitrogen before it.
obviated
articles
A
(3)
(2)
(4)
(5) (6)
(7) (8)
Hydrosodium carbonate.
Connecting tube. Corks, asbestos, rubber tubing,
etc.
(g)
Combustion
furnace.
tube observe
the
following
order: Insert,
cm. of hydrosodium carbonate, then copper oxide mixed 5 cm. of copper oxide, then 15 cm. of with the substance to be analyzed, next add about 28 cm. and of copper oxide, insert a copper spiral 5 cm. long,
first,
15
lastly a
Insert the remaining 2 cm. shown cork with connecting tube, and arrange apparatus as
plug of asbestos
in
in Fig, 93.
I08
QJTAMTITATIVK ANAI.YSIS.
:
Heat
;
a portion of
NaHCOs
of
until all
in
the air
is
expelled
;
test
KHO
an inverted test-tube
then heat
CuO
to red-
KHO
solu-
CuO
and substance
in
gas ceases to
come
the nitrogen
the combustion tube by again heating the NalTCO;;, some (Oxalic acid of which must have been left undecomposed.
may
352.)
cylinder
a vessel
of
water, hold
so
that
is
CaknlatioH of Results. To obtain the weight of nitrogen from its volume employ the following formula
:
Let
V = Volume
B
of
meters.
And
f= Tension
Then
if
expressed
mm.
+.003671''
760
The constant 0,0012566 is the weight in grammes of c. c. of N at o' C and 760 mm. The constant 0.00367 is
Example
:
Butvramide
~
:
C,,H:Oj
^'
I
^'^^
ANALYSIS OF UlUNE.
0.315 grms. of substance gave 43.9
c. c.
IO9
at ("=17''^
and B
= 753-^
/=
'ii"i-
/at
17. 3.
{Fres.,
I47-
Now V
= 43.9
"im-
1.0635^760
i^nd 2:25p4i<_lS?
0.31S
Theoretical Cotnposition of
C,
Hs
O
j^
18.4
i6.i
100.0
Urine.
George B. For brief methods of analysis consult Dr. " Manual of ChemFowler's " Urine Analysis," Thudicura's Sutton's " Systematic ical Physiology." pages 178-192, and Fof Handbook of Volumetric Analysis," part vi. 78HofUltzmann & figures of sedimentary deposits examine
raann's
The
"Guide
studied:
Attfieid's "
Leggs Chem-
JO
F.
QJJANTITATIVK ANALYSIS.
Hoppc-Seyler's
"
Ilandbuch dcr
Physiol,
and
2ur
Neubaucr & Vogefs " Anleitung Pathol Chem. Analyse," des ilarns;' Qualitative und Quantitative Analyse
Gonip
Jiesariez'
"
istry,"
Lehrbuch der Physiologischen Chemie," Hofmann's "Anleitung zur pages 5;6-s8o, Ultzmatin & Untersuchung des Harns."
Constituents of Urine.
Urine, the secretion of the kidneys, in a healthy individual, is a clear, yellowish, fluorescent liquid of a peculiar
odor, saline taste, with a
mean
:
The
follow-
ing are
1.
its
normal constituents
JVaier.
l-UO.
2.
Inorganic Salts.
IICl,
K, Na,
NH,
'3.
Urea,
Sugar,
uric
acid,
hip-
(ammonia,)
lactic, succinic,
and phenylic
quantities.
Pigments.
Urochrome, urohaematin.
Alhumenoid. matters.
torn,
indigo-blue, melanin,
acid,
oxaluric acid, taurocholic acid, glycocholic acid, many others. (See Watts" Dictionary,
and
vol. v. p. 962.)
ANALYSIS OF URINK.
II
These substances do not occur simultaneously in all urine, and many of them but rarely. Only those comraonly determined are considered in the Scheme
(page 112).
Chemical Composition of
Healthy.
XTrino.
(Dalto^.)
Numbers Approximate.
938.00
30.oo
i-^S
Water Urea
Creatine
Creatinine
Urate- of soda
"
\
i-S^
potassia
>
'
l-^O
"
ammonia
Phosphate
" " "
of
soda
potassa
1-
1 2.
45
magnesia
lime
....
7.80
6-9C>
1000.00
contain, also
(Bright's disease.)
(Diabetes.)
Excess of Urea,
Oxalate of calcium.
in
QUANTITATIVE ANALYSIS.
Action Of ReagontB on Urino. acid urine effects no cliange.
Boilin'^
makes
it
turbid
if
rich
earthy
phosphates.
color,
KHO
or
earthy phosphates.
a white ppt. of sul-
BaClj or PbA,
phates.
AgNOs
and
Collect
some
thrown
down by HCl, remove supernatant Hquid, add cone. HNO3, and evaporate to dryness. When cold add a drop of NHiHO. A purplish-crimson color shows formation of murexid
(CeH
NA)-
Reactions of Urea. Hg (NO^Oa throws down a gelatinous white ppt. containing COH^N^ .2HgO.
Boiling with
KHO
converted into
NH^HO
test with
Nessle'r reagent.
NaClO
or
NaBrO decomposes
Scheme
N.
I.
Physical Characters.
Odor.
(a)
(b) Consisimce.
whea
to 1025
marked H.
S.,
makes a
ANALYSIS OF URINE.
2.
113
Test
witji
alkaline.
3.
Pour
sample
12 hours.
and sediment separately. Filtered urine leaves a scum of mucus. (For sedunents, see Schemes, page 117 and 118.)
4.
Evaporate 4 to 6
c.
c,
weighed,
dryness
in
a weighed dish.
Dry
at 115
c.
(In-
accurate).
5.
Ash.
Evaporate 100
c. c.
6.
Determination of Ukea.
A.
CHjNiO.
Method.
of urea
Lieb ig$
of
Principle
molecule urea,
and 2HgO.
(Absence
NaCl
necessary.)
Requirements
{a)
{b)
{/)
Standard solution
Baryta solution.
Hg
(NO3),.
Carbonate of soda
test paper.
Dissolve Standard solution of mercuric nitrate. in strong HNOs, (50 grms.,) 72 grms. pure dry HgO If a yellow evaporate until syrupy, and dilute to i litre.
