Appendix A: Standard Solutions and Reference

Materials

A.1.01 at 105EC, and store in brown glass-stoppered bottle in dark over

AOAC Official Method 942.25 good desiccant.
Standard Solutions and Materials (b) Reference solution.To mixture of 5 mL HNO3 (1 + 1), 2 mL
First Action 1942 ferric alum solution, 941.18D(a) (see A.1.11), and 115 mL H2O, add
ca 0.02 mL 0.1M thiocyanate, B, noting exact volume used.
Use accurately calibrated equipment, which meets NIST specifi-
B. Preparation of Standard Solution
cations. Alkaline and other corrosive solutions dissolve glass. To
avoid volumetric errors, do not store such solutions in calibrated ap- Prepare ca 0.1M solution from reagent that shows no chlorine us-
paratus. Burets used continuously with such solutions should be ing 7.612 g NH4SCN or 9.718 g KSCN/L.
recalibrated periodically. C. Standardization
Working temperature of standard solution should approximate
that of its temperature during standardization. If temperature correc- Accurately weigh, on tared watch glass, enough purified AgNO3 to
tions are necessary, sufficient accuracy may be obtained by use of give titration of ca 40 mL (ca 0.7 g for 0.1M solution) and transfer with
Table 942.25. H2O through glass funnel to 250 mL glass-stoppered Erlenmeyer.
Dissolve in ca 75 mL H2O (halogen-free), and add 5 mL HNO3 (1 + 1)
Reference: JAOAC 25, 650(1942). and 2 mL ferric alum solution, 941.18D(a) (see A.1.11). Titrate with
thiocyanate solution until titrated solution achieves a reddish brown
A.1.02 color, which remains after shaking vigorously 1 min. Record buret
AOAC Official Method 942.26 reading and set flask aside 5 min, shaking occasionally and maintain-
Standard Solutions ing end point color by addition of thiocyanate solution as required.
of Ammonium and Potassium Thiocyanates Then add additional thiocyanate solution, if necessary, to produce
First Action 1942 permanent end point color, matching with color of reference solution,
Final Action A(b). From total volume thiocyanate solution used in titration, sub-
tract volume contained in reference solution.
A. Reagents
(a) Purified silver nitrate.Dissolve 50 g AgNO3 in 20 mL boil- Molarity (mol/L) = g AgNO3 1000/mL titer 169.87
ing H2O containing ca 5 drops NHO3. Heat to dissolve, filter while
still hot through fritted glass filter, using suction, and collect filtrate References: JAOAC 25, 661(1942); 30, 105, 496(1947).
in clean borosilicate beaker. Wash beaker and filter with ca 5 mL hot
H2O, adding washings to filtrate. Cool in ice bath, stirring to induce
crystallization, and place in refrigerator at ca 10C until equilibrium A.1.03
is reached. Decant liquid through fritted glass filter and transfer AOAC Official Method 939.12
crystals to filter. Cover filter with watch glass and draw air through Standard Solution of Arsenious Oxide
filter to remove adhering liquid. Transfer crystals to small, clean First Action 1939
borosilicate beaker. Cover beaker with watch glass and place inside Final Action
larger covered borosilicate beaker. Dry at 105EC and fuse at
A. Reagent
220250C (mp 208EC), holding at this temperature ca 15 min after
crystals are melted. Protect from dust during preparation. Cool in Arsenious oxide.Use NIST SRM 83. Dry 1 h at 105C immedi-
desiccator, remove product from beaker, powder in mortar, dry 0.5 h ately before using.

Table 942.25 Temperature corrections for volumes of aqueous solutions

Volume Correction in mL at (C)

standard
solution, mL 6 8 10 12 14 16 18 20 22 24 26 28 30
10 0.01 0.01 0.01 0.01 0.01 0.01 0.00 0.00 0.00 0.00 0.01 0.02 0.02
20 0.03 0.03 0.03 0.02 0.02 0.01 0.01 0.00 0.01 0.02 0.03 0.03 0.03
25 0.04 0.03 0.03 0.03 0.02 0.02 0.01 0.00 0.01 0.02 0.03 0.04 0.05
30 0.04 0.04 0.04 0.03 0.03 0.02 0.01 0.00 0.01 0.02 0.04 0.05 0.07
40 0.06 0.06 0.05 0.04 0.04 0.03 0.01 0.00 0.02 0.03 0.05 0.07 0.09
50 0.07 0.07 0.06 0.06 0.05 0.03 0.02 0.00 0.02 0.04 0.06 0.09 0.12

