Electrochemical Sensing Allows for Precise, Convenient Water Quality Measurements

Measuring and controlling water quality is a key operation in many industrial and environmental
applications. The pH value, for example, is regulated as part of wastewater treatment, and many
industrial processes are pH dependent. pH is also important in the food industry, as it plays a role in the
taste and the preservation of food. Conductivity is another important parameter: The electrical
conductivity of a sample can determine concentration of solutions, detect contaminants, and determine
the purity of the liquids.

Although a variety of techniques can be used to measure pH and conductivity, many of these require
expensive equipment or must be performed in a laboratory environment. Many important liquid
analyses rely on electrochemistry, a branch of chemistry that characterizes the behavior of reduction-
oxidation (redox) reactions by measuring the transfer of electrons from one reactant to another.

Electrochemical (EC) sensors use this principle to provide a quick, convenient and low-cost means of
measuring water quality. As part of their “Circuits from The Lab” portfolio, Analog Devices offers
reference designs that use EC sensors in conjunction with a variety of ADI components to address water
quality measurement challenges. Each one comes with design and integration files, factory-tested
evaluation hardware, and a comprehensive documentation package; click on the appropriate link for
more information or visit the Analog Devices website.

This article will cover the principle operation of electrochemical sensors used to measure water quality,
discuss interface design challenges and solutions, and review several Analog Devices reference designs
developed specifically for these applications.

Fundamentals of pH Measurements
The pH value is a measure of the relative amount of hydrogen (H+) and hydroxide ions (HO) in an
aqueous solution. Pure water at 25°C contains 1 × 10−7 moles/liter of hydrogen ions; this is a neutral
solution with pH = 7. pH and is defined as follows:

pH = -log10(H+)

Therefore, if the hydrogen ion concentration is 1.0 × 10−2 moles/liter, the pH is 2.00 and the solution is
a strong acid.
 Figure 1: Principle of operation of a pH probe
(Source: biologydiscussion.com)

A pH probe is an EC sensor that typically consists of a glass measuring electrode and a reference
electrode; its operation is analogous to that of a battery.

When the probe is placed in a solution, the glass measuring electrode generates a voltage relative to the
reference electrode that is a function of hydrogen activity of the solution. As the solution becomes more
acidic (lower pH), the glass electrode becomes more positive compared to the reference electrode.
Conversely, as the solution becomes more alkaline (higher pH), the potential of the glass electrode
becomes more negative compared to the reference electrode.

The voltages produced are very small, in the millivolt range. A typical pH probe ideally produces ±59.154
mV/pH units at 25°C. This is expressed in the Nernst equation as follows:
2.303𝑅(𝑇 + 273.1)
𝐸 =𝑎− 𝑥 (𝑝𝐻 − 𝑝𝐻𝐼𝑆𝑂 )
𝑛𝐹
where:

E is the voltage of the hydrogen electrode with unknown activity.

a = ±30 mV, zero-point tolerance.
T is the ambient temperature in °C.
n = 1 at 25°C, valence (number of charges on ion).
F = 96485 coulombs/mol, the Faraday constant.
R = 8.314 volt-coulombs/°K mol, the ideal gas constant.
pH is the hydrogen ion concentration of the unknown solution.
pHISO is the reference hydrogen ion concentration. Consult the probe documentation. Typical pHISO = 7.
The voltage generated is dependent on the acidity or alkalinity of the solution and varies with the
hydrogen ion activity in a known manner. Ideally electrodes with a pHISO of 7 are designed to produce a
zero volt potential when placed in a buffer solution with a pH of 7.

Design considerations for the pH interface

Figure 2: pH sensor front-end buffer interface to ADC

(Source: Analog Devices)

The glass electrode of a typical pH probe has an extremely high resistance from 1 MΩ to 1 GΩ that acts
as a resistance in series with the pH voltage source VOUT. The buffer amplifier bias current IBIAS flowing
through this series resistance introduces an offset error in the system. To isolate the circuit from this
high source resistance and minimize the offset error, a buffer amplifier with high input impedance and
very low input bias current is needed.

Figure 2 shows a pH sensor interface using an AD8603: a MicroPower precision single CMOS op amp
that features low-noise performance, rail-to-rail input and output (RRIO), and a maximum input bias
current of 1pA. The AD8603 drives an AD7793 3-channel, low noise, low power, 24-bit sigma-delta (Σ-Δ)
analog to digital converter (ADC).

