pH Control

Systems for pH control are characterized by extreme rangeability and sensitivity, and are also subject
to difficulties arising from contact between measuring electrodes and hostile fluids. Case histories of
representative installations show that success in implementing these control systems depends not only
on assessing the complexity of the loop and selecting a control strategy but also on recognizing and
avoiding pitfalls while specifying and installing instrumentation, equipment and piping. Read more
about it in the article below.

Why is pH control a problem?

Why is pH control a problem? After all, you've got an odd but simple scale of measurement from 0 to
14 dimensionless units, measuring electrodes that have been around long enough to be well
understood and readily applied, and instrument vendors who must have seen every possible
application by now.

Rangeability and Sensitivity

One basic source of difficulty is that - as countless articles, technical papers, and textbooks point out -
the pH scale corresponds to hydrogen ion concentrations from 100 to 10-14 moles per liter. No other
common measurement covers such a tremendous range. Another intrinsic constraint is that measuring
electrodes can respond to changes as small as 0.001 pH, so instruments can track hydrogen ion
concentration changes as small as 5x10-10 moles per liter at 7 pH. No other common measurement
has such tremendous sensitivity.

The implications of such great rangeability and sensitivity can be illustrated by considering a
continuous feedback neutralization system for a strong acid and a strong base. The reagent flow
should essentially be proportional to the difference between the hydrogen ion concentration of the
process fluid and the setpoint. A reagent control valve must therefore have a rangeability greater than
10,000,000:1 for a setpoint of 7 pH when the incoming stream fluctuates between 0 and 7 pH.
Moreover, uncertainties in the control valve stroke translate directly into pH errors, such that
hysteresis of only 0.00005% can cause an offset of 1 pH for a 7 pH setpoint.

The situation is like playing golf. The distance from the tee to the green represents rangeability and
the ratio of the hole diameter to this distance is analogous to sensitivity. For an application requiring a
strong base to neutralize a strong acid or vice versa, the tee would be about 1,000,000 yards from the
green and the hole would be about 3-1/2 inches in diameter. A hole-in-one is impossible. And using
the same size control valve at each stage would be like hiring a gorilla to drive the ball to the green in
one stroke, then finding that it tends to overshoot the hole on the putt.

How is it even possible to control a process under these conditions? Rangeability and sensitivity
limitations can be overcome by approaching the setpoint in stages, using successively smaller control
valves with high performance positioners.

The real world

A host of other constraints adds to the difficulties of pH control. These range from the necessity of
wetting the electrodes - with consequent susceptibility to leakage and attack by the fluid, to long
delays introduced by the need to mix large volumes of process material with small amounts of
reagent. Even with a good understanding of measurement and control concepts, these real-world
effects introduce an element of magical mystery into pH.

Typical problems in controlling pH

No pH complications are really typical. And the systems that are easy to implement don't get referred
back to those of us whom InTech refers to as the noodnicks from Central Engineering. But the
installations I will describe are typical of those I have encountered recently, and illustrate the types of
problems that you can expect.

To avoid arguments with our Legal Department about proprietary information, I will not mention any
places or names; I'd even prefer that you forget my name when you finish reading. Also, to help guide
you through my tribulations, and those you will encounter yourselves, I've prepared Table I,
enumerating what you can think of as the Facts of Life. Commit this Table to memory; you'll be
quizzed on it in the morning.

Where's the tank?

An application involved a strong acid waste flow, to be neutralized by a strong basic reagent. It was
called in because the pH was swinging from 0 to 14 despite efforts to tune the controllers, manually
manipulate the reagent, and regulate the influent flow. When I got to the plant, I gazed over the
horizon and didn't see any tanks. I suddenly realized that I had a major problem.

Figure 1a shows the original control system. This used a ratio controller to proportion reagent to acid
waste flow upstream of an in-line mixer. A separate pH controller was used in a loop on a sump. The
system designers did not realize that the flow measurement error and the flow control valve hysteresis
must both be less than 0.00005% to stay within 1 pH of the 7 pH setpoint. They assumed that
disturbances would be small since the change in waste composition was slow and its flow was fixed by
a controller. The design team did not know Fact of Life #1.

