pH measurement

pH basics

pH

pH

pondus hydrogenii = Weight of hydrogen

potentia hydrogenii = Power of hydrogen

pH

Why pH measurement?
pH measurement is an important measurement
and touches us all the time in our daily life.

Cleaning solutions: Soap, bleach, etc.

Food products: Yogurt, Cheese, Coke, Beer,
Water etc.
Waste water: Industrial, Municipal
Chemical production: Pesticide, TiO2, synthetic dye, epoxy
resin
Plastic production: PVC, PP, etc.
Pharmaceutical: insulin, penicillin, anti bodies, etc.
Pulp & paper : inlet of paper machine

pH

pH scale

pH

Measuring principle
pH is a potentiometric measurement method.
The measuring effect is based on a pH sensitive glass
membrane whose surface reacts to the acid content with
a specific voltage.
This voltage is then measured relative to a reference
element.
pH is calculated according the Nernst law equation.

pH

Measuring and reference electrode

pH transmitter
Measuring
electrode

Reference
electrode

3 mol KCl
+
Internal buffer

Glass membrane

3 mol
KCl

Diaphragm

pH

Two half cells make one combination electrode

pH

Working principle of the glass

membrane
Glass membrane
thickness:
0.2-0.5 mm

Acid
solution
pH < 7

H+

Gel layer:
0,0001 mm

Internal
buffer

Alkaline
solution
pH > 7

+
+ pH 7 +
+
+
H
-

If inside pH = outside pH
---> no potential difference = 0 mV (= pH 7)
with excess of H+-ions
= positive
charge outside
(resp. less H+-ions
= negative charge
outside)
--> result: potential difference

pH measurement in process applications

Nernst equation

Slope of the pH electrode:

54,20 mV/pH at 0 C
S lo p e at 25 C
59,16 mV/pH
0
74,04
5 9 , 1 6 mV/pH
m V a t at
2 5 100
C C

pH

pH calibration

+ mV

Zero
Slope

C02

9,2
4

Acid error
Alkali error
- mV

9,2

pH

Alkaline buffer
changes the
pH value !

pH

Types of diaphragms
Ceramic:
fast response
soiling sensitive
biocompatible

Open arperture:
very fast response
soiling sensitive
danger of poisoning

Liquid junction via

the diaphragm of
the
pH electrode

PTFE:
Very robust
slow response
dirt repellent

pH

Effects on the probe

pH

Installation of pH sensors

pH

Storing of pH sensors
Out of operation pH sensors should be stored
wet.
pH 7 or 3mol KCl-solution is the best storage
solution.
Do not store sensors in deionized water or
alkaline
buffers.
If a sensor dries out during storage, soaking it
overnight
in pH 7 or 3mol KCl will usually restore the
hydrated
glass layer and the reference junction.

pH

IsFET electrode - working principle

IsFET
H+

H+
H+

Gate
Source

Drain
-

Glass

H+
H+
H+

pH

IsFET-sensors
How it works:
Gate insulator:
Thickness: about 0,1 m
Material: Ta2O5 (Tantalum
oxide)

Reference system

H+
H+

IsFET

H+

IsFETs are
following the
NERNSTs law!

The insulator is an amphoteric

material (acting as acid or base),
thus surface charges are occuring
by the reversible reaction with H+
resp.
OH- -ions
Important:
Contrary to the
glass electrode no charges are
transported through the
insulator, it is just an
electrostatic effect.

