5328-5337 Volumetric Solutions
5328-5337 Volumetric Solutions
5328-5337 Volumetric Solutions
for 5 minutes with 1 g of aluminum oxide, and filter to concentration to between 94.5% and 95.5% (w/w) of
clarify. H2SO4.
Sodium Thioglycolate TS—Dissolve 1.5 g of sodium thi- [NOTE—Since the acid concentration may change upon
oglycolate in 450 mL of water, and add 50 mL of alcohol. standing or upon intermittent use, the concentration should
Use within 3 days. be checked frequently and solutions assaying more than
Sodium Thiosulfate TS—Use 0.1 N Sodium Thiosulfate 95.5% or less than 94.5% discarded.]
(see in the section Volumetric Solutions). Sulfuric Acid–Formaldehyde TS—Add 1 drop of formal-
Standard Lead Solution—See under Heavy Metals 〈231〉. dehyde TS to each mL of sulfuric acid, and mix. Prepare this
Stannous Chloride, Acid, TS—Dissolve 8 g of stannous solution fresh.
chloride in 500 mL of hydrochloric acid. Store in glass con- Tannic Acid TS—Dissolve 1 g of tannic acid in 1 mL of
tainers, and use within 3 months. alcohol, and dilute with water to 10 mL. Prepare this solu-
Stannous Chloride, Acid, Stronger, TS—Dissolve 40 g tion fresh.
of stannous chloride in 100 mL of hydrochloric acid. Store Tartaric Acid TS—Dissolve 3 g of tartaric acid in water to
in glass containers, and use within 3 months. make 10 mL. Prepare this solution fresh.
Starch TS—Mix 1 g of soluble starch with 10 mg of red Tetrabromophenolphthalein Ethyl Ester TS—Dissolve
mercuric iodide and sufficient cold water to make a thin 100 mg of tetrabromophenolphthalein ethyl ester in 90 mL
paste. Add 200 mL of boiling water, and boil for 1 minute of glacial acetic acid, and dilute with glacial acetic acid to
with continuous stirring. Cool, and use only the clear solu- 100 mL. Prepare this solution fresh.
tion. [NOTE—Commercially available, stabilized starch indica- Tetramethylammonium Hydroxide TS—Use an aqueous
tor solutions may be used, including mercury-free solutions solution containing, in each 100 mL, the equivalent of 10 g
preserved with other compounds such as salicylic acid.] of anhydrous tetramethylammonium hydroxide.
Starch, Iodide-Free, TS—Mix 1 g of soluble starch with Thioacetamide TS—Dissolve 4 g of thioacetamide in 100
sufficient cold water to make a thin paste. While stirring, mL of water.
add 100 mL of boiling water, and allow to cool. Prepare this Thioacetamide–Glycerin Base TS—Mix 0.2 mL of thio-
solution immediately before use. Iodide-free starch TS shows acetamide TS and 1 mL of glycerin base TS, and heat in a
a blue color when 20 mL of potassium iodide solution (1 in boiling water bath for 20 seconds. Use the mixture
400) and 0.05 mL of an iodine–potassium iodide solution immediately.
(prepared by dissolving 127 mg of iodine and 800 mg of Thorium Nitrate TS—Dissolve 1 g of thorium nitrate in
potassium iodide in water and diluting with water to 100 water to make 100 mL. Filter, if necessary.
mL) are added to 1 mL of the iodide-free starch TS. Thymol Blue TS—Dissolve 100 mg of thymol blue in
Starch Iodide Paste TS—Heat 100 mL of water in a 250- 100 mL of alcohol, and filter if necessary.
mL beaker to boiling, add a solution of 0.75 g of potassium Thymolphthalein TS—Dissolve 100 mg of thymolphtha-
iodide in 5 mL of water, then add 2 g of zinc chloride dis- lein in 100 mL of alcohol, and filter if necessary.
solved in 10 mL of water, and, while the solution is boiling, Titanium Trichloride TS—Dissolve 15 g of titanium
add, with stirring, a smooth suspension of 5 g of soluble trichloride in 100 mL of 10% hydrochloric acid solution.