A system involving a strong acid and a strong base normally requires three stages of control to hold a
solution within 1 pH of 7 pH (Ref 1). Since cost was stressed as a factor, I kept the existing mixer and
sump as one stage and added two vertical well-mixed tanks downstream for the second and third
stages. Further, I agreed to not install controls on the third stage until the need was demonstrated.
The third stage volume therefore served as a filter for the oscillation from the second stage.

For the first stage of control, we started by replacing the ratio flow system with a fast inline pH loop.
This received a remote setpoint from a second pH controller on the sump. The fast in-line loop would
initiate the correction and depend on the sump volume to average out hydrogen ion concentration
deviations. Linear control system analysis predicted that this combination would be as effective as a
single well-mixed vertical tank. It didn't work. Dynamic simulation showed that the in-line loop would
oscillate between 0 and 14 pH for all controller settings. A plant test confirmed the result.

At first, I thought the sump was somehow not providing the anticipated filtering. Then I remembered
Fact of Life #2. The filter was acting on hydrogen ion concentration, not pH. The sump was
attenuating concentration oscillations by a factor of 100, but is corresponded to a decrease of only 2
pH. Attenuation was improved by reducing the distance from the mixer to the control valve and
electrodes so the oscillation was faster.

The second state had a notch-gain pH controller was an output that provided a pulse frequency
proportional to an analog signal. Above 25% controller output, the valve was throttled normally;
below 25%, valve rangeability was extended using pulse frequency or interval control.
 FIGURE 1. Where's
the tank? (a)-unsuccessful and (b)-successful pH control systems for a continuous neutralization
process initially having no mixing tank.

Figure 1b shows the upgraded installation. This system could keep pH within the desired offset band
at the outlet of the third stage. However, the sump controller was difficult to tune and recovery from
startup or waste flow controller setpoint change was slow.

If I were designing this system today, I would place a feedforward loop on the sump and would install
controls on the third stage. I would also characterize the feedforward and feedback signals. The
characterization would involve calculating reagent demand from the pH measurement using the
titration curve, and using the result as the control command. This would reduce nonlinearity, recovery
time, sensitivity, and tuning difficulty. Microprocessor-based controllers can provide the necessary
calculation accuracy and ease of implementation.

As with any new system, startup was not without bugs. Some were of the common garden variety -
like transposed wires and incorrectly calibrated positioners. Others were of the magical mystery type
peculiar to pH systems.

For example, at high pH levels, the measurement went downscale as the strong base reagent flow
increased. As you can imagine, this drove the control system - and us - kind of crazy. The difficulty
turned out to be that the measuring electrodes in the in-line loop were not specified with high-pH
glass. Normally this would cause the measurement to read low by about 1 pH at the upper end of the
scale. In our case, it caused a reversed response. This performance was confirmed by the vendor, and
was corrected by replacing the electrodes with low sodium ion error devices.

Another magical mystery effect was that the electrode response for the well mixed tank became
erratic. We found water on the terminals inside the submersion assembly. The vendor told us if we
bought an assembly that cost twice as much, the leakage would stop. We did; it didn't. The vendor
then told us to buy a newly developed assembly, for four times the price of the original and the
leakage would surely stop. Rather than make the same mistake three times, I shopped around and
found a throwaway electrode assembly completely encapsulated in plastic - at half the price of the
original. It worked like a charm. A similar experience with a submersion assembly from another
vendor led me to Fact of Life #3.

Where's the valve?

Another application required small quantities of a highly concentrated viscous reagent for continuous
neutralization of a waste stream. The control system was so slow that disturbances passed through
the plant long before any corrective action took effect; further, the pH trend recording had a noise
band that far exceeded the allowable setpoint offset. When I inspected the system, I stood near the
injection point at the inlet to the pipeline mixer, scanned the horizon and didn't see any reagent
control valve. I quickly deduced I had a major problem. Figure 2a shows what I

found. FIGURE 2.
Where's the valve? (a)-unsuccessful and (b)-successful pH control systems for a process involving a
highly viscous concentrated reagent.

