Bekasi, 18 Sep 2018

Measurement theory
GEP™ MT Academy

pH Measurement Theory

What is pH?

Why is pH measured?

pH measurement principle

Calibration and adjustment

Measurement uncertainty

Agenda 5

1 What is pH?

2 Why is pH measured?

3 pH measurement principle

4 Calibration and adjustment

What is pH? 7

pH is…

 indicating its
A chemical property of a solution
degree of acidity or alkalinity

Acidic aqueous solutions taste sour or
lemon, Coca-Cola with lots
bitter (e.g.
of sugar)

 taste caustic
Alkaline aqueous solutions
(feels like soap water)

What is pH? 8

Acids and bases dissociate in solution (e.g. water)

+ -
HCl + H2O  H3O + Cl Hydrochloric acid
+ 2-
H2SO4 + 2 H2O  2 H3O + SO4 Sulfuric acid
+ -
HNO3 + H2O  H3O + NO3 Nitric acid
+ -
CH3COOH + H2O  H3O + CH3COO Acetic acid
+ -
NaOH  Na + OH Caustic soda
+ -
NH3 + H2O  NH4 + OH Ammonia


Amount of H3O+ and OH- ions in solution determines whether a solution is
acidic (more H3O+ than OH-) or alkaline (less H3O+ than OH-)
 + - 
The pH value is a measure of the H3O and OH ion concentrations

What is pH? 9

The solvent water is an acid and a base at the same time


It dissociates like an acid producing H3O+ and a
base producing OH-
 
Autoprotolysis

-14
Water KW *10
temperature
0C 0.1
10C 0.3
18C 0.7

  25C 1.2
The dissociation constant of water is
Kw = [H3O+] [OH-] = 10-14 (depending on temperature) 30C 1.8
 + -
50C 8.0
This means the range of possible H3O and OH concentration 60C 12.6
combinations is given at any temperature
70C 21.2
80C 35
90C 53
100C 73
What is pH? 10

A pH value is defined as
the negative logarithm of the hydrogen ion concentration (cH+) +

pH = - log cH+

-x
Of any number in the format 10 , its logarithm is x +
+

H
O
So for the concentration of H+ ions this means:

-
-1
 0.1 mol/l = 10 mol/l  pH = 1
-2
 0.01 mol/l = 10 mol/l  pH = 2
-3
 0.001 mol/l = 10 mol/l  pH = 3
 When the pH value is decreased by 1, the solution is 10 times more acidic!

+
OH-
+ +
-

+ OH +

+
10

What is pH? 11

+ -
pH H conc. (mol/L) OH conc. (mol/L)
0 1 0.00000000000001
1 0.1 0.0000000000001
2 0.01 0.000000000001
sour 3 0.001 0.00000000001
4 0.0001 0.0000000001
5 0.00001 0.000000001
6 0.000001 0.00000001
neutral 7 0.0000001 0.0000001
8 0.00000001 0.000001
9 0.000000001 0.00001
10 0.0000000001 0.0001
alkaline 11 0.00000000001 0.001
12 0.000000000001 0.01
13 0.0000000000001 0.1
14 0.00000000000001 1

What is pH? 12

Orange juice
Egg white
Coca Cola Antacida ( Mg(OH)2 )
Cheese Water
Lemon juice
Milk Borax
Beer

0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
acidic alkaline
Hydrochloric acid Caustic
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)
Sodium hydrogen carbonate 0.84% (0.1)
Agenda 14

1 What is pH?

2 Why is pH measured?

3 pH measurement principle

4 Calibration and adjustment

5 Measurement uncertainty

Why is pH measured? 16

Knowing the pH value of a solution is crucial

 
pH value characterizes a product
 
 pH value influences the development of biological habitats
 
 pH value influences the shelf life of pharmaceuticals
 
 pH value influences the taste of food and beverages
 
 pH value influences the rate of chemical reactions
 
 pH value influences the property of oils
 
 pH value influences the application of cosmetics
 
 pH value is mandatory to be measured according to various regulations
 
…and many more!

Where is pH measured? 17

Wide range of applications

 
Drinking water
 
 Food and beverages industries
 
 Pharma
 
 Communal and industrial waste water
 
 Cosmetic industry
 
 Chemical processes
 
 Education and universities
 
 Medical applications
 
 Biological processes
 
Many more

17
Agenda 18

1 What is pH?

2 Why is pH measured?

3 pH measurement principle

4 Calibration and adjustment

5 Measurement uncertainty

pH Measurement Principle 20

The pH value is measured by potentiometry

 Reference
The measuring system consists of Measuring
pH Meter electrode
- a potentiometer (pH meter) electrode
- a measuring electrode
(mV)
- a reference electrode

The potential difference ∆E (mV)
 between
both electrodes is measured:

∆E = E –E
Mono Pro

Meas ref
METTLER TOLEDO InLab ® Reference
TOLEDO


InLab®

Circuit: the measuring and the reference

electrode are in contact with each other
METTLE

via the sample solution

R

E

pH Measurement Principle 21

Reference electrode

 potential (ERef) must
The reference
be constant

  U
Change in measured potential difference Measuring
∆E only depends on the change of electrode
the potential of the measuring
(E )
electrode Meas
 
 Standard reference system: Ag/AgCl

 Electrolyte
Reference electrolyte must flow out
through the junction into the sample
 of
continuously (circuit, migration
charges, ions, electrons)
Ag wire