starch in 30 mL of cold water. Continue to boil for 2 min- Titanium Trichloride–Sulfuric Acid TS—Mix carefully 20
utes, then cool. Store in well-closed containers in a cold mL of titanium trichloride TS in 13 mL of sulfuric acid. Add
place. sufficient 30% hydrogen peroxide to produce a yellow
Starch iodide paste TS must show a definite blue streak color. Heat until white fumes are evolved, allow to cool, and
when a glass rod, dipped in a mixture of 1 mL of 0.1 M dilute with water. Repeat the evaporation and addition of
sodium nitrite, 500 mL of water, and 10 mL of hydrochloric water until a colorless solution is obtained. Dilute with water
acid, is streaked on a smear of the paste. to 100 mL.
Starch–Potassium Iodide TS—Dissolve 500 mg of potas- p-Toluenesulfonic Acid TS—Dissolve 2 g of p-tolu-
sium iodide in 100 mL of freshly prepared starch TS. Prepare enesulfonic acid in 10 mL of a mixture of 7 parts of acetone
this solution fresh. and 3 parts of water.
Stronger Cupric Acetate TS—See Cupric Acetate TS, Triketohydrindene Hydrate TS (Ninhydrin TS)—Dissolve
Stronger. 200 mg of triketohydrindene hydrate in water to make 10
Sudan III TS—Dissolve 0.05 g of Sudan III in 25 mL of mL. Prepare this solution fresh.
alcohol, with warming if necessary. Cool, add 25 mL of Trinitrophenol TS (Picric Acid TS)—Dissolve the equiva-
glycerin, and mix. Filter if undissolved material persists. lent of 1 g of anhydrous trinitrophenol in 100 mL of hot
Sudan IV TS—Dissolve 0.5 g of Sudan IV in chloroform water. Cool the solution, and filter if necessary.
to make 100 mL. Triphenyltetrazolium Chloride TS—Dissolve 500 mg of
Sulfanilic Acid TS—Dissolve 800 mg of sulfanilic acid in triphenyltetrazolium chloride in dehydrated alcohol to make
100 mL of acetic acid. Store in tight containers. 100 mL.
Diazotized Sulfanilic Acid TS—Dissolve 0.9 g of sulfan- Xylenol Orange TS—Dissolve 100 mg of xylenol orange
ilic acid in 9 mL of hydrochloric acid with warming, and in 100 mL of alcohol.
dilute with water to 100 mL. Cool 10 mL of this solution in Zinc Uranyl Acetate TS—Dissolve 50 g of uranyl acetate
iced water, and add 10 mL of a sodium nitrite solution (4.5 in a mixture of 15 mL of glacial acetic acid and water to
in 100) previously cooled in iced water. Allow to stand at 0° make 500 mL. Then dissolve 150 g of zinc acetate in a mix-
for at least 15 minutes (the solution may be kept for 3 days ture of 15 mL of glacial acetic acid and water to make 500
at this temperature). Immediately before use, add 20 mL of mL. Mix the two solutions, allow to stand overnight, and
sodium carbonate solution (1 in 10). pass through a dry filter, if necessary.
Sulfanilic-1-Naphthylamine TS—Dissolve 500 mg of sul-
fanilic acid in 150 mL of acetic acid. Dissolve 100 mg of 1-
naphthylamine hydrochloride in 150 mL of acetic acid, and VOLUMETRIC SOLUTIONS
mix the two solutions. The pink color that may develop on
standing can be removed by treatment with zinc. Normal Solutions—Normal solutions are solutions that
Sulfanilic-α-Naphthylamine TS—See Sulfanilic-1-Naph- contain 1 gram equivalent weight of the active substance in
thylamine TS. each 1000 mL of solution; that is, an amount equivalent to
Sulfomolybdic Acid TS—Dissolve, with the aid of heat, 1.0079 g of hydrogen or 7.9997 g of oxygen. Normal solu-
2.5 g of ammonium molybdate in 20 mL of water, add 50 tions and solutions bearing a specific relationship to normal
mL of 12 N sulfuric acid, and dilute with water to 100 mL. solutions, and used in volumetric determinations, are desig-
Store this solution in a polyethylene container. nated as follows: normal, 1 N; double-normal, 2 N; half-nor-
Sulfuric Acid TS—Add a quantity of sulfuric acid of mal, 0.5 N; tenth-normal, 0.1 N; fiftieth-normal, 0.02 N;
known concentration to sufficient water to adjust the final hundredth-normal, 0.01 N; thousandth-normal, 0.001 N.