Can you spot a control problem exclusive of the pH loop in this figure? The sump level controller sets
the flow in the upper outlet branch. The mixer flow controller simultaneously manipulates the valve in
the lower branch to keep a constant flow out of the sump. The system is obviously overcontrolled. We
got out of this mess by cascading the level controller output to flow controller setpoint.

Now for the pH loop. The reagent was being injected into the pipeline under the control of a positive
displacement metering pump. The pump was about 300 feet away from the mixer. This distance
caused a delay when the pump was activated - because process fluid would backfill the injection
piping and had to be pushed out of the line before any reagent could be delivered. It doesn't take
much fancy mathematics to figure that at one gallon per hour, it takes an hour to push a gallon
through a pipe. This led to Fact of Life #4. We also found a delay when the speed of the pump
changed, but never really identified the cause. We would have blamed it on air pockets, if there had
been any. The answer probably lies in the ketchup bottle - related to low flow of viscous fluids.

Anyway, we reduced the delays and resulting noise band by an order of magnitude when we replaced
the remote metering pump with a closecoupled control valve. The valve was manipulated using a ratio
controller to proportion the reagent flow to the sump discharge flow, correcting the ratio with the in-
line pH loop.

Some noise still remained, due to poor distribution of the injected reagent into the pipeline. This
couldn't be eliminated, because it required making the injection port smaller so the reagent velocity
would be larger. Unfortunately, a hole small enough to do the job was too small to keep from
plugging. The noise was more of a nuisance on the trend chart than in the system, so the record was
cleaned up by passing the measurement signal through an electronic filter.

We thought our problems were over, when magical mystery reared its ugly head. As the miniature
reagent valve was stroked from closed to open, the reagent flow measurement momentarily increased
and then went to zero. The magnetic flowmeter was immediately suspect - but came through with a
clean bill of health; we checked the wiring and found it to be correct; the vendor examined and
verified the integrity of the electronics; we tested the meter on water and observed that it respond
correctly. We than tried changing valve trim, but several tests yielded the same results.

I was about to throw the tiny but costly trims away, leave the engineering profession, and enter a
seminary. During this period of contemplation, I suddenly noticed what looked to be a reverse taper
on the trims. It was hard to tell for sure, because the parts were small, but I confirmed the
observation with a micrometer. In desperation to get home from this startup, I calculated the contour
of the plug for a linear characteristic, made a sketch, and had the parts machined.

The valve worked fine with the homemade trim. The reverse taper had caused the flow to decrease as
the stroke increased. The momentary surge inflow at the start of the stroke was caused by the plug
lifting off the seat just enough to provide a small annular clearance. How did the reverse taper get
there in the first place? I never found out for sure, but did learn that the trims were too small to be
standard and were specially machined by the vendor for the order. As far as I was concerned, they
were too special. You can imagine how difficult it would have been to diagnose this valve problem if
there was no reagent flow meter. This leads to Fact of Life #5.

Another instrumentation problem occurred later, when one of the design engineers decided to modify
the system and recover some panel space. He installed a feedforward controller in place of the ratio
station and pH-based flow controller. The device added the flow feedforward signal to the flow
command from the pH controller. The vendor, anxious to sell a feedforward element, thought it was a
great idea. In operation, as you should have guessed, the flow controller readjusted its output to
cancel the effect of the feedforward signal and maintain flow at its setpoint. To work as expected, the
feedforward action would have to be on the flow controller setpoint - multiplied by a not summed with
the pH controller output. Multiplication will force the reagent flow to zero if the process fluid flow is
zero or the fluid is at the setpoint. Also for you control jocks, multiplication cancels composition loop
gain - a term inversely proportional to sump flow. This leads to Fact of Life #6.

All of these corrections are reflected in Figure 2b above. The system, as shown, has been controlling
well since startup.

Where's the agitator?

A process used a vertical tank of neutralization. Performance was poor because response was slow and
the effluent was not uniformly mixed. I looked at the drawings and noted that the vertical unit seemed
a bit tall for its diameter. I asked how high it was, and the designer said, "50 feet," I gasped, "It's not
nice to kid an old engineer." He responded, "Who's kidding?" He replied, "You're the only agitator on
this project." I instantly knew I had a major problem.

