01 PHTheory AnaChem-pH Basic Jan07 MN

pH: Theory, measurement, and electrode
maintenance
Agenda
 Theory
- What is the pH?
- pH scale in aqueous solutions
- Why do we measure the pH value?
 pH electrodes
- Principle of measurement
- Combined pH glass electrode
- Choosing the right electrode for the right applications
 Storage and cleaning of electrodes
- Maintenance and storage
- Cleaning, reconditioning
 Adjustment and measurement
- Adjustment using pH buffers
- Temperature compensation
pH Theory 2 AnaChem/pH Lab Basic Course Jan/Feb 07

What is pH ?
pH
It‘s a measured value which indicates the
degree of acidity of an aqueous solution
Acid is ….
…. bitter
…. unpleasant
…. (almost) inedible/undrinkable

Why is it acidic ?
Acid is ….
…. bitter
…. unpleasant
…. (almost) inedible / undrinkable
Acids dissociate in water and release hydrogen ions H+:

 HCl  H+ + Cl- Hydrochloric acid
 H2SO4  2 H+ + SO42- Sulfuric acid
 HNO3  H+ + NO3- Nitric acid
 CH3COOH  H+ + CH3COO- Acetic acid
The degree of acidity is due to the presence of H+-ions

pH measuring range: 0 - 14
Food & Beverages / Household products
Orange juice
Egg white
Coca Cola
Cheese Water Antacida ( Mg(OH)2 )
Lemon juice
Milk
Beer Borax
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Caustic
Hydrochloric acid
Hydrocyanic acid soda 4%
0.37% (0.1 M) Calcium
0.27% (0.1 M) carbonate (sat)
Sulfuric acid Acetic acid Ammonia sol.1.7% (1 M)
4.9 % (1 M) 0.6% (0.1 M)
Ammonia sol. 0.017% (0.01 M)
Potassium acetate 0.98% (0.1 M)
Chemicals Sodium hydrogen carbonate 0.84% (0.1

Why is something alkaline?
Base (alkali) is….

…. caustic
…. feels like “soap water”
A base dissociates in water and release hydroxide ions OH- :
 NaOH  Na+ + OH- Caustic soda
 NH3 + H2O  NH4+ + OH- Ammonia
 CO32- + H2O  HCO3- + OH- Carbonate
The degree of alkalinity is due to the presence of OH --ions

Definition of pH
A pH value is defined as:
the negative logarithm of the hydrogen ion concentration (cH+)
pH = - log cH+
logarithm x of a number n: n = 10x
Concentration of H+ ions:
0.1 mol/L = 10-1  pH = 1

0.01 mol/L = 10-2  pH = 2
0.001 mol/L = 10-3  pH = 3

The pH scale
The pH scale is determined by the dissociation of water, H2O:
H2O = H+ + OH–
The product of the concentrations of these ions is constant:

cH+ * cOH- = 10-14 (25oC)
pH Theory AnaChem/pH Lab Basic Course Jan/Feb 07

Why do we measure pH ?
 to produce products with defined properties
 to produce products with less costs
 to avoid damage to people, materials and environment
 to fulfill regulatory requirements
 to protect equipment
 to get new knowledge, for research and development
pH Theory AnaChem/pH Lab Basic Course Jan/Feb 07

Where do we measure the pH value?
 Environment and water utilities
 Tap water
 Industrial water
- Cooling / Heating
- Production processes
 Waste water
 Chemical processes
 Swimming pools
 Nuclear power plants
 Food and beverages industries
 Pharmaceutical and cosmetic industry
 ……

Agenda
 Theory
- What is the pH?
 pH electrodes
- Combined pH glass eelctrode

Principle of pH measurement
The pH is measured by potentiometry
glass reference
The measuring system consists of: electrode electrode
pH glass electrode pH Meter
reference electrode
The potential difference (mV) is measured:
E = EGlass - EReference

Nernst equation
E = Eo + 2.3 RT/F • log cH+

E = Eo – 2.3 RT/F • pH
E Measured potential mV
Eo Standard potential
R Universal gas constant pH
T Temperature (Kelvin) 1 7 14
F Faraday constant
2,3 RT/F Nernst potential (slope)
cH+ H+ concentration of solution
Potential difference of 1 pH unit = 59.16 mV (at 25 °C)

Construction of pH Electrode
pH glass electrode reference electrode

S7 Connector
Filling port
Platinum lead-off wire
Reference electrolyte
Reference system
Internal buffer
Membrane glass Diaphragm
Combined pH Electrode
 Screw Cap, S7 or MultiPin head
 Refill opening, Safe Lock
 Reference electrolyte
 ARGENTHAL® Reference System
 Silver Ion Trap
 Ceramic junction
 Integrated temperature probe
 pH sensitive glass membrane