Note the use of coaxial cables between the pH sensor and the AD8603 to reduce the effects of external
noise.

The voltage output also depends on temperature of the solution since a change in temperature changes
the activity of the hydrogen ions. A temperature increase will increase the potential difference across
the two electrodes; a decrease will have the opposite effect, so the pH interface circuit must include
temperature compensation.

ADI reference designs for pH measurements

Analog Devices has several reference designs that address the issues associated with pH measurement.
CN-0326, for example, is an isolated low-power pH sensor signal conditioner and digitizer reference
design.
Figure 3: CN-0326 is a pH measurement reference design that includes temperature compensation and
an isolated interface
(Source: Analog Devices)

The circuit (Figure 3) uses the pH interface described above and includes temperature compensation via
a Pt1000 resistance-temperature device (RTD). Isolation of signal and power is provided by an
ADUM5401 quad-channel digital isolator; isolation gives immunity to noise and transient voltages that
are often encountered in industrial environments.

The design gives 0.5% accurate readings for pH values from 0 to 14 with greater than 14-bits of noise-
free code resolution and is suitable for a variety of industrial applications such as chemical, food
processing, water, and wastewater analysis.

Soil pH and moisture measurements: a complete solution

Agriculture is another industry where control of pH is key to success. Plants vary widely in their
tolerance to soil acidity and alkalinity; some plants grow well over a wide pH range, while others are
very sensitive to small variations. Measuring and controlling pH allow farmers to optimize the soil acidity
and alkalinity for a particular crop.

The soil water content is another important factor affecting crop growth and yield. Monitoring soil
moisture content helps determine when to irrigate, how much water to apply, when to conserve water,
track trends in soil moisture content with time, and other metrics.

Reference design CN-0398 is designed for these agricultural water quality applications. It is a single-
supply, low power, high precision complete solution for pH and soil moisture measurements; CN-0398
also includes temperature compensation since temperature greatly affects the measurement from the
pH probe.
 Figure 4: Reference design CN-0398 is optimized for soil measurement applications requiring pH
(Image source: Analog Devices)

The reference design (Figure 4) contains three independent analog measurement front ends for pH, soil
moisture, and temperature utilizing a single AD7124-8 24-bit, Σ-Δ, analog-to-digital converter (ADC). The
AD7124-8 is a low power, low noise, integrated analog front end for high precision measurement
applications; the device includes multiple gain stages to accommodate signals of small amplitude, as
well as precision current excitation sources. The CN-0398 PCB is designed in the Arduino Shield form
factor, making prototyping of these types of simple easy.

Fundamentals of conductivity measurements

Pure distilled water is an insulator, but typical water sources are conductive as they contain dissolved
mineral salts of elements such as sodium, calcium and magnesium. These salts produce free ions that
are capable of passing electrical current. A high conductivity correlates to a high level of TDS (total
dissolved solids); a high TDS level renders water less suitable for industrial processes, irrigation, and
drinking.
 Figure 5: The principle of operation of a conductivity cell; 2- and 4-pole versions
(Source: Analog Devices)

A conductivity cell (Figure 5) determines the conductivity of water by measuring the resistance between
two immersed electrodes. The simplest version consists of two conductivity electrodes, also referred to
as poles. An alternating signal applied to one of the conductivity electrodes causes the ions in the
solution to migrate towards the other electrode. The more ions in the solution, the greater the current
which flows between the conductivity electrodes. The interface design measures the current produced
by the conductivity cell and uses Ohm's law to calculate the conductance of the solution and hence the
conductivity.

There are two types of electrode configurations; the 2-pole cell which was described above and a 4-pole
cell. The extra poles helps eliminate errors introduced by polarization of the electrodes and field effects
that can interfere with the measurement. The actual arrangements of the electrodes can be that of
parallel rings, coaxial conductors, or others, rather than the simple parallel plates shown in Figure 5.