FIGURE 3. Where's the agitator? (a)-unsuccessful and (b)-

successful pH control systems for a process involving an extremely tall mixing tank without an
agitator

Figure 3a shows how the pH was originally being controlled. Axial agitation probably would have
corrected the difficulties, but could not be provided economically because the tank was too tall. A
shorter tank would also have worked - again at a higher price than the plant wanted to pay. I decided
that the best way to cope with the tank would be to use its volume as a filter, estimating that it would
attenuate the hydrogen ion concentration oscillations of an in-line loop by a factor of 10,000 - 4 pH
units. A circulation pump was installed as a low-deadtime in-line mixer. Influent and reagent were
added to the new suction; an injector probe was installed on the pump discharge. The new system is
shown in Figure 3b.

Upsets still occurred, due mainly to the quick opening characteristic and the large positioner hysteresis
of the plug valve on the influent. However, the in-line pH loop returned rapidly to setpoint after a
disturbance. Further, after passing through the tank volume, the pH drew the straightest line I have
ever seen; for a moment, we thought someone had tied down the pointer. Performance was so good
that the plant suggested we standardize on this type of system for pH control. I warned them that the
setpoint of this system was several pH units below the neutral zone, on a relatively flat position of the
titration curve. On a steep part of the curve, Fact of Life #2 would prevail and there would be lots of
oscillations.

Where's the electrode?

I was called in to troubleshoot the pH system shown in Figure 4a. This simple configuration should
have worked flawlessly, but was plagued by an unacceptably wide control band about the setpoint. I
went down to look at the exit nozzle of the vessel and couldn't find the electrodes. I rapidly surmised
that I had a major problem. In this case, the source of the difficulty was political. The instrument
maintenance department had specified that the electrodes be located in the analyzer house, to avoid
the discomfort of servicing them outside during the winter. Unfortunately, this location introduced
excessive deadtime in the loop. To help avoid this problem in other situations, I feel compelled to
state Fact of Life #7.

FIGURE 4. Where's the electrode? (a)-unsuccessful and (b)-

successful pH control systems for a process in which electrodes have to be installed in inconvenient
locations.

I succeeded in getting the electrodes moved by arguing about the extreme safety hazards and product
quality problems that accompanied large pH excursions. The change, indicated in Figure 4b, narrowed
the control band to about 0.1 pH.

We used injector electrodes for this application. Experience shows that these provide better
performance and require less maintenance than sample chamber electrode holders. These benefits are
especially evident when the electrodes are mounted in the discharge nozzle piping where fluid velocity
is high - because the flow ensures rapid response by minimizing boundary layer thickness and
prevents electrode coating by impurities in the stream.
Injection electrodes also appear to be less prone than sample chamber elements to leakage. In
checking 30 installations of injection devices from one manufacturer, I found no instances of leakage;
in fairness, when we obtained products from a different source, some leakage did occur. However,
every sample chamber electrode holder I have ever encountered has eventually leaked. Moreover,
leakage is visible with injector assemblies but not with sample chambers. For hazardous fluids, you
don't want any surprises when you open the top cover of the electrode holder. This leads me to Fact of
Life #8.

Is bigger better?
A plant used the system of Figure 5a for waste neutralization. The eductor shown in the figure had
been added because mixing deadtime was too long. But even with this device, the deadtime appeared
to be over 40 minutes. The consequent natural period of the pH loop was 160 minutes, so the
maximum reset should have been less than 0.01 repeats per minute. Since this was below the
minimum setting on the controller, the loop was in a continuous reset cycle; further, the integrated
error - which is proportional to the deadtime squared - was out of this world. I looked at the
engineering flow diagram and spotted the largest storage tank I had ever seen. I asked the process
engineer where the neutralization tank was, and he pointed to the elephant I just thought was for
storage. I immediately understood that I had major problem.

The intent of the large tank was plausible. It would serve to blend acidic and basic waste streams from
different sources and minimize the reagent demand. Now, as long as you don't have to put control
loops on them, large tanks are useful. Upstream of a control loop, a large tank can filter out
disturbances and reduce reagent requirements; downstream, it can filter out loop oscillations - which
is particularly advantageous because these fluctuations are usually faster than variations in influent
concentration and are therefore more effectively attenuated. This reminds me of Fact of Life #9.