AgCl coating

Junction
(sample contact)
pH Measurement Principle 22

Measuring electrode

 across the
EMeas is the potential
pH sensitive glass
U

EMeas is the difference between the Reference
potential at the glass outside and electrode
the potential at the glass inside
EMeas = Ea - Ei

A potential is being built up if Ea ≠ Ei
Shielding

Lead-off wire
Ei

Inner buffer
Ea
Glass (sample contact)

pH Measurement Principle 23

Nernst equation

E = Eo + 2.3 RT/F • log cH+

E = Eo + 2.3 RT/F • pH

mV
E Measured potential
Eo Standard potential pH

R Universal gas constant

1 7 14
T Temperature (Kelvin)
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)

For internal use - Confidential

pH Measurement Principle 24

Combined pH sensor – Two electrodes in one

Measuring Reference Electrode head with S7

electrode electrode or MultiPin connection
or fixed cable

Filling hole for

reference electrolyte,
SafeLock to close

+ =
Reference
electrolyte
®
ARGENTHAL
reference system
Reference junction:
ceramic diaphragm

pH sensitive
glass membrane

For internal use - Confidential

Agenda 30

1 What is pH?

2 Why is pH measured?

3 pH measurement principle

4 Calibration and adjustment

5 Measurement uncertainty

Calibration and Adjustment 32

Needed to compensate for non-ideal behavior


Calibration: establishing the
difference between what should be
measured and what really is measured

Adjustment: changing what is
 what
really measured to match
should be measured

 
Historically with pH, the term sensor
“calibration” is used for sensor 
“calibration followed by adjustment”

Is doneusing buffer solutions of known pH
values

Calibration and Adjustment 33

Using 1st buffer – offset adjustment

e.g. pH 7.00 buffer

mV

Theoretical behavior After adjustment:

Offset = 0 mV Offset = +10 mV
+10
0 pH
7
Calibration and Adjustment 34

Using 2nd buffer – slope adjustment

e.g. pH 4.01 buffer

mV

After adjustment:
Slope = -58.9 mV/pH
+10
0 pH
4 7

Theoretical behavior
Slope = -59.16 mV/pH

Calibration and Adjustment 35

Linear versus segmented calibration


 
Linear calibration uses linear regression
 
 one calibration curve for all calibration points

 Segmented calibration is possible for 3 or more calibration points 

 
 several calibration curves between consecutive calibration points
 
Segmented calibration is more accurate and recommended as of 3 points

mV
Linear calibration
Segmented calibration

4 7 9 pH

Agenda
36

1 What is pH?

2 Why is pH measured?

3 pH measurement principle

4 Calibration and adjustment

5 Measurement uncertainty
Measurement Uncertainty 37

Calibration buffer error

 
 Example
− Maximum ± 0.02 pH between 2 points
mV
− > ± 0.02 pH outside calibration points

3 and more point calibrations can be done
− Linear regression
− Segmented calibration

Buffer uncertainty
(e.g. ± 0,02 pH)

pH

Measurement Uncertainty 38

Sensor input error


 and
Sensor inputs must be calibrated
adjusted (also for temperature)

 (resistors, volt-meter etc.)
Calibrated tools
are needed


Example accuracy of pH sensor input:
max 0.2 mV
 
This means max. +- 0.002 pH at 25oC
 
Typical accuracies for temperature are:
± 0.5oC or ± 0.2oC

Measurement Uncertainty 39

Temperature errors

The pH of a solution changes with
temperature

 of a sensor changes
The calibration slope
with temperature


Isothermal intersection differs from
theoretical value
Measurement Uncertainty 40

pH value of a solution changes with temperature

Samples 20°C 30°C
Buffer Set 2 (ref. 25 C) MT Europa
HCl 0.001 mol/L pH 3.00 pH 3.00
5 7.09 4.01 9.45 2.02 11.72

NaOH 0.001 mol/L pH 11.17 pH 10.83 10 7.06 4.00 9.38 2.01 11.54
15 7.04 4.00 9.32 2.00 11.36

Phosphate buffer pH 7.43 pH 7.40 20 7.02 4.00 9.26 2.00 11.18

25 7.00 4.01 9.21 2.00 11.00
TRIS buffer pH 7.84 pH 7.56 30 6.99 4.01 9.16 1.99 10.82
35 6.98 4.02 9.11 1.99 10.64

 40 6.97 4.03 9.06 1.98 10.46

Each solution
has its own temperature 45 6.97 4.04 9.03 1.98 10.28
dependence! 50 6.97 4.06 8.99 1.98 10.10

 Buffer Set 3 (ref. 20 C) Merck

It is NOT possible to compensate for this effect 5 7.07 4.04 9.16 2.01 12.41
 at the
with a pH meter (only pH values measured 10 7.05 4.02 9.11 2.01 12.26
same temperature can be compared) 15 7.02 4.01 9.05 2.00 12.10

 20 7.00 4.00 9.00 2.00 12.00

 dependence of standard
Exception: temperature 25 6.98 4.01 8.95 2.00 11.88
buffers is well known 30 6.98 4.01 8.91 2.00 11.72

 35 6.96 4.01 8.88 2.00 11.67

Modern pH meters have tables integrated to 40 6.95 4.01 8.85 2.00 11.54
automatically compensate for this effect 45 6.95 4.01 8.82 2.00 11.44