pH

IsFet electrodes

Restricted life time in hot alkaline

safety: unbreakable
wider application range:
- higher amounts of solvents

- fast response at low temperatu

lower acidic and alcaline errors

pH

Fast response time of IsFET

electrode
9.0
8.5
8.0

pH

7.5

- 20-C20 C

7.0
6.5

CPS401 B2ESB1A1

IsFET electrode
pH - Glasselectrode
- Electrode
glass

6.0
5.5
5.0

10

Time/min

12

14

16

18

20

pH instrumentation

pH

The new pH sensor family

Glass pH-electrodes

OrbiSint
CPS 11/ CPS11D

CeraGel
OrbiPore
CeraLiquid
CPS 71/CPS71D CPS 91/CPS91D CPS 41/CPS41D

Non-glass electrodes

er
form 01
4
CPS

TopHit
CPS 471

Application

environmental

food/
pharma

TopHit
CPS 491

TopHit
CPS 441

chemical/
chemical/food/
environmental
pharma

pH

Sensor segmentation
CPS 11/CPS11D

CPS 71/CPS71D

CPS 471

CPS 91/CPS91D

CPS 491

CPS 41/ CPSD

CPS 441

ceramic
diaphragm

open
diaphragm

ceramic
diaphragm

double gel

double chamberreference

double gel

liquidreference

long-term
check of stable
processes

hygienic and
sterile applications

media with strong

changing
compositions

highest
accuracy

teflon diaphragm

poisoning media

suspensions
emulsions

ultrapure water
extremely
blocking media

precipitations
environmental

food / pharma

chemical,
environmental

chemical,
food, pharma

pH

Mounting options

Immersion mounting

Flow through

Pipe- or tankmounting

Flow through

pH

The Cleanfit family

CPA 471 / 472

selfsealing via
electrode lift tube
standard application

CPA473 / 474

ball valve sealing

to process
harsh process

application

CPA475

selfsealing via
electrode lift tube
hygienic application

pH

Electrode protection

CPA 471 / 472

CPA 475

inside and outside

O-ring

hygienic form
sealing

best results in
EHEDG certified
non abrasive media
cleanability

CPA 473

open
protection guard

CPA 474

stable
polymer guard

best result
for aggressive and
with fibrous
abrasive media
and abrasive media

pH

The new 2 wire instrument :

LIQUILINE

Easy and Safe

Quick set up within minutes via navigator button
Big graphic display and plain text menu
Strict safety requirement with SIL2

Flexible
SS or plastic housing
Quick parameter change via plug in module
All field bus protocols supported (HART, FF, ATEX)

Cost saving
No field calibration needed with Memosens sensors
Predictive maintenance system

pH

Liquiline M CM42 - Measuring

Parameters

pH and redox

conductivity
resistivity
concentration

dissolved
oxygen

Launching : 1st of Sept 05.

pH cleaning and calibration

systems

pH

Electrode cleaning
1. Rinse with tap water, if crystallization occurs
with hot tap water (> 70C)
2. Soak in cleaning agent for removal of:
Oil, fat:
Alkaline, Alcohol
Lime:
HCL (4%)
Metal hydroxide: HCL (4%)
Cyanide: HCL (4%)
Sulfide:
HCL (4%)+ thiourea (sat.)
Protein:
HCL (4%)+ pepsin (sat.)
Heavy biol. deposit:
HCL (4%)
Silicon:
Acetone
3. Wipe with paper tissue
4. Rinse with tap water

pH

CPA111 + CPM153 or CPM2x3 in

safe area
CCPM
P M 1153
5 2 // CCPM
P M 22x3
x3
Z e ile 1 z e ig t lin k s im m e r d e n
A u s w h lb a re P a r a m e te r w e r d e n in v e rs

pH

M EAS

CA L

DIAG

P A RA M

R e c o rd e r
re m o te
c o n tro l
Pow er
J u n c t io n
box

A c id
B ase
In le t

C PA 111
CYR 10
W a te r
C le a n in g a g e n t

pH

Automatic calibration - TopCal S

CPG 300
Mycom 153

air, water
CPA 471

air
buffer, cleaner
water, air
RS 485
supply

with TOP 68

container with
levelswitches

PA/DP
HART

power

max. 2 m

contol

Buffer 1+2+Cleaner

ISFET

2 add. valves
(optional)

CPS 71

pH applications

pH

Waste Water Treatment Plant

Overview

pH

Application: waste water treatment

Inlet waste water treatment: CPS11+CPM253, CPF81, CPR30

pH

pH-value in the wastewater lines of

the neutralisation basins
Challenge:

Monitoring the pH-value in

the waste water line of the
neutralisation basin

Environment:
Media: neutralised waste
water
Operation: 1 bar abs., max
20C
Meas. range: pH 6...8
Solution:
pH transmitter Liquisys with
pH electrode and flow
Benefit:
assembly electrode (with
pH combination
Product group: Analysis
Industry:

