METHODS MANUAL

pH

CONTENTS TM134.003

Summary Sheet...........................................................................................................................2
Equipment...................................................................................................................................2
Reagents / Chemicals................................................................................................................2
Test Procedure............................................................................................................................2
Purpose........................................................................................................................................3
Equipment...................................................................................................................................3
Reagents / Chemicals................................................................................................................3
Safety...........................................................................................................................................4
Equipment Preparation..............................................................................................................4
Sample Preparation....................................................................................................................4
Calibration – pH Meter...............................................................................................................5
Calibration - Temperature Measurement.................................................................................7
Flowchart.....................................................................................................................................7
Test Procedure............................................................................................................................8
Sanitation....................................................................................................................................8
Maintenance................................................................................................................................8
Troubleshooting.........................................................................................................................9
Principles and Theory of Operation.......................................................................................10
Definitions.................................................................................................................................10
References................................................................................................................................12
Appendix...................................................................................................................................12

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TM134.003 Page 1 of 13 Originator: Victoria Bedenko
Issued: 01/01/04 Revision # 3 Authorized by: Mike Finnerty
 METHODS MANUAL
pH
Summary Sheet
Acquire Sample
Equipment
 pH meter and electrode; preferably a combination electrode
Degas, if Carbonated
 Thermometer, or temperature compensator on pH meter
 250-mL beaker
 Magnetic stirring plate and stir bar
 Degassing equipment, as specified in Pepsi degassing Bring Sample
Temperature to 20oC
procedure
Reagents / Chemicals Pour Sample Into
Beaker
 At least 2-3 buffers for calibration, encompassing the expected
range of pH values
 3 molar potassium chloride (3 M KCl) to store electrode Begin Stirring
 Distilled water to rinse electrode

Test Procedure Lower pH Electrode

Into Sample
1. Pour about 100 mL of degassed sample beverage into a
clean and dry 250-mL beaker.
Record pH
2. Carefully place a clean dry stirring bar into the beaker. Place
the beaker on the magnetic stirrer, and turn the stirrer on until
the sample is gently agitated.
Rinse Electrode
3. Immerse the bottom 1/3 of the electrode in the sample. If the With Water
meter is not temperature compensated, measure the
temperature of the sample and adjust the temperature knob Dab Gently With a
of the meter accordingly. (Ensure the orifice at the top of the Tissue to Dry
electrode is uncovered during measurements.)
4. Allow the pH reading to stabilize and record the beverage pH.
Store Electrode in
5. Rinse the electrode with water. 3M KCl
6. Store the electrode in 3 M KCl.

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TM134.003 Page 2 of 13 Originator: Victoria Bedenko
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pH
Purpose
pH is a measure of the free acid in a sample solution.

Electrode

Stir Plate pH Meter

Figure 1: Diagram of typical pH setup.

Equipment
For Sample Testing:
 pH meter and electrode; preferably a combination electrode
 Thermometer, or temperature compensator on pH meter
 250-mL beakers
 Magnetic stirring plate and stir bar
 Degassing equipment, as specified in Pepsi degassing procedure
For Calibration:
 U.S. National Institute of Standards and Technology (NIST), or equivalent certified agency,
thermometer to check pH meter thermometer calibration, 0.2C

Reagents / Chemicals
For Electrode Storage:
 3 molar potassium chloride (3 M KCl) (223.6g KCl in 1000 mL distilled water)

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pH
For Calibration:
 Three buffer solutions of pH 3, pH 7 and pH 10, accurate to  0.02, traceable to NIST (or
equivalent), prepared and stored at temperature recommended by manufacturer
(working buffer solutions should normally be stored at 4°C (39F), but for no longer
than 1 week) for calibration of pH meter
OR buffer solutions of pH 2, 4, 7, and 9 for an automatic titrator
Buffer solutions should encompass the expected range of pH values.
 Distilled or deionized water, less than 10 S conductivity-use conductivity meter to
measure

Safety
Personal protective equipment must be worn at all times. For these procedures, this
equipment may include, but is not limited to:
 safety glasses with side shields to prevent chemicals from burning the eyes
 lab coat, and any other equipment the analyst thinks is necessary

If any of the chemicals used in these procedures comes in contact with the eyes or skin,
wash the affected part thoroughly with clean water and seek first aid if necessary. Check
MSDS.

