Appendix A Appendix A Standard Solutions and Reference Materials

Appendix A: Standard Solutions and Reference
Materials
at 105EC, and store in brown glass-stoppered bottle in dark over
good desiccant.
(b) Reference solution.To mixture of 5 mL HNO3 (1 + 1), 2 mL
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.
A.1.01
AOAC Official Method 942.25
Standard Solutions and Materials
First Action 1942
Use accurately calibrated equipment, which meets NIST specifications. Alkaline and other corrosive solutions dissolve glass. To
avoid volumetric errors, do not store such solutions in calibrated apparatus. Burets used continuously with such solutions should be
recalibrated periodically.
Working temperature of standard solution should approximate
that of its temperature during standardization. If temperature corrections are necessary, sufficient accuracy may be obtained by use of
Table 942.25.
Reference: JAOAC 25, 650(1942).
A.1.02
Standard Solutions
of Ammonium and Potassium Thiocyanates
First Action 1942
Final Action
B. Preparation of Standard Solution
Prepare ca 0.1M solution from reagent that shows no chlorine using 7.612 g NH4SCN or 9.718 g KSCN/L.
C. Standardization
Accurately weigh, on tared watch glass, enough purified AgNO3 to

give titration of ca 40 mL (ca 0.7 g for 0.1M solution) and transfer with
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)
and 2 mL ferric alum solution, 941.18D(a) (see A.1.11). Titrate with
thiocyanate solution until titrated solution achieves a reddish brown
color, which remains after shaking vigorously 1 min. Record buret
reading and set flask aside 5 min, shaking occasionally and maintaining end point color by addition of thiocyanate solution as required.
Then add additional thiocyanate solution, if necessary, to produce
permanent end point color, matching with color of reference solution,
A(b). From total volume thiocyanate solution used in titration, subtract volume contained in reference solution.
A. Reagents
(a) Purified silver nitrate.Dissolve 50 g AgNO3 in 20 mL boiling H2O containing ca 5 drops NHO3. Heat to dissolve, filter while
still hot through fritted glass filter, using suction, and collect filtrate
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
is reached. Decant liquid through fritted glass filter and transfer
crystals to filter. Cover filter with watch glass and draw air through
filter to remove adhering liquid. Transfer crystals to small, clean
borosilicate beaker. Cover beaker with watch glass and place inside
larger covered borosilicate beaker. Dry at 105EC and fuse at
220250C (mp 208EC), holding at this temperature ca 15 min after
crystals are melted. Protect from dust during preparation. Cool in
desiccator, remove product from beaker, powder in mortar, dry 0.5 h
Table 942.25
Volume
standard
solution, mL
Molarity (mol/L) = g AgNO3 1000/mL titer 169.87

References: JAOAC 25, 661(1942); 30, 105, 496(1947).
A.1.03
Standard Solution of Arsenious Oxide
First Action 1939
Final Action
A. Reagent
Arsenious oxide.Use NIST SRM 83. Dry 1 h at 105C immediately before using.
Temperature corrections for volumes of aqueous solutions

Correction in mL at (C)
6
10
12
14
16
18
20
10
0.01
0.01
0.01
0.01
0.01
0.01
0.00
0.00
20
0.03
0.03
0.03
0.02
0.02
0.01
0.01
0.00
25
0.04
0.03
0.03
0.03
0.02
0.02
0.01
0.00
30
0.04
0.04
0.04
0.03
0.03
0.02
0.01
40
0.06
0.06
0.05
0.04
0.04
0.03
50
0.07
0.07
0.06
0.06
0.05
0.03
22
24
26
28
30
0.00
0.00
0.01
0.02
0.02
0.01
0.02
0.03
0.03
0.03
0.01
0.02
0.03
0.04
0.05
0.00
0.01
0.02
0.04
0.05
0.07
0.01
0.00
0.02
0.03
0.05
0.07
0.09
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.