 – doesn’t help for sample

during calibration 50 6.95 4.00 8.79 2.00 11.33
measurement

Measurement Uncertainty 41

Sensor slope changes with temperature

mV
o
C s (mV/pH)
10 -56.2
20 -58.2
25 -59.2
pH
30 -60.1 7 20 oC
40 -62.1 25 oC
50 -64.1
40 oC
 
Nernst‘s law: slope s = - 2.3*R*T/F is temperature dependent
 
 Accurate and precise pH meas. mean accurate and precise Temp. meas.

 are operated with a temperature probe connected (often combined with
Modern pH meters
the pH sensor)

 during calibration and sample measurement by using
They automatically correct for this effect
the correct slope for the temperature

Measurement Uncertainty 42

Isothermal intersection differs from theoretical value

mV mV

pH

pH pH
o o
20 C 20 C
7 7
o
40 C meter
40 oC meter
o
40 C real
 
pH meters turn curve around theoretical isothermal intersection (at 0 mV)
 
 The real isothermal intersection is often somewhere else
 
Error of DpH due to this effect if calibration and measurement temp. differ
Measurement Uncertainty 43

Accuracy

 
Measurement accuracy of ± 0.02 pH theoretically possible assuming
- only taking into account errors from buffer and sensor inputs
- Sample behaves like ideal sample
- Temperature is constant
- No handling errors of buffers, sensors etc. during calibration and measurement
- Ideal sensor in perfect shape (sensitiveness, diaphragm, age, etc.)


Realistic accuracy in lab ± 0.05 pH
- Applying good practices
- Using “normal” sample

Low accuracy, not precise

Measurement Uncertainty 44

Precision
High precisions can be achieved dependent on:

Sample (size, consistency, sample matrix)

Handling(good practice with meter, sensor,
sample)
 
Environment (temperature, air flow)

Meter (calibration) including T-sensor input Precise, not accurate
 
 Sensors (calibration)

Method (sample preparation, endpoint
algorithm, stirring speed)

Precision study (repeatability, intermediate
precision, reproducibility)

 All except the sample itself can be more or


less influenced by you
Accurate and precise
 
Good measuring practice

Questions? 50
 Conductivity
Measurement Theory

What is conductivity?

Conductivity measurement
principle

Calibration and adjustment

Temperature effects

Other conductivity units

Agenda 52

1 What is conductivity?

2 Conductivity measurement principle

4 Calibration and adjustment

5 Temperature effects

6 Other conductivity units

What is Conductivity? 53

Conductivity is the ability of a solution to pass current


number of ions present in the solution
The amount of current flowing is proportional to the

- The more ions, the higher the conductivity!


Conductivity measurements give information abouttotal
content of all ions in a solution (ion concentration)
 
Conductivity is often measured to check
- the total ion concentration in a sample =>
compare with a theoretical value
- the purity of purified water
=> comply with a maximal value
What is Conductivity? 54

Wide range of applications

 
Fresh water monitoring
 
 Checking purity of deionized water
 
 Swimming pools
 
 Checking natural streams
 
 Industrial heating/cooling
 
 Effluent streams in industry
 
 Food & beverage industry
 
 Pharmaceutical industry
 
 Power plants
 
 Chemical processes
 
Many more

Agenda 55

1 What is conductivity?

2 Conductivity measurement principle

4 Calibration and adjustment

5 Temperature effects

6 Other conductivity units

Conductivity Measurement Principle 56

The principle of the conductivity measurement cell


A voltage U is applied to two parallel Applied voltage U
plates. Measured current I

The ions in the solution move towards
 A current I is
the contrary charged plate.
flowing and measured.

The resistance R in the solution
is calculated according to Ohm's
law: R = U / I.
The reciprocal value is called

conductance G: G = 1 / R

 
Calibration: 
Determination of cell constant Z through
measurement in a solution with known Distance L Surface A
conductivity C:
Z = C • R = C • U / I (unit: cm-1)
 The cell constant corresponds to the
Measurement: distance L divided by the surface A of
Determination of conductivity C: the plates: Z = L / A
C = Z / R = Z • G = Z • I / U (unit: S/cm)

For internal use - Confidential

Conductivity Measurement Principle 57

Cell constant of a conductivity sensor -+

 
The cell constant Z of the sensor is defined by Z = L/A
- Distance between the plates =L
- Area of the plates =A 1cm

 A =1cm 2
Each conductivity sensor has its own cell constant!
1cm
L =1cm

 
Standard cell
- Cell constant Z = L / A = 1.0/cm


For high conductivity
- Cell constant Z = L / A = 10.0/cm


For low conductivity
- Cell constant Z = L / A = 0.1/cm

Conductivity Measurement Principle 58

No sensor can cover the whole measuring range


 
4 pole sensor
with cell constant 0.5 ... 1.0 /cm
- for higher conductivity
(e.g. InLab®731, InLab®738)
- for wide conductivity
ranges (good linearity)
- for contaminated samples

 
2 pole sensor
with cell constant about 0.1 /cm
- for lower conductivity
(e.g. InLab®741, InLab®742)
- for miniaturized cells for small samples

"Big cell constant for high conductivity

® ®
small cell constant for low conducitivty" InLab 731 InLab 741

For internal use - Confidential

Conductivity Measurement Principle 59

Measuring ranges and applications

0.1 1.0 10 100 1000 µS/cm

1 10 100 1000 mS/cm

Pure
Tap water Waste water
water
Conc. acid
Deion water Sea water
& base

Cell constant 0.1 / cm Cell constant 1.0 / cm

Cell constant 0.5 / cm

Error
10 %
5%
0%
-5%
- 10 %
59 For internal use - Confidential
Conductivity Measurement Principle 60