()
produced by dilution, too little acid is present. It must be evaporated down, fresh acid added, and again di^To test the strength of luted. I c. c, =0.01 grm. urea.
ppt,
is
the mercuric nitrate dissolve 2 grms. cryst. urea in 100 c, c. water, i c, c. mercuric solution should equal o.oi grm. urea.
(^)
Solution of
Ba(NO,).+BaHA-
Mix
part cold
and add Soda test paper. Dip a sheet white cone. sol. Na. (CO.,) and dry.
paper into
"
j[^
QUANTITATIVE ANALYSIS.
24
huiirs,
and
measure carefully. Place 20 c. c. in a small beaker, add 20 c. c. barium solution, filter from the sulphates and phosOf the filtrate 20 c c. (containing 10 c. c. urine) phates.
are measured
off,
a drop of
AgNQj
added
to precipitate
added
until a
KHO (25
grms. to
litre
The
solution
alkaline.
Calculatioji
c. c.
Amount urine passed in 24 hours : mercuric solution used C each c. c. being equal
=A
in
then
Ax C = grms.
^^
urea passed
24
hours.
Caution:
The
hippuric acids.
sis,"
must be free from phosphoric and Consult Caldwell's " Agricultural Analyurine
page 220.
Cf.
Watts' Diet.
vol. V. p.
of Estimathtg Urea. Pour a small quantity of urine into a graduated glass tube one-third full of mercury. Fill the tube with a solution of sodic hypochlorite, close
B.~Daveys Method
tube,
ensues
CH.N,0-f-3(NaClO)=CO.,-t-2H,0+3NaCl+N,
6o-'^iia
3o^r.i7:i
r ^*'
'"^'^^ ^
ANALYSIS OF URINE.
11$
C.
Hcintz and
c. c.
Ragskys Method.
precipitation with PtCl^.
First determine
ammonia by
with equal
Heat
sule to
2 to
vol.
H^SO^
in a
covered cap-
i8o-2oo.
filter,
and defor
termine
loo
c.
NH.
formed by PtCU
Calci'Iate both
;
amounts
by
0.
c,
this multiplied
13425
D.AfijoJuis Method.
See "American Chemist," V. 431.
Provide the following apparatus glass tube 30 cm. long, subdivided into 30 equal (i)
:
parts,
whose aggregate volume is 55 c. c. The end of the tube is drawn out like a Mohr's burette. capacity. (2) A wide-mouthed gas bottle of 60 c. c. capacity, and long enough to (3) A test tube of 10 c. c.
be slightly inclined when introduced into the gas
bottle.
The
is
equation
2(CON2H0+3(CaBr2O,)=3CaBrs-f-2CO3+N4
To make
250
c.
c.
NaHO,
and set
bromine
agitate
Process
(r) is
depressed
15
the zero
mark and
surface of water
coincide,
250
c. c.
hypobromite solution (100 grms. NaHO, H2O, 25 c. c. Br) are placed in (2) and the testc. c. is
The
jl6
Stopper which
tube.
QUANTITATIVE ANAJLVSfS.
is
The
tube
urine
measuring tube.
c. c.
The
is
now
Since 55
equal
^
30
= 0.005
30' bar.)
7.
grm. urea.
c.
c. c.
filtered urine
The NH3
standard acid, in
Frcs. 99, 3 b.
cent.)
8,
by Schlosing's method. and absorbed by the cold under a bell jar. For details see
urine contains 0.078 to 0.143 per
(Human
Determination
I
passed
into
If
distilled water in a porcelain dish. the urine was alkaline add a drop of acetic acid, avoid excess. Allow the coagulated albumen to .settle, filter
through a weighed
filter,
Dry
at 100 C,
and weigh.
9_
Determination of Sugar.
Dilute urine
in
or 10
grape sugar.
See
hltered
Analysis
11.
Determination of Phosphoric Acid. urme add 5 c. c. sodic acetate and ''''' ^'"" ^''''^'^^ '"^ ^""""'^
To 50
titrate
c. c.
with
" ^''^""^^"'^
uruie add
_ To
m
-00 c
HCI
=;t-iiirl ^q stand 4S
k^ hours
,1*
a cool place,
DETERMINATION OF URINK.
filter
117
filter.
Wash-water should
mgm.
removed by coagulation.)
13.
(1)
Dry
at loo'^c.
HNO3.
green, yellow,
is
violet,
&c.
occurs
present.
If ether. Agitate concentrated urine with boiling will be greenish-yellow. bile is pr'esent the ether solution ppt with alcobaric acetate to urine, treat the
(3)
Add
hol,
decompose
it
dryness.
Water
with HCl, and evaporate the liquid to will dissolve out in the residue coloring
,
matter of the bile. u cr^ vol H.bU^, Pettenkofcrs Tcst.W\\. fluid with one-half (4) add a little powdered cane avoiding rise of temperature Liberation of cholalic sugar mix and add more II.SO,.
; ;
absorption spectrum.
for analysis of
Scheme
Warm the
INSOLUBLE. acid. Phosphates, oxalate of calcium and uric Warm with acetic acid, and filter.
INSOLUBLE. Oxalate of calcium and nric acid. Warm with HCl, and filter.
INSOLUBLE. SOLUBLE. Oxalate of cal
ciuin.
soLuin.E.
Pliosphates.
They
.ire
re-depos-
AddNHiHO,
and examine ppt. for PsOs,
mav
ined
acid
be
for
examuric
May
by
CaO
MgO.
and
and
usual
bases
tests.
be
pptd.
by
NIUHO.
jVisCe.
Urates
tnent purpurine.
owing
to the pig-
ri8
QUANTITATIVE ANALYSIS,
Scheme
for
(Attfibld.)
The sediment
is
white;
-wnrm
DETERMINATION OF SUGAR,
119
is
described by Prof. S.
W.
Johnson,
in
Am.
J.
of Sci. (3)xiii.
page 196(1877).
D.
Determination
to
little
Evaporate 10
addition of a
with
the
and
Dotermination
sum
of
tlie
of Protein Compounds.
butter, sugar,
is
Subtract the
total
For other methods, see " A Method for the Analysis of Milk," by E. H. von Baumhauer, Am. Chem,^ Vol. VII., 191.
