Cat. No.

45600-18
COD Reactor Model 45600
&
THM Reactor Model 49100
Instrument Manual
Hach Company, 1994-2004. All rights reserved. Printed in the U.S.A. te/dk 3/04 4ed
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TABLE OF CONTENTS
SAFETY PRECAUTIONS ........................................................................................................ 5
SPECIFICATIONS..................................................................................................................... 8
OPERATION.......................................................................................................................... 9
SECTION 1 OPERATION................................................................................................ 11
1.1 General Description............................................................................................................ 11
1.1.1 COD Reactor ............................................................................................................ 11
1.1.2 THM Reactor ............................................................................................................ 11
1.1.3 Additional Features................................................................................................... 12
1.2 Operation............................................................................................................................ 13
1.3 Operating Controls and Indicators ..................................................................................... 14
1.4 Line Voltage Selection ....................................................................................................... 15
1.5 Reactor Preparation, 150 !C or 100 C Mode.................................................................... 16
1.6 Reactor Preparation, Temperature Adjust Mode................................................................ 16
1.7 Operational Notes............................................................................................................... 17
SECTION 2 MAINTENANCE ........................................................................................ 19
2.1 150 !C Temperature Adjustment........................................................................................ 19
2.2 100 C Temperature Adjustment........................................................................................ 20
2.3 Fuse Replacement .............................................................................................................. 20
2.4 Block Removal and Installation (Cleaning the COD Reactor) .......................................... 22
2.5 Cleaning the THM Reactor ................................................................................................ 23
GENERAL INFORMATION........................................................................................... 25
REPLACEMENT PARTS........................................................................................................ 27
How To Order........................................................................................................................... 29
Repair Service .......................................................................................................................... 30
Warranty................................................................................................................................... 31
CERTIFICATION.................................................................................................................... 32
APPENDIX A: Hach COD Methods .............................................................................. 35
Dichromate Reactor Digestion Method.................................................................................... 37
Digestion .................................................................................................................................. 39
Colorimetric Measurement, 0 to 40 mg/L COD ...................................................................... 42
Colorimetric Measurement, 0 to 150 mg/L COD .................................................................... 44
Colorimetric Measurement, 0 to 1500 and 0 to 15,000 mg/L COD......................................... 46
Titrimetric Measurement, 0 to 150, 0 to 1500, and 0 to 15,000 mg/L COD............................ 48
4
TABLE OF CONTENTS, continued
APPENDIX B: Hach COD Methods .............................................................................. 57
Manganese III Reactor Digestion Method............................................................................... 59
APPENDIX C: THM Plus Method ............................................................................ 69
THM Reactor Method.............................................................................................................. 71
5
SAFETY PRECAUTIONS
Please read this entire manual before unpacking, setting up, or
operating this instrument. Pay particular attention to all danger
and caution statements. Failure to do so could result in serious
injury to the operator or damage to the equipment.
To ensure the protection provided by this equipment is not
impaired, do not use or install this equipment in any manner
other than that which is specified in this manual.
Use of Hazard Information
If multiple hazards exist, this manual will use the signal word
(Danger, Caution, Note) corresponding to the greatest hazard.
DANGER
Indicates a potentially or imminently hazardous situation which,
if not avoided, could result in death or serious injury.
CAUTION
Indicates a potentially hazardous situation that may result in minor
or moderate injury.
NOTE
Information that requires special emphasis.
Precautionary Labels
Read all labels and tags attached to the instrument. Personal
injury or damage to the instrument could occur if not observed.
This symbol, if noted on the instrument, references the
instruction manual for operational and/or safety information.
1.2 Operation
1.4 Line Voltage Selection
1.5 Reactor Preparation, 150 C or 100 C Mode
1.6 Reactor Preparation, Temperature Adjust Mode
2.3 Fuse Replacement
2.4 Block Removal and Installation (Cleaning the
COD Reactor)
6
SAFETY PRECAUTIONS, continued
COD Reactor Operation
This instrument is used to incubate glass vials containing small
quantities of hazardous ingredients at high temperature. Read and
comply with the precautionary labels on the instrument and read
the Material Safety Data Sheets (MSDS) supplied with the
reagent vials. Refer to SECTION 1 OPERATION.
THM Reactor Operation
This instrument is used to incubate glass vials at high
temperature. Read and comply with the precautionary labels on
the instrument and read the Material Safety Data Sheets (MSDS)
supplied with the reagent vials. Refer to SECTION 1
OPERATION.
Handling Reagent Vials
Use care when handling the vials and wear protective clothing.
Refer to SECTION 1 OPERATION. After completion of the
testing, dispose of used vials in accordance with all federal, state
and local regulations. Use only Hach prepared COD reagent vials
in the Model 45600 COD Reactor.
Safety Equipment
Use protective clothing when operating the Reactor, including
goggles or face mask, and gloves. Refer to SECTION 1
OPERATION. Use of the optional safety shield is strongly
recommended for use with the COD or THM Reactor.