Choosing the right electrode
Points to consider when selecting an electrode for a specific sample:
 Junction
 Reference electrolyte
 Shaft material
 Silver ion trap
 Temperature
 Membrane glass
 Membrane shape

Electrodes: Junctions - Examples
Different junctions
Ceramic
ceramic frit,
chemically inert connection,
slow electrolyte flow
approx. 1 mL / 24 h
Ground-glass
ground-glass junction
with movable sleeve.
Fast electrolyte flow
approx. 4 mL / 24 h
InLab412 InLab420

Electrodes: Junctions - Examples
polymer の
InLab413
Open junction with 構造的特徴
electrolyte
For dirty samples:
solid state
固体電解質
electrolyte PEEK
METTLER TOLEDO InLab413

開孔部
open junction
Temp sensor

What could cause an instable pH reading?
Contaminated diaphragm = Number one troublemaker!
 Solutions containing proteins
 Solutions containing sulfide Reference Sample

electrolyte solution
 Suspensions D
I
 Oils
Ag+ A
P
Sulfides
H
R
A
Proteins
G
M

Electrodes: Silver ion trap
For chloride- or sulfide containing samples
Silver wire coated with AgCl
Ag / AgCl cartridge (ARGENTHAL)

Silver ion
free
reference Glass wool
electrolyte Silver ion trap (based on Bi)
Silver ion free

Diaphragm reference electrolyte
No AgCl or Ag2S precipitation in the diaphragm

Electrodes: Inner electrolyte
Reference systems
Electrolyte Advantages Note

Liquid electrolyte Long lifetime, Maintenance required
Quick response, Breakable glass electrodes
Accurate,
Extreme pH
Gel electrolyte Robust, Slower response
Maintenance-free Electrolyte not refillable
Polymer Maintenance-free Slower response
electrolyte No clogged diaphragm Electrolyte not refillable
(open junction, e.g. InLab®413

Electrodes: Shaft material
Materials
 Glass breakable, but liquid electrolyte
 Polysulfone robust, clear, not for organic solvents
 PEEK robust, black, not for organic solvents
 Epoxy robust, clear, not for organic solvents
Generally, the question is „Glass or not?“

Electrodes: Temperature sensor
Need for a T-sensor?
Relationship between electrical resistance and temperature
Electrode with MultiPin, BNC/Cinch connectors or separate

T-sensor
• Pt1000 1000 Ohm @ 0°C

• NTC 30 kOhm 30 kOhm @ 25°C
OR
• No temperature sensor -> enter manually in the meter

Electrodes: Membrane shapes
Classical membrane shapes: examples
Spherical
(more resistant to
contraction at low T)
Hemispherical
Small sample volume
Cylindrical
higher surface area,
lower resistance
InLab®428 InLab®422 InLab®429

Electrodes: Membrane shapes
Special membrane shapes: examples
Spear
(puncture electrode)
e.g. for meat, cheese
Micro
for small reaction tubes
Flat InLab®427
for surface
e.g. skin, paper
InLab®423 InLab®426

Choosing the right electrode
 Sample
- Sample clarity and consistency
- Sample composition
- Temperature, pH range
 Size constraints
- Sample size (micro, semi-micro, normal)
- Beaker size (normal, long, test tube, small container)
 Technical specifications of the electrode

- In particular:
Junction, material, glass type and shape of pH sensitive membrane

Choosing the right electrode: Sample
 Sample clarity and consistency

- Clear  ceramic junction
- „dirty“  open or sleeve junction
 Sample consistency
- Liquid  any junction
- Emulsion  open junction
- Viscous  sleeve diaphragm
- Sludge / slurry / suspensions  open junction, sleeve
- Semi-solid  puncture electrode
- Solid / flat surfaces  flat membrane

Choosing the right electrode: Sample
 Sample composition
- Low ionic strength (e.g. DI water, suspensions)
 triple diaphragm, bridge electrolyte, membrane resistance
- High ionic strength (e.g. concentrated acids or bases)
 bridge electrolyte, high alkali glass
- Sulfides, TRIS, proteins
 open junction, Ag+ trap, (low membrane resistance for Tris)
- Non-aqueous solvent
 sleeve diaphragm (electrolyte flow) with LiCl soluble
in organic media (adapt electrolyte to sample)
- Hydrofluoric acid
 dedicated InLab®429 electrode (only to 0.1M HF!)
 Temperature
- high/low ATC or manual entry
 pH range
- appropriate glass material

Agenda
 Theory
- What is the pH?
 pH electrodes

Maintenance: Storage
 Always store in
- 3 mol/L potassium chloride (3 M KCl)
- Or buffer solutions pH 4 or 7,
- Or diluted HCl (approx. 0.1 mol/L)
Never store the electrode in distilled water or dry!

