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pubs.acs.org/doi/book/10.1021/acsreagents
Volumetric Solutions
Part 3, Solutions and Mixtures Used in Tests
eISBN: 9780841230460
Tom Tyner Chair, ACS Committee on Analytical Reagents
James Francis Secretary, ACS Committee on Analytical Reagents
ABSTRACT
Throughout the monographs in this book, the term “volumetric solution” is used to designate a solution prepared and
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Two background references that the analyst may find helpful are ASTM E20008(2008) and the section on Volumetric
Solutions in United States Pharmacopeia (see the bibliographies on Analytical Chemistry [Part 6: List of Bibliographies;
Analytical Chemistry], and on Physical Properties [Part 6: List of Bibliographies; Physical Properties]). Various textbooks
on chemical analysis also deal with volumetric solutions and volumetric analysis on both a theoretical and a practical
basis.
GENERAL INFORMATION
The concentrations of volumetric solutions usually are expressed as N, normality (number of gram-equivalent weights in each
liter of solution), although concentration sometimes is expressed as M, molarity (number of gram-molecular weights in each
liter of solution).
The accuracy of many analytical procedures is dependent on the manner in which such solutions are prepared, standardized,
and stored. The directions that follow describe the preparation of these solutions and their standardization against primary
standards or against already-standardized solutions. Alternatively, in cases where suitable primary standard chemicals are
available, volumetric solutions may be prepared by dissolving accurately weighed portions of these substances to make an
accurately known volume of solution. All volumetric solutions, of course, must be thoroughly mixed as part of their
preparation. Stronger or weaker solutions than those described are prepared and standardized in the same general manner,
using proportional amounts of reagents and standards. Lower strengths frequently may be prepared by accurately diluting a
stronger solution. However, when necessary because of the accuracy requirements of the analysis being performed, volumetric
solutions prepared in this manner should be standardized before use against a primary standard or by comparison with an
appropriate volumetric solution of known strength.
Certain reagents, such as arsenic trioxide, reductometric standard, are designated as standards in this book. Certified
standards of a number of chemical compounds are available as standard reference materials (SRMs) from NIST.
It is desirable to standardize a solution in such a way that the end point is observed at the same pH value (or
oxidation–reduction potential) anticipated during subsequent use.
For example, a sodium hydroxide solution found to be 0.1000 N when standardized against potassium hydrogen phthalate to
phenolphthalein (pH 8.5) may behave like 0.1002 N when used for titrating a strong acid to methyl red (pH 5). Only a small part
of this difference is due to the NaOH required to bring pure water from pH 5 to 8.5. In this case, the error can be avoided by
titrating the strong acid to phenolphthalein (pH 8.5), the same indicator that was used in standardizing the sodium hydroxide.
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Storage
Glass containers are suitable for the storage of most volumetric solutions. However, polyolefin containers are recommended
for alkaline solutions. Volumetric solutions are stable for varying lengths of time, depending on their chemical nature and
their concentration. Dilute solutions are likely to be less stable than those that are 0.1 N or stronger. If there is any doubt
about the reliability of a solution, it should be restandardized at the time of use. Volumetric solutions should be stored
appropriately to avoid environmental interaction that may adversely affect the stability of the assigned normality or
molarity. Opaque containers and carbon dioxide or oxygen traps may be appropriate under certain conditions.
Temperature Considerations
If possible, volumetric solutions should be prepared, standardized, and used at 25 °C. If a titration is carried out at a
temperature different from that at which the solution was standardized, a temperature correction may be needed,
depending on the accuracy requirement of the analysis being performed. If the temperature of use is higher than the
temperature of standardization, the correction is to be subtracted from the standardization value; if the temperature of
use is lower than the temperature of standardization, the correction is to be added. For guidance with respect to
temperature corrections, consider that a 5 °C temperature change will alter the normalities of solutions approximately as
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follows: For aqueous solutions 0.1 N or less, by 1 part in 1000; 0.5 N, by 1.2 parts in 1000; and 1 N, by 1.4 parts in 1000. For
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nonaqueous solutions, based on the expansion coefficients of the solvents, by 5.4 parts in 1000 for glacial acetic acid; 5.5
parts in 1000 for dioxane; and 6.2 parts in 1000 for methanol.
Errors caused by temperature differences, as well as by improper drainage of burettes or pipettes, can be avoided if
measurements are made on a weight basis. With a sensitive direct-reading balance and the use of squeeze bottles,
titrations by weight have become very practical and precise.
