Supplement No.
1
Reagent Chemicals, 5th Edition
The Fifth Edition of REAGENT
CHEMICALSwas published in 1974. As
stated a t the end of the Preface, two
supplements will be issued in ANA-
LYTICAL CHEMISTRY prior to publi-
cation of the next full edition, and re-
prints sized to fit REAGENTCHEMI-
CALS will be made available. The re-
prints will incorporate any modifica-
tions in specifications and tests for
which the American Chemical Society
Committee on Analytical Reagents has
given early notification following its
meetings. Since the publication of the
Fifth Edition, three such announce-
ments have appeared in ANALYTICAL
CHEMISTRY,as follows: 47, No. 7,1149
(1975);48, No. 4,792 (1976);and 48,No.
9, 1432 (1976).
Interpretation of
Requirements
O n page 5 delete the paragraph o n
Particle Size for Granular Materials.
Substitute the statement cited below.
When a mesh or a mesh range is stat-
ed on a reagent label, the label shall in-
clude reference to a coarse sieve and to
a finer sieve. The sieve number (mesh)
is related to the sieve opening as indi-
cated in the accompanying table.
Sieve No., Sieve opening,
Mesh mm
2 9.52
4 4.76
8 2.38
10 2.00
20 0.84
30 0.59
40 0.42
50 0.297
60 0.250
80 0.177
When tested according to the Proce-
dure given below, at least 95% of the
material shall pass through the coarse
sieve and at least 70% shall be retained
on the finer sieve. This requirement
applies only to materials that are 60
mesh or coarser.
Procedure. The sieves used in this
procedure shall be those known as the
U.S. Standard Sieve Series. For the de-
tails of the standardization of such
sieves, reference may be made to ASTM
E 11-70.
Place 25 to 100 g of the material to be
tested upon the appropriate coarser
standard sieve which is mounted above
the finer sieve t o which a close-fitting
524 ANALYTICAL CHEMISTRY, VOL. 49, NO. 3, MARCH 1977
pan is attached. Place a cover on the
coarser sieve, and shake the stack in a
rotary horizontal direction and verti-
cally by tapping on a hard surface for
not less than 20 min, or until sifting is
practically complete. Weigh accurately
the amount of material remaining on
each sieve.
An alternate procedure may be used
in which the screening through the
standard sieves is carried out in a me-
chanical sieve shaker. This shaker
reproduces the circular and tapping
motion given to the testing sieves in
hand sifting, but with a mechanical ac-
tion, following the directions provided
by the manufacturer of the shaker.
General Procedures
Measurement of Physical
Properties
At the end of page 14 insert the
statement on Color ( A P H A ) [American
Public Health Association] cited
below.
The color intensity of liquids may be
rapidly estimated by the use of plati-
num-cobalt standards, as described in
ASTM standard method D 1209-69.
This method is particularly applicable
to those materials in which the color-
producing bodies have light absorption
characteristics nearly identical with
those in the standards. Colors having
hues other than light yellow or reddish
yellow cannot be determined by these
standards.
The platinum-cobalt color standards
contain carefully controlled amounts of
potassium chloroplatinate and cobaltous
chloride. Each platinum-cobalt color
unit is equivalent to 1 mg of platinum
per liter of solution (1 ppm), and the
standards are named accordingly. For
example, the No. 20 platinum-cobalt
standard contains 20 ppm platinum.
These platinum-cobalt standards are
also called APHA and Hazen stan-
dards.
Apparatus. The apparatus for this
measurement consists of a series of
Nessler tubes, a color comparator, and
a light source. These tubes must match
each other with respect to the color of
the glass and height of the graduation
mark. They must be fitted with suitable
closures to prevent loss of liquid by
evaporation and contamination of the
standards by dust or dirt. The most
commonly used type of Nessler tube is
the 100-mL tall-form tube. However, for
some samples, particularly those having
darker colors, a better color match may
be obtained by using 100-mL short-form
Nessler tubes.
For the most accurate estimation of
color, it is desirable to use a comparator
constructed so that white light is re-
flected from a white glass plate with
equal intensity through the longitudinal
axis of the tubes being compared. The
tubes are shielded so that no light enters
the tubes from the side. In most cases,
satisfactory estimates of the color can be
obtained by holding the sample and
standards close to each other over a
white plate.