Molar Solutions—Molar solutions are solutions that con- sulfuric acids may be standardized against a sodium hydrox-
tain, in 1000 mL, 1 gram-molecule of the reagent. Thus, ide solution that recently has been standardized against a
each liter of a molar solution of sulfuric acid contains 98.07 certified primary standard.
g of H2SO4 and each liter of a molar solution of potassium All volumetric solutions, if practicable, are to be prepared,
ferricyanide contains 329.25 g of K3Fe(CN)6. Solutions con- standardized, and used at the standard temperature of 25°.
taining, in 1000 mL, one-tenth of a gram-molecule of the If a titration is carried out with the volumetric solution at a
reagent are designated “tenth-molar,” 0.1 M; and other markedly different temperature, standardize the volumetric
molarities are similarly indicated. solution used as the titrant at that different temperature, or
Empirical Solutions—It is frequently difficult to prepare make a suitable temperature correction.
standard solutions of a desired theoretical normality, and
this is not essential. A solution of approximately the desired Acetic Acid, Double-Normal (2 N)
normality is prepared and standardized by titration against a C2H4O2, 60.05
primary standard solution. The normality factor so obtained 120.10 g in 1000 mL
is used in all calculations where such empirical solutions are Add 116 mL of glacial acetic acid to sufficient water to
employed. If desired, an empirically prepared solution may make 1000 mL after cooling to room temperature.
be adjusted downward to a given normality provided it is
strong enough to permit dilution. Ammonium Thiocyanate, Tenth-Normal (0.1 N)
All volumetric solutions, whether made by direct solution NH4SCN, 76.12
or by dilution of a stronger solution, must be thoroughly 7.612 g in 1000 mL
mixed by shaking before standardization. As the strength of Dissolve about 8 g of ammonium thiocyanate in 1000 mL
a standard solution may change upon standing, the factor of water, and standardize the solution as follows.
should be redetermined frequently. Accurately measure about 30 mL of 0.1 N silver nitrate VS
When solutions of a reagent are used in several normali- into a glass-stoppered flask. Dilute with 50 mL of water,
ties, the details of the preparation and standardization are then add 2 mL of nitric acid and 2 mL of ferric ammonium
usually given for the normality most frequently required. sulfate TS, and titrate with the ammonium thiocyanate solu-
Stronger or weaker solutions are prepared and standardized tion to the first appearance of a red-brown color.
in the same general manner as described, using proportion-
ate amounts of the reagent. It is possible in many instances
to prepare lower normalities accurately by making an exact
dilution of a stronger solution. Volumetric solutions prepared
by dilution should be restandardized either as directed for
the stronger solution or by comparison with another volu- If desirable, 0.1 N ammonium thiocyanate may be re-
metric solution having a known ratio to the stronger placed by 0.1 N potassium thiocyanate where the former is
solution. directed in various tests and assays.
Dilute solutions that are not stable, as, for instance, potas-
sium permanganate 0.01 N and more dilute sodium thiosul-
fate, are preferably prepared by exactly diluting the higher Bismuth Nitrate, 0.01 M
normality with thoroughly boiled and cooled water on the Bi(NO3)3 · 5H2O, 485.07
same day they are required for use. 1000 mL of this solution contains 4.851 g of bismuth ni-
Blank Determinations—Where it is directed that “any trate pentahydrate
necessary correction” be made by a blank determination, Dissolve 4.86 g of bismuth nitrate pentahydrate in 60 mL
the determination is to be conducted with the use of the of dilute nitric acid, add 0.01 N nitric acid to make 1000
same quantities of the same reagents treated in the same mL, and standardize the solution as follows.