Dissolve 10.12 g dried (2 h at 110C) KHC8H4O4 (NIST SRM 185g)
in H2O and dilute to 1 L. (Elaborate precautions for exclusion of atmospheric CO2 are unnecessary, although solution should be protected against evaporation and contamination with molds. Replace
solution if mold appears.)
(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
H2O and dilute to 1 L. (Dry salts 2 h at 110130C before use.)
(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
and dilute to 1 L. (Dry salts 2 h at 110130C before use.)
(f) Borax buffer solution.0.00996M; 0.01m. Dissolve 3.80 g
Na2B4O7@10H2O (NIST SRM 187c) in H2O and dilute to 1 L. (Salt
must not be dried in oven before use.) To avoid contamination with
CO2, stopper bottle except when in use or protect with sodalime
tube. Use buffer solution within 10 min after removal from bottle.
(g) Sodium bicarbonatecarbonate buffer solution.0.0249M;
0.025m (each). Transfer 2.092 g NaHCO3 (NIST SRM 191a; do not
heat) and 2.640 g Na2CO3 (NIST SRM 192a; dry 2 h at 275C) to 1 L
volumetric flask. Dissolve and dilute to volume with CO2-free H2O.
(h) Calcium hydroxide buffer solution.Saturated solution at
25C, 0.02025M. Slowly heat finely granular CaCO3, low in alkalies, to 1000C in Pt dish and maintain at this temperature
4560 min. Cool in desiccator, and add to H2O with stirring. Heat to
bp with continuous stirring. Cool, and filter on medium fritted glass
filter. Dry at 110C, cool, and crush to fine, granular powder.
Place crushed CaO in polyethylene bottle, add H2O, shake vigorously,
let settle, and record temperature. [Keep large excess of Ca(OH)2 in bottle.] For use, filter solution through medium fritted glass filter. Use at
same temperature at which saturation took place, and discard filtered solution if it becomes turbid. When more buffer solution is needed, add additional H2O to suspension, resaturate, and filter as above.
Accurately weigh As2O3 by difference from small

glass-stoppered weighing bottle (use ca 4.95 g/L for 0.025M). Dissolve in 1M NaOH (50 mL/5 g As2O3) in flask or beaker by heating
on steam bath. Add ca same volume 0.5M H2SO4. Cool, quantitatively transfer mixture to volumetric flask, and dilute to volume.
(Solution must be neutral to litmus, not alkaline.)
Molarity (mol/L) = g As2O3 4000/mL final volume 197.84
A.1.04
Buffer Solutions
for Calibration of pH Equipment
First Action 1964
Final Action 1965
Use H2O with pH of $6.5 but #7.5, obtained by boiling H2O

15 min and cooling under CO2-free conditions. Store standard buffer
solutions except Ca(OH)2 in bottles of chemically resistant glass.
Protect phosphate, borax, and Ca(OH)2 buffers from CO2. pH values
as function of temperature are given in Table 964.24.
(a) Potassium tetroxalate buffer solution.0.0496M; 0.05m.
Transfer 12.61 g KHC2O4@H2C2O4@2H2O (air weight) (NIST SRM
189a) to 1 L volumetric flask, dilute to volume with H2O, and mix
thoroughly. (It is not necessary to remove dissolved CO2 from the
H2O or to dry salt before weighing.) Prepare fresh every 2 months.
(b) Potassium hydrogen tartrate buffer solution.Saturated solution at 25EC, 0.034M. Add excess (ca 100%) of KHC4H4O6 (NIST
SRM 188) to H2O in glass-stoppered bottle or flask, and shake vigorously; few minutes shaking is enough for saturation (100 mL H2O at
25C dissolves ca 0.7 g KHC4H4O6). Adjust to 25C, let solid settle,
and decant clear solution, or filter if necessary. Discard when mold appears. Few crystals of thymol added during preparation will retard mold
growth, and will alter pH by unit. For accuracy of 0.01 pH unit, temperature of solution at saturation must be between 20 and 30C.
Table 964.24
References: NIST Certificates for Standard Reference Materials

185g, 186e, 187c, 188, 189a, 191a, and 192a.
JAOAC 33, 223(1950); 41, 302(1958); 47, 43(1964).
pH Values for standard buffer solutions as function of temperature
0.05m
0.05m
Satd. Potassium
hydrogen
Potassium
Potassium
Temp., C tetroxalate, pH
tartrate, pH
phthalate, pH
0.025m
0.008695m
Phosphate, and 0.03043m
pH
Phosphate, pH
0.01m
Borax,
pH
0.025m NaHCO3
and 0.025m
Na2CO3, pH
Satd. calcium
hydroxide, pH
1.666
4.003
6.982
7.534
9.460
10.321
13.423
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
Table 941.17A Amounts of specific indicators required to

form monosodium salts
X
pH
Bromocresol green
14.3
3.85.4
Chlorophenol red
23.6
4.86.4
Bromothymol blue
Phenol red
16.0
28.2
6.07.6
6.88.4
A.1.05
Standard Buffers and Indicators
for Colorimetric pH Comparisons
First Action 1941
Final Action
A. Preparation of Sulfonphthalein Indicators
X = mL 0.01M NaOH/0.1 g indicator required to form

monosodium salt. Dilute to 250 mL for 0.04% reagent. (See Table 941.17A.)
B. Preparation of Stock Solutions
Use recently boiled and cooled H2O.