Power

Pt100) simplifies installation

and calibration
Optional contact outputs in
Liquisys for use in control
system
Bypass installation with pH-

pH

Fresh Water Treatment Plant

Overview

pH

pH measurement in tomato
slurry
Challenge:
pH-measurement in product,
no glass wanted
Viscous media
Environment:
Tomato slurry
Solution:
No-glass electrode TopHit
CPS471
Retractable holder CPS475
with special head
Product group:
Analysis
Industry:

Food

Installed at:

Netherlands

Benefit:
Unbreakable sensor (PEEK
100%)
EHEDG certified system

pH

pH measurement in saturation
process / sugar
Challenge:
pH-measurement high
viscous juice
soiling
Environment:
Sugar juice / carbonisation
Solution:
Orbisint CPS11
Retractable holder CPS473
with mechanical scraper and
cleaning flange
Cleaning with condensate
and 2% HCl

Product group:
Analysis
Industry:

Food

Installed at:

Hungary

Benefit:
Less maintenance with
automatic cleaning
Reliable measurement

pH

pH measurement in Saturation
Process

pH

Coal fired power plant

Process
View
power plant

DeNOx
Coal
handling
Steam
turbine

Generat
or

Steam
generator

Water-/steam
system

Electrosta
tic
precipitat
or

Residue
s
disposa
l
Desalinati
on

Cooling system

Desulphurizat
ion

Water
supply
Wastewater
treatment

pH

Flue Gas Desulphurisation in Power

Plant

Product group: Analysis

Industry:

Power

Installed at:

Plant Vresova,
Czech Republic

Challenge:
One of the most important
and decisive criteria for the
quality of flue gas washing
is the pH value of the
washing medium. Hence the
pH value should be closely
monitored.
Environment:
Temp. 5060C, Pressure :
2 bar g, medium : Gypsum
slurry
Solution:
CPS41
CPA 463S
Topcal S
Benefit:
Accurate and reliable pH
measurement
Increased lifetime of the
sensors via a retractable
assembly

pH

Automised pH in flue gas

desulphurization
Process:
gas washing
Process condition:
pH 0,5-0,6; T=75C
continuous measuring
lifetime electrode >4 weeks
Solution:
TopCal with CPS11
CPA463

pH

PuriSys CPF201
for high purity water pH measurement
designed to eliminate difficulties:
- flow sensitivity
- static charge
no electrolyte refill
for power plants, chemical-,
semiconductor-, pharmaceutical
industry

pH

pH measurement in resin
Challenge:
product is mixed with a fix
formulation,
exact dosing of caustic soda is
necessary due to an inconstant
quality of urea.
Product is gelatinizing if pH value is
not in the range of pH 7 0,15

Environment:

Very aggressive and sticky:

formalin, urea, caustic soda,
additives

Solution:
CPC 300, fully automatic
cleaning and calibration system
Cleaning chamber
Hygienic retractable holder
CPA475 with PTFE sealings
Liquid filled electrode CPS41
Benefit:
Cost saving inversion. With
the solution from E+H the
electrode lasts more than 3
months
Less maintenance

Product group: Analysis

Industry:
Industry

Chemical

Installed at:

Dynea, Austria

pH

pH Measurement in TiO2 pulp

Challenge:

The pH measurement in this

TiO2 pulp is decisive for the final
product quality. Highly abrasive
media. Each of the 4 reactors
work with two measuring units.

Environment:

Very corrosive.

Solution:

CPC 300, fully automatic

cleaning and calibration system.

Product group: Analysis

Benefit:
Industry:
Industry

Chemical

Installed at:
Altamira

DuPont,
Plant, Mexiko

Cost saving inversion. With

the solution from E+H the
electrode lasts more than 3
months
Less maintenance
Excellent service from E+H
Mexico

pH

Application: process
Measuring point:
nickel production
pH 7,7 /pH 8,8/ 81-90C / 0,8bar
Nickel precipitation
Nickel ore included also cobald
ore is desolved in H2SO4,
pH value < 3, NiSO4 and CoSO4
first precibitation step: at pH 7,7 cobald hydroxid
pH-value correction with soda ash Na2CO3
second precebitation step: at pH 8,8 nickel hydoxid