manner as the solution or mixture containing the portion of Accurately measure 25 mL of the prepared bismuth ni-
the substance under assay or test, but with the substance trate solution, add 50 mL of water and 1 drop of xylenol
itself omitted. Appropriate blank corrections are to be made orange TS, and titrate the solution with 0.01 M edetate di-
for all Pharmacopeial titrimetric assays (see Titrimetry 〈541〉). sodium VS until the red color changes to yellow. Calculate
All Pharmacopeial assays that are volumetric in nature in- the molarity factor.
dicate the weight of the substance being assayed to which
each mL of the primary volumetric solution is equivalent. In Bromine, Tenth-Normal (0.1 N)
general, these equivalents may be derived by simple calcula- Br, 79.90
tion from the data given under Molecular Formulas and 7.990 g in 1000 mL
Weights, in the Reference Tables. Dissolve 3 g of potassium bromate and 15 g of potassium
bromide in water to make 1000 mL, and standardize the
solution as follows.
Preparation and Methods of Standardization Accurately measure about 25 mL of the solution into a
of Volumetric Solutions 500-mL iodine flask, and dilute with 120 mL of water. Add
5 mL of hydrochloric acid, insert the stopper in the flask,
The following directions give only one method for stan- and shake it gently. Then add 5 mL of potassium iodide TS,
dardization, but other methods of standardization, capable again insert the stopper, shake the mixture, allow it to stand
of yielding at least the same degree of accuracy, may be for 5 minutes, and titrate the liberated iodine with 0.1 N
used. The values obtained in the standardization of volumet- sodium thiosulfate VS, adding 3 mL of starch TS as the
ric solutions are valid for all Pharmacopeial uses of these endpoint is approached.
solutions, regardless of the instrumental or chemical indica- Preserve in dark amber-colored, glass-stoppered bottles.
tors employed in the individual monographs. Where the ap-
parent normality or molarity of a titrant depends upon the
special conditions of its use, the individual monograph sets
forth the directions for standardizing the reagent in the
specified context. For those salts that usually are available as
certified primary standards, or that are available as highly
purified salts of primary standard quality, it is permissible to
prepare solutions by accurately weighing a suitable quantity Ceric Ammonium Nitrate, Twentieth-Normal (0.05 N)
of the salt and dissolving it to produce a specific volume of Ce(NO3)4 · 2NH4NO3, 548.22
solution of known concentration. Acetic, hydrochloric, and 2.741 g in 100 mL
Dissolve 2.75 g of ceric ammonium nitrate in 1 N nitric standard solution in terms of its equivalent in mg of as-
acid to obtain 100 mL of solution, and filter. Standardize corbic acid.
the solution as follows.
Accurately measure 10 mL of freshly standardized 0.1 N Edetate Disodium, Twentieth-Molar (0.05 M)
ferrous ammonium sulfate VS into a flask, and dilute with C10H14N2Na2O8 · 2H2O, 372.24
water to about 100 mL. Add 1 drop of nitrophenanthroline 18.61 g in 1000 mL
TS, and titrate with the ceric ammonium nitrate solution to Dissolve 18.6 g of edetate disodium in water to make
a colorless endpoint. 1000 mL, and standardize the solution as follows.
Accurately weigh about 200 mg of chelometric standard
calcium carbonate, previously dried at 110° for 2 hours and
cooled in a desiccator, transfer to a 400-mL beaker, add 10
mL of water, and swirl to form a slurry. Cover the beaker
with a watch glass, and introduce 2 mL of diluted hydro-
chloric acid from a pipet inserted between the lip of the
Ceric Sulfate, Tenth-Normal (0.1 N) beaker and the edge of the watch glass. Swirl the contents
Ce(SO4)2, 332.24 of the beaker to dissolve the calcium carbonate. Wash down
33.22 g in 1000 mL the sides of the beaker, the outer surface of the pipet, and
Use commercially available volumetric standard solution. the watch glass with water, and dilute with water to about
Standardize the solution as follows. 100 mL. While stirring the solution, preferably with a mag-
Accurately weigh about 0.2 g of sodium oxalate, primary netic stirrer, add about 30 mL of the edetate disodium solu-
standard, dried according to the instructions on its label, tion from a 50-mL buret. Add 15 mL of sodium hydroxide
and dissolve in 75 mL of water. Add, with stirring, 2 mL of TS and 300 mg of hydroxy naphthol blue, and continue
sulfuric acid that has previously been mixed with 5 mL of the titration with the edetate disodium solution to a blue
water, mix well, add 10 mL of hydrochloric acid, and heat endpoint.