Correction Factors
It is not necessary that volumetric solutions have the identical normalities (or molarities) indicated in this section or as
specified in many of the standardization and assay calculations in this book. It is necessary, however, that the exact value be
known because if it is different from the nominal value specified, a correction factor will have to be applied. Thus, if a
calculation is based on an exactly 0.1 N volumetric solution and the solution actually used is 0.1008 N, its volume must be
multiplied by a factor of 1.008 to obtain the corrected volume of 0.1 N solution to use in the calculation. Similarly, if the
actual normality is 0.0984 N, the factor is 0.984.
Replication
Because the results obtained by titrations depend on the reliability of the volumetric solutions used, it is imperative that
the latter be standardized at least in triplicate with particular care and preferably by experienced analysts. Triplicate
standardizations for solutions from 0.1 N to 1 N should agree at least to within 2 parts in 1000. Triplicates for 0.05 N
solutions may differ by as much as 10 parts in 1000. If deviations are greater than indicated, the determinations should be
repeated until the criteria are met.
SOLUTIONS
Note: When “measure accurately” is specified in this section, the volumetric ware used shall conform to the
tolerance accepted by NIST (see the bibliography on Measurement Techniques [Part 6: List of Bibliographies;
Measurement Techniques]).
Acetic Acid, 1 N
Add 61 g (58.1 mL) of glacial acetic acid to a 1 L volumetric flask, dilute to volume with water, and mix thoroughly.
Standardize as follows: Measure accurately 40 mL of the solution into a 250 mL conical flask, add 0.10 mL of
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phenolphthalein indicator solution, and titrate with freshly standardized 1 N sodium hydroxide volumetric solution to a
permanent pink color.
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or the solution is turbid, filter through a fine-porosity sintered-glass filter (do not filter through paper or similar material).
Transfer the filtrate to a 1 L volumetric flask, dilute to volume, and mix thoroughly. Standardize as follows: Titrate against
freshly standardized 0.1 N ferrous sulfate solution described in [Part 3: Volumetric Solutions; Solutions; Ferrous Sulfate]
using a Ferroin indicator, 0.025 M.
and continue to titrate with the 0.1 M copper sulfate volumetric solution to a permanent blue end point.
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EDTA, 0.1 M
Dissolve 37.22 g of Na2EDTA · 2H2O in 500 mL of water. Transfer quantitatively to a 1 L volumetric flask, dilute to volume
with water, and mix thoroughly. Standardize as follows: Weigh accurately 0.40 g of calcium carbonate, chelometric
standard (NIST SRM 915), previously dried at 210 °C for 4 h. Transfer to a 400 mL beaker, and add water. Cover the beaker
with a watch glass, and introduce 4 mL of hydrochloric acid (1:1) from a pipette inserted between the lip of the beaker and
the edge of the watch glass. Swirl the contents of the beaker to dissolve the calcium carbonate. Wash down the sides of the
beaker and the watch glass with water, and dilute to 200 mL. While stirring, add from a 50 mL burette about 30 mL of the
EDTA standard solution. Adjust the solution to pH 12–13 with 10% sodium hydroxide, and add 300 mg of hydroxy naphthol
blue indicator mixture. Continue the titration with the EDTA volumetric standard solution to a blue end point.
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Hydrochloric Acid, 1 N
Add 85 mL of hydrochloric acid to 50 mL of water in a 1 L volumetric flask. Cool to room temperature, dilute to volume with
water, and mix thoroughly. Standardize as follows: Weigh accurately about 2.2 g of sodium carbonate, alkalimetric standard
(NIST SRM 351), that previously has been heated at 285 °C for 2 h. Dissolve in 100 mL of water, and add 0.1 mL of methyl red
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indicator solution. Add the acid slowly from a burette, with stirring, until the solution becomes faintly pink. Heat the
solution to boiling, cool, and again titrate until the solution becomes faintly pink. Repeat this procedure until the faint
color is no longer discharged on further boiling.