2000 AOAC INTERNATIONAL

B. Preparation of Standard Solution (c) Acid potassium phthalate buffer solution.0.0496M; 0.05m.
Accurately weigh As2O3 by difference from small Dissolve 10.12 g dried (2 h at 110C) KHC8H4O4 (NIST SRM 185g)
glass-stoppered weighing bottle (use ca 4.95 g/L for 0.025M). Dis- in H2O and dilute to 1 L. (Elaborate precautions for exclusion of at-
solve in 1M NaOH (50 mL/5 g As2O3) in flask or beaker by heating mospheric CO2 are unnecessary, although solution should be pro-
on steam bath. Add ca same volume 0.5M H2SO4. Cool, quantita- tected against evaporation and contamination with molds. Replace
tively transfer mixture to volumetric flask, and dilute to volume. solution if mold appears.)
(Solution must be neutral to litmus, not alkaline.) (d) Phosphate buffer solution.0.0249M; 0.025m. Dissolve
3.387 g KH2PO4 and 3.533 g Na2HPO4 (NIST SRM 186e-I and II) in
Molarity (mol/L) = g As2O3 4000/mL final volume 197.84 H2O and dilute to 1 L. (Dry salts 2 h at 110130C before use.)
References: JAOAC 22, 568(1939); 24, 100, 639(1941). (e) Phosphate buffer solution.0.008663M, 0.008695m
KH2PO4 and 0.03030M, 0.03043m Na2HPO4. Dissolve 1.179 g
KH2PO4 and 4.303 g Na2HPO4 (NIST SRM 186e-I and II) in H2O
A.1.04 and dilute to 1 L. (Dry salts 2 h at 110130C before use.)
AOAC Official Method 964.24 (f) Borax buffer solution.0.00996M; 0.01m. Dissolve 3.80 g
Buffer Solutions Na2B4O7@10H2O (NIST SRM 187c) in H2O and dilute to 1 L. (Salt
for Calibration of pH Equipment must not be dried in oven before use.) To avoid contamination with
First Action 1964 CO2, stopper bottle except when in use or protect with sodalime
Final Action 1965 tube. Use buffer solution within 10 min after removal from bottle.
(g) Sodium bicarbonatecarbonate buffer solution.0.0249M;
Use H2O with pH of $6.5 but #7.5, obtained by boiling H2O 0.025m (each). Transfer 2.092 g NaHCO3 (NIST SRM 191a; do not
15 min and cooling under CO2-free conditions. Store standard buffer
heat) and 2.640 g Na2CO3 (NIST SRM 192a; dry 2 h at 275C) to 1 L
solutions except Ca(OH)2 in bottles of chemically resistant glass.
volumetric flask. Dissolve and dilute to volume with CO2-free H2O.
Protect phosphate, borax, and Ca(OH)2 buffers from CO2. pH values
(h) Calcium hydroxide buffer solution.Saturated solution at
as function of temperature are given in Table 964.24.
25C, 0.02025M. Slowly heat finely granular CaCO3, low in alka-
(a) Potassium tetroxalate buffer solution.0.0496M; 0.05m.
Transfer 12.61 g KHC2O4@H2C2O4@2H2O (air weight) (NIST SRM lies, to 1000C in Pt dish and maintain at this temperature
189a) to 1 L volumetric flask, dilute to volume with H2O, and mix 4560 min. Cool in desiccator, and add to H2O with stirring. Heat to
thoroughly. (It is not necessary to remove dissolved CO2 from the bp with continuous stirring. Cool, and filter on medium fritted glass
H2O or to dry salt before weighing.) Prepare fresh every 2 months. filter. Dry at 110C, cool, and crush to fine, granular powder.
(b) Potassium hydrogen tartrate buffer solution.Saturated solu- Place crushed CaO in polyethylene bottle, add H2O, shake vigorously,
tion at 25EC, 0.034M. Add excess (ca 100%) of KHC4H4O6 (NIST let settle, and record temperature. [Keep large excess of Ca(OH)2 in bot-
SRM 188) to H2O in glass-stoppered bottle or flask, and shake vigor- tle.] For use, filter solution through medium fritted glass filter. Use at
ously; few minutes shaking is enough for saturation (100 mL H2O at same temperature at which saturation took place, and discard filtered so-
lution if it becomes turbid. When more buffer solution is needed, add ad-
25C dissolves ca 0.7 g KHC4H4O6). Adjust to 25C, let solid settle,
ditional H2O to suspension, resaturate, and filter as above.
and decant clear solution, or filter if necessary. Discard when mold ap-
pears. Few crystals of thymol added during preparation will retard mold References: NIST Certificates for Standard Reference Materials
growth, and will alter pH by unit. For accuracy of 0.01 pH unit, tem- 185g, 186e, 187c, 188, 189a, 191a, and 192a.
perature of solution at saturation must be between 20 and 30C. JAOAC 33, 223(1950); 41, 302(1958); 47, 43(1964).

Table 964.24 pH Values for standard buffer solutions as function of temperature

0.05m Satd. Potassium 0.05m 0.025m 0.008695m 0.01m 0.025m NaHCO3

Potassium hydrogen Potassium Phosphate, and 0.03043m Borax, and 0.025m Satd. calcium
Temp., C tetroxalate, pH tartrate, pH phthalate, pH pH Phosphate, pH pH Na2CO3, pH hydroxide, pH
0 1.666 4.003 6.982 7.534 9.460 10.321 13.423
5 1.668 3.998 6.949 7.501 9.392 10.248 13.207
10 1.670 3.996 6.921 7.472 9.331 10.181 13.003
15 1.672 3.996 6.898 7.449 9.276 10.120 12.810
20 1.675 3.999 6.878 7.430 9.227 10.064 12.627
25 1.679 3.557 4.004 6.863 7.415 9.183 10.014 12.454
30 1.683 3.552 4.011 6.851 7.403 9.143 9.968 12.289
35 1.688 3.549 4.020 6.842 7.394 9.107 9.928 12.133
37 1.691 3.548 4.024 6.839 7.392 9.093 12.043
40 1.694 3.547 4.030 6.836 7.388 9.074 9.891 11.984
45 1.700 3.547 4.042 6.832 7.385 9.044 9.859 11.841
50 1.707 3.549 4.055 6.831 7.384 9.017 9.831 11.705
55 1.715 3.554 4.070 11.574
60 1.723 3.560 4.085 11.449