The best source of light is generally
considered to be diffuse daylight.
However, for general routine analyses,
the use of a titrating lamp equipped with
a “daylight” type fluorescent tube is
satisfactory.
Preparation of the APHA No. 500
Platinum-Cobalt Standard. Measure
500 mL of reagent water into a 1000-mL
volumetric flask, add 100 mL of hydro-
chloric acid, and mix well. Weigh 1.245
g of potassium chloroplatinate
(K2PtCld and 1.000 g of cobaltous
chloride (CoClz.6HzO) to the nearest
mg, and transfer to the flask. Swirl until
complete dissolution is effected, dilute
to the mark with reagent water, and mix
thoroughly. The spectral absorbance of
this APHA No. 500 standard must fall
within the limits given below, when
measured in a suitable spectrophotom-
eter, using a 1-cm light path and reagent
water as the reference liquid in a
matched cell.
Wavelength, nm Absorbance
430 0.110 to 0.120
455 0.130 to 0.145
480 0.105 to 0.120
510 0.055 to 0.065
Preparation of the APHA Plati-
num-Cobalt Standards. Prepare the
required color standards by diluting the
volume of APHA No. 500 platinum-
cobalt standard given in the following
table with reagent water to a total vol-
ume of 100 mL. The use of a buret is
recommended in measuring the No. 500
standard. This series of standards is
usually sufficient to permit an experi-
enced analyst to make color compari-
sons with the necessary precision and
accuracy. If a more exact estimate of
color is desired, additional standards
may be prepared to supplement those
given by using proportional amounts of
the No. 500 platinum-cobalt standard.
APHA Pt-Co ML of APHA No. 500 TESTS
Color Pt-Co
Standard to Dilute to Absorbance of reagent solution. Assay. Weigh accurately about 0.4 g,
Standard No. 100 mL Measure the absorbance of the reagent and dissolve in a mixture of 100 mL of
solution (see the test for Sensitivity to oxygen-free water and 25 mL of 10%
0 0.00 carbohydrates) in a spectrophotometer,
1 0.20 sulfuric acid. Titrate immediately with
using 1.00-cm cells, with sulfuric acid as 0.1 N iodine, adding 3 mL of starch in-
3 0.60 reference. Record the absorbance at 425
5 1.00 dicator solution near the end point. One
nm and 620 nm, respectively. The ab- milliliter of 0.1 N iodine corresponds to
10 2.00 sorbance should not exceed 0.75 a t 425
15 3.00 0.008806 g of C~Ha06.
nm and 0.045 a t 620 nm. Specific rotation. Weigh accurately
18 3.60 Solubility in ethyl acetate. Dissolve
20 4.00 about 10 g, dissolve in 90 mL of oxy-
1 g on 50 mL of freshly distilled ethyl gen-free water in a 100-mL volumetric
25 5.00 acetate in a dry 50-mL glass-stoppered
30 6.00 flask, and dilute with water to volume.
graduate. The mixture should not be Adjust the temperature of the solution
35 7.00 heated, dissolution should be complete,
40 8.00 to 25 OC. Observe the optical rotation in
and the resulting solution should be a polarimeter at 25 "C using sodium
50 10.00 clear.
60 12.00 light, and calculate the specific rotation.
Sensitivity to carbohydrates. It should not be less than f20.5" nor
70 14.00 Reagent Solution. Slowly add
80 16.00 more than f21.5".
132 mL of concentrated sulfuric acid Residue after ignition. Gently ignite
90 18.00 to 68 mL of ice cold water in an ice
100 20.00 1.0 g in a tared crucible or dish until
bath. Allow the mixture to cool to charred. Cool, moisten the char with 1
120 24.00 room temperature, add 0.100 g of the
140 28.00 mL of sulfuric acid, and ignite again
sample, and heat if necessary to dis- slowly until all carbon and excess sul-
160 32.00 solve.