(a) Acid potassium phthalate solution.0.2M. Dry to constant
weight at 1101 15C. Dissolve 40.836 g in H2O and dilute to 1 L.
(b) Monopotassium phosphate solution.0.2M. Dry KH2PO4 to
constant weight at 110115C. Dissolve 27.232 g in H2O and dilute
to 1 L. Solution should be distinctly red with methyl red, and distinctly blue with bromophenol blue.
(c) Boric acidpotassium chloride solution.0.2M. Dry H3BO3
to constant weight in desiccator over CaCl2. Dry KCl2 days in oven
at 115120C. Dissolve 12.405 g H3BO3 and 14.912 g KCl in H2O,
and dilute to 1 L.
(d) Sodium hydroxide standard solution.0.2M. Prepare and
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
try to adjust to exactly 0.2M.
Table 941.17B Amounts of buffer solutions and base

required to produce given pH solutions
PhthalateNaOH mixtures
pH
0.2M Potassium
hydrogen phthalate (mL)
0.2M NaOH (mL)
5.0
50
23.65
5.2
50
29.75
5.4
50
35.25
5.6
50
39.70
5.8
50
43.10
6.0
50
45.40
50
47.00
6.2
KH2PO4NaOH mixtures
pH
0.2M KH2PO4 (mL)
0.2M NaOH (mL)
5.8
50
3.66
6.0
50
5.64
6.2
50
8.55
6.4
50
12.60
6.6
50
17.74
6.8
50
23.60
7.0
50
29.54
7.2
50
34.90
7.4
50
39.34
7.6
50
42.74
7.8
50
45.17
8.0
50
46.85
H3BO3KClNaOH mixtures
pH
0.2M H3BO3, KCl (mL)
0.2M NaOH (mL)
7.8
50
2.65
8.0
50
4.00
8.2
50
5.90
8.4
50
8.55
8.6
50
12.00
C. Preparation of Buffer Solutions
Prepare standard buffer solutions from designated amounts stock

solutions, 941.17, and dilute to 200 mL. For use as calorimetric standard, mix 20 mL buffer solution with 0.5 mL indicator solution, A.
(See Table 941.17B.)
References: JAOAC 24, 583(1941).
Clark, Determination of Hydrogen Ions, 3rd Ed.,
pp 91, 94, 192202.
A.1.06
Standard Solution of Hydrochloric Acid
First Action 1936
Final Action
A. Preparation of Standard Solutions
Table 936.15 gives approximate volumes of 36.538% HCl required to make 10 L standard solutions.
B. Standard Sodium Hydroxide Method
Titrate 40 mL against standard alkali solution, 936.16CE (see

A.1.12), of ca same concentration as acid being standardized in
300 mL flask that has been swept free from CO2, using CO2-free
H2O and 3 drops phenolphthalein.
Molarity =
mL standard alkali molarity of alkali

mL HCl
If more concentrated than desired, dilute solution to required

molarity value by following formula:
V1= V2 M2/M1
where M2 and V2 represent molarity and volume of stock solution,
respectively, and V1 = volume to which stock solution should be diluted to obtain desired molarity, M1.
Check exact concentration of final solution by titration as above.
Molarity will be exact only if same indicator is used in determination
Table 936.15
Volumes of concentrated HCl required to

prepare solutions of different molarities
Approximate molarity
mL HCl to be diluted to 10 L
0.01
8.6
0.02
17.2
0.10
86.0
0.50
430.1
1.0
860.1
as in standardization. Restandardize if indicators other than

phenolphthalein are used.
References: JAOAC 19, 107, 194(1936); 49, 250(1966).
Kolthoff & Stenger, Volumetric Analysis, II,
52(1947).
B. Constant Boiling Method
Dilute 822 mL HCl (36.538% HCl) with 750 mL H2O. Check

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
connect to long, straight inner-tube condenser. Heat on electric hot
plate and distil at 510 mL/min, keeping end of condenser open to
air. When 1125 mL has distilled, change receivers and catch next
225 mL, which is constant boiling HCl, in Erlenmeyer with end of
condenser inserted into flask, but above surface of liquid. Read barometer to nearest mm at beginning and end of collection of 225 mL
portion and note barometer temperature. Average readings.
Calculate air weight in g (G) of this constant boiling HCl required to
give one equivalent weight of HCl from one of following equations:
For P0 = 540669 mm Hg:
(c) Standard borax.Saturate 300 mL H2O at 55EC (not higher)

with Na2B4O7@10H2O (ACS) (ca 45 g). Filter at this temperature
through folded paper into 500 mL Erlenmeyer. Cool filtrate to ca
10EC, with continuous agitation during crystallization. Decant
supernate, rinse precipitate once with 25 mL cold H2O, and dissolve
crystals in just enough H2O at 55EC to ensure complete solution (ca
200 mL). Recrystallize by cooling to ca 10EC, agitating flask during
crystallization.
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. Follow with two 20 mL portions ether. (Just before use, free alcohol and
ether from any possible reacting acids by vigorously shaking each
with 23 g of the pure, dry Na2B4O7@10H2O and then filtering.)
Spread crystals on watch glass, immediately place dried
Na2B4O7@10H2O in closed container over solution saturated with respect to both sucrose and NaCl, and let it remain $24 h before using.
Then transfer the pure Na2B4O7@10H2O to glass-stoppered container
and store in closed container over solution saturated with respect to
both sucrose and NaCl (stable under these conditions 1 year).
D. Standardization
Accurately weigh enough standard Na2B4O7@10H2O to titrate ca