2000 AOAC INTERNATIONAL

Table 941.17A Amounts of specific indicators required to Table 941.17B Amounts of buffer solutions and base
form monosodium salts required to produce given pH solutions

X pH PhthalateNaOH mixtures
Bromocresol green 14.3 3.85.4 0.2M Potassium
pH hydrogen phthalate (mL) 0.2M NaOH (mL)
Chlorophenol red 23.6 4.86.4
5.0 50 23.65
Bromothymol blue 16.0 6.07.6
5.2 50 29.75
Phenol red 28.2 6.88.4
5.4 50 35.25
5.6 50 39.70

A.1.05 5.8 50 43.10

6.0 50 45.40
AOAC Official Method 941.17
Standard Buffers and Indicators 6.2 50 47.00
for Colorimetric pH Comparisons KH2PO4NaOH mixtures
First Action 1941 pH 0.2M KH2PO4 (mL) 0.2M NaOH (mL)
Final Action 5.8 50 3.66
6.0 50 5.64
A. Preparation of Sulfonphthalein Indicators
6.2 50 8.55
X = mL 0.01M NaOH/0.1 g indicator required to form
6.4 50 12.60
monosodium salt. Dilute to 250 mL for 0.04% reagent. (See Ta-
6.6 50 17.74
ble 941.17A.)
6.8 50 23.60
B. Preparation of Stock Solutions
7.0 50 29.54
Use recently boiled and cooled H2O. 7.2 50 34.90
(a) Acid potassium phthalate solution.0.2M. Dry to constant 7.4 50 39.34
weight at 1101 15C. Dissolve 40.836 g in H2O and dilute to 1 L.
7.6 50 42.74
(b) Monopotassium phosphate solution.0.2M. Dry KH2PO4 to
7.8 50 45.17
constant weight at 110115C. Dissolve 27.232 g in H2O and dilute
to 1 L. Solution should be distinctly red with methyl red, and dis- 8.0 50 46.85
tinctly blue with bromophenol blue. H3BO3KClNaOH mixtures
(c) Boric acidpotassium chloride solution.0.2M. Dry H3BO3 pH 0.2M H3BO3, KCl (mL) 0.2M NaOH (mL)
to constant weight in desiccator over CaCl2. Dry KCl2 days in oven 7.8 50 2.65
at 115120C. Dissolve 12.405 g H3BO3 and 14.912 g KCl in H2O, 8.0 50 4.00
and dilute to 1 L.
8.2 50 5.90
(d) Sodium hydroxide standard solution.0.2M. Prepare and
8.4 50 8.55
standardize as in 936.16 (see A.1.12); 0.04084 g KHC8H4O4 = 1 mL
0.2M NaOH. It is preferable to use factor with solution rather than 8.6 50 12.00
try to adjust to exactly 0.2M.
C. Preparation of Buffer Solutions
Prepare standard buffer solutions from designated amounts stock B. Standard Sodium Hydroxide Method
solutions, 941.17, and dilute to 200 mL. For use as calorimetric stan- Titrate 40 mL against standard alkali solution, 936.16CE (see
dard, mix 20 mL buffer solution with 0.5 mL indicator solution, A. A.1.12), of ca same concentration as acid being standardized in
(See Table 941.17B.) 300 mL flask that has been swept free from CO2, using CO2-free
References: JAOAC 24, 583(1941). H2O and 3 drops phenolphthalein.
Clark, Determination of Hydrogen Ions, 3rd Ed.,
pp 91, 94, 192202. mL standard alkali molarity of alkali
Molarity =
mL HCl

A.1.06 If more concentrated than desired, dilute solution to required

AOAC Official Method 936.15 molarity value by following formula:
Standard Solution of Hydrochloric Acid
First Action 1936 V1= V2 M2/M1
Final Action where M2 and V2 represent molarity and volume of stock solution,
respectively, and V1 = volume to which stock solution should be di-
A. Preparation of Standard Solutions
luted to obtain desired molarity, M1.
Table 936.15 gives approximate volumes of 36.538% HCl re- Check exact concentration of final solution by titration as above.
quired to make 10 L standard solutions. Molarity will be exact only if same indicator is used in determination