Parallel conductivity and pH measurements


 pH electrode changes the
Electrolyte outflow (KCl) from
conductivity of the solution
Ceramic diaphragm 1 mL KCl/24 h
Movable sleeve 3 mL KCl/24 h

Time Ceramic Sleeve

30 s 4 µS/c m 10 µS/c m

1 min 6 µS/cm 18 µS/cm

2 min 12 µS/cm 37 µS/cm

3 min 18 µS/cm 55 µS/cm KCl

4 min 25 µS/c m 75 µS/c m

5 min 33 µS/cm 100 µS/cm



Low conductivity: separate measurement of pH and
conductivity required

For internal use - Confidential

Agenda 61

1 What is Conductivity?

2 Conductivity measurement principle

4 Calibration and adjustment

5 Temperature effects

6 Other conductivity units

Calibration and Adjustment 62

Misleading terms (similar to pH)


Calibration: establishing the difference
between what should be measured and
what really is measured

Adjustment: changing what is
 what
really measured to match
should be measured
 
Historically sensor calibration used for

„calibration followed by adjustment“

For conductivity sensors: „calibration“
 means
determining their cell constants
 
First (zero) point (0 uS/cm) is fixed

Second point is measured using a
standard solution of known conductivity 
(e.g. 10, 84, 1413 μS/cm or 12.88 mS/cm)


Some meters allow multiple point calibration
(e.g. SevenExcellence) for wider range
Calibration and Adjustment 63

Sensor calibration = determination of cell constant

 
If only the "nominal cell constant" is known:
- Calibration with a conductivity standard solution is required
- For most conductivity sensors

-1
Cell constant Nominal 0.57 cm ± 20%

 
If a "certified cell constant" is known:
- Enter the given cell constant (or calibrate the sensor)
- Verify it with a conductivity standard solution
- For InLab 741, InLab 742 and InLab Trace

Cell constant 0.101238 cm-1

For internal use - Confidential

Agenda 64

1 What is Conductivity?

2 Conductivity measurement principle

4 Calibration and adjustment

5 Temperature effects

6 Other conductivity units

Temperature Effects 65

Conductivity is highly temperature dependent


 faster / more with higher temperatures (higher
Ions move
energy)
 
The conductivity of a solution increases with temperature

Temperature dependence is based on the type and
 present in the sample and is different
concentration of ions
for every solution

To compare measurements made at different
temperatures, they are referenced to a reference 
temperature (20 for USA or 25 for Europe, Asia °C).

 value but
the value shown in the instrument is not the measured
the calculated conductivity at reference temperature

 measure at the reference temperature to be
Ideal (least error):
referenced to

If not possible, the meter compensates the measured
conductivity value for the temperature difference
(temperature of measurement and temperature  of reference)
using the so called alpha coefficient (% / °C)
 
Alpha expresses the change of the conductivity value per °C. For internal use - Confidential
 
these values typically are between 1.50 and 5.00 %/°C
Temperature Effects 66

Temperature coefficient 

Alpha is
different for every sample (and therefore needs to be known or determined for every
sample)

(at 25 °C) Concentration Temp. coeff.  Concentration Temp. coeff. 

HCI 5% 1.58 %/°C 30% 1.52 %/°C

NaOH 5% 2.01 %/°C 30% 4.50 %/°C
KCl 5% 2.01 %/°C 20% 1.68 %/°C
Water Ultra pure 5.5 %/°C Tap water ~ 2 %/°C



Alpha is factor (expressing a linear relationship) which is generally valid only over a small
temperature range
 
In many meters, setting alpha to 0 means switching the temperature compensation off

For internal use - Confidential

Conductivity: Temperature effects

Check of the α value (% / °C)

Measure conductivity at different temperatures: e.g. 20 and 25 °C

If the conductivity measurement of a sample at two different temperatures does not give the
same reading, the α value is wrong.

Reading Reading Reading

at 20 °C at 25 °C at 30 °C

No compensation (α = 0) 639 µS/cm 706 µS/cm 776 µS/cm

α value too low 654 µS/cm 706 µS/cm 758 µS/cm

α value correct 711 µS/cm 706 µS/cm 708 µS/cm

α value loo high 737 µS/cm 706 µS/cm 675 µS/cm

67

Temperature Effects (advanced) 68

Determination of the alpha value


 and at reference
Measure the conductivity of a solution at measuring temperature (T1)
temperature (Tref) without temperature compensation (alpha = 0)

: o
Temp. coef. of the solution betw. T1 and Tref [%/ C]
CT1: Conductivity at T1
Conductivity (S/cm) CTref: Conductivity at Tref
o
T1: Measuring temperature [ C]
Tref: Reference temperature (20 or 25 oC)
C
Tref

C C
CTref
T1 T1 -
C
=
Tref
T
T1 ref T (°C) –T  100%
T1 ref

For internal use - Confidential

Temperature Effects (advanced) 69

Checking the alpha value

 Conductivity
Measure the conductivity of a solution at measuring
temperature (T1) and at reference temperature
(Tref) using the determined alpha coefficient

 of the two measurements differ, the
If the conductivity values
alpha value is wrong
 Temperature

Over a wider temperature range, the temperature
dependence of the conductivity value is not linear