FIGURE 5. Is bigger better? (a)-unsuccessful and (b)-

successful pH control systems for a process in which an extremely large tank was initially employed
for mixing.

The new control system is shown in Figure 5b. The large tank was replace with two small vessels in
series. A pulse frequency controller was installed to avoid valve pluggage at low reagent flows and to
meet the extreme rangeability requirements imposed by the wide variations in influent flow and pH.
Signal characterization was used to counteract the steep slope of the titration curve at the setpoint.

Startups are no fun without magical mystery. In this instance, we noticed that the pH measurement
on the first tank was erratic. The problem could not be duplicated when we removed the electrodes
and inserted them directly into the buffer solution or connected them to the measurement system of
the second tank. We replaced the pH transmitter, preamplifier, cable, and electrodes individually but
the erratic measurements continued. Eventually, someone remembered that the fiberglass
preamplifier enclosure supplied by the manufacturer was replaced by the field maintenance
department with a metal housing - to provide more room for access. The enclosure mounting plate
was grounded. This created a second ground point in the circuit, and caused a significant current flow
through the circuit. The problem did not occur on the second tank because the preamplifier housing
was not mounted on a conductive structure. Likewise, the erratic behavior was not observed during
buffering because the bottle was plastic. The problem was solved by isolating the preamplifier
enclosure from ground with a plastic mounting plate.

The control system has performed well from startup except for periodic pluggage of the electrodes in
an overflow sample line. Liquid head is too low to achieve a sample velocity sufficient to sweep the
electrodes clean. A new electrode holder that provides a large flat electrode surface will be tried. If
that doesn't work, we may have to shake loose enough money to install a sample pump and an
injector electrode assembly.

Where's the reagent piping?

The pH in a neutralization tank was fluctuating in what appeared to be a square wave. The system
was also subject to periodic glass electrode failures caused by etching and severe upsets due to a
high-temperature interlock that sets due to a high-temperature interlock that shut off the reagent
flow. Plant people were especially anxious to improve this system because reliability was critical to
plant productivity. I stood at the top of the vessel wondering what to do, and noticed that the reagent
was being transported by a conveyor rather than a pipe. I soon perceived that I had a major problem.

FIGURE 6. Where's the reagent piping? (a)-unsuccessful and

(b)-successful pH control systems for a process iin which a powdered line reagent is delivered by a
conveyor.

Figure 6a shows the original installation. The reagent, pulverized lime, was controlled by a rotary
feeder at the discharge of the hopper. Feeder speed was set by the pH controller output. Reagent
delivery was subject to several minute's lag due to transportation delay on the conveyor and solids
dissolution time. We made precise measurements of the pH in the tank and found that the square
waves were worse than the plant thought - the process instruments recorded only the high end of the
pH scale, but the fluctuations actually covered almost the whole range from 0 to 14.

Luckily, a huge tank upstream of the waste flow provided enough inventory so the pH controller could
be used to throttle the waste stream. The lime feeder speed was determined by selecting the lower of
a manually-entered throughput setpoint and a command from the temperature override controller.
The low signal selector therefore provided smooth transition between between normal and override
control. The feeder speed signal is also multiplied by the pH controller command, passed through a lag
unit whose delay is set equal to the reagent delivery time, and fed forward to establish the waste flow
setpoint.

To eliminate downtime due to electrode failures, a system was installed using three measuring
elements and voting logic to establish the output signal. Use of three rather than two electrode
assemblies make it possible to determine which signal to use, if the electrode outputs disagree. This
leads me to Fact of Life #10.

Control improved dramatically. Electrode failure due to etching, which had occurred when the solution
was acidic - at the unrecorded lower portion of the square wave - also stopped. And use of voting logic
to control using three electrode assemblies has virtually eliminated downtime, even when an element
becomes nonfunctional.