Typical materials for conductivity cell electrodes include Type 316 stainless steel, titanium palladium
alloy, or graphite; cells are specifically sized and spaced to provide a known cell constant (K). The cell
constant for a 2-pole cell typically ranges from approximately 0.1/cm to 1/cm; a 4-pole cell typically
offers values ranging from 1/cm to 10/cm. The 2-pole sensor is more suitable for low conductivity
measurements, such as purified water, and various biological and pharmaceutical liquids. The 4-pole
sensor is more suitable for high conductivity measurements, such as industrial wastewater or seawater
analysis.

Design considerations for the conductivity cell interface

As shown in Figure 6, water samples can have a wide range of conductivities, so cell constants must be
matched to the analyzer for a given application. A measuring instrument can operate over the same
range of cell resistance for both ultra- pure water and high conductivity seawater by using cells with
different cell constants.
 Figure 6: The conductivity of a water sample can cover a wide range
(Source: Fondriest.com)

Like pH, conductivity is highly temperature-dependent, so temperature compensation must be included

in the design. Solution temperature coefficients are non-linear and can vary from 1%/°C to 3%/°C or
more, so calibration at the actual measuring temperature yields the best accuracy.

ADI reference designs for conductivity measurements

Reference design CN-0349 is a fully isolated data acquisition system for conductivity measurement. The
design is optimized for low cost and high precision: the circuit has a total error of less than 1% Full Scale
Range after calibration. The small footprint with only five active devices makes CN-0349 ideal for space-
constrained applications. The digital output of the circuit is fully isolated to eliminate ground loop
interference.
 Figure 7: CN-0349 has four functional blocks: (1) impedance to digital converter; (2) programmable
feedback & calibration; (3) isolated serial data; (4) isolated power
(Source: Analog Devices)

Figure 7 shows the simplified block diagram of the CN-0349 reference design. The AD5934 12-bit
impedance-to-digital converter, the ADG715 octal SPST switch, and the two resistor blocks make up
blocks 1 and 2 and form the heart of the circuit, allowing the design to accommodate a wide range of
conductivity cells and digitize the outputs. Functional blocks 3 and 4 can be omitted if isolation is not
required.

The design gives accurate conductivity measurements, extending from the low μS range to several
hundred mS, and it also optimizes the overall accuracy of the AD5934 over a wide range of admittances.
Temperature measurement using a Pt100 resistance temperature detector (RTD) is also incorporated.
The circuit can be connected to an evaluation microprocessor board using the 8-pin IMOD (I2C interface)
connector for rapid prototyping.

Microcontroller reference designs for conductivity applications

CN-0349 is designed to be used with an external microcontroller (MCU), but other reference designs
integrate MCUs with specialized analog front ends (AFEs) that allow them to accommodate water-
quality measurement applications with fewer components.
 Figure 8: CN-0428 block diagram
(Image source: Analog Devices)

Reference design CN-0428, shown in Figure 8, implements a complete water quality measurement
system using an LTC6078 op amp as the front-end buffer. With up to four channels, the system can
perform multiple water quality measurements, such as conductivity, pH, and oxidation reduction
needed for different water quality applications.

The ADuCM355, a precision analog Arm Cortex-M3 microcontroller with an integrated EC sensor
interface, is at the heart of the reference design. The ADuCM355 peripheral set is optimized for EC
sensor applications which includes specialized functions such as an analog hardware accelerator, and
two bias potentiostat and TIA amplifiers.

Reference design CN-0359 is a self-contained design for conductivity measurement. This design is based
around the ADuCM360 low-power precision analog MCU. The ADuCM360 utilizes an ARM cortex M3; its
feature set includes with dual 24-bit Σ-Δ ADCs with programmable gain amplifiers (PGA) capable of
simultaneous sampling, programmable current sources for sensor excitation, and a 12-bit voltage output
DAC for system biasing.

CN-0359 features automatic detection of either 100 Ω or 1000 Ω platinum (Pt) resistance temperature
devices (RTDs), allowing conductivity measurements to be temperature compensated. The system also
accommodates 2- or 4-wire conductivity cells, and 2-, 3-, or 4-wire RTDs for added accuracy and
flexibility.
 Figure 9: The CN-0359 evaluation board includes an LCD display
(Image source: Analog Devices)

Conclusion
Electrochemical sensors provide a convenient and low-cost method of measuring various water quality
parameters, but it can be challenging to design a precision measurement circuit. Analog Devices offers a
range of EC reference designs and modular systems, complete with reference design boards, open
source software, and comprehensive documentation that simplifies this task.