40 mL and transfer to 300 mL flask. Add 40 mL CO2-free H2O,
936.16B(a) (see A.1.12), and stopper flask. Swirl gently until sample dissolves. Add 4 drops methyl red and titrate with solution that is
being standardized to equivalence point as indicated by reference
solution.
Molarity (mol/L) = g Na2B4O7@10H2O 1000/mL acid 190.69
Reference: JAOAC 22, 102, 563(1939).
Standard Sodium Carbonate Method
G = 162.255 + 0.02415 P0
For P0 = 670780 mm Hg:
G = 164.673 + 0.02039 P0
where P0 = barometric pressure in mm Hg corrected to 0EC for expansion of Hg and of barometer scale. For brass scale barometer, following correction is accurate enough:
P0 = Pt (l 0.000162t)
where t = barometer temperature in EC.
Weigh required amount of constant boiling HCl in tared,
stoppered flask to at least 1 part in 10 000. Dilute immediately, and
finally dilute to volume with CO2-free H2O at desired temperature.
References: JAOAC 25, 653(1942); 36, 96, 354(1953);
37, 122, 462(1954).
Standard Borax Method
C. Reagents
(a) Methyl red indicator.Dissolve 100 mg methyl red in 60 mL

alcohol and dilute with H2O to 100 mL.
(b) Reference solution.Prepare reference solution of H3BO3,
NaCl, and indicator corresponding to composition and volume of solution at equivalence point. For use in determination of end point of
titration with 0.1M HCl, reference solution should be 0.1M in
H3BO3 and 0.05M in NaCl.
E. Reagents
(a) Methyl orange indicator.0.1% in H2O.

(b) Reference solution.80 mL CO2-free H2O containing 3 or
4 drops methyl orange.
(c) Anhydrous sodium carbonate.Heat 250 mL H2O to 80EC
and add NaHCO3 (ACS), stirring until no more dissolves. Filter solution through folded paper (use of hot H2O funnel is desirable) into
Erlenmeyer. Cool filtrate to ca 10EC, swirling constantly during
crystallization. Fine crystals of trona that separate out have approximate composition: Na2CO3@NaHCO3@2H2O. Decant supernate,
drain crystals by suction, and wash once with cold H2O.
Transfer precipitate, being careful not to include any paper fibers,
to large flat-bottom Pt dish. Heat 1 h at 290EC in electric oven or furnace with pyrometer control. Stir contents occasionally with Pt wire.
Cool in desiccator. Place the anhydrous Na2CO3 in glass-stoppered
container and store in desiccator containing efficient desiccant. Dry
at 120EC and cool just before weighing.
References: Kolthoff & Stenger, Volumetric Analysis, II,
80(1947).
Ind. Eng. Chem., Anal. Ed. 9, 141(1937).
JAOAC 22, 563(1939).
F. Standardization
Accurately weigh enough anhydrous Na2CO3, E(c), to titrate ca

40 mL, transfer to 300 mL Erlenmeyer, and dissolve in 40 mL H2O.
Add 3 drops methyl orange and titrate until color begins to deviate
from H2O tint (reference solution). (Equivalence point has not been
reached.) Boil solution gently 2 min and cool. Titrate until color is
barely different from H2O tint of indicator.
A.1.09
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
A.1.07
Standard Solution of Iodine
First Action 1939
Final Action
A. Preparation of Standard Solution
Dissolve weighed amounts of I2 (12.7 g/L for 0.1M solution) and

KI, in proportion of 20 g KI to 13 g I2, in 50 mL H2O. When I2 dissolves, transfer solution to glass-stoppered volumetric flask. Dilute
to volume with H2O and mix thoroughly. Store in dark brown,
glass-stoppered bottle away from light and restandardize as frequency as necessary.
B. Standardization
Transfer accurately measured portion of standard As2O3 solution,

939.12B (see A.1.03) (4050 mL ca 0.025M solution for 0.1M solution), to Erlenmeyer. Acidify slightly with H2SO4 (1 + 10), neutralize with solid NaHCO3, and add ca 2 g excess. Titrate with I2
solution, using ca 0.2% starch solution (5 mL/100 mL) as indicator.
Saturate solution with CO2 at end of titration by adding 1 mL H2SO4
(1 + 10) just before end point is reached.
Molarity (mol/L) = mL As2O3 molarity As2O3/mL I2
Starch solution.Mix ca 1 g arrowroot starch with 10 mL H2O

and pour slowly, with constant stirring, into 200 mL boiling H2O.
Boil until thin, translucent fluid is obtained. Let settle and use clear
supernate. Preserve with Hg.
B. Assay of Stock Potassium Dichromate
If K2Cr2O7 is in small crystals, mix by shaking thoroughly in