180 36.00 furic have been volatilized. Finally, ig-
Glucose Standard (1000 pg in 1 nite a t 800 f 25 "C for 15 min. The
200 40.00 mL). Dissolve 1.00 g of glucose in
250 50.00 weight of the residue should not exceed
water, and dilute with water to 100 0.001 g. Retain the residue for the test
300 60.00 mL. Pipet 10.0 mL of this solution (1
350 70.00 for Iron.
mL = 10 mg) into a 100-mL volu- Heavy metals. To 0.1 g add 1mL of
400 80.00 metric flask, and dilute to volume
450 90.00 sulfuric acid, heat cautiously until the
with water. sample is charred, and ignite in an oven
500 100.00 Mark four 25-mL volumetric flasks a t 500 "C until most of the carbon is
Procedure. Transfer 100 mL of the as 0 pg (blank), 250 pg, 500 pg, and 750 volatilized. Cool, add 2 mL of nitric acid,
sample to a matched 100-mL tall form pg. Add the glucose standard and water heat until the acid is evaporated, and
Nessler tube. (If the sample is turbid, as specified, and dilute to volume with ignite again at 500 "C until all of the
filter or centrifuge before filling the tube the reagent solution. carbon is volatilized. Cool, add 4 mL of
to remove visible turbidity.) Compare Flask, Glucose standard, Water, +
dilute hydrochloric acid (1 l),digest
the color of the sample with those of the pg mL mL on the steam bath for 10 min, and
series of platinum-cobalt standards in evaporate to dryness. Moisten the resi-
matching Nessler tubes. View vertically 0 0 0.75 due with 0.05 mL of hydrochloric acid,
down through the tubes against a white 250 0.25 0.50 add 10 mL of hot water, and digest for 2
background. Report as the color the 500 0.50 0.25 min. Add ammonium hydroxide (10%
number of the APHA standard that 750 0.75 0 NH3) until the solution is just alkaline,
most nearly matches the sample. In the Place all flasks in a vigorously boiling and dilute with water to 25 mL. For the
event that the color lies midway between water bath for 7.0 min, allow the flasks standard, dilute a solution containing
two standards, report the darker of the to cool to room temperature, and de- 0.02 mg of lead ion (Pb) with water to 25
two. termine the absorbance of each a t 620 mL. Adjust the pH of the sample and
nm against the blank in 1.00-cm cells. A standard solutions to between 3 and 4
plot of the absorbance against concen- (using a pH meter) with 1N acetic acid
New Reagents tration should be linear, and the ab- or ammonium hydroxide (10% NHs),
sorbance of the 750-pg flask should not dilute with water to 40 mL, and mix.
be less than 0.90. Add 10 mL of freshly prepared hydrogen
Anthrone sulfide water to each and mix. Any color
in the solution of the sample should not
L-Ascorbic Acid exceed that in the standard.
Iron, To the residue for the test for
C6H806 Formula Wt 176.13 Residue after ignition, add 3 mL of di-
+
lute hydrochloric acid (1 1)and 0.10
REQUIREMENTS mL of nitric acid, cover with a watch
REQUIREMENTS glass, and digest on the steam bath for
Appearance. Off-white to light yel- 15 to 20 min. Remove the watch glass
low crystals. Assay. Not less than 99.0% C6HsOfi. and evaporate to dryness. Dissolve the
Absorbance of reagent solution. To Specific rotation [ a I z 5 "Not
~ . less residue in a mixture of 2 mL of hydro-
pass test. than +20.5" nor more than chloric acid and 10 mL of water, and
Melting point. No more than a 3" +21.5". dilute with water to 50 mL. To the so-
range including 156 "C. Residue after ignition. Not more lution, add 30 to 50 mg of ammonium
Solubility in ethyl acetate. T o pass than 0.1%. peroxydisulfate crystals and 3 mL of
test. Heavy metals (as Pb). Not more ammonium thiocyanate reagent solu-
Sensitivity to carbohydrates. To than 0.002%. tion. Any red color should not exceed
pass test. Iron (Fe). Not more than 0.001%. that produced by 0.01 mg of iron (Fe) in

ANALYTICAL CHEMISTRY, VOL. 49, NO. 3, MARCH 1977 525

an equal volume of solution containing
the quantities of reagents used in the
test.
Lithium Perchlorate
LiC104 Formula Wt 106.39
REQUIREMENTS
Insoluble matter. Not more than
0.005%.
pH of a 5% solution. From 6.0 to 7.5
a t 25 "C.
Chloride (Cl). Not more than
0.003%.
Sulfate ( 5 0 4 ) . Not more than
0.001%.
Heavy metals (as Pb). Not more
than 5 ppm.
Iron (Fe). Not more than 5 ppm.