Equipment Preparation
 Perform daily pH meter and electrode calibration

Sample Preparation
 If sample is carbonated, degas the sample according to the Pepsi degassing method
(vacuum or bubbling) in the quality manual.
 Bring sample temperature to 20-25°C (68-77F) range before testing. Since pH
measurements are temperature-dependent, a temperature-compensated probe should
be used to correct the pH of the sample based on its temperature.
 Note: Some pH buffers are certified at 25°C (77F), but should contain temperature
corrections for measurement at 20°C (68F).

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TM134.003 Page 4 of 13 Originator: Victoria Bedenko
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 METHODS MANUAL
pH
Calibration – pH Meter
This procedure is offered for general calibration. For accurate and precise pH
measurements, it is essential that the calibration schedule and procedure recommended by
the manufacturer be observed. If calibration buffer solution results are beyond the
tolerances specified below for Brinkmann electrodes, then go to the maintenance section,
troubleshooting section, or see the manufacturer’s manual if using a non-Brinkmann pH
electrode. (Orion ROSS electrodes should have a slope of 92-102%).
Calibration tolerances for pH electrode
Lower Limit Upper Limit
% Slope 95% 105%
U asymmetry - 15 mV + 15 mV

1. Prepare pH reference buffer samples in testing beakers from stock solution.

1. Rinse the electrode with distilled water; dab carefully to remove any drops. Do not wipe.
2. Lower electrode in a pH 7 buffer solution, immersing bottom 1/3 of electrode.
3. Measure temperature of the buffer solution and record.
4. When electrode reading is constant, record potential value in mV on the measuring
instrument (for pH 7.0, this is the isoelectric point).
5. Remove the electrode from the first buffer solution. Rinse with distilled water, dab to
remove any drops.
6. Immerse in the second buffer solution of pH 3.
7. When electrode reading is constant, record potential value in mV.
8. Rinse electrode with distilled water.
9. Calculate the % slope by dividing the measured slope by the theoretical slope. Obtain
theoretical slope from the table below.
10. Recheck the calibration using a 3rd buffer solution of pH 10. Recalibrate if the 3rd
reference buffer reading varies by more than  0.05 pH.
11. NOTE: Many newer pH meters perform calibration calculations automatically.
This is just one example of how to calibrate your pH meter. In general, you want to calibrate
with at least two buffers – one on the low end of your working pH range and one on the high
end. Please check the manufacturer’s instructions on how to calibrate.

CALCULATIONS
Note: Many newer pH meters perform calibration calculations automatically.

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 METHODS MANUAL
pH
This is just one example of how to calibrate your pH meter. In general, you want to calibrate
with at least two buffers – one on the low end of your working pH range and one on the high
end. Please check the manufacturer’s instructions on how to calibrate

Theoretical Slope Values

Temperature Nernst Slope
(C) (F) (DmV/DpH)
10 50.0 -56.18
15 59.0 -57.16
18 64.4 -57.77
19 66.2 -57.97
20 68.0 -58.17
21 69.8 -58.37
22 71.6 -58.57
25 77.0 -59.16
30 86.0 -60.15

The pH meter sensitivity can be calculated as follows:

mV per pH = mV of pH 2.00 buffer – mV of pH 7.00 buffer =  mV
pH 2.00 - pH 7.00  pH
Meter sensitivity should equal -59  3 mV per pH unit at 25°C

Calibration Example:
Temperature 20°C (68F)
1st buffer solution pH = 7 +6 mV
2nd buffer solution pH = 3 +239 mV
Measured slope 239 mV - 6mV = 233 mV = -58.25 mV / pH
3pH – 7pH 4 pH
Theoretical slope at 20°C (68F) = -58.17 mV / pH
% slope = measured slope = -58.25 / -58.17 = 100.1%
theoretical slope
Electrode calibration data: Asymmetry potential: +6 mV
% slope: 100.1%
Therefore, calibration is within tolerance range.