Analysis No.
35.
Raw
Sugar.
A.
Determination
of Moistiure.
until
it
Heat a weighed amount of sugar at 110 Loss ^moisture. longer loses in wciglit.
no
E. Dotermination
Weigh
of Ash.
H2S04and heat
all
Weigh
the ash.
give results at
concordant
seldom
C Determination
(i)
of Grape Sugar,
Qualitative
reactions.
Glucose
is
colored
dark-
120
QUANTITATIVE ANALYSIS.
hy-
dissolves
in
cold
cone.
H,SO, without
mixed with
beinr/
blackened.
If a
cone,
glucose
is
cobaltic
and a small quantity of fused NaHO, the solution remains clear on being boiled if very concentrated it denitrate,
;
[Cane sugar solutions similarly treated give a violet ppt which turns green on standing].
'
BaH.O. added
a white
ppt.
to
soda is added to a solution of glucose and hen drop by drop a dilute solution of CuSO, a deep b ue hciuKi fonns after some time in the cold, b 't imme;
If a little caustic
,,^^'^^^ ' S^^^^se may be easily deI ^^"^^^^^^.'''" S'^'^^ ^ '-eel tint to the solution cZ'- acetate is Cupnc similarly reduced Pot-i.^Jn c otassio-tartrate of copper acts likewise.
teetcd
,..\
^oZ n
win .educe
Preparation of FcIUing^s Solution. Dissolve exactly u6-n orm. , ^ ^'^ ^^'^O, in about ^ 200 c. c. water I^ atntlf T'*" ^"""^ '"'''' ''^ S''^'- "^ P" Rochelle salts
-Hydrate
(CHK NO
:^f^^:^f^^-f^
!
,
^ ^
P-e
sodi-
^Ponds to 0.0S0
corre-
TuitT ^ ^^^^er, f
'^^'-
^^^^
121
The
iT
stronger, dilute.
Performance of Analysis :
water, (or a dilute solution of NaHO,) the solution the liquid conheat' to boiling and run into gradually, from an accurate taining the glucose, slowly and green Continue until the last shade of bluish burette. filtered, gives no liquid disappears, and a small portion of
flask,
Run
exactly lo
c. c.
c. c.
add 40
HC^U.O^ and
K^Fe^Cy,,
solution, Since we took 10 c. c, Fehlings glucose, we read off corresponding to 0.050 grms, anhydrous solution taken this shows us the number of c, c. of glucose grms. grape sugar. how much of the substance contains 50
Calculation,
Example.
\i^<t^ 9-
c
;
c,
9.5
If solution
.05
= roo
.a:
was
diluted, then
;rX^=per cent
glucose.
cane sugar, by first conThis method may be applied to boiling one to two hours verting it into grape sugar by This is not P^rts water) with dilute H.Sa (I part acid S Milk sugar to formation of caramel.
very accurate, owing but in another proporreduces Fehling's solution direct, 134 milk s"?^"^' tion, 100 glucose
the whole
*Tho
Crystaliaable Cane SugarD. -Determination of syrup, add water so that Weigh out :. grms.* of sugar or and add for about 8oc.c. Dissolve
will
form
Instruc-
siiccharimeter.
122
QUANTITATIVE ANALYSIS.
5 to
syrup
lO
c. c.
for
c.
raw sugar
c,
;
less
pour into a Dilute for pure sugar, none. and filter do not beaker, and add piilverizeci bone-black, Dubosq Saccharimeter Fill the tube of a Soleil or wash.
lOO
;
with
this
solution,
perfectly
tint.
full,
insert
details,
the
tube,
and
observe
the transition
For
iii.
sec Atkinson's
Cf.
Fowncs' Chem-
673-5.
Analysts of a sample of
Water,
...
.
Raw
.
Sugar.
,
2.07
.
Ash,
1.58 1,82
Grape Sugar,
Cane Sugar
86.00
Petroleum.
For information as
the
"
to
it yields by distillation, and methods of testing kerosene, see Dr. C. F. Chandler's Report on Petroleum Oi!" in the " American Chemist,"
and Vol.
III. pp.
20 and 41.
A. Distillation of Petroleum.
The method
nation
of its
in
distillation
true,
scientific
wliich separates the liquid into a of aliquot parts, having determinable densities, and flashing points and the value of the sample depends upon the proportion of the light and heavy procertain
process of distillation
number
ducts.
The process
lect a tubulated
of distillation
is
conducted as
follows.
Se-
from
flaws,
and
DISTILLATION OF PETROLEUM,
of about 500
c. c.
i^t
capacity
connect
this
with a Liebig's
manner.
Provitk ten glass cylinders of 50 to 75 c. c. in capacity, and mark each with a file, so as to show the volume occupied by 25
c. c.
of liquid.
to serve as
Pour 250
c. c.
and apply
Collect
coked.
25
c. c. of the distillate in
the
first cylinder,
temperature indicated by the thermometer in the retort collect the second 25 c c. in another recipient, note also temperature, and continue in this manner, changing the
recipient for every 2$
tilled over.
c. until
B.
Examination
of the Distillates.
Determine the sp. gr. of each distillate by floating in it of each sama small Baumd Hydrometer, note the color by means of Tagliaple, and determine its flashing point description of which are *' Tester," a figure and
bue's
Open
Chemist." found on page 41, Vol. HI. of the "American pour a To test the flashing point, proceed as follows the open into small quantity of the sample to be e.Kamined Light the of water. cup, which is surrounded by a vessel the temperalamp beneath and apply heat very gradually a mmute. should not rise faster than two degrees
: ;
ture
surface The thermometer bulb should dip beneath the vapors From time to time test the inflammable the oil.
of
which
using a small flame, arise from the surface of the oil, and noting simultaneflitting it quickly across the surface, at the moment of ously the height of the thermometer
ignition.
Record
J24
QUANTITATIVE ANALYSIS.
The following report of an actual distillaExample. This distillation shows how the rcKults may be reported. with the phenomena technically tion was accompanied called "cracking," by which the heavier hydrocarbons split
up
into lighter ones.
No.
1.
of
(;;,,j.
fr.iclioii.
Colorless,
2.
"
. ..