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
at 100EC.
Weigh, into each of 3 glass-stoppered Erlenmeyers, enough
K2Cr2O7, (NIST SRM 136e) to give titer of 100.5102.0 mL 0.1M
Na2S2O3, 942.27A (see A.1.13) (4.905.00 g for 0.01667M solution). Completely dissolve in 100 mL H2O, add 4.0 g KI, and swirl
mixture until dissolved. With buret, add 4.0 mL HCl, stopper flask,
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.
Add 5 mL starch solution and complete titration with Na2S2O3 solution added from 10 mL microburet (graduated in 0.05 mL). End
point is from bluish green to clear green; change takes place within
0.01 mL. Record volume to nearest 0.01 mL. Calculate apparent
molarity of Na2S2O3 solution for each of the 3 titrations, and average. Designate this average as MNIST.
Similarly titrate 3 portions of stock K2Cr2O7 and calculate the
3 apparent molarities. Designate each of these results as Mstock. Calculate percent purity of stock K2Cr2O7 = (MNIST 100)/Mstock.
Take average of the 3 results as percent purity of stock K2Cr2O7.
C. Preparation of Standard Solution
A.1.08
Standard Solution
of Potassium BromideBromate
First Action 1947
Final Action
Dissolve theoretical weight K2Cr2O7 (NIST SRM 136e) (4.9032 g

for 0.01667M solution), or weight stock K2Cr2O7, B, found to have
oxidimetric value 99.95100.05% of NIST SRM, in enough H2O to
make 1 L. (Dry K2Cr2O7 2 h at 100EC before using.)
References: JAOAC 32, 587(1949); 33, 225(1950).
A.1.10
Dissolve ca 2.8 g KBrO3 and 12 g KBr in boiled H2O and dilute to

1 L with boiled H2O for ca 0.01667M solution.
B. Standardization
Measure 40 mL standard As2O3 solution, 939.12B (see A.1.03),

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
solution until #1 drop causes color of methyl orange to fade completely. Swirl solution constantly and add last mL dropwise, swirling between drops.
Molarity (mol/L) =
mL As2O3 molarity As2O3/mL KBrKBrO3

Standard Solution
of Potassium Permanganate
First Action 1940
Final Action
Dissolve slightly more than desired equivalent weight (3.2 g for

0.02M) of KMnO4 in 1 L H2O. Boil solution 1 h. Protect from dust
and let stand overnight. Thoroughly clean 15 cm glass funnel, perforated 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
ca 0.02M KMnO4 that has been acidified with few drops H2SO4 (1 +
3). Let settle, decant, and replace with H2O. To prepare glass funnel,
place porcelain plate in apex, make pad of asbestos ca 3 mm thick on
plate, and wash acid-free. (Pad should not be too tightly packed and
only moderate suction should be applied.) Insert stem of funnel into
neck of bottle and filter KMnO4 solution directly into bottle without
aid of suction.
B. Standardization
For 0.02M solution, transfer 0.3 g dried (1 h at 105EC) sodium oxalate (NIST SRM 40) to 600 mL beaker. Add 250 mL H2SO4 (5 +
95), previously boiled 1015 min and then cooled to 27 3EC.
Stir until Na2C2O4 dissolves. Add 3940 mL KMnO4 solution at
rate of 2535 mL/min, stirring slowly. Let stand until pink disappears (ca 45 s). If pink persists because KMnO4 solution is too concentrated, discard and begin again, adding few mL less of KMnO4
solution. Heat to 5560EC, and complete titration by adding KMnO4
solution until faint pink persists 30 s. Add last 0.51 mL dropwise,
letting each drop decolorize before adding next.
Determine excess of KMnO4 solution required to turn solution
pink by matching with color obtained by adding KMnO4 solution to
same volume of boiled and cooled diluted H2SO4 at 5560EC. This
correction is usually 0.030.05 mL. From net volume KMnO4, calculate molarity:
Molarity (mol/L) = g Na2C2O4 1000/mL KMnO4 133.999
J. Research NBS 15, 493(1935), Research Paper
No. 843.
Volhard Method
D. Reagents
(a) Ferric alum indicator solution.Saturated solution of

