42.1.04 D.
Standardization of Analog pH Meter
AOAC Official Method 981.12 Note temperature of buffer solution and set temperature compen-
pH of Acidified Foods sator control of instrument at observed temperature (ca 25°C). Stan-
First Action 1981 dardize instrument and electrodes with 0.05M acid potassium
Final Action 1982 phthalate buffer solution, 964.24(c) (see A.1.04).
Rinse electrodes with distilled or deionized H2O and blot—do not
A. Principle wipe—with soft tissue.
Immerse electrode tips in buffer solution and read pH, letting me-
pH is measurement of H ion activity and indicates acidity. It may
ter stabilize 1 min. Adjust standardization control so that meter read-
be measured by determining electric potential between glass and ref-
ing corresponds to known pH of buffer (ca 4.0) for ambient
erence elctrodes, using commercial apparatus standardized against
temperature. Rinse electrodes with distilled or deionized H2O and
NIST primary standard pH buffers.
blot with soft tissue.
Check expanded scale pH meters with pH 4.0 or 7.0 standard buff-
B. Apparatus and Reagents
ers. Buffers and instruments can be further checked by comparison
(a) pH meter.—Commercial instrument with scale graduated in with values obtained using another properly standardized instrument.
≤0.1 pH unit and reproducibility of ≤0.05 unit. Some instruments Check indicating electrodes for proper span by using 2 separate
permit expansion of any 2 pH unit range to cover entire scale and buffers. For example, first standardize electrodes by using pH 7.0
have accuracy of ca ±0.01 pH unit and reproducibility of ±0.005 pH buffer at ca 25°C. Adjust standardization control so that meter reads
unit. Other instruments have digital read-outs with similar capabili- exactly 7.0. Rinse electrodes with H2O, blot, and immerse in pH 4.0
ties. Operate meter in accordance with manufacturer’s instructions. buffer. If the electrode fails span test, rejuvenation or electrode re-
In this method, several procedures for standardization and operation placement may be necessary.
of pH meters and electrodes are outlined. When these procedures
E. For Digital pH Meters with Slope Control
differ from manufacturer’s instruction, the latter should prevail, ex-
cept that NIST standard buffers must be used as primary reference. Select 2 standard buffer solutions, preferably such that difference in
Working buffer standards should be checked at least daily against pH levels does not exceed 3 units and such that expected pH of sample
NIST reference buffers. to be tested falls within their range, i.e., standard buffer solutions of
(b) Standard buffer solutions.—See 964.24 and Table 964.24 (see pH 4.0 and 7.0. For most accurate results, one standard buffer should
A.1.04). be chosen with pH at or near pH of solution to be evaluated. Standard-
(c) Electrodes.—Glass membrane indicator electrode and calo- ize meter first in one pH buffer (i.e., pH 7.0 buffer) with standardized
mel reference electrode (single or combination). Keep calomel elec- control, and then use slope control to standardize meter in second pH
trodes filled with saturated KCl solution because they may be buffer, i.e., pH 4.0 buffer. This procedure establishes the proper in-
damaged if allowed to dry out. Maintain uniform temperature of ca strument response (slope) for particular pH electrode used, and results
25°C for electrodes, standard buffer solutions, and samples. Soak in more accurate pH reading.
new electrodes several hours in distilled or deionized H2O before Sometimes difficulty is encountered with drifting of combination
electrode. When this occurs, identify and correct source of trouble.
use. Store glass electrode in pH 4 buffer. Store reference electrodes
Very often, reference electrode junction is responsible.
in their own electrolyte filling solution. Store combination electrode
In case of faulty meter operation, refer to manufacturer’s
in pH 4 buffer with a few drops of saturated KCl solution added.
operating manual for proper trouble-shooting techniques.