APPENDIX.
TABLE
I.
Name.
Atomic
^Veifihl.
I*
Aluminium Antimony
Arsenic
Bai'iuni
Molybdenum
Nickel
Nitroiien
.
Mo
Ni
96.
58. 14.
&
N
,
Osmium
Oxygyn
.
Os Pd P
Pt
195.2
16.
Cadmium
Caesium Calcium Carbon Cerium
Ciilorinc
106.6
31-
194.S
39-1
104.4-
K
Rh
Rhodium
Rubidium Ruthenium Samarium Scandium
Selenium
Silicon
Silver
.
Rb Ru
Sa
So
85.4
103(?)
Chromium
Cobalt
.
44-
Se
Si
.
79-4
28.
Columbiu Copper
Didymium Erbium
Fluorine
Sodium
Ag Na
Sr
loS. 23.
S7.6>
Stiontium Sulphur
32183.
128.
i?)
Gallium
Tantalum
Tellurium
Ta
Te
.
Glucinum
Gold
.
Terbium
Thallium
Tb
Tl
204.
Hydrogen
Indium
Iodine
.
Thorium
Tin Titanium
.
Th
Sn Ti
232.
118.
SO-
Iridium Iron
Tungsten
.
W
u
Zn Zr
184.
Lanthanum Lend
. .
Uranium
Ytterbium Yttrium
Zinc
.
.
240.
17390.
Yb Y
Lithium
65.2
Magnesium Mancancse
Mercury
.
Zirconium
S9.6
135
126
APPENDIX.
TABLE
PRECIPITATING VALUE OF
II.
COMMON REAGENTS.
recommended
b,
Johnson's edition
amount of
may
be
One cubic
ccntiintitrc
of
Will precipitate
Barium chloride
Hydrodisodic phosphate
0.033
"
"
SOj.
....
con
0.024
o.oor
MgO,
Magnesia mixture
"
"
Ammonium Ammonium
moiybdate
oxalate
P P
O-
Q.
o.ot6
o.oio
CaO.
"
CI.
Argentic nitrate
TABLE
in.
Xo.
APPENDIX.
I=;
TRINITY COLLEGE.
Hartford^
Report of
Analysis of
iSS
-
Determination of
Grammes
taken
Analysis.
Method of
r'-ilcnl'ilnl
Theoretical
Speci.ii
Remarks,
IThK
I. .
reduced
f-cl.
Mriliiil
is8
APPENDIX.
OFFICIAL
METHODS OF ANALYSIS
1887-88.
portions shall accurately anjd properly prepared, so that separate the substance under examination, without loss or gain of represent
moisture.
(2)
DiUrmination of Moisiure.~-{d)
In potash
to
S
salts,
nitrate of
till
ammonia
heat
grams
at 130 C,
the
weight is constant, and reckon water from the loss. {!>) In all other secure fertilizers heat 2 ijrams, or if the sample is too coarse to 2 grams each, 5 grams for live hours at 100 in a uniform lots of
steam bath. Phosphoric Acid.^x'xw^ 1 grams on a filter, (3) Water-soluble add a little water, let it run out before adding more water, and repeat
this
is
likely to precipitate in
washings show turbidity after passing the filter When the substance is nearly washed in this clear up with acid. it is transferred to a mortar and rubbed with a rubber-tipped manner
the
If the
pesde to a homogeneous
returned to the
ures not
less
filter
paste
(l>ut
not
washings.
Take an
aliquot
(usually corresponding to i or
gram
mine phosphoric acid, as under total phosphoric acid. Wash the residue of the (4) CHratc-imohibte Phosphoric Acid. treatment with water into a 200 cc. flask with 100 cc. of strictly
neutral
citrate solution of 1.09 density, prepared as hereCork the flask securely and place it in a water bath, the water of which stands at 65' C. (The water bath should be of
after directed.
ammonium
such a size that the introduction of the cold flask or flasks shall not cause a reduction of the temperature of the bath of more than 2 C.)
.is
practicable to 65"
C, which
is
APPENDIX.
129
on'anic matter
destroyed, treat with 10 to 15 cc, of concentrated tiame until the phoshydrochloric or nitric acid, digest over a low pass throus^h a dry filti-r. mis, phate is dissolved, dilute to 200 cc, phosphoric acid as under total. take an aliquot and determine citrate-insoluble phosphoric acid is reIn case a determination of
is
quired in non-acidulated jjoods, it is to be without previous washmg with water, of the phosphatic material, except that in case the subprecisely in the way above described, matter (bone, fish, etc.) tlie residue st-mcc contains much animal the pro citrate is to be treated by one of
insoluble in
made by
treating 2
grams
ammonium
grams and
;
treat by
cc.
one of
the
(i)
Evaporation with
in acul.
magnesium
nitrate, igniiion.
tratevl nitric
30
cc.
hydrochloric acid. (3 Add acid with a small quantity of and acid, heat, and add cautiously
and solution
(2)
gram
of finely pulverised
,
potassium chlorate.
'
all
dilute to destroyed hydrochloric acid neotralize with ammonia (in case 50 of filtrate grams dry ammonium add about ts has been used as a solvent deagram To the hot solutions for every equivalent). nirate or its molybdic solution. D.ge.t at of that is oresent add 50 cc. with -ionium nurate forgone hour, tilter, and wash 'Hg-ion and ad .on_ of renewed Llution.' (Test the filtrate by ter w th precipitate on the molybdic solution.) Dissolve the more J a ^;^.'^^^^/, \7/''' ammonia and hot water and wash into ^^ with 7^*^ "^;;;^^; ;''J; more than too cc. Nearly neutralize ^^>f P^"^burette add add magnesia mixture from a and ^'-J-^^^"^^'^';' e^ After ^^-n second), stifrin, vigorously
organic matter phosphates are dissolved and all a dry hUer take 200 cc; mix and pass through
;
JpO
luf;C
ju
-^
^^J^_;
ammonia
hours
is
solution ot
usuallv enough),
ignit.
and
and weigh. ,vater-soluble phosphoric -' (6) Citrate-soluble Tj "^^^fthe d^rate-soluble. tnecn from the total gives citric insoluble subtracted
APPENDIX.