The alpha value is not constant over wide temperature Tref T1
range

Conductivity real

linear

Temperature

10 50

Agenda 71

1 What is Conductivity?

2 Conductivity measurement principle

4 Calibration and adjustment

5 Temperature effects

6 Other conductivity units

Other Conductivity Units 72

Some meters offer more units for special applications

 
TDS (total dissolved solids)
- TDS is a measurement of ion concentration (mg/L or ppm).
- TDS factor = TDS / conductivity (mS/cm)
- When working with TDS, select the appropriate TDS
factor (0.40-1.00).
- This conversion factor allows to give a TDS value referred
to a calibration standard (usually KCl, NaCl or CaCO3)
 
 Salinity
- Ratio of salt in a sample to salt in seawater (NaCl)
 
 Resistivity
- Resistivity is the reciprocal of conductivity
- Raw data of conductivity measurement (ohm• cm)
- Resistivity is common in industries where ultra pure water
is required
 
Conductivity ash
- Special ICUMSA method and calculations for
sugar applications
For internal use - Confidential
 Questions? 73

For internal use - Confidential

Bekasi, 18 Sept 2018

Measuring practice
GEP™ MT Academy

Agenda 103

1 Introduction

2 Meter and operator

3 Sensor and solutions

4 Measurement practice
Introduction 104

Good practice increases measurement accuracy and precision

High precision and accuracy is

dependent on…
 
sensors (type, calibration, maintenance)

sample (size,
consistency, sample matrix,
 temperature)

 practice with meter, sensor, buffers
handling (good
and sample) Low accuracy, not precise
 
environment (temperature, air flow)
 
meter (calibration), including T-sensor input



method (sample preparation, endpoint Accurate and precise
algorithm, stirring speed)

Realistically an accuracy of
Precise, not accurate
± 0.02 to ± 0.05 pH can be achieved

For internal use - Confidential

Agenda 105

1 Introduction

2 Meter and operator

3 Sensor and solutions

4 Measurement practice

Meter and Operator 106

Installation and qualification is crucial


 only shortly
Due to time reasons
discussed here

Necessary to make sure that the system
specifications at your site
works according to manufacturer’s

- ....and is suitable for your purpose

- ....which is proven with
suitable documentation

Parts of it need to be repeated in
qualification, performance qualification)
defined intervals (operational

- This is part of routine use

and maintenance
Meter and Operator 107

Calibration of sensor inputs

Once to twice annually as part of

operational qualification

 includes a full check of all
A meter calibration
sensor inputs

A meter certification includes a
(certificates for prove)
calibration as well as documentation

- Sensors can not be certified as they require

calibration/adjustment every day

Meter calibration 
service can be included in
service contracts


Important: Meter calibration is NOT the 
same as sensor calibration (adjustment)

Meter and Operator 108

Environment

During installation qualification, the

suitability of the environment is verified:

- Appropriate temperature

- Minimal temperature fluctuations

- Appropriate humidity

- No strong air flow close to the meter

- Enough working space (accidents)

Meter and Operator 109

Training

The more you are aware of possible

risks, the better you can minimize them
 
Ensures correct handling of the system
 
 Saves time troubleshooting

 and
Helps understanding possibilities
limits of the measuring system
Meter and Operator 110

Settings on the meter

Depending on the sample and

method, settings on the instrument
need to be changed
 
Calibration settings
- E.g. select the correct buffer group
for calibration
 
General settings
- E.g. which endpoint criterion is
appropriate? automatic, manual, timed
- How to capture temperature?
automatic / manual

 
Measurement settings
- E.g. which unit? Decimal places?

 
Settings for peripherals
- E.g. stirrer, printer, sample changer

pH Measurements

pH sensor and solutions

pH measurement practice

FAQ

Agenda 112

1 pH sensor and solutions

2 pH measurement practice

3 pH FAQ
pH sensors 113

Lifetime of a pH electrode

The longest lifetime of an electrode

is reached when …
 
appropriately stored
 
suitably maintained

 
measured in aqueous solutions

 
used in the pH range of 1 – 12

Approximate lifetimes
 
at ambient temperature: 1 – 3 years
 
at 90 °C: 3 – 9 months

 
at 120 °C: a few weeks

pH sensors 114

Sensor storage

A proper storage ensures that the pH

sensitive gel layer remains hydrated and
ion rich. Open for
measurement
Recommended storage (pressure)
  Close for storage
In special storage solution
 
(contamination)
 In electrolyte solution (e.g 3 mol/L KCI)
 
 In buffer solution (e.g pH 4 or 7)
 
In diluted HCl solution (approx. 0.1 mol/L)

Never store
 
Dry
 
 In distilled water or non-aqueous solutions
 
 Reduces lifetime

 conditioning before use (costs
Needs
time)

115

pH sensors
Sensor preparation – reference electrolyte

The reference chamber needs to be

properly filled with clean electrolyte.

  Ideal reference
 Refill electrolyte regularly electrolyte
- Electrolyte level must be higher level
than sample level
- Ensures electrolyte flow into the
sample and avoids contamination
 Typical sample

Replace reference electrolyte regularly level
(e.g. once per months)
- Avoids crystallization and impurities
of electrolyte

 
Check for air bubbles behind junction
- Vertical shaking to get rid of them
pH sensors 116

Sensor cleaning

Rinse the electrode before and after

every measurement.
 