Using your skills

One of the prices you pay for being an instrumentation expert in the processing industries is that
occasionally, someone will ask you to control pH. The job rarely proves to be easy, for instance
because you are on a flat portion of the titration curve or have wide tolerance on response and
accuracy, because changes are then high that someone has done it satisfactorily without you. So the
problems you get are usually major problems. You'll have to call on all you know about the installation
and operation of electrodes, control valves, piping, and mixing equipment. You'll have to brush the
cobwebs off your basic understanding of feedback and feedforward loop strategies. You'll have to
home your skills as a diplomat to get the plant to install, replace, or eliminate vessels or instruments
that make life convenient for the operators or maintenance people - or represent investments for
which somebody has a neck on the line - but are preventing satisfactory pH control. And you'll have to
resign yourself to living out of your suitcase for a while while the plant starts up and experiences the
magical mystery of pH.

REFERENCE
1. McMillian. G K; pH Control. Independent Learning Module Series, Instrument Society of America
(Research Triangle Park NC), 1964.
Instruments Society of America. Intech, September, 1984. All rights reserved.

Technical Conductivity and Resistivity

Conductivity measures the ability of a solution to conduct an electric current between two electrodes. In solution, the
current flows by ion transport. Therefore, with an increasing amount of ions present in the liquid, the liquid will have a
higher conductivity. If the number of ions in the liquid is very small, the solution will be "resistive" to current flow. AC
current is used to prevent complete ion migration to the two electrodes.

Conductance = 1/Resistance

Conductivity: mho = Siemen

Normal unit of measurement is:
1 micromho (ho) = 1 microSiemen (),
1 millimho (mmho) = 1 milliSiemens (mS) = 1,000

Resistivity: ohm
Normal unit of measurement is:
megohm = 1,000,000 ohm

Example - Conductivity to Resistivity Conversion:

Conductivity:

= 20
= 20 x 10-6 S
= 2 x 10-5 S
= 2 x 10-5 mho

Resistivity:
1 ohm/2 x 10-5

= 1/conductivity
= 1/2 x 10-5 ohm
= 0.5 x 10-5 ohm
= 5 x 10 4 ohm

Conductivity and Resistivity (NaCl and CaCO3 Solutions at 25)

ppm as CaCO3 ppm Conductivity Resistivity megohm-

NaCl micromhos/cm cm
1700 2000 3860 0.00026
1275 1500 2930 0.00034
850 1000 1990 0.00050
425 500 1020 0.00099
170 200 415 0.0024
127.5 150 315 0.0032
85.0 100 210 0.0048
42.5 50 105 0.0095
17.0 20 42.7 0.023
12.7 15 32.1 0.031
8.5 10 21.4 0.047
4.25 5.0 10.8 0.093
1.70 2.0 4.35 0.23
1.27 1.5 3.28 0.30
0.85 1.00 2.21 0.45
0.42 0.50 1.18 0.88
0.17 0.20 0.49 2.05
0.13 0.15 0.38 2.65
.085 0.10 0.27 3.70
0.042 0.05 0.16 6.15
0.017 0.02 0.098 10.2
0.012 0.015 0.087 11.5
0.008 0.010 0.076 13.1
0.004 0.005 0.066 15.2
0.002 0.002 0.059 16.9
0.001 0.001 0.057 17.6
none none 0.055 18.3

Probe Constants
Probe constant defines the volume between the electrodes. Solutions with an extremely high conductivity require a sensor
with a probe constant greater than 1.0. Solutions with extremely low conductivity require a sensor with a probe constant
less than 1.0. The greater the distance between the electrodes, the smaller the current signal.

Conductivity Resistivity Dissolved Solids

(Micromhos/cm) (Ohms-cm) (ppm)
.056 18,000,000 .0277
.084 12,000,000 0.417
.167 6,000,000 0.833
 1.00 1,000,000 .500
2.50 400,000 1.25
20.0 50,000 10.0
200 5000 100
2000 500 1,000
20,000 50 10,000

Technical Dissolved Oxygen - The Fundamentals

Introduction

Dissolved oxygen (DO) is the term commonly used in liquid analytical work for the measurement of the amount of oxygen
dissolved in a unit volume of water. It is an important indicator of the degree of usefulness of a sample of water for a
specific application. The requirements of a given application determine the level of DO that can be tolerated.