Iodine, 0.1 N
Place approximately 40 g of potassium iodide and 10 mL of water in a large glass-stoppered weighing bottle. Mix the
contents by swirling, allow to come to room temperature, and then weigh accurately. Add approximately 12.7 g of assayed
iodine [Part 4: Iodine], previously weighed on a rough balance, and reweigh the stoppered bottle and contents to obtain the
exact weight of the iodine added. Mix and transfer quantitatively to a 1 L amber volumetric flask. Dilute to volume with
water, and mix thoroughly. Standardize as follows: Weigh accurately 0.21 g of arsenic trioxide reductometric standard (NIST
SRM 83), previously dried for 12 h at 110 °C and cooled in a desiccator for 2 h, into a 250 mL iodine flask. Add 10 mL of 1.0 N
sodium hydroxide, warm gently, and swirl to hasten dissolution, being certain that no particles of arsenic trioxide remain on
the sides of the flask, and add 0.15 mL of phenolphthalein indicator solution. Neutralize with 6 M hydrochloric acid, and add
1 mL in excess of the acid. Add 75 mL of water and 2 g of sodium bicarbonate dissolved in 20 mL of water. Titrate with the
iodine solution until within about 2 mL of the anticipated equivalence point. Then add 3 mL of starch indicator solution, and
continue the titration to the first permanent blue color of the starch–iodine complex. Store in an opaque or amber glass
bottle.
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C a u t i o n : Perchloric acid in contact with some organic materials can form explosive mixtures. Use safety goggles and
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rubber gloves when preparing the solution. Rinse any glassware that has been in contact with perchloric acid before
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setting it aside.
Add slowly, with stirring, 8.5 mL of 70% perchloric acid to a mixture of 500 mL of glacial acetic acid and 21 mL of acetic
anhydride. Cool, dilute to volume in a 1 L volumetric flask with glacial acetic acid, and mix thoroughly. Wait 30 min and
determine the water content of the solution by titrating 30 g with Karl Fischer reagent [Part 3: Reagents, Buffers, and
Indicators; Solutions and Mixtures; Karl Fischer Volumetric Reagent]. If the water content is greater than 0.05%, add a small
amount of acetic anhydride, mix thoroughly, and again determine the water. Repeat until the water content is between
0.02% and 0.05%. In a similar manner, if the original water content is below 0.02%, add water to bring the water content into
the 0.02–0.05% range. Allow the solution to stand for 24 h, and check the water content to be certain that it remains in this
range. Standardize as follows: Weigh accurately about 0.7 g of potassium hydrogen phthalate, acidimetric standard (NIST
SRM 84), previously lightly crushed and dried for 2 h at 120 °C. Dissolve in 50 mL of glacial acetic acid, add 0.1 mL of crystal
violet indicator solution, and titrate with the perchloric acid solution until the violet color changes to blue-green. Perform a
blank titration on 50 mL of glacial acetic acid in the same manner, and subtract the volume of perchloric acid solution
consumed in the blank titration from that consumed in the first titration.
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250 mL iodine flask, and add 100 mL of water, 3 g of potassium iodide, and 3 mL of hydrochloric acid. Stopper immediately,
and allow to stand in the dark for 5 min. Titrate the liberated iodine with a freshly standardized 0.1 N sodium thiosulfate
solution. Add 3 mL of a starch indicator solution near the end of the titration, and continue to the absence of the blue
starch–iodine complex.
phenolphthalein indicator solution, and titrate with the methanolic potassium hydroxide solution to a permanent faint pink
color.
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Sodium Hydroxide, 1 N
Dissolve 162 g of sodium hydroxide in 150 mL of carbon dioxide-free water, and cool the solution to room temperature.
Prepare a 1 N solution by diluting 54.5 mL of the concentrated solution to 1 L with carbon dioxide-free water. Mix
thoroughly, and store in a tight polyolefin container. Standardize as follows: Weigh accurately about 8.5 g of potassium
hydrogen phthalate, acidimetric standard (NIST SRM 84), previously lightly crushed and dried for 2 h at 120 °C. Dissolve in
100 mL of carbon dioxide-free water, add 0.15 mL of phenolphthalein indicator solution, and titrate with the sodium
hydroxide solution to a permanent faint pink color.
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Sulfuric Acid, 1 N
Add slowly (use caution), with stirring, 30 mL of sulfuric acid to about 500 mL of water. Allow the mixture to cool to room
temperature, dilute to 1 L, and mix thoroughly. Standardize against sodium carbonate, alkalimetric standard, as directed
for hydrochloric acid, 1 N.
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of dithizone indicator solution. Titrate with the zinc sulfate solution to a pink end point.
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