Rinse with distilled water
 
 Dip it dry with paper towel

 paper towel
Never wipe it with
(electrostatics)

Non-aqueous or dirty sample


 to
First rinse with solvent (Ethanol, Acetone)
get rid of dirt which is not water soluble
 
Rinse with distilled water

 solution
Condition in aqueous
(e.g. 3 mol/L KCL)
DO NOT wipe !

pH sensors 117

Sensor calibration (adjustment)

pH sensors must be calibrated

regularly (at least once a day)
 
Perform minimal a two point calibration

Calibration
points shall frame the expected
sample pH


Conditions at calibration and measurement
(temperature, stirring etc.) shall be equal

 
Use fresh buffers: mV
 
accurate buffers  calibration
accurate
accurate measurement + 180 Calibration curve:

Segmented calibration is recommended  as of Linear
3 calibration points (more accurate)
Segmented
Possible errors pH
  0
4 7 10
Not done frequently enough

 than
Done at a different temperature
subsequent measurement - 180
 
Wrong or contaminated buffers used

pH buffer solutions 118

Sensor Calibration – buffer handling

The quality of calibration solutions is only

guaranteed before expiry date is reached
and before opened. With some tricks,
usage after opening can be optimized:

 have an expiry date – don’t order in
Buffers
bulk

Store bottleswell sealed at room
temperature

Take out needed amount and close bottle 
immediately again, avoid contamination

Never calibrate electrode directly in the
bottle
 
Never re-use already used buffer solution
 
Consider using single-use buffer sachets
pH sensors 119

Sensor Calibration – indicating sensor condition

The sensor calibration provides

valuable data on the sensor condition


Offset” value (mV) – indicates the age
of electrode and provides an estimation
when the electrode need to be change

Calibration Slope (%) – indicates 
the
sensitivity of the glass membrane

 
(DIN 19263 requirements: Offset 0
± 30
mV; Zero Point: pH0 = 7 ± 0.5 pH)

Slope Offset pH sensor condition

95 – 105% +/- (0 – 20) mV Sensor is in good condition

94 – 90% +/- (20 – 35) mV Sensor needs cleaning
89 – 85% +/- (> 35) mV Sensor is defective or too old

pH sensors 120

pH sensor troubleshooting – contaminated membrane or diaphragm

Problems like unstable or slow readings my be caused by a contaminated diaphragm or
membrane.
Blocked with silver chloride (AgCl)  Clean with concentrated ammonia
Blocked with silver sulfide (Ag2S)  Clean with 8 % thiourea in 0.1 molar HCl
Blocked with proteins  Clean with 5 % pepsin in 0.1 molar HCl
Other junction blockages  In ultrasonic bath with water or 0.1 molar HCl
Treat for one hour, rinse with distilled water, and perform a new calibration

pH sensors 121

pH sensor troubleshooting – dry membrane

Unstable readings may be caused by a

dry membrane.
Possible causes

 in non-aqueous or ion deficient
Measuring
media
 
Wrong storage
 
Old sensor

Effect

Reduced sensitivity of glass (gel layer
 
“washed out”) unstable readings
Action
 
Conditioning in 0.1 mol/L HCl during 12 hours

Reactivation of membrane: place

electrode in reactivation solution
(NH4HF2) for 1-2 minutes
 
Replace electrode
pH sensors 122

pH sensor troubleshooting - In brief

If electrode is not performing well:

dehydrated, contaminated or
Membrane
damaged

Electrolyte contaminated, has
crystallized, hasn’t been filled enough or 
is missing, has too low ion concentration
 
Air bubbles behind the ceramic junction

 (junction) contaminated or
Diaphragm
blocked
 
Electrode worn out (out of specs), is too old

Agenda 123

1 pH sensor and solutions

2 pH measurement practice

3 pH FAQ

pH measurement practice 124

Stirring

Before starting a pH measurement, it is

recommended to stir the sample to
ensure that it is homogeneous.
 
Fist stir to equilibrate and homogenize
- Especially needed if sample
is heterogeneous
 
Then switch off the stirrer and measure

 gently (DIN19268 requires
Or just stir
stirring)
- Unstable diffusion conditions at the
diaphragm when stirring strongly lead
to unstable readings

Always do the
same for calibration and
measurement
pH measurement practice 125

Temperature

Every sample has a characteristic

temperature and pH behavior. Knowing
or measuring the temperature is key for
accurate pH measurements.
 
Two options to measure temperature:
- Integrated temperature sensor
- External temperature sensor

If temperature is very
constant and well
known: manual entry
 InLab Power Pro
With integrated temperature probe

 and
Temperature of calibration buffer
sample should be identical.


To compare the pH value of samples,
they should ideally alwaysbe measured
at the same temperature.

For internal use - Confidential

pH measurement practice 126

Temperature – small samples

Temperature measurement of small

samples is difficult.


The sample massis negligible compared to
the sensor mass


Therefore the sensor temperature
as the
is wrongly interpreted
sample temperature


Store the sensor at the same temperature as
the samples to get accurate results

For internal use - Confidential

pH measurement practice 128

Simply the wrong way

 
Filling hole closed during measurement
 
 Storage in deionized water
 
 Wipe to clean glass membrane
 
 Calibration once a week
 
 Temperature has no influence
 
 Never replace electrolyte
 
 Re-use buffers for calibration
 
Stir extremely fast during measurement
pH measurement practice 129

USP / EP / JP compliance
pH is one of the main parameters measured in
many different areas and applications.