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TM134.003 Page 6 of 13 Originator: Victoria Bedenko
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Calibration - Temperature Measurement

At least once per month, check the calibration of the thermometer or temperature
compensator with the NIST-certified thermometer. Temperature should agree to within 
0.2°C.

Flowchart

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Test Procedure
1. Pour about 100 mL of sample to be tested into a 250-mL beaker.
2. Add a magnetic stir-bar, place the beaker on the magnetic stirrer, and turn on the stirrer
until the sample is gently agitated.
3. Remove the calibrated pH electrode from its storage solution and rinse it with deionized
water.
4. Gently shake off any large drops of water that remain on the glass bulb, or dab gently
with tissue paper. Do not wipe!
5. Immerse the bottom 1/3 of the electrode in the sample. If the meter is not temperature
compensated, measure the temperature of the sample and adjust the temperature knob
of the meter accordingly. (Ensure the orifice at the top of the electrode is uncovered
during measurements.)
6. Allow the pH reading to stabilize and record the sample pH. For viscous materials such
as syrups, a longer time is needed for pH to stabilize. (High-fructose corn syrups may
be analyzed neat. If it contains about 80% dry solids, then dilute with distilled water to
about 40% solids and mix before analyzing).
Note: DO NOT WIPE the pH electrode. Always blot gently with soft tissue paper between
rinses, then store in appropriate storage solution (see Maintenance section).

Sanitation
 See electrode manufacturer’s instructions.
 Clean all glassware after each use.

Maintenance
Proper storage and handling is required to ensure accurate results. Perform cleaning of the
diaphragm or regeneration of the glass membrane when the slope and/or symmetry are
beyond the calibration tolerances. Replace electrode if necessary. Having an extra electrode
at all times is highly recommended.
Storage of Combined Glass Electrode
Store bottom 1/3 of the electrode in the reference electrolyte, saturated 3 molar KCl. Do not
allow the gel layer to dry out (Figure 2, p.10). If a combined electrode is stored in water,
silver chloride (AgCl) can precipitate in the diaphragm. Change the silver chloride (AgCl)
solution in the combined electrode regularly.
If the electrode is filled with saturated KCl, some KCl may precipitate and build up at the
bottom of the electrode. This can cause erratic results. To remove the KCl solution, gently
shake the electrode with the hole exposed. Then, add warm distilled water and shake

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gently. Repeat until the KCl crystals have been removed from the electrode. Fill the
electrode with fresh saturated KCl solution and allow to stand overnight before use.

Storage of Separate Glass Electrodes

Store bottom 1/3 of the electrode in distilled water, or follow manufacturer’s instructions. Do
not allow the gel layer to dry out (Figure 2, p.10).
Cleaning the diaphragm
Some electrode manufacturers provide diaphragm-cleaning instructions. However, these
cleaning procedures can require the use of hazardous chemicals. It is recommended the
electrode simply be replaced. If a replacement is not readily available, as a last resort, you
can try filing the diaphragm. Very carefully file down diaphragm with a diamond nail file. The
outflowing electrolyte should be visible as a dark ring.