130
PREPARATION
..^ (,)
O!-'
REAGENTS,
PrepareT6 Prcpau
Anunonium
Citrate
Soluiion.^
.
37o grams of
^^ ^^ ^^^^^^
^^,^,,1^,
neutralize wLth
"^'"^^TfrepareMolymc
4^ gr.ms tdplthesoLion
di "acid in
.
awarm p ace Keep tt,e n,Lxturc gravity 1.20. nitricacid of specific C. deposHs no yel ow heated to 40' or undl a portion evcral day ?o phospho-molybdate. Decant the solution predp'ute of ammoniun. preserve in glass-sloppered vessels. from any sediment, and Nitrate 5'./^.-.-Dissol ve 200 grams
il To Prepare
of molybSolution. ^T^^s^oX.. 100 grams of sp.c.hc gravUy 0.96 or 4-7 cc. of a..mon,a grams or ,,350 cc of thus obtained into ,,sco
Ammonium
of commercial
ammonium
nitrate in
to a
volume
ol
''^''\^\?o Prepare
5
Jtcd
calcined magnesia
Jf the latter
Add
little
excess dilute hydrochloric acid, avoiding calcined magnesia in excess, and boil a
few minutes
to precipitate iron,
filter,
grams of ammonium chloride, 700 cc. of ammonia make tiie volume of two liters. gravity 0.96. and water enough to 22 grams of calcined magnesia i to grams Instead of the solution of (MgCU, 6H,0) may be used. of crystallized magnesium chloride Washing. One volume ammonia of Ammonia for (5) DiluU volumes of water, or usually specific gravity o.g6 mixed with three ammonia with six volumes of water, one volume of concentrated Yy\sso\\'^ 320 grams of calcined mag(6) Nilrate of Magnesia. then add a little nesia in nitric acid, avoiding an excess of the latter
add
of specific
'80
;
filter from excess of magnesia, calcined magnesia in excess, boil ferric oxide, etc., and bring to volume of two liters,
;
APPENDIX.
excess, thus precipitating
all
131
alumina,
etc.,
make up
I
to 500 cc,
mix
thoroii!>)ily
I
a dry
filter;
to drynfss,
add
ness and
ii;iiiie
and a This full red heal nui^t drops of HCl 5 cc. of a plus a few residue is dissolved in liot wau solution of pure NaCl (containing,' :o grams NaCl to the liter) and an excess of ])latinum solution {4 cc.) arc now added, and the whole evaporated as usual. The precipitate is washed thoroug-lily with The washing should alcohol hy decantation and on fdter, as usual.
phate, no loss
of potasli,
hi; ii:^ed
and filter through gram, evaporate nearly 1), and evaporate to dryjiotash is in lorm of sulis
the residue
perfectly white.
;
t-
be continued
fdtrate
is
NHiCl
These
away.
filter
cc.
of the
filter.
the
NHiCl
now
I'he fdter
then
washed thoroughly
with pure alcohol, dried, and weighed as usual. The platinum solugram metallic platinum in every 10 cc. tion used contains
i
(2) Mitrialcs of J'o!ash~\r\ the analysis of these salts an aliquot portion, containing .500 gram is evaporated with 10 cc. platinum solution phis a few drops of HCl, and washed as before. &>. liMhe analysis of these salts (3) Sulphate of Potash, Kainite,
an aliquot portion containing .500 gram is taken, .250 gram of NaCl added, plus a few drops of HCl, and the whole evaporated with 15 In this case special care must be taken, in the cc. platinum solution. washing with alcohol, to remove all the double chloride of platinum and sodium. The washing should be continued for some time aOer
Twenty-five cubic centimeters of tlie NH^Cl solution are employed, instead of 10 cc, and the 25 cc. pouretl through at least six times to remove all sulphates and chlorides. Wash fin.i!ly with alcohol, dry and weigh as usual. To prepare the washing solution of NH4CI. place in a bottle 500
the filtrate
is
colorless.
cc. H.,0,
TOO grams of
NH.Cl
shake
till
disolved.
Now
pulveri>:e
put in the bottle, and shake at intervals for S or JO grams of K^PtCU, then filter otT liquid into a let seUle over night six or eight hours second bottle. The first bottle is then ready for a preparation of a
;
;
fresh supply
when needed.
1^2
APPENDIX.
ALTERNATE METHOD,
Pulverize
the
prams,
without
In
tills
take 10 1200 or 300 grams) in a mortar minutes with 200 cc. water, and after cooling, and make up to i.ooo cc, and filter througii a dry paper.
ferlilizer
;
method,
is
tobacco stems, cottonseed hulls, &c., the substance is to be saturated with strong sulphuric acid and ignited in a muffle to delike
[f
the
sample have 10
;
to
15
per cent
In
K,0
take 50 cc. of
tlic tiltrate
if
nary potash
fertilizers),
lake
100 cc.
maKc
the
volume up
to
of bariuni
chloride; without
same manner, add barium hydrate in slight excess .Add 10 Meat, filter, and wash until preci]iitate is free of chlorides. filtrate cc. strong ammonium liydrate, and then a saturated soiu.ion of ammonium carbonate until excess of barium is precipitated. Heat.
i
Add now, in line powder, o.J gram pure oxalic acitl or 0,75 gram ammonium oxalate. Filter, wash free of chlorides, evaporate filtrate
to dryne-ss in a
di.sh witii
crucibie longs,
all volatile
until
matter
is
driven
off.
is now digested with hot water, filtered through a. and washed with successive small portions of water until the filtrate amounts to 30 cc. or more. To this filtrate, after adding two drops of strong hydrochloric acid, is added, in a porcelain dish. 5
The
residue
small
filter,
to 10 cc. of
a solution of to
is
grams of
water.
the water-bath to a thick syrup, or further treated with strong alcohol washed by decantation. collected in a Gooch crucible or other form offdter,
The mixture
now evaporated on
washed with
cc. ether,
C, and weighed.
desirable,
sail,
if
is an appearance of white foreign matter in should be washed, according to the previous method, with to cc. of the half-concentrated solution of NH.Cl, which has been saturated by shaking with K.PtCU. as recommended by Gladding.
there
it
the double
that
The use
of the
K.PtCU
to
KCI and
K,0
is
continued.