Several pharmacopeias (P) prescribe
quality specifications, with which
 must
pharmaceutical manufacturers
demonstrate compliance

Mettler-Toledo instruments and
sensors fully comply with the requested
 of regulations like USP,
requirements
EP and JP

Furthermore the pharmacopeias
describe requirements  for calibration
followed by a verification

For internal use - Confidential

pH measurement practice 130

USP / EP / JP compliance
The different pharmacopeias are similar, but not exactly the same:

Requirements USP EP JP
Precision of pH meter ± 0.02 pH units ± 0.05 pH units ± 0.05 pH units
(Input resistance
of meter at least
100 times higher
than of electrode)
Electrode Glass membrane Glass membrane Glass membrane
Calibration 2 points 2 points 2 points
Verification pH in both pH in buffer pH in both
calibration buffers between calibration buffers
± 0.02 pH calibration buffers ± 0.02 pH
± 0.05 pH
Temperature 25 °C ± 2 °C all measurements ± 2 °C
at same
temperature

For internal use - Confidential

Agenda 131

1 pH sensor and solutions

2 pH measurement practice

3 pH FAQ
pH FAQ 132

Example 1

Why do I see “7.02” on the pH meter

screen when calibrating using the
7.00 pH buffer?

 o  C 4.00 4.01 6.86 7.00 9.18 9.21 10.01

The temperature is not 25 C
0 4.00 4.01 6.98 7.12 9.46 9.52 10.32
5 4.00 4.01 6.95 7.09 9.40 9.45 10.25
10 4.00 4.00 6.92 7.06 9.33 9.38 10.18
15 4.00 4.00 6.90 7.04 9.28 9.32 10.12
METTLER TOLEDO pH meters 20 4.00 4.00 6.88 7.02 9.23 9.26 10.06
automatically correct for temperature 25 4.00 4.01 6.86 7.00 9.18 9.21 10.01
30 4.01 4.01 6.85 6.99 9.14 9.16 9.97
35 4.02 4.02 6.84 6.98 9.10 9.11 9.93
40 4.03 4.03 6.84 6.98 9.07 9.06 9.89
45 4.04 4.04 6.83 6.97 9.04 9.03 9.86
50 4.06 4.06 6.83 6.97 9.01 8.999 9.83

pH FAQ 133

Example 2

Why do I see “7.00” on the pH meter

screen when calibrating using the
6.86 pH buffer?

 C 4.00 4.01 6.86 7.00 9.18 9.21 10.01

 buffer group has been
The wrong
0 4.00 4.01 6.98 7.12 9.46 9.52 10.32
chosen
5 4.00 4.01 6.95 7.09 9.40 9.45 10.25
10 4.00 4.00 6.92 7.06 9.33 9.38 10.18
15 4.00 4.00 6.90 7.04 9.28 9.32 10.12
Before you calibrate, select the right 20 4.00 4.00 6.88 7.02 9.23 9.26 10.06
buffer group in the meter’s setup 25 4.00 4.01 6.86 7.00 9.18 9.21 10.01
30 4.01 4.01 6.85 6.99 9.14 9.16 9.97
35 4.02 4.02 6.84 6.98 9.10 9.11 9.93
40 4.03 4.03 6.84 6.98 9.07 9.06 9.89
45 4.04 4.04 6.83 6.97 9.04 9.03 9.86
50 4.06 4.06 6.83 6.97 9.01 8.999 9.83

pH FAQ 134

Example 3

Why do I not see a new slope after

the calibration? mV


process has been stopped
The calibration
after one point
pH
A one point calibration yields a new offset
7
value but keeps the existing slope
pH FAQ 135

Example 4

How often do I need to calibrate my

pH electrode?



It depends on the type of sample, the
electrode and the required accuracy



For accurate measurements, at least
 daily

 need
Dirty and non-aqeous samples
 more frequent calibrations

 need more frequent
Old electrodes
 calibrations


Always after changing electrode or
after long storage, after replacement of
electrolyte, after cleaning of blocked
diaphragm, after rehydration of
electrode, after regeneration of
electrode

pH FAQ 136

Example 5

How many times can I use my pH buffers?

 
Only once

 
 Always use fresh buffers

Buffers are your calibration
tools and
need to be treated as such
 
Buffers have an expiry date

pH FAQ 137

Example 6

Why does it take 3 minutes or more to get a result?

 
 Wrong electrode selected (select correct one)
 
 Electrode is too old (regenerate or buy new one)


Not enough electrolyte or electrolyte is diluted or
contaminated (empty  old electrolyte and fill up
with fresh electrolyte)
 
 Electrode is dry (rehydrate)
 
 Sample is not homogenious (homogenize, stir)


 on meter too strict for
Settings for auto endpoint
application (change)
 
Continous temperature fluctuations (change)
pH FAQ 138

Example 7

How do I get rid of air bubbles behind the

junction?


 gently (similar to
Shake electrode
thermometer)

Air bubbles behind the junction keep

electrolyte from flowing out
This causes unstable signals

pH FAQ 139

Example 8

What is the right electrolyte for my

sample?


For aqueous solutions, generally use 3 M
KCl in water (sat. with AgCl if nosilver
 reservoir available in electrode)

For non-aqeous solutions, generally use 1 M
 LiCl in ethanol

Special applications might need special
electrolytes or even bridge
 electrolytes (2
electrolytes in electrode)

If you are not sure, mix 1 mL sample and 1 mL

electrolyte
It is likely to be fine if no precipitation and no
turbidity can be observed

pH FAQ 140

Example 9

How often shall I replace the

reference electrolyte?