The pH sensitive glass membrane will be affected.
 Shorten lifetime.
 Not ready to use, needs conditioning.

Maintenance: Reference electrolyte
 Replace/refill reference electrolyte regularly.
- E.g. every 14 days
 Electrolyte level must be higher than in the sample solution.

- Otherwise the sample flows into the reference system -> wrong results.
 No air bubbles behind the junction.

- Vertical shaking of the electrode.
 Which electrolyte?
- for aqueous solution 3 mol/L KCl
- for non aqueous solution 1 mol/L LiCl in ethanol
Test: if you don’t know….

 Mix 1 mL sample and 1 mL electrolyte.
 If no turbidity or no precipitation will appear: OK!.

Measurements in non-aqueous sample
Non-aqueous solutions:
- Acetic acid, methanol and ethanol mixtures,..
- Mineral and edible oils, silicon oils,
 Electrode with sleeve diaphragm.

 Electrode conditioning in water.
- After 5 - 10 samples condition electrode approx. 5 minutes.
 After daily use:

- store electrode over night in diluted acid or KCl 3 mol/L for regeneration and
hydration.
 After regeneration of the electrode needs new calibration.

Maintenance: Cleaning
Cleaning the electrode
 After each measurement rinse the electrode

with distilled water.
 Never wipe
the membrane
with a paper towel.

Maintenance: Cleaning
Cleaning the diaphragm
 blocked with AgCl

- with concentrated ammonia
 blocked with Ag2S

- with 8 % thiourea in 0.1 molar HCl (ME-51 340 070)
 blocked with proteins:

- with 5 % pepsin in 0.1 molar HCl (ME-51 340 068)
 other contaminations
- in ultrasonic bath with water or 0.1 molar HCl
Treat one hour, rinse with distilled water,

and perform a new electrode adjustment.

Maintenance: Reconditioning
Reconditioning of the pH glass membrane
 Dry electrode
- Dry membrane:
Re-conditioning in 0.1 mol/L HCl during 12 hours.
 Electrode out of specs

- Reactivation of the membrane:
Place electrode in reactivation solution containing NH 4HF2
for 1-2 minutes (ME-51 340 073).
Rinse with distilled water,

and perform a new electrode adjustment.

Lifetime of a pH electrode
The approximate lifetime of a pH electrode
appropriate storage
suitable maintenance
measurement in aqueous solutions
pH range pH 1 to pH 12
at ambient temperature 1 - 3 years

at 90°C 3 - 9 month
at 120 °C a few weeks

Agenda
 Theory
- What is the pH?
 pH electrodes

Accuracy of pH measurement
What does the accuracy of pH measurement depend on?
 Calibration
- correct and frequent procedure
- new and accurate buffers
 Temperature
- differences between calibration and measurement
- temperature measurement and control
 Electrode
- correct type (correct membrane glass)
- clean diaphragm
Realistic accuracy in the laboratory: ± 0.05 pH

Adjustment
1. Offset adjustment
Buffer pH 7.00
mV
After adjustment:
Offset = -10 mV
Before adjustment:
(calibration)
pH
4 7 9
Offset = 0 mV (ideally)

Adjustment
2. Slope adjustment
Buffer pH 4.01
mV
Before adjustment:
(calibration)
pH
4 7 9
After adjustment
Slope = -58.9 mV/pH

Adjustment
Conditions
 Always use fresh buffers.

- Use the same buffer solution only once,
- Otherwise there is no guarantee for the correct
value of the buffer solution.
 Clean the electrode after the measurement.
 Measure the temperature.

- All METTLER TOLEDO pH meters and
titrators have an automatic temperature
compensation.

Adjustment
How frequently should the electrode be adjusted?
 Depends on the type of sample.
- Dirty and non aqueous sample needs frequent adjustment.
 Depends on the requested accuracy.

- For very accurate measurements, at minimum do it daily.
 Depends on the quality of the electrode.

- Old electrodes need to be adjusted (calibrated) more frequently.
 After replacement of the electrolyte.
 After cleaning a blocked diaphragm.
 After long or wrong storage.

Temperature compensation
What is the temperature compensation in a pH meter?
According to the Nernst‘s law the slope of the electrode is temperature dependent:
o
C mV/pH
E = Eo - 2,3 RT/F • pH 0 -54.2
10 -56.2
mV 20 -58.2
25 -59.2
30 -60.1
40 -62.1
50 -64.1
60 -66.1
pH 80 -70.1
20 C o
90 -72.1
7
25 oC 100 -74.0
110 -76.0
40 oC

Temperature compensation
The T-compensation in a pH meter doesn’t compensate for:
 pH value of a solution at different temperature
 Each solution has its own temperature dependence!