APl'ENDfX.
133
APPARATUS.
CombusHon 21;^^ of best hard Bohemian glass, about26 inches long and one-half inch internal diameter. Azotomcter of at least 100 cubic centimeters capacity, accurately
calibrated.
Sprd/igel
stiff
writing-paper.
to
before using.
mortar. reduced Metallic Coppcr.~-GtAnn\s.iQd copper or fine copper gauze of hydrogen. and cooled in slcam Sodium Bicarbonate. x&G from organic matter. potash in Caustic Potash &/Ki'w?i. Dissolve commercial stick of water so that crystals are deposited on cooling. less than its weight When absorption of carbonic acid ceases to be prompt solution must
be
cliscardt:d.
LOADING TUBE.
Of ordinary commercial
fertilizers
take
to 2
the In the case of highly nitrogenous substances by the amount of nitrogen estimated to be presmust be regulated cupric oxide. (t) About 1 inches of coarse Fill tube as follows ent. cupric oxide to scoop enough of the fine (2) Place on the small ijaper
1
analyzed, about having been mixed with the substance to be rinsing watch glass substance, 4 inches of the tube pour on this the with spatula pour of the fine oxide and mix thoroughly with a little
fill,
after
(5^ About 12 little fine oxide. into tube, rinsing the scoop with a ot metallic copper. inches inches of coarse cupric oxide. (4) About 3
APPENDIX.
oxide (anterior layer). (6) Small of coarse cupric fO Aboutsl inches gram of sod.um b.c.rbonatc
p u. of asbestos.
(7)
Eight-tenths to
;
place tab.
.n
furnace, leav.ng
fboutoneinchof
tight.
itprojectinj,;
connect w,th
OPERATION.
Exhaust
air
When
vacuum has
gas under
metallic copper, anterior layer of cupnc that part of tube containing As soon as vacuum bicarbonate of soda. oxide (see 5th above) and carbonic acid gas, shut off the apparatus tiUeci with is destroyed and delivery tube of the pump mercury, and at once introduce the flow of azotometer and just below the surface of into the receiving arm of the
the
to continue, light
mercury
seal of the
aMtometer, so that the escaping bubbles will and not into the azotometer, thus avoiding the use-
or completely the flow of carbonic acid has very nearly delivery tube down into the receiving arm, so that ceased, pass the Light the jets under the bubbles will escape into the azotometer. of oxide, heat gently for a few monicnts to drive out the 12-inch layer Heat moisture that may be present, and bring to red heat.
When
any gradually mixture of substance and oxide, lighting one jet at a time. Avoid too rapid evolution of bul:ibles, which should be allowed lo
escape at rate of about one per second or a little faster. When the jets under mixture have all been turned on,
liglit jets
at
end of tube.
When
and anterior layer of o.xidc, and allow to cool for a few moments. Exhaust with pump and remove azotometer before flow of mercury Break connection of tube with pump, stop flow of meris stopped. Allow azotometer to stand at least an cury, and extinguish lights. hour or cool with stream of water until permanent volume and temperature are reached.
KOH
The
barom-
be
usual.
labor of calculation
may
use of
APPENDIX,
Battle
'35
and
Daticy.
of
the
North
Carolina
Experiment
Station
(Raleigh, N. C.).
The above
the
details
are, with
some
rSyg
([).
124),
which may
(a)
Hydrochloric acid whose absolute strength has been determined, by precipitating with silver nitrate an<l weighing the silver chlo-
by sodium carbonate, as described in Fresenius's Quantitasecond American edition, page 680, and (c) by determining the amount netUralixed by the distillate from a weighed quantity of pure ammonium chloride boiled with an excess of sodium
ride, {d)
tive Analysis,
hydrate.
(2) Standard ammonia whose strength, been accurately determined,
(3)
nitrates
"C, P." sulphuric acid, specific gravity 1,83, free from and also from ammoniLtm sulphate, which is sometimes
in the process of manufacture to destroy oxides of nitrogen. Mercuric oxide, HgO, prepared in the wet way. That prepared from mercury nitrate cannot safely be used. (5) Potassium permanganate tolerably finely pulverized. (6) Granulated iiinc. (7) A solution of 40 grams of commercial potassium sulphide in
added
(4)
one
liter
of water.
saturated solution of sodium hydrate free from nitrates, which are sometimes added in the process of manufacture to destroy organic matter and improve the color of the product. That of the Greenbank Alkali Company is of good quality.
(S)
19)
Solution
of
cochineal
prepared
according
edition,
to
Fresenius's
American
in all
well-annealed glass. (11) Digestion flasks of hard, moderately thick, long, with a round, pear-shaped These flasks are about 9 inches bottom, having a maximum diameter of 2] inches, and tapering out gradually in a long neck, which is three-fourths of an inch in diam-
APPENDIX.
the
eter
at
little
at the edge.
The
is total capacity
^"^^^
.'ibe
^^^^^^
.vhich
is
is
equally
-"-"^^^^f,^ wh.ch
^.'^
f^
rS'condc.sed
shall
be of
^-;"^^^7;;; ",',",,
,y,,,,n^ aad
ammonia
^W .ndHe
So es
Tame
stands
okl
Ber. d.
34-)
Jo
1
Ion,
its
botton.
is
widening above to 6 inc es. It . and a larger tnbe which goes to the bottom, ^vith a water-supply whose extertin condensu:^ tube., overflow pipe above. The block through seven in nnmber, enter the tank nal diameter is f of an inch, the overthe top. above the level o! boles in the front side of it near through the tank and out and pass down perpendicularly flow holes m the bottom. They through rubber stoppers, tightly fitted into bottom of the tank, and are conproject about \\ inches below tlie tubes of the usual shape, nected by short rubber tubes with glass buib These beakers are which dip into glass precipitating beakers. somewhat narrower below, 6^ inches high, 3 inches in diameter can be made and of about 500 cc. capacity. The titration above, supported on a The seven distillation flasks are directly in them. tank to the wooden frame that supports the
This tank
.6
a wooden on which inches above the work-bench x and 3 .-l-s inches high. 3^ i-hes long
provu^d
Se fro.