FeNH4(SO4)2@12H2O in H2O.
(b) Potassium or ammonium thiocyanate standard solution.Prepare ca 0.lM solution, 942.26B (see A.1.02). Determine
working titer by accurately measuring 4050 mL standard AgNO3
solution, adding 2 mL ferric alum solution and 5 mL HNO3 (1 + 1),
and titrating with the thiocyanate solution until solution appears pale
rose after vigorous shaking.
E. Standardization
Accurately weigh enough KC1, B(a), to yield titration of ca 40 mL

(ca 0.3 g for 0.1M solution) and transfer to 250 mL glass-stoppered
Erlenmeyer with 40 mL H2O. Add 5 mL HNO3 (1 + 1) and excess
AgNO3 solution. Mix, and let stand few minutes protected from
light. Filter through Gooch prepared with medium pad of asbestos
previously rinsed with 2% HNO3. Wash flask and precipitate with
several small portions of 2% HNO3, passing washings through crucible 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 volume AgNO3 solution. (Errors of blank are compensating and may be
disregarded.) From net volume AgNO3, calculate molarity as in C.
Reference: JAOAC 24, 100, 631(1941).
A.1.12
A.1.11
Standard Solution
of Silver Nitrate
First Action 1941
Final Action
Dissolve slightly more than theoretical weight of AgNO3 (equivalent weight, 169.87) in halogen-free H2O and dilute to volume.
Thoroughly clean glassware, avoid contact with dust, and keep prepared solution in amber glass-stoppered bottles away from light.
Mohr Method
B. Reagents
(a) Potassium chloride.Recrystallize KCl 3 times from H2O,

dry at 110EC, and then heat at ca 500EC to constant weight. Equivalent weight KCl = 74.555. Or, preferably, use NIST SRM 999.
(b) Potassium chromate solution.5% solution of K2CrO4 in
H2O.
C. Standardization

Standard Solution
of Sodium Hydroxide
Standard Potassium Hydrogen Phthalate Method
First Action 1936
Final Action
A. Apparatus
Use buret and pipet calibrated by NIST or by analyst. Protect exits

to air of automatic burets from CO2 contamination by suitable guard
tubes containing sodalime. Use containers of alkali-resistant glass.
B. Reagents
(a) Carbon dioxide-free water.Prepare by one of following

methods: (1) Boil H2O 20 min and cool with sodalime protection;
(2) bubble air, freed from CO2 by passing through tower of
sodalime, through H2O 12 h.
(b) Sodium hydroxide solution.(1 + 1.) To 1 part NaOH (reagent quality containing <5% Na2CO3) in flask add 1 part H2O and
swirl until solution is complete. Close with rubber stopper. Set aside
until Na2CO3 has settled, leaving perfectly clear liquid (ca 10 days).
(c) Acid potassium phthalate.NIST SRM for Acidimetry 84.
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
Erlenmeyer with 40 mL H2O. Add 1 mL K2CrO4 solution and titrate
with AgNO3 solution until first perceptible pale red-brown appears.
From titration volume, subtract mL of the AgNO3 solution required
to produce end point color in 75 mL H2O containing 1 mL K2CrO4
solution. From net volume AgNO3, calculate molarity:
Table 936.16 gives approximate volumes of NaOH solution (1 +

1) necessary to make 10 L standard solutions.
Add required volume of NaOH solution (1 + 1) to 10 L CO2-free
H2O. Check molarity, which should be slightly high, as in D, and adjust to desired concentration by following formula:
Molarity (mol/L) = g KCl 1000/mL AgNO3 74.555
V1 = V2 M2/M1
C. Preparation of Standard Solution
Table 936.16
Volumes of (1 + 1) NaOH solution required to

mL NaOH to be diluted to 10 L
solution in dark, cool place; do not return unused portions to stock

bottle. If solutions less concentrated than 0.1M are desired, prepare
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
0.50
270.0
1.0
540.0
Accurately weigh 0.200.23 g K2Cr2O7 (NIST SRM 136e dried

2 h at 100EC) and place in glass-stoppered iodine flask (or
glass-stoppered flask). Dissolve in 80 mL chlorine-free H2O containing 2 g KI. Add, with swirling, 20 mL ca 1M HCl and immediately 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, respectively, and V1, volume to which stock solution should be diluted
to obtain desired molarity, M1. Standardize final solution as in D or E.
D. Standardization
Accurately weigh enough dried KHC8H4O4 to titrate ca 40 mL

and transfer to 300 mL flask that has been swept free from CO2. Add
50 mL cool CO2-free H2O. Stopper flask and swirl gently until sample dissolves. Titrate to pH 8.6 with solution being standardized, taking precautions to exclude CO2 and using as indicator either
glass-electrode pH meter or 3 drops phenolphthalein. In latter case,
determine end point by comparison with pH 8.6 buffer solution,
941.17C (see A.1.05), containing 3 drops phenolphthalein. Determine volume NaOH required to produce end point of blank by
matching color in another flask containing 3 drops phenolphthalein
and same volume CO2-free H2O. Subtract volume required from that
used in first titration and calculate molarity.
Molarity (mol/L) = g KHC8H4O4 1000/mL NaOH 204.229
References: JAOAC 19, 107, 194(1936).
NIST Certificate for Standard Reference Material 84.
Constant Boiling Hydrochloric Acid Method
E. Standardization
Accurately weigh from weighing buret enough constant boiling