In a water quality application, for example, where we want to maintain a fresh water stream fit for recreational purposes
such as swimming and fishing and as a source of potable water, we must keep the DO content high. If the DO level falls
too low, the fish will suffocate and conditions will become favorable for the growth of harmful bacteria.

In sewage treatment, solids are allowed to settle in large basins to which are added solutions rich in bacteria to speed the
decomposition of the solids. There is an optimum DO level for this process and the level is maintained by mechanically
aerating the "activated sludge" as the bacteria impregnated content of the basins is called. If the DO level falls too low, the
bacteria die and the decomposition ceases; if the DO level is excessive, more power is used than necessary for aeration
and the process becomes unnecessarily costly. Another important application of DO is the control of the quality of boiler
make up water. In this case, since the presence of oxygen in the water will enhance corrosion and cause the build up of
boiler scale that inhibits heat transfer, it is very desirable to hold the DO concentration to a minimum.

Theory

The amount of oxygen that a given volume of water can hold is a function of:
1. The pressure the atmospheric oxygen is exerting at the air- water
interface. 2. The temperature of the water.
3. The amount of other substances dissolved in the water.

Effect of Partial Pressure of Oxygen on Dissolved Oxygen

A volume of water in contact with air will absorb air and hence oxygen until
the pressure the absorbed oxygen exerts at the air-water interface equals the
pressure exerted at the same interface by the oxygen in the air. At this point,
the water is said to be saturated with oxygen. The amount of oxygen actually
absorbed is quite small being of the order of about five or ten parts of oxygen
to one million parts of water.

Effect of Temperature on Dissolved Oxygen

As everyone who has ever watched a pot boil knows, bubbles form on the side
and bottom of the pot. The number and size of the bubbles increase with
temperature. These are bubbles of air that have been dissolved in the water.
Figure 1-A represents a beaker of oxygen saturated water at room
temperature. The partial pressures of oxygen above and below the water
surface are equal. Figure 1- B shows what happens when we begin to heat the
system. In essence, we are putting energy into the system. The oxygen molecules
which have a low solubility become readily energized by the infusion of energy
into the system. The more sluggish water molecules step up their molecular
activity at a slower pace. As a result, more oxygen molecules break through the
air-water interface to the space above the water surface than water molecules do, leaving fewer oxygen molecules
dissolved in the water. When the water boils as is shown in Figure 1-C, all of the oxygen molecules have been driven out of
the water and now the water molecules are coming out of the beaker so fast that they form a layer of water vapor
immediately above the water surface. This layer effectively isolates the water from atmospheric oxygen and the DO
content of the water is zero.
We can think of a volume of water as if it were a homogeneous
medium with a number of holes interspersed throughout the
volume. The pressure of the air immediately above the water
surface will cause these holes to be filled with air. If now a
substance such as salt is dissolved in the water, the dissolved salt
will occupy some of the holes used by the oxygen molecules as they
constantly shift from air to water and water to air in an equilibrium
situation. The amount of oxygen the water can hold at given
temperature has now decreased, but the partial pressure of the
dissolved oxygen remaining in the solution must still equal the
partial pressure of the atmospheric oxygen above the water surface.
This situation is graphically portrayed in Figure 2 where curve A
represents fresh water and curve B represents salt water.

Measurement Techniques
Basically there are two general techniques for measuring DO. Each
employs an electrode system wherein the dissolved oxygen reacts
at the cathode producing a measurable electrochemical effect. The effect may be galvanic, polarographic or potentiometric.

One technique uses a Clark-type cell which is merely an electrode system separated from the sample stream by a semi-
permeable membrane. This membrane permits the oxygen dissolved in the sample to pass through it to the electrode
system while preventing liquids and ionic species from doing so. The cathode is a hydrogen electrode and carries a
negative applied potential with respect to the anode. Electrolyte surrounds the electrode pair and is contained by the
membrane. In the absence of a reactant, the cathode becomes polarized with hydrogen and resistance to current flow
becomes infinite. When a reactant, such as oxygen that has passed through the membrane is present, the cathode is
depolarized and electrons are consumed. The anode of the electrode pair must react with the product of the depolarization
reaction with a corresponding release of electrons. As a result, the electrode pair permits current to flow in direct
proportion to the amount of oxygen or reactant entering the system; hence, the magnitude of the current gives us a direct
measure of the amount of oxygen entering the system.