front to back,
Where each
flask is to
under with three projecting lips, which support the wire gauze and prethe flask, and three other lips which hold the flask in place on. vent its moving laterally out of place while distillation is going Beiow
Bunsen this sheet-iron siielf is a metal tube carrying seven burners, each with a stop-cock like those of a gas-combustion furprenace. These burners are of larger diameter at the top, wliich
vents smoking
fine
gauze
to
APPENDIX,
(14)
137
holding the digestion flasks consists of a pan of sheet-iron 29 inches long by 8 inches wide, on the front of which is fastt:ned a shelf of sheet-iron as long as the pan, 5 inches wide and 4 inches high. In tliis are cut six holes i| inches in diameter. At the bacl< of the pan is a stout wire running lengthwise of the stand, 3
The stand
for
inches high, with a bend or depression opposite each hole in the The dijjestion flask rests with its lower part over a hole in shelf. shelf and its neck in one of the depressions in the wire frame> tlie
which holds
it
securely
in position.
Heat
is
With
THE DETERMINATION.
One gram
tion flask
is
brought
into a diges-
gram
is
of mercuric
oxide and
20
The
flask
above de-
scribed heat
of an inclined position and heated below the boiling point The until froihuig has ceased. the acid for from 5 to 15 minutes, or
ill
No further attention then raised till the acid boils briskly. have become a clear liquid, flask is required tiU the contents of the straw color. Th.; whicli is colorless or at least has only a ver>' pale upright, and. while stil! held flask is then removed from the frame, in small is dropped in carefully and
i.'i
potassium permanganate liquid remains <iuantity at a time till after shaking the
hot,
ol
a green or
transferred After cooling, the contents of the flask are purple color. ot potassium this 25 cc. to the distilling flask with water, and to solution, or sutlicient solution are added, 50 cc. of the soda sulphide few pieces oi -ranothe reaction strongly alkaline, and a
to
make
all ammonia has passed the contents of the flask are distilled til! precipitating flask preover into the standard acid contained in the solution can no longer be viously described and the concentrated 20 10 40 minutes. This operation usually requires from
lated zinc
The
flask is at
safely boiled.
The distillate is then titrated with standard ammonia. greatly The use of mercuric oside in this operation
shortens the
halt rarely over an hour and a time necessary for digestion, wluch is more comdifficult to osidi^e and is in the case of substances most permost cases the use of potassium monly less than an hour. In excepbelieved that in manganate is quite unnecessary, but h is
APPENDIX.
tional c.ses
view of the all merpissiam ^nc.n^^^^-^y^^^^-J^^ the formation of mercuro-0' '^"^ "';: complcldy decomposed by d Mi'cn .. .ot ammonium compound. wlch ^,:ys ^ise to an evolution of soda solution. '' '^ -''''^!^" ", .ij ,? Previous to use, the ^^ ''^^"^ violent bumping,'. iwflmi^en and prevents
.
>.
;s
^H--^^' ^^
vfi
and
in
sulphide r.mo.es
S;.rtially
re<iace
"'u^rSCnrmodification must
which nitrogen in substances
use this method
:
heated over a low flame until all danger raised until the acid from frothing has passed. The heat is then white fumes no longer boils briskly, and the boilinsr continued until
digestion flasks,
where
it is
Add pour ont of the flask. This requires about five or ten mintites. now approximately 0,7 gram mercuric oxide and continue the boil(In case ing until the liquid in the flask is colorless, or nearly so.
become solid before this point more of sulphuric acid.) Complete this o.xidais reached add 10 cc, tion with a little permanganate of potash in the usual way, and proceed with the distillation as described in the method above.
the contents of the flask are likely to
by Prof. M, A. ScovcU.
APPENDIX,
I
^39
.^
.vefghfofsoda-H^e
mumg equal part by iLosuiphite .^/i.r..-Pr.pared by .oc!>um and fmdy powdered cry.tall.ed
An
,,,,
k^
....r/....-This is prepared by mi.ing '';il''^llr .rf -^///''' granulated sugar and flowers weightof finely powered equal paS by
of sulphur.
(6)
APPARATUS.
^.*-- of hard Bohemian 0) C-..^.A-.. ponit.
glass,
drawn
to a
U tubes,
Aspirator.
PREPARATtON.
(0 Clean and
acid.
fill
the
p:ii
f^,g
tube as follows
' loosely fittng piu o (,v jl^e weighed portion inches of the ^ ' , ,0 t^ '^yP'^^f ^'^^'ely i.ed with from 5 to lo analyzed is mumateiy n . ^^ of the substance to be ""' 'J" " i UJ r .1 c>,o-ir- nntl sulohur mixture. hyposuU grams of the sugar ^"'^ ^"'P ^ ^^f^^-ie^t quantity of the
(I
J^
glared paper, or P-^'^:;; "^^^Xes oVt^^ lo '"^'^^^ ^' phhe mixture to fill about ^' as knee to be analysed,
tube
If
pour
shake
paper or mortar with ture and pour into ^^^^^;^^^'\^\Z\.o.^^^ plug of ignited the tuOe. j^^,^ ^^e 2 inches of the end of
^^'/J^
f^f
^^
tube. asbestos at the end of the ^1 1 unUl there is a gas pos.Uon a.d Up on tl^^^^ tube in a l^ori-ntal ^^^^^^^ .^^ ^^.^^ ^^^ of the tu^e. channel all along the top the apparatus is aspirate, and see tube containing the acid,
-^^'^-^
t'S'^^-
tube in the T,, .i rpn-ired combustion the PJ^^P^^" ^ The Combustion.-V\^'^^ t to burn the ^^ ^^ end project .^ .^ ^^^^^^j^^ furnace, letting the open soda-hme port>o by heatmg the Commence ^^^^^^^^ ^^^ cork.
_
to a
full
red heat.
outer end
Then
two or three a
APPENDIX.
second,
I
Whrn hen
is
[^rl^^^S^'-toU.