TESTS
Insoluble matter. Dissolve 20 g in
200 mL of water, heat to boiling, and
digest in a covered beaker on the steam
bath for 1 h. Filter through a tared fil-
tering crucible, wash thoroughly, and
dry at 105 "C. The weight of the residue
should not exceed 0.001 g.
pH of a 5 % solution. Dissolve 10 g in
200 mL of carbon dioxide- and ammo-
nia-free water. Determine the pH by the
method described on page 27. The p H
should be from 6.0 to 7.5 a t 25 "C.
Chloride. Dissolve 1.0 g in 20 mL of
water, filter if necessary through a
chloride-free filter, and add 1mL of ni-
tric acid and l mL of silver nitrate re-
agent solution. Any turbidity should not
exceed that produced by 0.03 mg of
chloride ion (Cl) in an equal volume of
solution containing the quantities of
reagents used in the test.
Sulfate. Dissolve 40 g in 300 mL of
water, add 2 mL of hydrochloric acid,
filter, and heat to boiling. Add 5 mL of
barium chloride reagent solution, digest
in a covered beaker on the steam bath
for 2 h, and allow to stand overnight. If
a precipitate is formed, filter, wash
thoroughly, and ignite. The weight of
the precipitate should not be more than
0.001 g greater than the weight obtained
in a complete blank test.
Heavy metals. Dissolve 6.0 g in about
20 mL of water and dilute with water to
30 mL. For the control, add 0.02 mg of
lead ion (Pb) to 5.0 mL of the solution
and dilute with water to 25 mL. Adjust
the pH of the control and sample solu-
tions to between 3 and 4 (using a pH
meter) with 1 N acetic acid or ammo-
nium hydroxide (10% NH3), dilute with
water to 40 mL, and mix. Add 10 mL of
freshly prepared hydrogen sulfide water
to each and mix. Any color in the solu-
tion of the sample should not exceed
that in the control.
Iron. Dissolve 1.0 g in 20 mL of water.
526 ANALYTICAL CHEMISTRY, VOL. 49, NO. 3, MARCH 1977
Add 1 mL of hydroxylamine hydro-
chloride reagent solution, 4 mL of
1,lO-phenanthroline reagent solution,
and 1 mL of 10% sodium acetate solu-
tion, and mix. Any red color should not
exceed that produced by 0.005 mg of
iron (Fe) in an equal volume of solution
containing the quantities of reagents
used in the test. Compare 1 h after
adding the reagents to the sample and
standard solutions.
p-Methylaminophenol Sulfate
(CHSNHC~H~OH)~*H~SO~
Formula Wt 344.38
REQUIREMENTS
Assay. Not less than 99.0 nor more
than 101.5%.
Residue after ignition. Not more
than 0.1%.
Suitability for determination of
phosphate. To pass test.
TESTS
Assay. Weigh about 250 mg to the
nearest 0.1 mg. Transfer to a 500-mL
conical flask containing 100 mL of water
and 10 mL of 0.1 N sulfuric acid. Dis-
solve, add 0.15 mL of ferroin indicator
solution,* and titrate with 0.1 N ceric
ammonium nitrate* to a light green
color which persists for 15 s.
%HOC6H4NHCH3-1/2H2S04
-
- V X N X 8.61
W
where V = volume, in mL, of standard
ceric ammonium nitrate, N = normality
of ceric ammonium nitrate solution, and
W = weight, in grams, of sample.
*Reagents. 1. Ferroin Indicator
Solution. Dissolve 0.70 g of ferrous
sulfate, F e S 0 ~ 7 H 2 0 , and 1.5 g of
1,lO-phenanthroline in 100 mL of
water.
2. Standard Ceric Ammonium Ni-
trate Solution, 0.1 N. Preparation. Mix
59 g of ceric ammonium nitrate,
(NH4)2Ce(NO&, with 31 mL of con-
centrated sulfuric acid in a 500-mL
beaker with stirring. Cautiously add
water in 20-mL portions, with stirring,
allowing 2 to 3 min between each addi-
tion. Continue the addition of water
until the ceric ammonium nitrate is
completely dissolved. Filter, dilute to 1
liter with water in a volumetric flask,
and mix.
Standardization. Weigh about 200
mg of dry arsenic trioxide to the nearest
0.1 mg. Transfer to a 500-mL conical
flask, add 15 mL of 10% sodium hy-
droxide reagent solution, and warm the
mixture gently to hasten dissolution.