HCl, 936.15C (see A.1.06), to titrate ca 40 mL, into Erlenmeyer previously swept free from CO2. Add ca 40 mL CO2-free H2O, then 35
drops desired indicator, and titrate with solution being standardized.
Molarity (mol/L) = g HCl 1000/mL titer G
where G has value given in 936.15C (see A.1.06).
Molarity (mol/L) = g K2Cr2O7 1000/mL Na2S2O3 49.032

References: JAOAC 25, 659(1942); 27, 557(1944); 28, 594(1945);
38, 382(1955); 47, 43, 46(1964); 48, 103(1965).
A.1.14
Standard Solutions
of Sulfuric Acid
First Action 1890
Final Action
Table 890.01 gives approximate volumes of 9598% H2SO4 necessary to make 10 L standard solutions.
B. Standard Borax Method Standardization
See 936.15E (see A.1.06).

C. Specific Gravity Method
Dilute H2SO4 with enough H2O to make convenient volume of ca

70% H2SO4 by weight. Determine specific gravity in air at convenient temperature (040EC) as in 945.06C (see 26.1.06) (or specific
gravity may be determined with Sprengel pycnometer), protecting
solution from contact with air. Calculate exact percent H2SO4 by
weight:
P = S(85.87 + 0.05T 0.0004t2) 69.82
where S = specific gravity (in air) at TE, compared with H2O at tE.
Weigh exactly W g prepared acid containing P% H2SO4 and dilute
to n L to make required solution containing G g H2SO4/L. Calculate
W from equation:
W = nG 100/P
References: JAOAC 25, 653(1942); 36, 96, 354(1953);

37, 122, 462(1954).
A.1.13
Standard Solutions
of Sodium Thiosulfate
First Action 1942
Final Action
Dissolve ca 25 g Na2S2O3@5H2O in 1 L H2O. Boil gently 5 min and

transfer while hot to storage bottle previously cleaned with hot chromic acid cleaning solution and rinsed with warm boiled H2O. (Temper bottle, if not heat-resistant, before adding hot solution.) Store
Table 890.01
Volumes of concentrated H2SO4 required to

mL H2SO4 to be diluted to 10 L
0.005
2.8
0.01
5.6
0.05
27.7
0.25
138.1
0.50
276.1
References: J. Chem. Soc. Trans. 57, 64(1890).

J. Soc. Chem. Ind. 1091(1899).
JAOAC 24, 636(1941).
Table 982.35
Sources of reference materials

organizations and addresses
Source code
Name and address
AACC
American Association of Cereal Chemists

Check Sample Service
3340 Pilot Knob Rd
St. Paul, MN 55121, USA
aacc@scisoc.org
www.scisoc.org/aacc
AOAC
AOAC INTERNATIONAL
www.aoac.org/techprog/tdrm
AOCS
American Oil Chemists Society

Smalley Check Sample Program
Champaign, IL, USA
www.aocs.org
BCR
Commission of the European Communities

IRMM/MRM
B-2440 Retieseweg
Geel, Belgium
Weigh 3 g FeSO4(NH4)2SO4@6H2O and transfer to 500 mL flask.

Introduce stream of CO2, and add 50 mL recently boiled H2O and
25 mL 40% (by weight) H2SO4. Then, without interrupting current
of CO2, rapidly add 40 mL 0.01667M K2Cr2O7, 949.13C (see
A.1.09). Add TiCl3 solution until near calculated end point. Then
quickly add 5 g NH4SCN, and complete titration. Determine blank
on 3 g FeSO4(NH4)2SO4@6H2O, using same volumes of H2O, H2SO4,
and NH4SCN, and current of CO2. From net volume TiCl3, calculate
molarity:
IAEA
International Atomic Energy Agency

Analytical Quality Control Services
Laboratory Seibersdorf
PO Box 100
A-1400 Vienna, Austria
www.iaea.org
LGC
Laboratory of the Government Chemist

National Physical Laboratory
Office of Reference Materials
Teddington, Middlesex TW11 OLY, UK
orm@lgc.co.uk
Molarity (mol/L) = mL K2Cr2O7 molarity K2Cr2O7/mL TiCl3
NIES
National Institute for Environmental Studies

Yatabe-Machi, Tsukuba, Ibaraki 305, Japan
NIST
National Institute of Standards and Technology

Standard Reference Materials Program
Building 202, Room 204
Gaithersburg, MD 20899, USA
http://ts.nist.gov
NRCC
National Research Council of Canada

Marine Analytical Chemistry Standards
Montreal Rd
Ottawa, Ontario, Canada K1A 0R9
USP
U.S. Pharmacopeial Convention, Inc.