Troubleshooting
Symptom Cause Solution
Display of pH Meter  Loose contact  Check the contact
drifts  Electrode not plugged in, or  Rectify fault
cable faulty
 Meter not grounded  Ground meter
Display of pH meter  Reference electrode is not  Top up with electrolyte solution,
is erratic filled free from air bubbles
 Reference electrode filled with  Empty out water and fill with
water by mistake reference electrolyte
 Diaphragm clogged  Clean the diaphragm (p.8)
 Measurement in poorly  Add supporting electrolyte (i.e.,
conducting solution 3M KCl) to the sample
Sluggish  Absorption at glass  Replace electrode
establishment of membrane
pH  Dirty diaphragm  Clean diaphragm (p.8)
Slope too low  Poor buffer solutions  Use fresh buffer solutions
 Absorption at glass  Replace electrode
membrane
 Shrunken glass membrane  Soak electrode in water between
after measurements in the measurements
anhydrous solvents.
 Old electrode  Replace the electrode
 Diaphragm contaminated  Clean diaphragm (p.8)
Slope cannot be  Diaphragm blocked  Clean diaphragm (p.8)
adjusted  Wrong order of buffer  Check order of buffers in
solutions manufacturer’s instructions (p.5)
Shows same value  Crack in the glass membrane  Replace the electrode
in different pH  Connector damp, dirty, or not  Dry or clean connector, or rectify
buffers plugged-in fault

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TM134.003 Page 9 of 13 Originator: Victoria Bedenko
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 METHODS MANUAL
pH
Principles and Theory of Operation

The pH value is the measure of acidity or alkalinity of a sample. Values below pH 7.0
indicate acidity, and values above pH 7.0 indicate alkalinity. pH is also very temperature-
dependent.
The pH of a sample is also affected by other factors:
 As treated water alkalinity increases, the pH will increase.
 As residual CO2 increases (i.e., the sample is incompletely degassed) the pH decreases
because CO2 is converted to carbonic acid which adds to the total acidity.
 When caustic carryover occurs, the pH increases because the residual caustic has already
neutralized some of the beverage acidity.
The pH meter electrode converts voltage differences between an external and an internal
electrode into pH values. The sample composition determines the external electrode
potential.

Definitions
Mole: A mole is a chemical term that means simply “the atomic weight of a substance
expressed as grams”. Atoms and molecules are too tiny to be seen and to be mixed
individually. Therefore, representative weights of atoms and molecules are used when they
are mixed and measured. For example, one oxygen atom (O) that weighs 16 atomic mass
units will react with one hydrogen molecule (H 2) that weighs 2 atomic mass units to give one
molecule of water (H2O) having a molecular weight of 18. Likewise, 16 grams of oxygen will
react with 2 grams of hydrogen to give 18 grams of water. So, one mole of water weighs 18
g, one mole of hydrogen weighs 2 g, and one mole of oxygen weighs 32 g (because in
reality hydrogen and oxygen always come in pairs, H2, O2).
Ion: An ion is a particle that has either a positive (+) or negative (-) charge. Hydrogen is the
simplest element, consisting of a positively charged proton with a negatively charged
electron that flies around the proton. If the hydrogen atom loses its electron, it becomes an
ion with a positive charge and is written H +. Hydrogen ions in water are what make the
water acidic. In Pepsi’s case, the hydrogen ions come from phosphoric acid, which releases
them into the syrup when water is added to the concentrate. The phosphoric acid goes from
being H3PO4 (a molecule with no charge) to H2PO4- and H+, both of which are ions.
pH is defined as the negative logarithm of the hydrogen ion concentration in moles per liter:
pH = -log [H+]
A mole of H+ weighs 1 g. If there is 1 g H+ in 1 L water, then a 1mole/liter solution is made.
The pH of this solution would be:
pH = -log [H+] = - log [1] = 0 extremely acidic!
The pH scale is based on the ionization of water.
H2OH+ + OH-

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It is found that in pure water, the concentration of the hydrogen ions and the concentration
of the hydroxide ions (OH-) in the solution are both 10 –7 moles/liter. The concentrations are
balanced, so pure water is neutral by definition. Furthermore, if the pH is taken of a 10 -7
moles/liter solution, then the following is obtained:
pH = -log [H+] = - log [10-7] = 7
This is why pure water has a pH of 7. The pH scale goes from 0 to 14 and is logarithmic.
This means each pH unit differs from the next unit by a factor of 10. For example, pH 2 has
10 times more hydrogen ions than pH 3 and 100 times more hydrogen ions than pH 4.

