P2 FACTS:

pH Control
One in a series of fact sheets produced by The Narragansett Bay Commission’s Pollution Prevention Program.

pH Range
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Strongly Weakly Neutral Weakly Strongly
Acidic Acidic Basic Basic

C
ONTROL AND MONITORING OF pH is an important • The ability to change the color of an acid-base
aspect of many industrial wastewater treatment indicator (red to blue).
processes. The following information is • The ability to react with and neutralize an acid.
designed to assist the industrial pretreatment opera-
• The ability to form a precipitate when added
tor with understanding pH neutralization theory, pH
to a solution containing certain metals in
monitoring techniques, and regulatory compliance
solution.
requirements; and to conduct these activities in an
environmentally safe and sound manner. A solution with a pH = 7 is considered neutral and
has neither properties of an acid or a base.
What is pH?
The pH of a solution is an indication of its Why Monitor and Control pH?
acidic/basic properties and is measured on a scale The pH of wastewater is important for the
ranging between 0 and 14. following reasons:
• A low pH can be corrosive to sewer facility
Properties of Acids and Bases components such as pipes, screening equip-
A solution with a pH < 7 is acidic and has the follow- ment, and pumps.
ing properties: • A very low or a very high pH can be damaging
• The ability to change the color of acid-base to the biological activity of a municipal waste-
indicators (blue to red). water treatment plant.
• The ability to release gaseous carbon dioxide • Low pH wastewater has the ability to dissolve
when carbonate ions are added. large quantities of toxic heavy metals which
in turn can be detrimental to the biological life
• The ability to react with and neutralize a base.
within a municipal wastewater treatment
• The ability to react and dissolve certain metals. plant.
A solution with pH > 7 is basic (also referred to as • Low or high pH wastewater may mix with
alkaline) and has the following properties: other industrial wastes within the sewer
• A “soapy” or slippery feeling to the touch (this system forming undesirable by-products such
is due to the base dissolving a layer of skin). as toxic gases and heavy metal precipitates.
For reasons mentioned above it is very important that A typical automated batch pH adjust system is
the pH of wastewater entering a sewer system be depicted in Figure 1, however, both reagent addition
maintained within certain limits. Acceptable pH dis- and pH monitoring can be done manually. When
charge limits may vary depending on permit limita- manually handling strong reagents such as sodium
tions imposed by your local sewer authority, but are hydroxide or sulfuric acid all precautions listed on
typically within the U.S. EPA range of 5 through 10. the reagent’s Material Safety Data Sheet (MSDS) must
be carefully followed. Knowing the volume of the
batch tank and reaction time required the amount of
pH Adjustment reagent needed can be determined with the use of a
Wastewater with a pH outside of acceptable limits titration curve. For automated batch treatment sys-
will require adjustment prior to discharge. If the solu- tems it is important that the influent and reagent feed
tion is too acidic a base must be added to raise the pH point be located away from the pH probe and effluent
and if the solution is too alkaline an acid must be discharge pipes.
added to lower the pH. In both cases the adjustment
material (acid or base) is referred to as a reagent and Reagent Feed pH Recorder/
System Controller
must be added at a controlled rate so as not to over-
Manual or
shoot the desired pH range. Typical pH adjustment Automatic
reagents used are sulfuric acid and sodium hydrox-
ide. However, use of a particular reagent will depend
on the nature of the wastewater. An effective and well
controlled pH adjustment system will use as little pH
Influent Probe
reagent as possible.
When adding reagents it is important to understand
that a one unit change in pH represents a ten fold Air
Effluent
change in the effective strength of an acid or base. For Batch Reaction
example, if 1000 gallons of wastewater requires 10 Tank
gallons of a particular reagent to raise its pH from 3 to
4 it will require only one additional gallon of the Figure 1. Batch pH Adjustment System
same reagent to continue to increase its pH from 4 to
5. Please refer to the enclosed fact sheet “pH Theory” It is very important that the contents of the batch
for a more detailed description of why this is so. treatment tank be thoroughly mixed during reagent
addition. This is best accomplished using a mechani-
cal mixer or air sparger installed along the entire
pH Adjustment and bottom of the tank. Slow addition of reagent and
Control Systems good mixing will allow for better control and will
A pH adjustment and control system may be reduce the likelihood of overshooting the desired pH.
designed to operate on either a batch or continuous Upon completion of reagent addition and reaction the
basis. final pH reading of the solution may be measured
A batch system, used for low volume wastewater using a hand-held or portable laboratory pH meter.
streams, consists of: This pH reading is then recorded in the Pretreatment
System Logbook and the contents of the tank are dis-
1) a wastewater storage tank; charged.
2) a mixing device; The location of the effluent discharge pipe is an
3) a pH sensor and recording device; and important consideration when adjusting wastewater
4) appropriate equipment necessary to safely add containing heavy metals or high concentrations of
the pH adjustment reagents. suspended solids. The discharge pipe must be located
at a sufficient height above the level of settled solids
at the bottom of the tank in order to prevent carry- used. The probe portion of the meter is held in the
over into the discharge effluent. The location of the wastewater until a steady-state reading can be taken.
effluent discharge pipe will thus depend on the If the reading is within allowable discharge limits it is
amount of solids in the wastewater and how often recorded in the Pretreatment Log Book and the waste-
these settled solids are removed from the tank. water is then discharged to the sewer. If a steady-state
Continuous control systems are used when waste- pH reading is outside of discharge limitations addi-
water is continuously being generated and generally tional pH adjustment and recordings must be made.
one work days worth of flow is too large to be effec- Continuous discharge of a wastewater stream
tively captured in a batch system storage tank. As requires continuous pH monitoring. This is accom-
with batch control good mixing and safety precau- plished using a continuous automatic pH
tions are very important, but also automatic reagent controller/recorder and a remote monitoring probe.
addition and continuous pH recording is required. A Various process control systems can be used to regu-
typical system is depicted in Figure 2. Please note that late reagent flow rates and the choice of one particu-
the pH monitoring probe is located downstream of lar control system will depend on the overall system
the reagent addition portion of the tank system. The configuration and wastewater characteristics.
time required for influent flow to reach the pH probe While continuous pH monitoring is less labor inten-
is an important factor for properly setting the reagent sive than the manual method used with batch dis-
feed control rate. The baffles shown in this diagram charges there are many operational issues that can
help to prevent channeling of wastewater flow affect the final pH reading such as:
through the system and assist with mixing, however,
air should still be added to assure proper mixing of 1) The time required for wastewater flow to travel
wastewater with pH adjustment reagents. By the time from reagent addition to the pH sensor probe,
the added reagent reaches the pH sensor probe, it referred to as “deadtime”, should be maintained
should be mixed enough so that the sensor does not between 5 and 30 seconds. Longer deadtime may
measure large variations in pH. result in cyclic control and excess use of reagent, and
shorter deadtime may not allow for proper mixing
pH and reagent reaction prior to the pH recording.
Reagent Feed System Recorder/
Controller 2) The cable connecting the pH probe and recording
device should be no longer than 30 feet. If longer
Pumpor
Solenoid cable lengths are used a preamplifier may be needed
Valve to boost the measured signal.
3) The proximity of cabling to fluorescent lighting
Effluent and mechanical devices emitting AC power are fac-
Influent Baffles pH
Probe tors that can effect the signal passing through the
Air cable. Connection cables should be made to run at
least 6 inches from AC power lines, and if fluorescent
Continous Reaction lights are a consideration, use of an insulating conduit
Tank
may be necessary.
Figure 2. Continuous pH Adjustment System