 It is NOT possible to compensate for this effect with a pH meter.
Samples 20°C 30°C

HCl 0.001 mol/L pH 3.00 pH 3.00
NaOH 0.001 mol/L pH 11.17 pH 10.83
Phosphate buffer pH 7.43 pH 7.40
TRIS buffer pH 7.84 pH 7.56
Always measure the temperature with each pH measurement

Temperature Compensation
What does the pH meter compensate for?
 The pH meter or titrator has a temperature compensation for the slope of

the electrode.
 There is no compensation for the temperature dependence of the pH

value of the sample itself.
 Exception: Standard buffers

 The temperature dependence of the buffers (METTLER TOLEDO, MERCK,
etc.) are stored in the pH meters and titrators.

Summary
 If an electrode is not performing well:
- Membrane dehydrated, contaminated or damaged
- Electrolyte contaminated or missing
- Air bubbles behind the ceramic junction or membrane
- Diaphragm (junction) contaminated
- Crystallized KCl blocking outlet of electrolyte
- Electrode worn out (out of specs)
 ……simply the WRONG way:

- Filling hole closed.
- Storage in deionised water.
- Wipe to clean glass membrane.
- Calibration once a week.
- Temperature has no influence.
- Always the same electrolyte.
- pH measurement can’t go wrong

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pH: Theory, measurement, and electrode

pH Theory 2 AnaChem/pH Lab Basic Course Jan/Feb 07

pH Theory 3 AnaChem/pH Lab Basic Course Jan/Feb 07

Acids dissociate in water and release hydrogen ions H+:

 HNO3  H+ + NO3- Nitric acid

 CH3COOH  H+ + CH3COO- Acetic acid

The degree of acidity is due to the presence of H+-ions

Chemicals Sodium hydrogen carbonate 0.84% (0.1

pH Theory 5 AnaChem/pH Lab Basic Course Jan/Feb 07

Base (alkali) is….

A base dissociates in water and release hydroxide ions OH- :

 NaOH  Na+ + OH- Caustic soda

 NH3 + H2O  NH4+ + OH- Ammonia

 CO32- + H2O  HCO3- + OH- Carbonate

The degree of alkalinity is due to the presence of OH --ions

A pH value is defined as:

the negative logarithm of the hydrogen ion concentration (cH+)

logarithm x of a number n: n = 10x

0.1 mol/L = 10-1  pH = 1

pH Theory 7 AnaChem/pH Lab Basic Course Jan/Feb 07

The pH scale is determined by the dissociation of water, H2O:

The product of the concentrations of these ions is constant:

pH Theory AnaChem/pH Lab Basic Course Jan/Feb 07

 to produce products with less costs

 to avoid damage to people, materials and environment

 to fulfill regulatory requirements

 to get new knowledge, for research and development

pH Theory AnaChem/pH Lab Basic Course Jan/Feb 07

 Nuclear power plants

 Food and beverages industries

 Pharmaceutical and cosmetic industry

pH Theory 10 AnaChem/pH Lab Basic Course Jan/Feb 07

pH Theory 11 AnaChem/pH Lab Basic Course Jan/Feb 07

The pH is measured by potentiometry

The potential difference (mV) is measured:

pH Theory 12 AnaChem/pH Lab Basic Course Jan/Feb 07

E = Eo + 2.3 RT/F • log cH+

R Universal gas constant pH

Potential difference of 1 pH unit = 59.16 mV (at 25 °C)

pH glass electrode reference electrode

Platinum lead-off wire

 Screw Cap, S7 or MultiPin head

 Refill opening, Safe Lock

 ARGENTHAL® Reference System

 Silver Ion Trap

 Integrated temperature probe

 pH sensitive glass membrane

pH Theory 15 AnaChem/pH Lab Basic Course Jan/Feb 07

Points to consider when selecting an electrode for a specific sample:

 Silver ion trap

pH Theory 16 AnaChem/pH Lab Basic Course Jan/Feb 07

pH Theory 17 AnaChem/pH Lab Basic Course Jan/Feb 07

For dirty samples:

METTLER TOLEDO InLab413

pH Theory 18 AnaChem/pH Lab Basic Course Jan/Feb 07

Contaminated diaphragm = Number one troublemaker!

 Solutions containing proteins

 Solutions containing sulfide Reference Sample

pH Theory 19 AnaChem/pH Lab Basic Course Jan/Feb 07

Silver wire coated with AgCl

Ag / AgCl cartridge (ARGENTHAL)

Silver ion free

No AgCl or Ag2S precipitation in the diaphragm

pH Theory 20 AnaChem/pH Lab Basic Course Jan/Feb 07