:;;':::dat:l
titrate.
tube...... or a fe. . -rrent o h^nd of the tube, n.d dr.w into a Ueaker wash the contents ... Dptich the U tube and solution, and few drops or the cochineal
o.her
or the
red hot and the evolution of Ihe gas ^ .^^^ ^^ ^^^^^^^ ^^^^^^^^ ^^^^ ^^^^^
U.b
a. .oug
add a
DETERMINATION
I5Y
to
draw one end of it glass 14 to 16 inches long, Select a tube of hard is passed other end fit a cork, throu-h which a fine point, and to the
arm
combustion tube first slip a loosely fitting to 2 inches of sodaand then plug of asbestos previously ignited, from 0.7 to 2.8 grams of the substance to be Weigh out lime. glazed paper or porcelain moranalyiied, and mix it on a piece of pulverized soda-lime, and introduce the mixwith some finely
tar
is
tiien
rinsed
tube. out with a small quantity of soda-lime and poured into the filled up to within i to 2 inches oi the open end The tube is then with granulated soda-lime, then with a plug of ignited asbestos.
free
passage
is
formed
for the
evolved gases by holding the and tapjjing gently on the table. In-
troduce the prepared combustion tube into the furnace, letting the open end project a little so as not to burn the cork, supporting
the
tube by a clamp.
The tube
is
mencing
obtain
towards the
carried
a steady and
out, the acid
flow of gas.
is
the
tube
never
acid begins to
the
the other limb of and start it slowly, then break off the point of the combustion tube and draw a current of air through the apparatus
the
recede
attach
aspirator to
tube,
order to sweep
all
Detach the
ponx-tain basin,
neal,
tube and
wash
and
titrate.
to
be the same
as that
used in
INDEX.
Aeidimcuy,
(
45-
Calorific
power of
coal,
31).
Albumen dctcrminnlion of, in urine, 116. Alkalies, determination of, in potable water,
in feldspar, estimation of, 5*-
C^na
Carbon, estimation
total,
of,
iti
coal, 39,
determination
of, in
pig-iron, 79.
Alkalimetry, 42.
Alloys, dctermiii-ition of
vdlimatc determination
of, in
sugar, toj.
(wo metals
in, too.
Ahim,
determination of
total
49'
of, 20.
Ammonia,
deterniinalion
of, in
gunnn, 83,
properties
of, 11,
Atnmonio-magncsic
of, 19.
phospbalc,
determination
of, in
Chromic
gravimetric determination
of, of,
Ammonium,
^.
phospho-molybdate, properties
Analysis, organic, 101.
70.
Cobalt, determination
of,
of, in
Analyips, calculations
reporting of,
tj".
15.
Copper,
estimation
S6.
Ash, estimation
[14-
Dolomite, analysis
of, 30.
Barium, determination
sulphate, properties
in pig-
of, 14.
of, iS.
carbon in pig-
Elliott's
determination of
total
carbon in
valuation
of,
49.
of, 35.
pig-iron, 79-
Broxue, analysis
of,
no.
in, 107.
nitrogen
Flight's
in. 105.
Calcium, determination
of, 31.
Fusion of an iron
INDEX.
142
Pearl-ash, valuation of, 4s.
of, ii")Olocosi!, estim.ition sugSf dclcrminalioii
Cmpe
of, iiq.
valu.itioji
of chloride of
GMiihim, (kicrmiiution
of,
in pi-iron, 76.
Guano,
Hciniz
.in>f
urea, 115.
of, 38.
of, 6j.
guano,
8;j.
vsUialion
of, 46.
determination
Flight's
Hydrodisodic pliosphate,
Hydrogen,
of, 74.
phates,
tjO.
6S.
reduced, delctminatioti
phates,
9<J.
oli
in
superphos-
determinalion
31.
of,
in
nmmoiiia-iron-aUim,
Phosphorus, determination
76,
S:!.
of,
in
pig iron,
detcrminiiion determination
of,
by
precipitation, 22-
of, 26.
of, in
hematite, 6j.
anaKsis
of, 60.
of, 11,
Rravimetrio estimation
71.
of, 16,
volumttric determination
Raw
sugar, analyses
of, itt).
Rcponins
Lead, estimation
Lieblg's
of,
analyses. 17.
of,
<^of, ^i.
of, iS.
Sllica,
deicrminauoii
59-
soluble silicates,
30.
determination
separation
of.
from
tit.iuiifm,
64.
method
for determination of
iiS.
of, in coal, j6.
Moisture, deierniiuation
Molybdenum, use
of, in
estimation of phos-
Soap test fur potable water, 93. Soda ash, valuation of, 44. Sodium, deternunalion cf, 27. Specific ,i>r.ivities of solids and liquids,
Standard solutions,
4s.
99.
Nickel ore, arsenical, analysis of, S6. Nitrogen, determination of, by Varrenlrapp
determination
of, in
milk, tiS.
uUtmate analysis
Norma]
solutions, 41.
Sulphur, determination
Sulphuric
01",
pig-iron, Si.
acid,
18.
gravimetric
deterroioasion
INDEX.
Sulphoiic
l[on of,
iicid
')3.
'43
in
of, 90.
tif,
in coal, jj.
Tin, dctctmiiniioii
dclerniinalion
of, in
of, in
Lirome, 35,
IV liter analys],
Titanium, catiinalion
Tilr-ilion, nsaidual
of, in
method
Type
metal, analysis
of, 3".
dcteruiinJlion
rf, is
milk, 118,
Weyl'a detcrmiiution of
iron, Bj.
total
carbon
in pig-
Urine,
compoailloB
of,
nt.
APPENDIX.
AKiiculJural
on;i!jsia, I3B.
chemist*,
official
methods
of
method of dewyniin*
Alomic weight! o( dtmsms, table 1. 135, Filters, diimcttrs and wctsht oi ashes, is6.
CbddinK's mcth^^^^^ of dctcrmipiinE potash, Kitldahl'smcThnd nf dctcrmiiiinc nilroEerii
Msiatufe,o(lif:i.il
i;o.
TotaaSi, official
method
of detenninaiion, \yt.
tS5
Report blank, 117. RujUc method of detetmining iutixtn, I^. Soda-lime method of determining nitioecn, 1*1.
Zettflcrs^'s
Nitt'!C<^n."ff"^i'">'''hcd5
Official
Jctcrminatloii,
1^
^heme
meihMls
of :isrictiliural chemists,
ista
leg paj;e.