pH Probe Maintenance
pH Monitoring and Recording and Operation
Equipment In order to insure accurate pH monitoring the follow-
The type of pH monitoring equipment used will ing maintenance and operating procedures should be
depend on how a wastewater stream is discharged, followed:
i.e., batch or continuous. For batch discharges a sim-
a) Probe Handling and Maintenance
ple hand-held or bench top laboratory meter can be
1) Probes should always be installed in a vertical posi- tions. Improving mixing with air sparger and/or relo-
tion in a non-turbulent zone. This will allow for opti- cation of probe are possible solutions to this problem.
mum contact between the probe sensor and waste- c) Straight Line Readings
water being monitored. An unvarying pH recording may be an indication of a
2) Cleaning of the probe should be conducted on a faulty probe or failure of the probe signal to reach the
regular basis in accordance with the manufacturer’s analyzer/controller. In this situation both the probe
recommended procedures and at a frequency depen- and the cabling should be inspected and replaced if
dent on the characteristics of the wastewater being necessary.
monitored. Probes immersed in wastewater contain-
ing sulfides, chlorides, ammonia, or oil and grease
may require more frequent cleaning than probes What Should I Do if the pH
immersed in relatively clean wastewater. The probe Equipment Fails?
should be located within the pretreatment system to If your pH equipment fails you should immediately
allow for easy access for inspection and cleaning pur- notify the NBC pretreatment staff at 277-3738 to
poses and should never be allowed to come into con- determine the appropriate action to be taken.
tact with solids that may settle in the bottom of the Generally, you will be required to obtain a portable
adjustment tank. After every cleaning the probe pH recording system or you may be allowed to take
should be calibrated. manual readings at half hour intervals.
b) Probe Calibration
1) Prior to calibrating the pH probe all process dis- Glossary of Common Terms
charges must cease. Acidity: the capacity of an aqueous solution to neu-
2) The pH chart should be advanced and a line drawn tralize a base.
across the chart to indicate the beginning of calibra- Alkalinity: the capacity of an aqueous solution to neu-
tion. Below this line the date, time, and person per- tralize an acid.
forming the calibration should be recorded.
Buffer: solution that has a constant pH and the ability
3) Calibrate the pH probe in accordance with the to resist changes at that pH level. Buffers are used to
operator’s manual. calibrate pH electrodes and meters.
4) Upon completion a line must be drawn on the Molarity: a concentration unit, equal to the number of
chart indicating the end of the calibration and the moles of solute divided by the number of liters
chart paper advanced. solution.
Following these procedures will eliminate the need to Mole: a chemical mass unit defined equal to 6.022 x
report calibration spikes on monthly pH Monitoring 1023 molecules, atoms, or other units. The mass of
Reports. one mole of a substance is equal to the gram
formula weight of that substance.
Trouble Shooting Spike: abrupt pH change lasting for a brief period of
a) Erratic Spiking time (several minutes or less).
Electrical interferences such as fluorescent lights, rec- Titration Curve: a plot of solution pH versus volume
tifiers, and electric motors can all contribute to erro- of added reagent. A titration curve gives a visual rep-
neous spiking on pH recording charts. Every attempt resentation of the amount of reagent required to neu-
should be made to minimize exposure of pH monitor- tralize a particular solution.
ing equipment to these items.
b) Wide or cyclic pH swings
Inadequate mixing and extended deadtime between For More Information
reagent addition and pH sensing can cause wide pH For more information about pollution prevention,
swings resulting in excessive use of reagent materials, contact the Narragansett Bay Commission’s Pollution
wear and tear of equipment, and potential pH viola- Prevention Manager at 401/277-6680.
7/96