to between 70° and 75°. Titrate with 0.1 N ceric sulfate to a
permanent slight yellow color. Each 6.700 mg of sodium
oxalate is equivalent to 1 mL of 0.1 N ceric sulfate.
suitable, tight container, and standardize the solution as end of the titration, and continue to the absence of the
follows. blue-starch-iodine complex.
Accurately measure about 25 mL of 0.5 N hydrochloric
acid VS. Dilute with 50 mL of water, add 2 drops of phenol-
phthalein TS, and titrate with the alcoholic potassium hy-
droxide solution until a permanent, pale pink color is
produced.
[NOTE—Store in tightly stoppered bottles, protected from
light.] Potassium Permanganate, Tenth-Normal (0.1 N)
KMnO4, 158.03
3.161 g in 1000 mL
Dissolve about 3.3 g of potassium permanganate in 1000
mL of water in a flask, and boil the solution for about 15
minutes. Insert the stopper in the flask, allow it to stand for
at least 2 days, and filter through a fine-porosity, sintered-
Potassium Hydroxide, Alcoholic, Tenth-Molar (0.1 M) glass crucible. If necessary, the bottom of the sintered-glass
KOH, 56.11 crucible may be lined with a pledget of glass wool. Stan-
Dilute 20 mL of 0.5 M alcoholic potassium hydroxide to dardize the solution as follows.
100.0 mL with aldehyde-free alcohol. Accurately weigh about 200 mg of sodium oxalate, dried
according to the instructions on its label, and dissolve it in
Potassium Hydroxide, Methanolic, Tenth-Normal (0.1 250 mL of water. Add 7 mL of sulfuric acid, heat to about
N) 70°, and then slowly add the permanganate solution from a
5.612 g in 1000 mL buret, with constant stirring, until a pale pink color, which
Dissolve about 6.8 g of potassium hydroxide in 4 mL of persists for 15 seconds, is produced. The temperature at the
water, and add methanol to make 1000 mL. Allow the solu- conclusion of the titration should be not less than 60°. Cal-
tion to stand in a tightly stoppered bottle for 24 hours. culate the normality. Each 6.700 mg of sodium oxalate is
Then quickly decant the clear supernatant into a suitable, equivalent to 1 mL of 0.1 N potassium permanganate.
tight container, and standardize the solution as follows. Since potassium permanganate is reduced on contact
Accurately measure about 25 mL of 0.1 N hydrochloric with organic substances such as rubber, the solution must
acid VS. Dilute with 50 mL of water, add 2 drops of phenol- be handled in apparatus entirely of glass or other suitably
phthalein TS, and titrate with the methanolic potassium hy- inert material. It should be frequently restandardized. Store
droxide solution until a permanent, pale pink color is in glass-stoppered, amber-colored bottles.
produced.
[NOTE—Store in tightly stoppered bottles, protected from
light.]
Sodium Arsenite, Twentieth-Molar (0.05 M) tions, through the top of the condenser. Regulate the addi-
NaAsO2 129.91 tion of the methanol so that the vapors are condensed and
6.496 g in 1000 mL do not escape through the top of the condenser. After addi-
Transfer 4.9455 g of arsenic trioxide, which has been pul- tion of the methanol is complete, connect a drying tube to
verized and dried at 100° to constant weight, to a 1000-mL the top of the condenser, and allow the solution to cool.
volumetric flask, dissolve it in 40 mL of 1 N sodium hydrox- Transfer the solution to a 1-L volumetric flask, dilute with
ide, and add 1 N sulfuric acid or 1 N hydrochloric acid until anhydrous methanol to volume, and mix. Standardize the
the solution is neutral or only slightly acid to litmus. Add solution as follows.