Instrumentation:
Liquisys M
CPA 111 with spray head
CPS 41, liquid filled electrode
Cleaning with HCl

pH

Application: process
Measuring point:
floatation cell, copper production
water, solids (40%) copper (7%)
stable pH value
Instrumentation:
TopCal S
CPA463
CPS 41
Advantages/Benefits:
dosing of lime can be
automised because of reliable
pH measurement
increased life time of
electrodes, ~4,5months
cost reduction

Memosens

pH

Todays solution - just working on

symptoms
Use of high sophisticated golden contacts
Use of high impedance material for the plugging
system, esp. round the
contacts (no absorption of water)
Watertight systems
Use of special cables with special isolating material
(no absorption of water)
Use of transmitters with ultra high impedance on
transmitter entrance
Avoid extended cable length
Use of 3- or 4-wire technique for temperature sensors
(esp. Pt 100 and long cables)

Nevertheless moisture is the main

reason for
breakdown of measuring point

pH

MemoSens

MemoSens converts the glass electrode into a digital

sensor
USP !!

contactless transfer of signal

USP !!

pH

MemoSens

r
Ene

fer
s
n
a
r
gy t

Sign

sfer
n
a
r
al t

Cable coupling
Sensor head

primary coil
coupling electronics

secondary coil
sensor electronics

pH

Memosens - electrical advantages

Cable design and attribute does

not affect the measurement
Semiconductor coated cables are not
anymore necessary,cable length is not any
more important

The pH electrode is a welldefined and

complete sensor
The sensor is self-checking, cable attributes
do not affect the sensor checks

pH

Memosens - analog vs. digital

Memosens:
pH signal gets digitised
and transferred contactless

= moisture is
not a
nightmare
anymore!

Standard electrodes:

Low impedance
components

UpH

(caused by moisture) lead to

Electrode with
plug-in head

Cablecoupling

Cable

Transmitter

diminished
electrode slope
because of voltage sharing
with internal resistance of the
electrodes

pH

Memosens - control of data

transmission
Cable pinched off ?
Cable defect ?
Cable disconnected from sensor ?

Standard pH-sensor:
No alarm,
pH-value shows around pH 7 (0mV)
Digital pH-sensor ( Memosens):
Alarm,
measured value is fixed (frozen)

No communication
between sensor and
transmitter results
in an alarm:
automatically !

pH

Memosens - total galvanic

separation
Contactless
coupling with
inductive data and
energy
transmission:
No interference between
potentials of solution and
transmitter

No EMC problems

No potential interference and

measured value shift
No choice symmetric - non
symmetric
No impedance converter
needed

pH

Memosens - sensor with memory

Memosens turns the pH
sensor into a digital
sensor
with integrated memory

pH sensors with Memosens technology store

the actual calibration data as well as other information
used for predictive maintenance eg. overall time in operation, maximum
and minimum pH value, maximum and minimum temperature.

pH

Calibration independent from

measuring point

The result :
A system breakdown caused by a faulty pH sensor is
reduced to the time between recognising and
sensor exchange.

pH sensors
with
Memosens
technology
are the very
first sensors
to allow a
calibration of
the sensor
independent
from the
actual
measuring
point in the
laboratory.

pH

Measurement

Calibration
in the field

Ins
th tall
e s ati
en on
so of
r

Sensor with
Memosens

Disassembly
of the sensor

Standard
sensor

Disassembly
of the sensor

Availability and work

Measurement
Calibration
in the lab
Calibration/adjustment
Storage of sensor data

of
n
tio
la sor
al
st en
In e s
th

Maintenance of the measuring point

QS documentation
Ideal laboratory conditions

Measurement

A measuring point failure is reduced to the space of

time between recognition and exchange of the
sensors.

pH

Memocal T - calibration unit

Based on:
- Liquisys M CPM253
Functionality:
- Measure pH by using digital
sensors
- Wet calibration (digital sensors)
- Numeric calibration (digital
sensors)
Handling:
- Like Liquisys M
Scope of supply:
- Transmitter Memocal T
- 3m CYK10

pH

Portfolio Memosens Functionality

CPS12D

CPS72D
CPS42D

CPS11D

CPS41D

CPS71D

CPS91D

pH

Memosens : what is available ?

New!

Upgrade Kit
for
CPM2x3 and
CPM153

CPS1xD - CPS91D CPS7xD CPS4xD

Liquisys M
CPM223/253 -

CYK10

Memocal T

Mycom S
CPM153 -

pH measurement