2000 AOAC INTERNATIONAL

Table 936.15 Volumes of concentrated HCl required to (c) Standard borax.Saturate 300 mL H2O at 55EC (not higher)
prepare solutions of different molarities with Na2B4O7@10H2O (ACS) (ca 45 g). Filter at this temperature
Approximate molarity mL HCl to be diluted to 10 L through folded paper into 500 mL Erlenmeyer. Cool filtrate to ca
0.01 8.6
10EC, with continuous agitation during crystallization. Decant
supernate, rinse precipitate once with 25 mL cold H2O, and dissolve
0.02 17.2
crystals in just enough H2O at 55EC to ensure complete solution (ca
0.10 86.0 200 mL). Recrystallize by cooling to ca 10EC, agitating flask during
0.50 430.1 crystallization.
1.0 860.1 Filter crystals onto small Bchner with suction, wash precipitate
once with 25 mL ice-cold H2O, and dry crystals by washing with two
20 mL portions alcohol, drying after each washing with suction. Fol-
low with two 20 mL portions ether. (Just before use, free alcohol and
as in standardization. Restandardize if indicators other than
ether from any possible reacting acids by vigorously shaking each
phenolphthalein are used.
with 23 g of the pure, dry Na2B4O7@10H2O and then filtering.)
References: JAOAC 19, 107, 194(1936); 49, 250(1966). Spread crystals on watch glass, immediately place dried
Kolthoff & Stenger, Volumetric Analysis, II, Na2B4O7@10H2O in closed container over solution saturated with re-
52(1947). spect to both sucrose and NaCl, and let it remain $24 h before using.
B. Constant Boiling Method Then transfer the pure Na2B4O7@10H2O to glass-stoppered container
and store in closed container over solution saturated with respect to
Dilute 822 mL HCl (36.538% HCl) with 750 mL H2O. Check
both sucrose and NaCl (stable under these conditions 1 year).
specific gravity with spindle and adjust to 1.10. Place 1.5 L in 2 L
flat-bottom distilling flask, add ca 10 SiC grains (ca 20 mesh), and D. Standardization
connect to long, straight inner-tube condenser. Heat on electric hot Accurately weigh enough standard Na2B4O7@10H2O to titrate ca
plate and distil at 510 mL/min, keeping end of condenser open to 40 mL and transfer to 300 mL flask. Add 40 mL CO2-free H2O,
air. When 1125 mL has distilled, change receivers and catch next 936.16B(a) (see A.1.12), and stopper flask. Swirl gently until sam-
225 mL, which is constant boiling HCl, in Erlenmeyer with end of ple dissolves. Add 4 drops methyl red and titrate with solution that is
condenser inserted into flask, but above surface of liquid. Read ba- being standardized to equivalence point as indicated by reference
rometer to nearest mm at beginning and end of collection of 225 mL solution.
portion and note barometer temperature. Average readings.
Calculate air weight in g (G) of this constant boiling HCl required to Molarity (mol/L) = g Na2B4O7@10H2O 1000/mL acid 190.69
give one equivalent weight of HCl from one of following equations:
For P0 = 540669 mm Hg: Reference: JAOAC 22, 102, 563(1939).

Standard Sodium Carbonate Method

G = 162.255 + 0.02415 P0
E. Reagents
For P0 = 670780 mm Hg:
(a) Methyl orange indicator.0.1% in H2O.
G = 164.673 + 0.02039 P0 (b) Reference solution.80 mL CO2-free H2O containing 3 or
4 drops methyl orange.
where P0 = barometric pressure in mm Hg corrected to 0EC for ex- (c) Anhydrous sodium carbonate.Heat 250 mL H2O to 80EC
pansion of Hg and of barometer scale. For brass scale barometer, fol- and add NaHCO3 (ACS), stirring until no more dissolves. Filter so-
lowing correction is accurate enough: lution through folded paper (use of hot H2O funnel is desirable) into
Erlenmeyer. Cool filtrate to ca 10EC, swirling constantly during
P0 = Pt (l 0.000162t) crystallization. Fine crystals of trona that separate out have approxi-
where t = barometer temperature in EC. mate composition: Na2CO3@NaHCO3@2H2O. Decant supernate,
Weigh required amount of constant boiling HCl in tared, drain crystals by suction, and wash once with cold H2O.
stoppered flask to at least 1 part in 10 000. Dilute immediately, and Transfer precipitate, being careful not to include any paper fibers,
finally dilute to volume with CO2-free H2O at desired temperature. to large flat-bottom Pt dish. Heat 1 h at 290EC in electric oven or fur-
References: JAOAC 25, 653(1942); 36, 96, 354(1953); nace with pyrometer control. Stir contents occasionally with Pt wire.
37, 122, 462(1954). Cool in desiccator. Place the anhydrous Na2CO3 in glass-stoppered
container and store in desiccator containing efficient desiccant. Dry
Standard Borax Method at 120EC and cool just before weighing.
References: Kolthoff & Stenger, Volumetric Analysis, II,
C. Reagents
80(1947).
(a) Methyl red indicator.Dissolve 100 mg methyl red in 60 mL Ind. Eng. Chem., Anal. Ed. 9, 141(1937).
alcohol and dilute with H2O to 100 mL. JAOAC 22, 563(1939).
(b) Reference solution.Prepare reference solution of H3BO3,
F. Standardization
NaCl, and indicator corresponding to composition and volume of so-
lution at equivalence point. For use in determination of end point of Accurately weigh enough anhydrous Na2CO3, E(c), to titrate ca
titration with 0.1M HCl, reference solution should be 0.1M in 40 mL, transfer to 300 mL Erlenmeyer, and dissolve in 40 mL H2O.
H3BO3 and 0.05M in NaCl. Add 3 drops methyl orange and titrate until color begins to deviate