30 g of sodium bicarbonate, dilute with water to volume, Accurately measure about 20 mL of freshly standardized
and mix. 1 N hydrochloric acid VS into a 250-mL conical flask, add
0.25 mL of phenolphthalein TS, and titrate with the sodium
Sodium Hydroxide, Alcoholic, Tenth-Normal (0.1 N) methoxide solution to the first appearance of a permanent
NaOH, 40.00 pink color.
To 250 mL of alcohol add 2 mL of a 50% (w/v) solution
of sodium hydroxide.
Dissolve about 200 mg of benzoic acid, accurately
weighed, in 10 mL of alcohol and 2 mL of water. Add 2
drops of phenolphthalein TS, and titrate with the alcoholic
sodium hydroxide solution until a permanent pale pink color
is produced. Sodium Methoxide, Tenth-Normal (0.1 N) in Toluene
CH3ONa, 54.02
5.402 g in 1000 mL
Cool in ice-water 150 mL of methanol contained in a
1000-mL volumetric flask, and add, in small portions, about
2.5 g of freshly cut sodium metal. When the metal has dis-
solved, add toluene to make 1000 mL, and mix. Store pref-
erably in the reservoir of an automatic delivery buret suita-
Change to read: bly protected from carbon dioxide and moisture.
Standardize the solution as follows.
Accurately weigh about 400 mg of primary standard ben-
Sodium Hydroxide, Normal (1 N) zoic acid, and dissolve in 80 mL of dimethylformamide in a
NaOH, 40.00 flask. Add 3 drops of a 1 in 100 solution of thymol blue in
40.00 g in 1000 mL dimethylformamide, and titrate with the sodium methoxide
Dissolve 162 g of sodium hydroxide in 150 mL of carbon to a blue endpoint. Correct for the volume of the sodium
dioxide-free water, cool the solution to room temperature, methoxide solution consumed by 80 mL of the dimethyl-
and filter through hardened filter paper. Transfer 54.5 mL of formamide. Each 12.21 mg of benzoic acid is equivalent to
the clear filtrate to a tight, polyolefin container, and dilute 1 mL of 0.1 N sodium methoxide.
with carbon dioxide-free water to 1000 mL.
Accurately weigh about 5 g of potassium biphthalate, pre-
viously crushed lightly and dried at 120° for 2 hours, and
dissolve in 75 mL of carbon dioxide-free water. Add 2 drops
of phenolphthalein TS, and titrate with the sodium hydrox-
ide solution to the production of a permanent pink color. [NOTES—(1) To eliminate any turbidity that may form fol-
Each ▲204.22 mg▲USP35 of potassium biphthalate is equiva- lowing dilution with toluene, add methanol (25 to 30 mL
lent to 1 mL of 1 N sodium hydroxide. usually suffices) until the solution is clear. (2) Restandardize
▲ the solution frequently.]
Sodium Tetraphenylboron, Fiftieth-Molar (0.02 M) Add slowly, with stirring, 30 mL of sulfuric acid to about
NaB(C6H5)4, 342.22 1020 mL of water, allow to cool to 25°, and determine the
6.845 g in 1000 mL normality by titration against tromethamine as described
Dissolve an amount of sodium tetraphenylboron, equiva- under Hydrochloric Acid, Normal (1 N).
lent to 6.845 g of NaB(C6H5)4, in water to make 1000 mL,
and standardize the solution as follows. Tetrabutylammonium Hydroxide, Tenth-Normal (0.1 N)
Pipet two 75-mL portions of the solution into separate (C4H9)4NOH, 259.47
beakers, and to each add 1 mL of acetic acid and 25 mL of 25.95 g in 1000 mL
water. To each beaker add, slowly and with constant stir- Dissolve 40 g of tetra-n-butylammonium iodide in 90 mL
ring, 25 mL of potassium biphthalate solution (1 in 20), and of anhydrous methanol in a glass-stoppered flask. Place in
allow to stand for 2 hours. Filter one of the mixtures an ice bath, add 20 g of powdered silver oxide, insert the
through a filtering crucible, and wash the precipitate with stopper in the flask, and agitate vigorously for 60 minutes.
