Theory of Liquid Measurements

Conductivity/Resistivity pH ORP

THORNTON / METTLER TOLEDO

Ionic Conductance
~

H+

O H

Na+

O H H

Cl-

THORNTON / METTLER TOLEDO

Cell Constant

1 cm

1 cm 1 cm

Conductivity Cell Constant =

Length Area

1 cm 1 cm2

= 1 cm-1

THORNTON / METTLER TOLEDO

Other Cell Constants

1cm 0.1cm 1cm

1cm 10cm 1cm

0.1constant

10.0constant

Cell Constant = Multiplier

THORNTON / METTLER TOLEDO

Resistivity/Conductivity Cell
Concentric Electrodes

OUTER ELECTRODE

INNER ELECTRODE

INSULATOR

THORNTON / METTLER TOLEDO

Units of Conductivity/Resistivity
Resistance Conductance Resistivity ohm mho, siemens = 1/ohm ohm-cm, megohm-cm, M-cm mho/cm, mho/cm siemens/cm, microsiemens/cm, S/cm
THORNTON / METTLER TOLEDO

Conductivity

Units of Conductivity/Resistivity
Industry Preferences:
Resistivity - Semiconductor ultrapure water Conductivity - Power, Pharmaceutical, Pretreatment stages, Cooling towers, Wastewater Total Dissolved Solids (ppm TDS)

THORNTON / METTLER TOLEDO

Cell Constant Traceability

ASTM D1125 Primary Standard and Pure Water at 15, 25, 40C

Standards Lab Cell Constant

Production Cell Constant

THORNTON / METTLER TOLEDO

Ultrapure Water Sensor Calibration/ Certification System

Thornton Inc.

THORNTON / METTLER TOLEDO

Conductivity, Resistivity, TDS Ranges

Resistivity 100M 10M 1M 100K 10K 1K 100 10 1 ohm-cm Ultrapure water Deionized water Distilled water Condensate Drinking water Cooling tower water Percentage of acids, bases and salt Waste water Brackish water, Sea water Water for Industrial Process 5% Salinity 2% NaOH 20% HCl Conductivity TDS 0.01 .1 0.021 1 0.4 10 4.6 100 46 1000 460 10k 4.6k 100k 1000k S-cm ppm

Conductivity and resistivity are measured at 25C; TDS is expressed as Sodium Chloride (NaCl)

THORNTON / METTLER TOLEDO

On-Line Conductivity Sensor Calibration/Verification

on-line instrument

in-line cell Process flow sample take-off calibrated reference instrument

factory-certified reference cell 200-500 mL/min sample flow flow chamber

to drain

THORNTON / METTLER TOLEDO

Temperature Effects on Conductivity

H+ O H H

Na+

Cl-

THORNTON / METTLER TOLEDO

Conductivity/Resistivity Temperature Coefficients

Natural waters, etc. (>2 S/cm)

~ 2 %/C

High purity water (0.055 S/cm or 18.2 Megohm-cm) 4 - 7 %/C

THORNTON / METTLER TOLEDO

Dissociation of Water
H+ H+ O2O2H+ H+

H2O

H+ + OHTHORNTON / METTLER TOLEDO

Conductivity of Pure Water vs. Temperature

Resistivity (M -cm) Conductivity (S/cm)

100

0.01

10

0.1

1 0 10 20 30 40 50 60 70 80 90

1 100

Temperature (C)
THORNTON / METTLER TOLEDO

Conductivity vs. Temperature

10.00
NaCl Concentration
4390 ppb

C onductivity (S/cm)

1730 ppb

1.00
840 ppb 395 ppb 129 ppb

0.10
40 ppb

0 ppb

0.01
0 10 20 30 40 50 60 70 80 90 100

Temperature (C)

THORNTON / METTLER TOLEDO

Temperature Compensation
Standard -- high purity water with mineral contamination Linear, %/C -- special applications with known coefficient Cation/Ammonia/ETA -- power plant cycle chemistry and semiconductor acid etch rinse operations Alcohol -- special semiconductor rinse operations Glycol -- semiconductor coolant monitoring Light 84 -- same as Standard but with 1984 pure water data
(reads slightly higher resistivity)

Direct % Concentration Readout of HCl, H2SO4, NaOH automatically selects appropriate compensation

THORNTON / METTLER TOLEDO

Cell Installation
Recommended Cell Installation...
OUTLET

INLET

Flow should be directed at the end of the sensor

THORNTON / METTLER TOLEDO

High Conductivity Measurements

Applications
Reverse Osmosis feedwater Acid/Base deionizer regenerant concentration Process fluids Recycle water Wastewater/effluent Cooling towers

Conductivity Measurement Technologies

Two-electrode contact Four-electrode contact Inductive (non-contact, electrodeless, toroidal)

THORNTON / METTLER TOLEDO

Conductivity vs. Concentration

0.9 0.8

0.7

HCl

H2SO4

Conductivity (S/cm)