2000 AOAC INTERNATIONAL

from H2O tint (reference solution). (Equivalence point has not been A.1.09
reached.) Boil solution gently 2 min and cool. Titrate until color is AOAC Official Method 949.13
barely different from H2O tint of indicator. Standard Solution
of Potassium Dichromate
Molarity (mol/L) = g Na2CO3 1000/mL acid 105.988 First Action 1949
Final Action
Reference: JAOAC 22, 102, 563(1939).
A. Reagent
Starch solution.Mix ca 1 g arrowroot starch with 10 mL H2O
A.1.07 and pour slowly, with constant stirring, into 200 mL boiling H2O.
AOAC Official Method 939.13 Boil until thin, translucent fluid is obtained. Let settle and use clear
Standard Solution of Iodine supernate. Preserve with Hg.
First Action 1939 B. Assay of Stock Potassium Dichromate
Final Action
If K2Cr2O7 is in small crystals, mix by shaking thoroughly in
A. Preparation of Standard Solution large, clean jar; if it is in lumps, grind representative sample to pass
No. 60 sieve, and then mix by shaking. Dry portion for weighings 2 h
Dissolve weighed amounts of I2 (12.7 g/L for 0.1M solution) and at 100EC.
KI, in proportion of 20 g KI to 13 g I2, in 50 mL H2O. When I2 dis- Weigh, into each of 3 glass-stoppered Erlenmeyers, enough
solves, transfer solution to glass-stoppered volumetric flask. Dilute K2Cr2O7, (NIST SRM 136e) to give titer of 100.5102.0 mL 0.1M
to volume with H2O and mix thoroughly. Store in dark brown, Na2S2O3, 942.27A (see A.1.13) (4.905.00 g for 0.01667M solu-
glass-stoppered bottle away from light and restandardize as fre- tion). Completely dissolve in 100 mL H2O, add 4.0 g KI, and swirl
quency as necessary. mixture until dissolved. With buret, add 4.0 mL HCl, stopper flask,
B. Standardization mix by swirling, and let stand in dark 10 min. Cool flask ca 1 min in
ice-H2O. While swirling flask, pipet in 100 mL Na2S2O3 solution.
Transfer accurately measured portion of standard As2O3 solution,
Add 5 mL starch solution and complete titration with Na2S2O3 solu-
939.12B (see A.1.03) (4050 mL ca 0.025M solution for 0.1M solu-
tion added from 10 mL microburet (graduated in 0.05 mL). End
tion), to Erlenmeyer. Acidify slightly with H2SO4 (1 + 10), neutral-
point is from bluish green to clear green; change takes place within
ize with solid NaHCO3, and add ca 2 g excess. Titrate with I2
0.01 mL. Record volume to nearest 0.01 mL. Calculate apparent
solution, using ca 0.2% starch solution (5 mL/100 mL) as indicator.
molarity of Na2S2O3 solution for each of the 3 titrations, and aver-
Saturate solution with CO2 at end of titration by adding 1 mL H2SO4
age. Designate this average as MNIST.
(1 + 10) just before end point is reached.
Similarly titrate 3 portions of stock K2Cr2O7 and calculate the
3 apparent molarities. Designate each of these results as Mstock. Cal-
Molarity (mol/L) = mL As2O3 molarity As2O3/mL I2 culate percent purity of stock K2Cr2O7 = (MNIST 100)/Mstock.
References: JAOAC 22, 568(1939); 24, 100, 639(1941). Take average of the 3 results as percent purity of stock K2Cr2O7.
C. Preparation of Standard Solution
Dissolve theoretical weight K2Cr2O7 (NIST SRM 136e) (4.9032 g
A.1.08
for 0.01667M solution), or weight stock K2Cr2O7, B, found to have
AOAC Official Method 947.13 oxidimetric value 99.95100.05% of NIST SRM, in enough H2O to
Standard Solution make 1 L. (Dry K2Cr2O7 2 h at 100EC before using.)
of Potassium BromideBromate
References: JAOAC 32, 587(1949); 33, 225(1950).
First Action 1947
Final Action
A.1.10
A. Preparation of Standard Solution AOAC Official Method 940.35
Dissolve ca 2.8 g KBrO3 and 12 g KBr in boiled H2O and dilute to Standard Solution
1 L with boiled H2O for ca 0.01667M solution. of Potassium Permanganate
First Action 1940
B. Standardization Final Action
Measure 40 mL standard As2O3 solution, 939.12B (see A.1.03),
A. Preparation of Standard Solution
from buret into 300 mL Erlenmeyer. Add 10 mL HCl and 3 drops
methyl orange, 936.15F(a) (see A.1.06). Titrate with KBrKBrO3 Dissolve slightly more than desired equivalent weight (3.2 g for
solution until #1 drop causes color of methyl orange to fade com- 0.02M) of KMnO4 in 1 L H2O. Boil solution 1 h. Protect from dust
pletely. Swirl solution constantly and add last mL dropwise, swirl- and let stand overnight. Thoroughly clean 15 cm glass funnel, perfo-
ing between drops. rated porcelain plate from Caldwell crucible, and glass-stoppered
bottle (preferably of brown glass) with warm chromic acid cleaning
solution. Digest asbestos for use in Gooches on steam bath 1 h with
Molarity (mol/L) =
ca 0.02M KMnO4 that has been acidified with few drops H2SO4 (1 +
mL As2O3 molarity As2O3/mL KBrKBrO3
3). Let settle, decant, and replace with H2O. To prepare glass funnel,
References: JAOAC 30, 502(1947); 31, 119, 572(1948). place porcelain plate in apex, make pad of asbestos ca 3 mm thick on

