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
Reference
electrode
electrode

3 mol KCl
+
Internal buffer 3 mol
KCl

Glass membrane Diaphragm

pH

Two half cells make one combination electrode

pH

Working principle of the glass membrane

Glass membrane
thickness: Gel layer:
0.2-0.5 mm 0,0001 mm

Acid Internal Alkaline

buffer solution
solution + - pH > 7
pH < 7 + pH 7 -
+
H+
+ - 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
59,16 mV/pH
Slopeat 25 °C
74,04
59,16mV/pH
mV at at 25
1000C
°C
pH

pH calibration

+ mV

Zero C02
Slope

9,2

pH
4 7 9,2 Alkaline buffer
changes the
pH value !
Acid error
Alkali error

- mV
pH

Types of diaphragms
Ceramic:
fast response
soiling sensitive
biocompatible

Open arperture:
very fast response
soiling sensitive
danger of poisoning

PTFE:
Liquid junction via Very robust
the diaphragm of slow response
the dirt repellent
pH electrode
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 G
Drain
S D - - -

Glass

H+

H+

H+
pH

IsFET-sensors

How it works:
Gate insulator:
Thickness: about 0,1 µm Reference system
Material: Ta2O5 (Tantalum
oxide)

H+
H+ H+

The insulator is an amphoteric material

IsFET - - - (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
IsFETs are following through the
insulator, it is just an electrostatic
the NERNSTs law!
effect.
pH

IsFet electrodes

 Restricted life time in hot alkaline

 safety: unbreakable

 wider application range:

- higher amounts of solvents
- fast response at low temperatures
 lower acidic and alcaline errors
pH

Fast response time of IsFET electrode

9.0

8.5

8.0

7.5

7.0
- 20 °C
pH

- 20 °C
6.5
CPS401
IsFET B2ESB1A1
electrode
6.0 glass
pH - electrode
Glass - Electrode

5.5

5.0
0 2 4 6 8 10 12 14 16 18 20

Time/min
pH instrumentation
pH

The new pH sensor family

Glass pH-electrodes

OrbiSint CeraGel OrbiPore CeraLiquid

CPS 11/ CPS11D CPS 71/CPS71D CPS 91/CPS91D CPS 41/CPS41D

Non-glass electrodes

TopHit TopHit TopHit

CPS 471 CPS 491 CPS 441

food/ chemical/ chemical/food/

Application environmental
pharma environmental pharma
pH

Sensor segmentation
CPS 11/CPS11D CPS 71/CPS71D CPS 91/CPS91D CPS 41/ CPSD

CPS 471 CPS 491 CPS 441

 ceramic  open  ceramic

 teflon diaphragm diaphragm diaphragm diaphragm

 double gel  double chamber-  double gel  liquid-

reference reference

 long-term  hygienic and  highest

sterile applications  media with strong
check of stable changing compositions accuracy
processes  poisoning media  ultrapure water
 suspensions
 emulsions  extremely
blocking media
 precipitations

 environmental  food / pharma  chemical,  chemical,

 environmental  food, pharma
pH

Mounting options

Immersion mounting

Pipe- or tank-
mounting
Flow through

Flow through
pH

The Cleanfit family

CPA 471 / 472 CPA473 / 474 CPA475

selfsealing via ball valve sealing selfsealing via

electrode lift tube to process electrode lift tube
standard application  harsh process hygienic application
application
pH

Electrode protection

CPA 471 / 472 CPA 475 CPA 473 CPA 474

inside and outside hygienic form open stable

O-ring sealing protection guard polymer guard

best results in EHEDG certified best result for aggressive and

non abrasive media cleanability 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
pH

Liquiline M CM42 - Measuring Parameters

conductivity
pH and redox resistivity dissolved oxygen
concentration

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 (> 70°C)

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

153 // CPM
CPM 152 CPM 2x3
2x3
Ze ile 1 zeigt links imm e r d en
Auswählba re Param ete r werden invers

pH

MEAS CA L

DI AG PARAM

Recorder

remote
control
Power
Junction
box

Acid
Base CPA 111
Inlet CYR 10

Water

Cleaning agent
pH

Automatic calibration - TopCal S

CPG 300

Mycom 153
air, water

air CPA 471

buffer, cleaner
water, air

RS 485
supply

with TOP 68
contol

max. 2 m
container with ISFET CPS 71

PA/DP levelswitches
HART
2 add. valves
(optional)
Buffer 1+2+Cleaner
power
pH applications
pH

Waste Water Treatment Plant Overview

pH

Application: waste water treatment

Inlet waste water treatment: CPS11+CPM253, CPF81, CPR´30

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 20°C
 Meas. range: pH 6...8

Solution:
 pH transmitter Liquisys with pH
electrode and flow assembly

Benefit:
• pH combination electrode (with
Pt100) simplifies installation and
Product group: Analysis calibration
• Optional contact outputs in
Industry: Power
Liquisys for use in control system
• Bypass installation with pH-
assembly
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 Benefit:

• Unbreakable sensor (PEEK 100%)
Industry: Food
• EHEDG certified system
Installed at: Netherlands
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 Benefit:
• Less maintenance with automatic
Industry: Food
cleaning
Installed at: Hungary • Reliable measurement
pH

pH measurement in Saturation Process

pH

Coal fired power plant

Process

View
DeNOx power plant

Coal handling
Steam
generator Electrostatic Desulphurization
Steam turbine precipitator

Generator

Water-/steam system
Residues
disposal

Desalinatio
n
Water
supply

Wastewater
Cooling system treatment
pH

Flue Gas Desulphurisation in Power Plant

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. 50…60°C, Pressure : 2 bar
g, medium : Gypsum slurry
Solution:
 CPS41
 CPA 463S
 Topcal S

Product group: Analysis Benefit:

• Accurate and reliable pH
Industry: Power
measurement
Installed at: Plant Vresova, • Increased lifetime of the sensors
Czech Republic via a retractable assembly
pH

Automised pH in flue gas desulphurization

Process:
• gas washing
Process condition:
• pH 0,5-0,6; T=75°C
• 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

Product group: Analysis Benefit:

• Cost saving inversion. With the
Industry: Chemical Industry solution from E+H the electrode lasts
more than 3 months
• Less maintenance
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:

• Cost saving inversion. With the
Industry: Chemical Industry solution from E+H the electrode lasts
more than 3 months
Installed at: DuPont, Altamira • Less maintenance
Plant, Mexiko • Excellent service from E+H Mexico
pH

Application: process

Measuring point:
 nickel production
 pH 7,7 /pH 8,8/ 81-90°C / 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

Today´s 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

Cable coupling

Sensor head

primary coil secondary coil

coupling electronics 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 well-defined

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:

UpH
Low impedance
components (caused by
moisture) lead to
diminished
Electrode with
plug-in head
Cable-
coupling
Cable Transmitter
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

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

Availability and work

of the sensor

of the sensor
Standard Sensor with

Disassembly

Disassembly
sensor Memosens

Measurement Calibration Measurement

in the field

Calibration
in the lab
 Calibration/adjustment
 Storage of sensor data
 QS documentation
 Ideal laboratory conditions

Maintenance of the measuring point 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 ?

Upgrade Kit for

CPM2x3 and Liquisys M
CPM153 CPM223/253 -

New!
+ +

CPS1xD - CPS91D -
CPS7xD – CPS4xD CYK10
Mycom S
CPM153 -

Memocal T
pH measurement