0.6

0.5

0.4

NaOH

0.3

0.2

NaCl
0.1

0 0 10 20 30 40 50 60 70 80 90 100

Concentration (% by weight)
THORNTON / METTLER TOLEDO

Two-Electrode Conductivity Measurement

50/cm Constant Cell

Graphite Electrodes

Bottom view

THORNTON / METTLER TOLEDO

Two-Electrode Conductivity Measurement

10/cm Constant Cell

Sheath Slot RTD

Graphite Electrodes

Bottom view

THORNTON / METTLER TOLEDO

Four-Electrode Conductivity Measurement

AC Current Source

Four-Electrode Measuring Instrument

AC Voltage Measurement

Measuring Electrodes

Four Electrode Sensor

Drive Electrodes
THORNTON / METTLER TOLEDO

Four-Electrode Conductivity Measurement

Four-electrode sensors and instruments can tolerate poor measuring conditions due to three factors:
1. Electrode metal surface condition is less important. 2. Electrode fouling or coating has much less effect. 3. Four-electrode sensors do not have the narrow channels of high, two-electrode cell constants. The resulting flat surface design is much less vulnerable to fouling.
THORNTON / METTLER TOLEDO

Inductive Conductivity Measurement

Energized

Measured

Inductive (non-contact, electrodeless, toroidal) Conductivity Sensor

THORNTON / METTLER TOLEDO

Inductive Conductivity Measurement

Virtually non-fouling No metal/solution contact Reliable high conductivity measurements Relatively large sensor size Cell constant can be affected by surrounding pipe

THORNTON / METTLER TOLEDO

pH Range

THORNTON / METTLER TOLEDO

pH Measurement
Dissociation of water

H2O

H+ + OH-

Kw =

[H+] [OH-]

THORNTON / METTLER TOLEDO

pH Scale
pH ~ -log10 [H+] [H+] ~ 10-pH

0 1

3 4 5

6 7

8 9 10 11 12 13 14 pH [H+] [OH+]

10-0 10-1 10-2 10-3 10-4 10-5 10-6 10-7 10-8 10-9 10-10 10-1110-1210-1310-14

10-14 10-13 10-12 10-1110-10 10-9 10-8 10-7 10-6 10-5 10-4 10-3 10-2 10-1 10-0

at 25C

THORNTON / METTLER TOLEDO

Conductivity vs pH

Conductivity

Acid

Base

0.055 S/cm 18.2 M-cm 7

pH
THORNTON / METTLER TOLEDO

Conductivity vs pH

THORNTON / METTLER TOLEDO

pH vs. Temperature for Pure Waters

11 10 9

pH
8 7 6 0 10 20 30 40

0.5 ppm NH3

Pure Water

50

60

70

80

90

100

Temperature (C)

THORNTON / METTLER TOLEDO

pH Electrode System
Glass pH Reference Temperature Compensator To Measuring Circuit

THORNTON / METTLER TOLEDO

Combination pH Electrode

Electrolyte

RTD (insulated)

Reference junction

Measuring membrane

THORNTON / METTLER TOLEDO

pH Electrode Output
25C 50C 100C 0C

400 200

mV

-200

-400

9 10 11 12 13 14

pH

THORNTON / METTLER TOLEDO

pH Temperature Compensation

Adder (standardize offset, asymmetry) Multiplier (slope)

Solution Temperature Coefficient

Electrode mV Temperature

Nernst Electrode Temperature Compensation

pHT

Solution Temperature Compensation

pH25C

THORNTON / METTLER TOLEDO

Detachable pH Electrode System

VP Preamplifier

VP pH Electrode

Housing

THORNTON / METTLER TOLEDO

High Purity pH Sensor Assembly

Preamp Electrolyte Reservoir to Instrument

Combination pH Electrode Buffer solution Calibration Funnel 3-way Valve Sample Inlet to drain RTD

THORNTON / METTLER TOLEDO

pH Standards
NIST standards--materials to make up buffers at: 1.681, 3.557, 4.006, 6.863, 7.41, 9.180, 10.011, 12.46 pH Commercial standard buffer solutions
NIST recipes Integral pH values

Have unique temperature dependence

THORNTON / METTLER TOLEDO

High Purity pH Measurement Equipment

Low volume, stainless steel flow chamber Low sample flowrate with atmospheric discharge Flowing junction reference electrode Solution temperature compensation as well as electrode temperature compensation Convenient disabling of Solution temperature compensation during buffer calibration NIST-traceable buffer solutions

THORNTON / METTLER TOLEDO

ORP:
Oxidation-Reduction (redox) Potential Oxidation-reduction chemical reactions
Oxidationloss of electrons, higher potential Reductiongain of electrons, reduced potential

Examples
Chlorine, ozone, permanganate can oxidize organics (color, odor, bacteria) Bisulfite or carbon beds can reduce chlorine (protect RO membranes & DI resins); Hydrazine can reduce oxygen

ORP monitors the status of these reactions

THORNTON / METTLER TOLEDO

ORP Response to Dechlorination

THORNTON / METTLER TOLEDO

ORP Electrode System

To Measuring Circuit

Measuring

Reference

Platinum Disk

Reference Junction

THORNTON / METTLER TOLEDO