When dissolution is complete, cool to
room temperature and add 25 mL of
+
dilute sulfuric acid (1 5 ) . Dilute to 100
mL with water and add, as catalyst, 0.15
mL of 0.01 M osmium tetroxide (0.25 g
of OsO4 in 100 mL of 0.1 N sulfuric acid).
(Warning. Osmium tetroxide is poi-
sonous; avoid contact!) Add 0.05 mL of
ferroin indicator solution, and titrate
with the ceric ammonium nitrate solu-
tion until the reddish orange color
changes to colorless or very pale blue.
(Note. As the osmium tetroxide catalyst
ages, 0.15 to 0.65 mL may be needed to
achieve the desired action. A sluggish
end point indicates insufficient osmium
tetroxide.)
Normality of Ceric
Ammonium Nitrate
= ( W x lOOO)l(V x 49.45)
where W = weight, in mg, of As203 and
V = volume, in mL, of (NH&Ce(NO&
solution.
Residue after ignition. Weigh ac-
curately 4.9-5.1 g in a previously ignited
and tared plantinum crucible or dish.
Gently ignite until charred, and ignite
again slowly until all carbon has been
+
volatilized. Finally, ignite at 800 25 "C
for 15 min. The weight of the residue
should not exceed 0.005 g.
Suitability for determination of
phosphate. Dissolve 2 g in 100 mL of
water. To 10 mL of this solution, add 90
mL of water and 20 g of sodiuh bisulfite,
dissolve, and mix. Transfer 1 mL of this
solution to each of two solutions con-
taining 25 mL of 0.5 N sulfuric acid and
1 mL of ammonium molybdate reagent
solution (for direct colorimetric phos-
phate). For the control, add 0.005 mg of
phosphate ion (PO,) to one of the solu-
tions. For the sample, use the remaining
solution. Allow the solutions to stand a t
room temperature for 2 h. The control
should turn perceptibly darker blue
than the sample.
Sodium Bromide
NaBr Formula Wt 102.89
REQUIREMENTS
Insoluble matter. Not more than
0.005%.
pH of a 5% solution. From 5.5 to 7.5
at 25 "C.
Bromate (Br03). To pass test (limit
about 0.001%).
Chloride (Cl). Not more than 0.2%.
Nitrogen compounds (as N). Not
more than 5 ppm.
Sulfate (Sod). Not more than
0.002%.
Barium (Ba). Not more than
0.002%.
Calcium, magnesium, and Rz03
precipitate. Not more than
0.005%.
Heavy metals (as Pb). Not more
than 5 ppm.
Iron (Fe). Not more than 5 ppm.
 Potassium (K). Not more than
0.005%.
TESTS
Insoluble matter. Dissolve 20 g in
150 mL of water, heat to boiling, and
digest in a covered beaker on the steam
bath for 1 h. Filter through a tared fil-
tering crucible, wash thoroughly, and
dry at 105 "C. The weight of the residue
should not exceed 0.001 g. Save the fil-
trate separate from the washings for the
test for Calcium, magnesium, and
R203 precipitate.
pH of a 5% solution. Dissolve 10 gin
200 mL of carbon dioxide- and ammo-
nia-free water. Determine the pH by the
method described on page 27. The pH
should be from 5.5 to 7.5 a t 25 "C. The
pH of a 5% solution of pure sodium
bromide would be 7.0 a t 25 "C.
Bromate. Dissolve 1.0 g in 10 mL of
freshly boiled and cooled water. Add
0.10 mL of 10% potassium iodide re-
agent solution, 1 mL of starch indicator
solution, and 0.25 mL of 1 N sulfuric
acid. No blue or violet color should be
produced after standing 10 min a t 25
"C.
Chloride. Dissolve 0.50 g in 15 mL of
+
dilute nitric acid (1 2) in a small flask.
Add 3 mL of 30%hydrogen peroxide and
digest on the steam bath until the solu-
tion is colorless. Wash down the sides of
the flask with a little water, digest for an
additional 15 min, cool, and dilute with
water to 200 mL. Dilute 2.0 mL with
water to 20 mL, and add 1 mL of nitric
acid and 1 mL of silver nitrate reagent
solution. Any turbidity should not ex-
ceed that produced by 0.01 mg of chlo-
ride ion (Cl) in an equal volume of so-
lution containing the quantities of re-
agents used in the test.