cold water. Transfer the precipitate to a container, add 50 Centrifuge a few mL, and test the supernatant for iodide
mL of water, shake intermittently for 30 minutes, filter, and (see Iodide 〈191〉). If the test is positive, add an additional
use the filtrate as the saturated potassium tetraphenylborate 2 g of silver oxide, and continue to allow to stand for 30
solution in the following standardization procedure. Filter minutes with intermittent agitation. When all of the iodide
the second mixture through a tared filtering crucible, and has reacted, filter through a fine-porosity, sintered-glass fun-
wash the precipitate with three 5-mL portions of saturated nel. Rinse the flask and the funnel with three 50-mL por-
potassium tetraphenylborate solution. Dry the precipitate at tions of anhydrous toluene, adding the rinsings to the fil-
105° for 1 hour. Each g of potassium tetraphenylborate trate. Dilute with a mixture of three volumes of anhydrous
(KTPB) is equivalent to 955.1 mg of sodium toluene and 1 volume of anhydrous methanol to 1000 mL,
tetraphenylboron. and flush the solution for 10 minutes with dry, carbon diox-
ide-free nitrogen. [NOTE—If necessary to obtain a clear solu-
tion, further small quantities of anhydrous methanol may be
added.] Store in a reservoir protected from carbon dioxide
and moisture, and discard after 60 days. Alternatively, the
solution may be prepared by diluting a suitable volume of
[NOTE—Prepare this solution just before use.] commercially available tetrabutylammonium hydroxide solu-
tion in methanol with a mixture of 4 volumes of anhydrous
Sodium Thiosulfate, Tenth-Normal (0.1 N) toluene and 1 volume of anhydrous methanol. [NOTE—If
Na2S2O3 · 5H2O, 248.19 necessary to obtain a clear solution, further small quantities
24.82 g in 1000 mL of methanol may be added.]
Dissolve about 26 g of sodium thiosulfate and 200 mg of Standardize the solution on the day of use as follows.
sodium carbonate in 1000 mL of recently boiled and cooled Dissolve about 400 mg of primary standard benzoic acid,
water. Standardize the solution as follows. accurately weighed, in 80 mL of dimethylformamide, add 3
Accurately weigh about 210 mg of primary standard po- drops of a 1 in 100 solution of thymol blue in dimethyl-
tassium dichromate, previously pulverized and dried accord- formamide, and titrate to a blue endpoint with the tetrabu-
ing to the instructions on its label, if necessary, and dissolve tylammonium hydroxide solution, delivering the titrant from
in 100 mL of water in a glass-stoppered, 500-mL flask. Swirl a buret equipped with a carbon dioxide absorption trap.
to dissolve the solid, remove the stopper, and quickly add Perform a blank determination, and make any necessary
3 g of potassium iodide, 2 g of sodium bicarbonate, and 5 correction. Each mL of 0.1 N tetrabutylammonium hydrox-
mL of hydrochloric acid. Insert the stopper gently in the ide is equivalent to 12.21 mg of benzoic acid.
flask, swirl to mix, and allow to stand in the dark for exactly
10 minutes. Rinse the stopper and the inner walls of the
flask with water, and titrate the liberated iodine with the
sodium thiosulfate solution until the solution is yellowish
green in color. Add 3 mL of starch TS, and continue the
titration until the blue color is discharged. Perform a blank
determination. Tetrabutylammonium Hydroxide in Methanol/
Restandardize the solution as frequently as supported by Isopropyl Alcohol, 0.1 N
laboratory stability data. In the absence of such data, Prepare as described for Tetrabutylammonium Hydroxide,
restandardize the solution weekly. Tenth-Normal (0.1 N) using isopropyl alcohol instead of tolu-
ene, and standardize as described. Alternatively, the solution
may be prepared by diluting a suitable volume of commer-
cially available tetrabutylammonium hydroxide solution in
methanol with 4 volumes of anhydrous isopropyl alcohol.
of ferric ammonium sulfate TS, and titrate the excess silver stopper to the titration buret, an inlet tube for carbon diox-
nitrate with 0.1 N ammonium thiocyanate VS. ide, and an exit tube. Arrange for mechanical stirring. All
joints must be air-tight. Arrange to have both the hydrogen
and the carbon dioxide pass through wash bottles contain-
ing titanium trichloride solution (approximately 1 in 50) to
remove any oxygen.