Gel Layer

Figure 2: Schematic of the bottom half of a typical glass-membrane electrode .

pH Glass Electrodes
The pH of a solution is measured with a pH meter, an electronic device with a pH electrode,
a reference half-cell, and a temperature-measuring probe. If the pH electrode and the half-
cell are contained as one unit, it is referred to as a combination electrode.
pH glass electrodes respond to hydrogen ions, i.e. they are ion selective electrodes for H +.
The ion selective measuring element is a glass membrane of special composition. Before
the electrode is ready for measurement, the glass membrane must be soaked in water. It
then forms a thin, gel-like hydrated layer. If the glass electrode is immersed in water at room
temperature, the swelling of the membrane is complete within 24-48 hours. The formation of
this gel layer is accelerated at higher temperatures. This is called “conditioning” the
electrode, and all electrodes should be conditioned according to the specific manufacturer’s
instructions.
The pH electrode contains a reference solution of dilute hydrochloric acid in contact with the
thin glass membrane in which a silver wire coated with silver chloride has been embedded.
When this electrode is dipped into a solution containing H + ions of unknown concentration,
the electrode potential is determined by the difference in hydrogen ion concentration
between the unknown solution and the diluted hydrochloric acid solution. The glass
electrode functions as a concentration cell. If the solution inside and outside the glass
membrane differ in H+ ion concentration, then a potential difference develops across the
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membrane. Thus the electromotive force varies with the pH of the solution being tested by
the equation
U = U° - UN (pH)
U = potential measured between indicator and reference electrode
U° = standard potential of electrode assembly, which depends on the construction
UN = Nernst slope, defined by (2.3026RT)/F
R = universal gas constant (8.31441 JK-1mol-1)
T = absolute temperature in °K (°K = °C + 273.15)
F = Faraday constant (96,484.56 Coulombs/mol)
2.3026 = the conversion factor for the natural logarithm to base ten
Slope: Slope is a measure of electrode response compared to perfect theoretical response.
The slope is determined with at least 2 known buffers. According to Nernst, the theoretical
slope of a pH electrode assembly is 58.16 mV/pH at 20°C (68F) and 59.16 at 25°C
(77F). This means 1°C temperature difference corresponds to 0.2 mV.
Isoelectric Point is an indicator of the integrity of the hydrogen ion sensitive glass bulb of
the electrode. When the glass electrode is immersed in an analysis solution that is identical
to the internal buffer, theoretically the measured potential U should be zero, presupposing
that the electrode assembly is symmetrical, i.e. its external and internal reference electrodes
are identical. The deviation of a few mV that is found is called the asymmetry potential. It
depends on the construction of the electrode assembly. The internal buffer usually has a pH
value of 7, thus at pH 7, theoretically 0 mV should be measured.

References
 National Bureau of Standards Special Publication, no. 260
 Corn Refiners Association-pH method E-48
 International Society of Beverage Technologists-Determination of pH, procedure 10.0
Appendix
Buffer Temperature Correction Table:
pH 4 buffer pH 7 Buffer pH 9 buffer pH 10 Buffer
o
C pH pH pH pH
0 4.00 7.12 9.46 10.32
10 4.00 7.06 9.33 10.18
20 4.00 7.02 9.23 10.06
25 4.00 7.00 9.18 10.01
30 4.01 6.99 9.14 9.97
35 4.02 6.98 9.10 9.93

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40 4.03 6.97 9.07 9.89

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TM134.003 Page 13 of 13 Originator: Victoria Bedenko
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