Nitrogen compounds. Dissolve 1.0
g in 60 mL of water in a flask connected
through a spray trap to a condenser, the
end of which dips beneath the surface of
10 mL of 0.1 N hydrochloric acid. Add to
the flask 20 mL of freshly boiled 10%
sodium hydroxide reagent solution and
about 0.5 g of aluminum wire in small
pieces, allow to stand for 1h, and slowly
distil about 35 mL. To the distillate add
1 mL of 10% sodium hydroxide reagent
solution, dilute with water to 50 mL, and
add 2 mL of Nessler reagent. Any color
should not exceed that produced when
a quantity of ammonium salt containing
0.005 mg of nitrogen (N) is treated ex-
actly like the sample.
Sulfate. Dissolve 20 g in 200 mL of
water, filter if necessary, and add 1mL
of hydrochloric acid. Bring to a boil, add
5 mL of barium chloride reagent solu-
tion, digest in a covered beaker on the
steam bath for 2 h, and allow to stand
overnight. If a precipitate is formed,
filter, wash thoroughly, and ignite. The
weight of the precipitate should not be
more than 0.0012 g greater than the
weight obtained in a complete blank
test.
Barium. For the sample dissolve 6.0
g in 15 mL of water. For the control
dissolve 1.0 g in 15 mL of water and add
0.1 mg of barium ion (Ba). To each so-
lution add 5 mL of acetic acid, 5 mL of
30% hydrogen peroxide, and 1 mL of
hydrochloric acid. Digest in a covered
beaker on the steam bath until reaction
ceases, uncover, and evaporate to dry-
ness. Dissolve the residues in 15 mL of
water, filter if necessary, and dilute with
water to 23 mL. Add 2 mL of 10% po-
tassium dichromate reagent solution
and add ammonium hydroxide until the
orange color,is just dissipated and the
yellow color persists. Add 25 mL of
methanol, stir vigorously, and allow to
stand for 10 min. Any turbidity in the
solution of the sample should not exceed
that in the control.
Calcium, magnesium, and Rz03
precipitate. T o the filtrate from the
test for Insoluble matter, add 5 mL of
ammonium oxalate reagent solution, 2
mL of ammonium phosphate reagent
solution, and 10 mL of ammonium hy-
droxide. Allow to stand overnight, filter,
wash with water containing 2.5% am-
monia and about 0.1% ammonium oxa-
late, and ignite. The weight of the resi-
due should not exceed 0.001 g.
Heavy metals. Dissolve 6.0 g in about
20 mL of water and dilute with water to
30 mL. For the control add 0.02 mg of
lead ion (Pb) to 5.0 mL of the solution
and dilute with water to 25 mL. For the
sample, use the remaining 25-mL por-
tion. Adjust the p H of the control and
sample solutions to between 3 and 4
(using a pH meter) with 1N acetic acid
or ammonium hydroxide (10% NH3),
dilute with water to 40 mL, and mix.
Add 10 mL of freshly prepared hydrogen
sulfide water to each and mix. Any color
in the solution of the sample should not
exceed that in the control.
Iron. Dissolve 2.0 g in 40 mL of water
plus 2 mL of hydrochloric acid, and di-
lute with water to 50 mL. Add 30 to 50
mg of ammonium peroxydisulfate
crystals and 3 mL of ammonium thio-
cyanate reagent solution. Any red color
should not exceed that produced by 0.01
mg of iron (Fe) in a n equal volume of
solution containing the quantities of
reagents used in the test.
Potassium. Determine the potassium
by the flame photometric method de-
scribed on page 20. Dissolve 10 g in
water and dilute with water to 100
mL.
Sample Solution A. Dilute 10 mL of
the solution with water to 100 mL.
Control Solution B. To another 10
mL of the solution, add 0.05 mg of po-
tassium ion (K) and dilute with water to
100 mL.
Observe the emission of Control So-
lution B a t the 767-nm potassium line.
Observe the emission of Sample Solu-
ANALYTICAL CHEMISTRY, VOL. 49, NO. 3, MARCH 1977
tion A a t the 767-nm potassium line and
a t a wavelength of 750 nm. The differ-
ence (01) between the intensities ob-
served for Sample Solution A at 750 nm
gnd 767 nm should not exceed the dif-
ference ( 0 2 ) observed at 767 nm be-
tween Sample Solution A and Control
Solution B.