2000 AOAC INTERNATIONAL

plate, and wash acid-free. (Pad should not be too tightly packed and Volhard Method
only moderate suction should be applied.) Insert stem of funnel into
D. Reagents
neck of bottle and filter KMnO4 solution directly into bottle without
aid of suction. (a) Ferric alum indicator solution.Saturated solution of
FeNH4(SO4)2@12H2O in H2O.
B. Standardization
(b) Potassium or ammonium thiocyanate standard solu-
For 0.02M solution, transfer 0.3 g dried (1 h at 105EC) sodium ox- tion.Prepare ca 0.lM solution, 942.26B (see A.1.02). Determine
alate (NIST SRM 40) to 600 mL beaker. Add 250 mL H2SO4 (5 + working titer by accurately measuring 4050 mL standard AgNO3
95), previously boiled 1015 min and then cooled to 27 3EC. solution, adding 2 mL ferric alum solution and 5 mL HNO3 (1 + 1),
Stir until Na2C2O4 dissolves. Add 3940 mL KMnO4 solution at and titrating with the thiocyanate solution until solution appears pale
rate of 2535 mL/min, stirring slowly. Let stand until pink disap- rose after vigorous shaking.
pears (ca 45 s). If pink persists because KMnO4 solution is too con-
E. Standardization
centrated, discard and begin again, adding few mL less of KMnO4
solution. Heat to 5560EC, and complete titration by adding KMnO4 Accurately weigh enough KC1, B(a), to yield titration of ca 40 mL
solution until faint pink persists 30 s. Add last 0.51 mL dropwise, (ca 0.3 g for 0.1M solution) and transfer to 250 mL glass-stoppered
letting each drop decolorize before adding next. Erlenmeyer with 40 mL H2O. Add 5 mL HNO3 (1 + 1) and excess
Determine excess of KMnO4 solution required to turn solution AgNO3 solution. Mix, and let stand few minutes protected from
pink by matching with color obtained by adding KMnO4 solution to light. Filter through Gooch prepared with medium pad of asbestos
same volume of boiled and cooled diluted H2SO4 at 5560EC. This previously rinsed with 2% HNO3. Wash flask and precipitate with
correction is usually 0.030.05 mL. From net volume KMnO4, cal- several small portions of 2% HNO3, passing washings through cruci-
culate molarity: ble until filtrate and washings measure ca 150 mL. Add 2 mL ferric
alum solution and titrate residual AgNO3 with thiocyanate solution.
From titration, together with ratio of the 2 solutions, calculate net vol-
Molarity (mol/L) = g Na2C2O4 1000/mL KMnO4 133.999
ume AgNO3 solution. (Errors of blank are compensating and may be
References: JAOAC 23, 543(1940); 31, 568(1948). disregarded.) From net volume AgNO3, calculate molarity as in C.
J. Research NBS 15, 493(1935), Research Paper
Reference: JAOAC 24, 100, 631(1941).
No. 843.

A.1.12
A.1.11 AOAC Official Method 936.16
AOAC Official Method 941.18 Standard Solution
Standard Solution of Sodium Hydroxide
of Silver Nitrate Standard Potassium Hydrogen Phthalate Method
First Action 1941 First Action 1936
Final Action Final Action