 
 Regularly, e.g. every 14 days

 depending on usage and electrode
Or more
type

 
 Make sure you don’t just top-up

Make sure you use freshand
 concentrated electrolyte

Make sure youfill enough (more than
sample level)
 
Calibrate afterwards
pH FAQ 141

Example 10

What can I do if the electrode is

not performing well?



Check membrane: contaminated, dry,
damaged
 
 Check electrolyte: contaminated, missing

Check junction: blocked with precipitate, air
bubble
 
Check electrode: age, correct type

Questions? 142

For internal use - Confidential

Conductivity measurements

Conductivity sensor and solutions

Conductivity measurement practice

FAQ
Agenda 144

1 Conductivity sensor and solutions

2 Conductivity measurement practice

3 Conductivity FAQ

Conductivity sensors 145

Sensor storage and cleaning

Conductivity sensors do not need

much maintenance. Some points still
are important.

Recommended storage

 (< 1 day): dry or in
Short term storage
deionized water
 
Long-term storage (> 1 day): dry

Cleaning


Rinse with deionized water after every
measurement

 (ethanol or
If needed, rinse with a solvent
InLab 731 InLab 741
acetone) followed by water

Conductivity sensors 146

Sensor calibration = determination of cell constant

 
If only the "nominal cell constant" is known:
- Calibration with a conductivity standard solution is required
- For most conductivity sensors

-1
Cell constant Nominal 0.57 cm ± 20%

 
If a "certified cell constant" is known:
- Enter the given cell constant (or calibrate the sensor)
- Verify it with a conductivity standard solution

Cell constant (e.g.) 0.101238 cm-1

For internal use - Confidential

Conductivity sensors 147

Sensor verification

Verification is done to confirm the

cell constant.
Two procedures are possible:

Compare the reading with the value of
the standard
solution at the measured
temperature
  no temperature correction needed 

values are printed on the label or the
certificate

Compare the reading with the value of the
certified standard solution
 
 use linear temperature correction
 
 For low conductivities:

- Calibrate with 84 μS/cm
- Verify with standard of lower conductivity
(e.g. 10 μS/cm)

Conductivity solutions 148

Sensor calibration and verification – standard handling

Conductivity standards require

special handling:

Standards are directly affected by dilution,

contamination or the influence of CO2 in air

 an expiry date – don’t
Standards have
order in bulk

Store bottles
well sealed at room
temperature


Take out needed amount and close bottle
immediately again
 
Never calibrate sensor directly in the bottle

 already used standard
Never re-use
solution

using single-use standard
Consider
sachets

Agenda 149

1 Conductivity sensor and solutions

2 Conductivity measurement practice

3 Conductivity FAQ
Conductivity measurement practice 150

Temperature effects

The conductivity of a sample is highly

temperature dependent. Knowing the
temperature is key for accurate measurements.
 
Two options to measure temperature:
- Integrated temperature sensor
- External temperature sensor
 T-sensor
manual entry
If temperature is very constant and well known:

 
Immerse temperature sensor fully into the sample T-sensor


Temperature of calibration standard and sample
should be identical


To compare measurements made at different InLab 731 InLab 741
temperatures, they are referenced to
a
reference temperature (20°C / 25°C)

 at
the instrument calculates the conductivity
reference temperature using the α-factor

For internal use - Confidential

Conductivity measurement practice

151

Stirring

In general, conductivity measurements

in stirred samples are preferred.

 solutions, measurement drift is
In unstirred
possible.
 
No stirring in low conductivity samples
stirring increases exposure to air and
carbon dioxide contamination

Use the same stirring conditions for
both calibrationor verification and
measurement.

Conductivity measurement practice 152

Low conductivity measurements

Measurements of samples with conductivity <
10 μS/cm need a special procedure..

an inert gaseous layer
Protect samples with
(nitrogen or helium)

Use a closed system like a
flow cell to exclude
carbon dioxide completely.
- Avoid air bubbles inside the flow
- After every measurement first rinse
with deionized water
- Then rinse with sample or standard which
is measured next

Calibrate with 84 μS/cm and verify with
 standard
of lower conductivity (e.g. 10 μS/cm)

®
InLab Trace
with flow through cell
For internal use - Confidential
Agenda 157

1 Conductivity sensor and solutions

2 Conductivity measurement practice

3 Conductivity FAQ

Conductivity FAQ 158

Example 1

When do I need to perform a

calibration or a verification?



If the exact cell constant is NOT known,
 then calibration must be performed.

When the exact cell constant is known,
then a verification is sufficient. This is
the case with sensors with a certified
cell constant or sensors which have
been previously calibrated.

InLab 731 InLab 741

Conductivity FAQ 159

Example 2

What is the general life expectancy of

a conductivity sensor?


age in the
Conductivity sensors do not
 same way as pH sensors.

Their lifetime is not limited as long as their
measuring cell is not attacked by any

harsh chemicals, mishandling, mechanical
 damage or fouling.

The lifetime mostly dependson the usage
 and handling of the sensor.


Proper cleaning and storage increase the
lifetime of the sensor.

InLab 731 InLab 741

Conductivity FAQ 160

Example 3

Can conductivity be measured in

non-aqueous solutions?



Yes, it is possible. Organic substances also
 have dissociative properties.

Organic compounds like benzene,
alcohols, and petroleum products 
 generally have very low conductivity.

It should be recognized that an increase
in conductivity can indicate an increase in
ionic contamination and/or an increase in
water contentthat allows increased
 dissociation.

Before measuring non-aqueous InLab 731 InLab 741
 the resistance of the
samples first check
sensor material.

Questions? 161