Thiourea
NH2CSNH2
Formula Wt 76.12
REQUIREMENTS
Assay. Not less than 99.0%
NHzCSNHz calculated on the dry
basis.
Melting point. Not below 174 "C nor
above 177 "C.
Solubility in water. T o pass test.
Residue after ignition. Not more
than 0.1%.
Loss on drying. Not more than
0.5%.
Sensitivity to blismuth. T o pass
test.
TESTS
Assay. Weigh accurately about 1 g,
dissolve in water, and dilute to 250 mL
in a volumetric flask. To 20.0 mL of this
solution in a glass-stoppered flask, add
25.0 mL of 0.1 N silver nitrate and 10
mL of ammonium hydroxide (10%
"3). Stopper the flask, shake vigor-
ously for 2 min, heat to boiling, and cool.
To the cooled solution, add 60 mL of
dilute nitric acid, shake vigorously, and
filter through a filtering crucible or a
sintered glass funnel which has been
cleaned with dilute nitric acid, and wash
the funnel and flask well with water. To
the filtrate plus washings, add 2 mL of
ferric ammonium sulfate indicator so-
lution, and titrate with 0.1 N thiocy-
anate. One milliliter of 0.1 N silver ni-
trate corresponds to 0.003806 g of
NHzCSNHz.
Solubility in water. Dissolve 1 g in
20 mL of water. The solution should be
clear and colorless.
Residue after ignition. Ignite 10 g in
a tared crucible or (dish. The rate of
heating should be such that from 1to 2
h is required to volatilize the sample.
When nearly all of the sample has been
volatilized, cool, and moisten the residue
with 0.10 mL of sulfuric acid. Continue
the heating until the remainder of the
sample and excess sulfuric acid have
been volatilized. Finally, ignite a t 800 f:
25 "C for 15 min. The weight of the res-
idue should not exceed 0.01 g.
Loss on drying. Weigh accurately
about 1.5 g and dry to constant weight at
105 "C. The loss in weight should not be
more than 0.5%.
Sensitivity to bismuth. Dissolve 0.10
527
g in 10 mL of water. Add 1.0 mL of this
solution to 10 mL of bismuth solution.*
A distinct yellow color is produced im-
mediately.
*Bismuth Solution. Dissolve 0.23 g
of bismuth subnitrate in a mixture of 12
mL of nitric acid and 80 mL of water.
When dissolution is complete, dilute
with water to 2000 mL.
o-Tolidine Dihydrochloride
REVISIONS IN
REQUIREMENTS
( - C G H ~ - ~ N H ~ - ~ C H ~ ) ~ ~ ~ H C I AND TESTS
Formula Wt 285.22
REQUIREMENTS
Assay. Not less than 98%.
Residue a f t e r ignition. Not more
than 0.1%.
Sensitivity. To pass test (0.1 ppm
free chlorine).
Solubility. To pass test.
Water (HzO). Not more than 1%.
TESTS
Assay. Weigh accurately about 1.5 g
and transfer to a 400-mL beaker. Dis-
solve in 250 mL of water, warming
gently if necessary, then cool to 0 “C.
Add 5 mL of concentrated hydrochloric
acid and 5 g of potassium bromide, and
titrate with 0.5 N sodium nitrite, keep-
ing the temperature below 5 “C. As the
end point is approached, titrate drop-
wise, stirring thoroughly after each ad-
dition, until a blue color is produced
immediately when a glass rod dipped
into the titrated solution is streaked on
starch-iodide test paper. One milliliter
of 0.5 N sodium nitrite corresponds to
0.01426 g of o-tolidine dihydrochlo-
ride.
Residue a f t e r ignition. Place 1 g in
a tared porcelain crucible, add 0.5 mL of
sulfuric acid, and slowly ignite in a hood.
Heat in a furnace at 800 f 25 “ C to
constant weight. The weight of the res-
idue should not exceed 0.001 g.
Sensitivity. Dissolve 0.135 g in 50 mL
of water. Add this solution, with con-
stant stirring, to 50 mL of dilute hydro-
+
chloric acid (3 7 ) . Add 1 mL of this
solution to 20 mL of water containing
0.0025 g of free chlorine.* A distinct
yellow color is produced.