A. Apparatus
A. Preparation of Standard Solution
Use buret and pipet calibrated by NIST or by analyst. Protect exits
Dissolve slightly more than theoretical weight of AgNO3 (equiva-
to air of automatic burets from CO2 contamination by suitable guard
lent weight, 169.87) in halogen-free H2O and dilute to volume.
tubes containing sodalime. Use containers of alkali-resistant glass.
Thoroughly clean glassware, avoid contact with dust, and keep pre-
pared solution in amber glass-stoppered bottles away from light. B. Reagents
(a) Carbon dioxide-free water.Prepare by one of following
Mohr Method
methods: (1) Boil H2O 20 min and cool with sodalime protection;
B. Reagents (2) bubble air, freed from CO2 by passing through tower of
sodalime, through H2O 12 h.
(a) Potassium chloride.Recrystallize KCl 3 times from H2O, (b) Sodium hydroxide solution.(1 + 1.) To 1 part NaOH (re-
dry at 110EC, and then heat at ca 500EC to constant weight. Equiva- agent quality containing <5% Na2CO3) in flask add 1 part H2O and
lent weight KCl = 74.555. Or, preferably, use NIST SRM 999. swirl until solution is complete. Close with rubber stopper. Set aside
(b) Potassium chromate solution.5% solution of K2CrO4 in until Na2CO3 has settled, leaving perfectly clear liquid (ca 10 days).
H2O. (c) Acid potassium phthalate.NIST SRM for Acidimetry 84.
C. Standardization Crush to pass No. 100 sieve. Dry 2 h at 120EC. Cool in desiccator
containing H2SO4.
Accurately weigh enough KCl to yield titration of ca 40 mL (ca
0.3 g for 0.1M solution), and transfer to 250 mL glass-stoppered C. Preparation of Standard Solution
Erlenmeyer with 40 mL H2O. Add 1 mL K2CrO4 solution and titrate Table 936.16 gives approximate volumes of NaOH solution (1 +
with AgNO3 solution until first perceptible pale red-brown appears. 1) necessary to make 10 L standard solutions.
From titration volume, subtract mL of the AgNO3 solution required Add required volume of NaOH solution (1 + 1) to 10 L CO2-free
to produce end point color in 75 mL H2O containing 1 mL K2CrO4 H2O. Check molarity, which should be slightly high, as in D, and ad-
solution. From net volume AgNO3, calculate molarity: just to desired concentration by following formula:

Molarity (mol/L) = g KCl 1000/mL AgNO3 74.555 V1 = V2 M2/M1

2000 AOAC INTERNATIONAL

Table 936.16 Volumes of (1 + 1) NaOH solution required to solution in dark, cool place; do not return unused portions to stock
prepare solutions of different molarities bottle. If solutions less concentrated than 0.1M are desired, prepare
Approximate molarity mL NaOH to be diluted to 10 L by dilution with boiled H2O. (More dilute solutions are less stable
and should be prepared just before use.)
0.01 5.4
0.02 10.8 B. Standardization

0.10 54.0 Accurately weigh 0.200.23 g K2Cr2O7 (NIST SRM 136e dried
0.50 270.0 2 h at 100EC) and place in glass-stoppered iodine flask (or
glass-stoppered flask). Dissolve in 80 mL chlorine-free H2O con-
1.0 540.0
taining 2 g KI. Add, with swirling, 20 mL ca 1M HCl and immedi-
ately place in dark 10 min. Titrate with Na2S2O3 solution, A, adding
starch solution after most of I2 has been consumed.
where M2 and V2 represent molarity and volume stock solution, re-
spectively, and V1, volume to which stock solution should be diluted Molarity (mol/L) = g K2Cr2O7 1000/mL Na2S2O3 49.032
to obtain desired molarity, M1. Standardize final solution as in D or E. References: JAOAC 25, 659(1942); 27, 557(1944); 28, 594(1945);
D. Standardization 38, 382(1955); 47, 43, 46(1964); 48, 103(1965).
Accurately weigh enough dried KHC8H4O4 to titrate ca 40 mL
and transfer to 300 mL flask that has been swept free from CO2. Add A.1.14
50 mL cool CO2-free H2O. Stopper flask and swirl gently until sam- AOAC Official Method 890.01
ple dissolves. Titrate to pH 8.6 with solution being standardized, tak- Standard Solutions
ing precautions to exclude CO2 and using as indicator either of Sulfuric Acid
glass-electrode pH meter or 3 drops phenolphthalein. In latter case, First Action 1890
determine end point by comparison with pH 8.6 buffer solution, Final Action
941.17C (see A.1.05), containing 3 drops phenolphthalein. Deter- A. Preparation of Standard Solution
mine volume NaOH required to produce end point of blank by
matching color in another flask containing 3 drops phenolphthalein Table 890.01 gives approximate volumes of 9598% H2SO4 nec-
and same volume CO2-free H2O. Subtract volume required from that essary to make 10 L standard solutions.
used in first titration and calculate molarity. B. Standard Borax Method Standardization
See 936.15E (see A.1.06).
Molarity (mol/L) = g KHC8H4O4 1000/mL NaOH 204.229
C. Specific Gravity Method
References: JAOAC 19, 107, 194(1936).
Dilute H2SO4 with enough H2O to make convenient volume of ca
NIST Certificate for Standard Reference Material 84.
70% H2SO4 by weight. Determine specific gravity in air at conve-
nient temperature (040EC) as in 945.06C (see 26.1.06) (or specific
Constant Boiling Hydrochloric Acid Method
gravity may be determined with Sprengel pycnometer), protecting
E. Standardization solution from contact with air. Calculate exact percent H2SO4 by
weight:
Accurately weigh from weighing buret enough constant boiling
HCl, 936.15C (see A.1.06), to titrate ca 40 mL, into Erlenmeyer pre-
P = S(85.87 + 0.05T 0.0004t2) 69.82
viously swept free from CO2. Add ca 40 mL CO2-free H2O, then 35
drops desired indicator, and titrate with solution being standardized. where S = specific gravity (in air) at TE, compared with H2O at tE.
Weigh exactly W g prepared acid containing P% H2SO4 and dilute
Molarity (mol/L) = g HCl 1000/mL titer G to n L to make required solution containing G g H2SO4/L. Calculate
W from equation:
where G has value given in 936.15C (see A.1.06).
References: JAOAC 25, 653(1942); 36, 96, 354(1953); W = nG 100/P
37, 122, 462(1954).