If the solution to be titrated is to be heated before or
during titration, connect the titration flask with an upright
Tetramethylammonium Chloride, Tenth-Molar (0.1 M) reflux condenser through the rubber stopper.
(CH3)4NCl, 109.60 Standardization—Place an accurately measured volume of
10.96 g in 1000 mL about 40 mL of 0.1 N ferric ammonium sulfate VS in the
Dissolve 10.96 g of tetramethylammonium chloride in titration flask, and pass in a rapid stream of carbon dioxide
water to make 1000 mL, and standardize the solution as until all the air has been removed. Add the titanium trichlo-
follows. ride solution from the buret until near the calculated
Transfer an accurately measured volume of about 40 mL endpoint (about 35 mL), then add through the outlet tube
of the solution to a flask, add 10 mL of diluted nitric acid 5 mL of ammonium thiocyanate TS, and continue the titra-
and 50.0 mL of 0.1 N silver nitrate VS, and mix. Add 5 mL tion until the solution is colorless.
of nitrobenzene and 2 mL of ferric ammonium sulfate TS,
shake, and titrate the excess silver nitrate with 0.1 N ammo-
nium thiocyanate VS.
Chromatographic Columns
The following list of packings (L), phases (G), and sup- L6—Strong cation-exchange packing–sulfonated fluoro-
ports (S) is intended to be a convenient reference for the carbon polymer coated on a solid spherical core, 30 to
chromatographer. [NOTE—Particle sizes given in this listing 50 µm in diameter.
are those generally provided. Where other, usually finer,
sizes are required, the individual monograph specifies the
desired particle size. Within any category of packings or Change to read:
phases listed below, there may be a wide range of columns
available. Where it is necessary to define more specifically L7—Octylsilane chemically bonded to totally porous ■or
the chromatographic conditions, the individual monograph superficially porous■1S (USP35) silica particles, 1.5–10 µm in di-
so indicates.] ameter, or a monolithic silica rod.
L8—An essentially monomolecular layer of aminopropylsi-
lane chemically bonded to totally porous silica gel support,
Packings 3 to 10 µm in diameter.
L9—Irregular or spherical, totally porous silica gel having
a chemically bonded, strongly acidic cation-exchange coat-
Change to read: ing, 3 to 10 µm in diameter.
L10—Nitrile groups chemically bonded to porous silica
particles, 3 to 10 µm in diameter.
L1—Octadecyl silane chemically bonded to porous ▲or L11—Phenyl groups chemically bonded to porous silica
nonporous▲USP35 silica or ceramic microparticles, 1.5 to 10 particles, 1.5 to 10 µm in diameter.
µm in diameter, or a monolithic silica rod. L12—A strong anion-exchange packing made by chemi-
L2—Octadecyl silane chemically bonded to silica gel of a cally bonding a quaternary amine to a solid silica spherical
controlled surface porosity that has been bonded to a solid core, 30 to 50 µm in diameter.
spherical core, 30 to 50 µm in diameter. L13—Trimethylsilane chemically bonded to porous silica
L3—Porous silica particles, 1.5 to 10 µm in diameter, or a particles, 3 to 10 µm in diameter.
monolithic silica rod. L14—Silica gel having a chemically bonded, strongly basic
L4—Silica gel of controlled surface porosity bonded to a quaternary ammonium anion-exchange coating, 5 to 10 µm
solid spherical core, 30 to 50 µm in diameter. in diameter.
L5—Alumina of controlled surface porosity bonded to a L15—Hexylsilane chemically bonded to totally porous sil-
solid spherical core, 30 to 50 µm in diameter. ica particles, 3 to 10 µm in diameter.