*Chlorine Standard (0.5 mL = 0.002
mg Cl). Pipet 1.0 mL of sodium hypo-
chlorite and dilute with carbon diox-
ide-free water to 1 L.
Solubility. Dissolve 0.5 g in 50 mL of
water. Dissolution is complete and the
solution is colorless to light yellow. (Any
blue color seen initially will be caused by
free chlorine in water, since this is a
basic or neutral solution.)
Water. Place 25 mL of methanol in a
dry titration flask and add Karl Fischer
reagent to a visually or electrometrically
528 ANALYTICAL CHEMISTRY, VOL. 49, NO. 3 , MARCH 1977
determined end point. Add 3 g of the
sample, taking care to protect the con-
tents of the flask from moisture. Stir
vigorously and titrate with Karl Fischer
reagent to the same end point. Calculate
the water content of the sample from the
titer and volume of Karl Fischer reagent
consumed by the sample.
Calcium Chloride, Anhydrous
(For drying)
O n page 166 change the name of the
reagent to Calcium Chloride Desic-
cant.
Formamide
On page 276, change the requirement
for Freezing point to “Not below 2.0 “C
nor above 3.0 “C.” On page 276-277,
delete the requirement and test for pH
of 50% aqueous solution.
Hydrochloric Acid
O n page 299, add the test for Ap-
pearance cited below.
Appearance. Mix the material in the
original container, pour 10 mL into a
test tube (20 X 150 mm), and compare
with distilled water in a similar tube.
The liquids should be equally clear and
free from suspended matter.
Magnesium Perchlorate
(For drying)
On page 373, change the name of the
reagent to Magnesium Perchlorate
Desiccant.
Methanol
O n pages 400 and 402, change the
expression for Acidity (as HCOOH) to
Acidity (as CH3COOH).
Nitric Acid
On page 418, add the Note cited
below.
Note. This material may darken
during storage due to a photochemical
reaction.
Picric Acid
O n page 446 add the Caution cited
below.
Caution. Trinitrophenol explodes
when heated rapidly or when subjected
.
to percussion. For safety in transporta-
tion, trinitrophenol is usually mixed
with a minimum of 10% of water.
O n page 446, add the test cited
below.
Melting point (dried). Carefully
transfer a small amount of dried sample
(prepared in the test for Insoluble in
benzene) to a capillary tube, and run
the melting point using an oil immersion
bath.
O n page 446 i n the test for Insoluble
in benzene, increase the quantity of
sample i n the first sentence from “5 g”
to “5 to 15g.”Also insert after the first
sentence the note cited below.
* (Note. Add water to the remaining
dried sample before discarding it.)
On page 446 in the test for Insoluble
a n d resinous matter, replace “10 g” by
“a sample equivalent to 10 g on a dry
basis” i n the first line.
Potassium Perchlorate
O n pages 503-504, revise the test for
Heavy metals to read as follows:
Heavy metals. Dissolve 3 g in hot
water and dilute with water to 60 mL.
For the control, add 0.01 mg of lead ion
(Pb) to 10 mL of this solution and dilute
with water to 50 mL. For the sample use
the remaining 50-mL portion. Adjust
the pH of the control and sample solu-
tions to between 3 and 4 (using a pH
meter) with 1 N acetic acid or ammo-
nium hydroxide (10% NH3), and equal-
ize if necessary the volumes of the two
solutions with water. Add 10 mL of
freshly prepared hydrogen sulfide water
to each and mix. Any color in the solu-
tion of the sample should not exceed
that in the control.
Silica Gel
(For drying)
On page ,528, change the name of the
reagent to Silica Gel Desiccant.
On line 5 of the test for Suitability
f o r moisture absorption, change the
limit for the increase i n weight from
31 r/O to 27%.
Sulfuric Acid
On page 630 i n the requirements for
Appearance a n d f o r Color (APHA),
delete the phrase “as received and after
dilution to 2 N.” Also on page 631 in the
test for Color (APHA), delete the last
sentence, and add the test for Ap-
pearance cited below.
Appearance. Mix the material in the
original container, pour 10 mL into a
test tube (20 X 150 mm), and compare
with distilled water in a similar tube.
The liquids should be equally clear and
free from suspended matter.