Store electrodes in manner consistent with manufacturer’s recom-
mendations if they differ from above. Store electrodes so that junc- F. Process pH Determination
tion and hole are covered. Rinse electrodes with next solution to be Obtain test sample portions of material for pH determination as
measured. If test sample material is insufficient, rinse electrodes follows:
with distilled or deionized H2O. Lag in meter response may indicate For process test liquids, let temperature equilibrate to ca 25°C,
aging effects or fouling of electrodes, and cleaning and rejuvenation and determine pH by immersing electrodes in liquid.
of electrodes may be necessary. Clean electrodes by placing in 0.1M Drain solid materials on No. 8 sieve (ss preferred) and blend to
NaOH solution 1 min and then transferring to 0.1M HCl solution workable paste. Let temperature of prepared paste equilibrate to ca
1 min. Repeat twice, ending with electrodes in acid solution. Rinse
25°C, and determine pH.
electrodes thoroughly with H2O before proceeding with standard-
Where appropriate, mix representative aliquots of liquid and solid
ization. Oil and grease from samples may coat electrodes; therefore,
materials at same liquid-to-solid ratio as original sample, and blend
clean electrodes with ethyl ether and restandardize instrument fre-
to workable paste. Let temperature of prepared paste equilibrate to
quently, usually after 3 determinations.
ca 25°C, and determine pH.
C. Standardization and Operation of pH Meter
If pH meter is equipped with temperature compensator, then it
may be used in lieu of equilibrating samples to specified tempera-
Switch instrument on and let electronic components warm up and ture, provided it is ±15° of 25°C standard temperature.
stabilize before proceeding.
Standardize specific instrument according to manufacturer’s in- G. Preparation of Test Samples
structions, using NIST SRM buffers. Equilibrate electrodes, buffers, (a) For estimating degree of pH equilibrium or uniformity.—Use
and samples at same temperature (ca 25°C) before pH measure- for foods which have not come to pH equilibrium, i.e., production
ments. Set temperature compensator control of instrument at ob- line samples, warehouse samples.
served temperature. When determining pH of either unknown (1) Liquid and solid component mixtures.—Drain contents of
sample or buffer, gently stir solution before testing. container 2 min on No. 8 ss sieve inclined at 17–20° angle. Record
© 2000 AOAC INTERNATIONAL
weights for liquid and solid portions and retain separately. If liquid (b) For confirming pH equilibrium.—If product has been stored
contains sufficient oil to cause electrode fouling, separate layers in long enough to attain pH equilibrium, then determine pH on normal
separator and retain aqueous layer. Determine pH of aqueous layer containers as follows:
at ca 25°C. Remove drained solids from sieve, blend to uniform (1) Determine pH on container mixture only, by opening con-
paste, adjust temperature to ca 25°C, and determine pH. Mix tainer, inserting electrode(s), and measuring pH.
aliquots of solid and liquid fractions in same ratio as found in origi- (2) For products in oil, follow procedures outlined in (a)(2) above
nal container, and blend to uniform consistency. Adjust temperature to remove oil and obtain accurate pH reading.
to ca 25°C, and determine pH.
H. Determination
(2) Marinated oil products.—Separate oil from solid, and
blend solid to paste in blender. Add small amount (≤20 mL/100 g Adjust test sample temperature to ca 25°C, and set temperature
product) of CO2-free H2O if necessary. Determine pH by immers- compensator control to observed temperature. With some expanded
ing electrodes in prepared paste after adjusting temperature to ca scale instruments, test sample temperature must be same as tempera-
25°C. ture of buffer solution used for standardization.
(3) Semi-solid products (puddings, potato salad, etc.).—Blend to Rinse and blot electrodes. Immerse electrodes in sample and read
paste, adding 10–20 mL CO2-free H2O/100 g product if necessary. pH, letting meter stabilize 1 min. Rinse and blot electrodes and re-
peat on fresh portion of test sample.
Adjust temperature of prepared paste to ca 25°C, and determine pH.
Determine 2 pH values on each test sample. Readings in close
(4) Special product mixtures (e.g., antipasto).—Pour off all oil,
agreement indicate that test sample is homogeneous. Report values
blend remaining product to paste, add 10–20 mL CO 2-free
to 2 decimal places, e.g., 4.73.
H2O/100 g product if necessary, and blend. Adjust temperature of
prepared paste to ca 25°C, and determine pH. Reference: JAOAC 64, 332(1981).
© 2000 AOAC INTERNATIONAL