USP-NF Reference Standards
12601 Twinbrook Parkway
Rockville, MD 20852, USA
www.usp.org
A.1.15
Standard Solutions
of Titanium Trichloride
First Action 1948
Final Action
To 200 mL commercial 15% TiCl3 solution add 150 mL HCl and

dilute to 2 L. Make solution ca 0.1M, place in container with H2 atmosphere provision [e.g., JAOAC 5, 207(1921)], and let stand 2 days
for absorption of residual O2.
B. Standardization
A.1.16
Reference Materials
First Action 1982
A. Definitions
Reference material (RM).Homogenous and stable material or

substance one or more properties of which are sufficiently well established to be used for calibrating apparatus, assessing measurement method, or assigning values to materials.
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 organizations.
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 changing, inquiries should be made of the organizations concerning current availability of specific RMs.
Reference: Technical Division on Reference MaterialsMinutes
of Executive Committee Meeting, January 31, 2000,
AOAC INTERNATIONAL, Gaithersburg, MD,
USA.

Appendix A Appendix A Standard Solutions and Reference Materials

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Appendix A Appendix A Standard Solutions and Reference Materials

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Appendix A: Standard Solutions and Reference

B. Preparation of Standard Solution

Accurately weigh, on tared watch glass, enough purified AgNO3 to

Molarity (mol/L) = g AgNO3 1000/mL titer 169.87

Temperature corrections for volumes of aqueous solutions

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

Use H2O with pH of $6.5 but #7.5, obtained by boiling H2O

References: NIST Certificates for Standard Reference Materials

pH Values for standard buffer solutions as function of temperature

2000 AOAC INTERNATIONAL

Table 941.17A Amounts of specific indicators required to

A. Preparation of Sulfonphthalein Indicators

X = mL 0.01M NaOH/0.1 g indicator required to form

Use recently boiled and cooled H2O.

Table 941.17B Amounts of buffer solutions and base

0.2M NaOH (mL)

0.2M KH2PO4 (mL)

0.2M NaOH (mL)

0.2M H3BO3, KCl (mL)

0.2M NaOH (mL)

C. Preparation of Buffer Solutions

Prepare standard buffer solutions from designated amounts stock

A. Preparation of Standard Solutions

B. Standard Sodium Hydroxide Method

Titrate 40 mL against standard alkali solution, 936.16CE (see

mL standard alkali molarity of alkali

If more concentrated than desired, dilute solution to required

Volumes of concentrated HCl required to

as in standardization. Restandardize if indicators other than

Dilute 822 mL HCl (36.538% HCl) with 750 mL H2O. Check

(c) Standard borax.Saturate 300 mL H2O at 55EC (not higher)

Accurately weigh enough standard Na2B4O7@10H2O to titrate ca

(a) Methyl red indicator.Dissolve 100 mg methyl red in 60 mL

(a) Methyl orange indicator.0.1% in H2O.

Accurately weigh enough anhydrous Na2CO3, E(c), to titrate ca

Molarity (mol/L) = g Na2CO3 1000/mL acid 105.988

First Action 1949

Reference: JAOAC 22, 102, 563(1939).

A. Preparation of Standard Solution

Dissolve weighed amounts of I2 (12.7 g/L for 0.1M solution) and

Transfer accurately measured portion of standard As2O3 solution,

Starch solution.Mix ca 1 g arrowroot starch with 10 mL H2O

If K2Cr2O7 is in small crystals, mix by shaking thoroughly in

Dissolve theoretical weight K2Cr2O7 (NIST SRM 136e) (4.9032 g

Dissolve ca 2.8 g KBrO3 and 12 g KBr in boiled H2O and dilute to

Measure 40 mL standard As2O3 solution, 939.12B (see A.1.03),

AOAC Official Method 940.35

A. Preparation of Standard Solution

Dissolve slightly more than desired equivalent weight (3.2 g for

(a) Ferric alum indicator solution.Saturated solution of

Accurately weigh enough KC1, B(a), to yield titration of ca 40 mL

A. Preparation of Standard Solution

(a) Potassium chloride.Recrystallize KCl 3 times from H2O,

AOAC Official Method 936.16

Use buret and pipet calibrated by NIST or by analyst. Protect exits

(a) Carbon dioxide-free water.Prepare by one of following

Accurately weigh enough KCl to yield titration of ca 40 mL (ca

Table 936.16 gives approximate volumes of NaOH solution (1 +

Molarity (mol/L) = g KCl 1000/mL AgNO3 74.555

C. Preparation of Standard Solution