Membrane probes readily lend themselves to conditions of high interfacial turbulence. In the case of the thallium probe, a
high degree of turbulence may decrease the life of the probe because high turbulence will sweep away the thallium ions,
thus causing electrode depletion.

Although dissolved organic materials are not known to interface with

the output from dissolved oxygen probes, inorganic salts are a factor
in the performance of the probes. As we saw in Figure 2, we must
apply a correction factor to the output of probes with membranes
when used in salt solutions. The thallium probe requires the presence
of salts in concentrations which provide a minimum conductivity of
approximately 200 micromhos.

The two principle gaseous interferers of membrane probe

measurements are chlorine and hydrogen sulfide. Sulfur compounds
such as hydrogen sulfide, sulfur dioxide and mercaptans cause
erroneous outputs from the thallium probe. Halogens do not interfere
with the thallium probe.Figure 3 - Velocity, Agitation, and/or
Turbulence Effects of Interfacial Dynamics on Probe Output.Figure 2 -
Typical Curves Concentration of Dissolved Oxygen at Saturation

At low dissolved oxygen concentrations, pH variations below pH 5

and above pH 9 interfere with the performance of the thallium probe.
This interference amounts to about 0.5 mg/L DO per pH unit. The
performance of membraned probes is not affected by pH changes. A
serious limitation of the thallium probe is the fact that thallium is quite toxic and you must exercise care in using it.
Membrane probes do not have this drawback. Since all of the oxygen that passes through the membrane reacts and since
the amount of oxygen that passes through the membrane is a function of the partial pressure of the oxygen in solution,
this technique actually measures the partial pressure of the oxygen in solution. It does not measure the actual
concentration of the oxygen in the solution. For this reason, we must correct the readings of DO concentration given by
this technique when some substance, for example salt, is dissolved in the water. As we saw above, the dissolved salt will
reduce the number of holes available for carrying oxygen and hence reduce the actual concentration of oxygen without
changing its partial pressure in the solution. If the electrode materials are selected so that the difference in potential is -
0.5 volts or greater at the cathode, an external potential is not required and we have what is called a galvanic system.
Some workers in this field, instead of relying on their selection of electrode materials to give them the required -0.5 volts
difference of potential at the cathode, use an external potential source to give them the required potential difference. This
system is known as a polarographic system. In either case, since the partial pressure of dissolved oxygen is a function of
the temperature of the sample, we must either hold the temperature of the sample constant or compensate for varying
sample temperature. Generally, the former is impractical so the latter is the more popular approach. A suitably selected
thermistor or resistance thermometer in a properly designed electric circuit does a fair job of temperature compensation.

The second basic measuring technique uses an electrode system that consists
of a reference electrode and a thallium measuring electrode. No semi-
permeable membrane is used; the electrode system is immersed directly into
the sample. Oxygen concentration is determined by measuring the voltage
potential developed, in relation to the reference electrode, when dissolved
oxygen comes in contact with the thallium electrode. At the surface of the
electrode the thallous-ion concentration is proportional to the dissolved
oxygen. The voltage potential developed by the cell is dependent upon the
thallous-ion concentration in this layer and varies as the dissolved oxygen
concentration changes. The cell output rises 59 millivolts for each decade rise
in oxygen concentration. This technique uses a potentiometric system. The
method measures directly the concentration of oxygen in the sample. As in
the first technique, temperature compensation is a must and is achieved in
about the same way. In both techniques, interfacial dynamics at the probe-
sample interface are a factor in the probe response. A significant amount of
interfacial turbulence is necessary and for precision performance, turbulence
should be constant. This situation is portrayed in Figure 3. As long as the operating point remains above the knee of the
curve, small changes in turbulence can be tolerated.

Curve A 0 mg/L chlorides Curve B 5,000 mg/L chlorides Document #1234On-line Publishing Service U.S.A. and Canada For
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Reproduced with permission of Royce Instruments.