A.1.13
AOAC Official Method 942.27
Standard Solutions Table 890.01 Volumes of concentrated H2SO4 required to
of Sodium Thiosulfate prepare solutions of different molarities
First Action 1942
Final Action Approximate molarity mL H2SO4 to be diluted to 10 L
0.005 2.8
A. Preparation of Standard Solution
0.01 5.6
Dissolve ca 25 g Na2S2O3@5H2O in 1 L H2O. Boil gently 5 min and 0.05 27.7
transfer while hot to storage bottle previously cleaned with hot chro- 0.25 138.1
mic acid cleaning solution and rinsed with warm boiled H2O. (Tem-
0.50 276.1
per bottle, if not heat-resistant, before adding hot solution.) Store

2000 AOAC INTERNATIONAL

References: J. Chem. Soc. Trans. 57, 64(1890). Table 982.35 Sources of reference materials
J. Soc. Chem. Ind. 1091(1899). organizations and addresses
JAOAC 24, 636(1941). Source code Name and address
AACC American Association of Cereal Chemists
A.1.15 Check Sample Service
AOAC Official Method 948.28 3340 Pilot Knob Rd
St. Paul, MN 55121, USA
Standard Solutions [email protected]
of Titanium Trichloride www.scisoc.org/aacc
First Action 1948
AOAC AOAC INTERNATIONAL
Final Action www.aoac.org/techprog/tdrm
A. Preparation of Standard Solution AOCS American Oil Chemists Society
Smalley Check Sample Program
To 200 mL commercial 15% TiCl3 solution add 150 mL HCl and Champaign, IL, USA
dilute to 2 L. Make solution ca 0.1M, place in container with H2 at- www.aocs.org
mosphere provision [e.g., JAOAC 5, 207(1921)], and let stand 2 days BCR Commission of the European Communities
for absorption of residual O2. IRMM/MRM
B-2440 Retieseweg
B. Standardization Geel, Belgium
Weigh 3 g FeSO4(NH4)2SO4@6H2O and transfer to 500 mL flask. IAEA International Atomic Energy Agency
Introduce stream of CO2, and add 50 mL recently boiled H2O and Analytical Quality Control Services
25 mL 40% (by weight) H2SO4. Then, without interrupting current Laboratory Seibersdorf
PO Box 100
of CO2, rapidly add 40 mL 0.01667M K2Cr2O7, 949.13C (see A-1400 Vienna, Austria
A.1.09). Add TiCl3 solution until near calculated end point. Then www.iaea.org
quickly add 5 g NH4SCN, and complete titration. Determine blank LGC Laboratory of the Government Chemist
on 3 g FeSO4(NH4)2SO4@6H2O, using same volumes of H2O, H2SO4, National Physical Laboratory
and NH4SCN, and current of CO2. From net volume TiCl3, calculate Office of Reference Materials
molarity: Teddington, Middlesex TW11 OLY, UK
[email protected]
Molarity (mol/L) = mL K2Cr2O7 molarity K2Cr2O7/mL TiCl3 NIES National Institute for Environmental Studies
Yatabe-Machi, Tsukuba, Ibaraki 305, Japan
References: JAOAC 31, 573(1948); 32, 589(1949). NIST National Institute of Standards and Technology
Standard Reference Materials Program
Building 202, Room 204
A.1.16
Gaithersburg, MD 20899, USA
AOAC Official Method 982.35 http://ts.nist.gov
Reference Materials
NRCC National Research Council of Canada
First Action 1982 Marine Analytical Chemistry Standards
Montreal Rd
A. Definitions Ottawa, Ontario, Canada K1A 0R9
Reference material (RM).Homogenous and stable material or USP U.S. Pharmacopeial Convention, Inc.
substance one or more properties of which are sufficiently well es- USP-NF Reference Standards
tablished to be used for calibrating apparatus, assessing measure- 12601 Twinbrook Parkway
ment method, or assigning values to materials. Rockville, MD 20852, USA
www.usp.org
Certified reference materials (CRM).Reference material one or
more of whose property values are certified by valid procedure, or
accompanied by or traceable to certificate or other documentation
which is issued by certifying body.
B. General Information
Table 982.35 lists selected issuing organizations and shows
source codes together with names and addresses of these organiza-
tions.
Organizations listed are only representative of those supplying
RMs. No claim is made as to completeness of information supplied.
Catalogs or literature describing RMs are available from individual
organizations. Because inventories of RMs are continually chang-
ing, inquiries should be made of the organizations concerning cur-
rent availability of specific RMs.
Reference: Technical Division on Reference MaterialsMinutes
of Executive Committee Meeting, January 31, 2000,
AOAC INTERNATIONAL, Gaithersburg, MD,
USA.

2000 AOAC INTERNATIONAL