Reagent Spills
Clean up spilled reagents immediately. Refer to Section 1.7 on
page 17. If reagent contacts skin, rinse the affected area
thoroughly with water. Avoid breathing released vapors. Read the
Material Safety Data Sheets (MSDS) supplied with each reagent
for complete chemical information.
Fire Hazard
Avoid the presence of flammable liquids near the operating
Reactor. A fire hazard could be created.
7
SAFETY PRECAUTIONS, continued
Power Cord
A power cord suitable for U.S. and Canadian 115 V ac line
voltage is supplied with the Model 45600 COD Reactor and
Model 49100 THM Reactor. If either model is to be configured
for 230 V ac, an approved UL/CSA power cord with NEMA
6-15P type cord cap must be used in place of the 115 V ac power
cord supplied.
The Model 45600-02 COD Reactor and Model 49100-02 THM
Reactor are factory configured for European 230 V ac line
voltage. The power cord supplied with this model has a
Continental European type plug and is listed by VDE for
250 Vac line voltage.
Line Voltage Selection
Verify proper line voltage select switch position and appropriate
fuse rating. Refer to Section 1.4 on page 15.
Fuse Replacement
Use fuses with the specified current and voltage ratings. Refer to
Section 2.3 on page 20.
8
SPECIFICATIONS
Specifications subject to change without notice.
Ambient Operating Temperature: +10 to +45 C
Storage Temperature: 40 to +60 C
Temperature Stability: 0.5 C (100 to 150 C)
Capacity (COD): 25 16 " 100-mm vials, one thermometer.
Optional accessory block available with capacity for twenty-one
16-mm and four 22-mm tubes, and one thermometer.
Capacity (THM): 10 1-inch vials, one thermometer
COD Accuracy (150 C mode): 2 C @ 25 C ambient
THM Accuracy (100 C mode): 2 C @ 25 C ambient
Range Adjustment (COD):100 to 155 C adjustment minimum
Range Adjustment (THM):50 to 105 C adjustment minimum
Timer: 0 to 120 minutes with audible alarm and automatic
shutoff mode
Block: Removable, black anodized aluminum,
11.4 cm square " 6.3 cm high
Thermometer: 1-inch dial type, 0 to 200 C, 1% accuracy, can
be recalibrated, 2 C divisions
Power Requirements: Selectable 115 V ac/230 V ac, 8.5%,
50/60 Hz, 2.4/1.2 Amp ac, 220 W
Dimensions: 20.3 cm wide " 12 cm high " 30.5 cm deep
Weight: Net: 3.5 kg; Shipping: 4 kg
Warm-up Time: 30 to 40 minutes from +25 C to +150 C
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DANGER
Handling chemical samples, standards, and reagents can be dangerous. Review the necessary
Material Safety Data Sheets and become familiar with all safety procedures before handling
any chemicals.
DANGER
La manipulation des chantillons chimiques, talons et ractifs peut tre dangereuse. Lire les Fiches
de Donnes de Scurit des Produits (FDSP) et se familiariser avec toutes les procdures de scurit
avant de manipuler tous les produits chimiques.
PELIGRO
La manipulacin de muestras qumicas, estndares y reactivos puede ser peligrosa. Revise las fichas
de seguridad de materiales y familiarcese con los procedimientos de seguridad antes de manipular
productos qumicos.
GEFAHR
Das Arbeiten mit chemischen Proben, Standards und Reagenzien ist mit Gefahren verbunden.
Es wird dem Benutzer dieser Produkte empfohlen, sich vor der Arbeit mit sicheren Verfahrensweisen
und dem richtigen Gebrauch der Chemikalien vertraut zu machen und alle entsprechenden
Materialsicherheitsdatenbltter aufmerksam zu lesen.
PERIGO
A manipulao de amostras, padres e reagentes qumicos pode ser perigosa. Reveja a folha dos
dados de segurana do material e familiarize-se com todos os procedimentos de segurana antes
de manipular quaisquer produtos qumicos.
PERICOLO
La manipolazione di campioni, standard e reattivi chimici pu essere pericolosa. La preghiamo di
prendere conoscenza delle Schede Techniche necessarie legate alla Sicurezza dei Materiali e di
abituarsi con tutte le procedure di sicurezza prima di manipolare ogni prodotto chimico.
OPERATION
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SECTION 1 OPERATION
1.1 General Description
1.1.1 COD Reactor
The Model 45600 COD Reactor (Figure 1) is a 25-well, dry-bath
incubator that provides the 150 !C temperature environment
required in Hach's test system for chemical oxygen demand
(COD) determinations. In addition to the COD requirements,
this model provides features for timed operation as well as
temperature adjustment. In the COD digestion mode,
the temperature switch is set in the 150 !C position and the
temperature is maintained within 2 !C constantly. Heater block
temperature can be verified by placing the thermometer supplied
with the instrument in the temperature well provided in the block.
In the adjustable temperature mode (100 to 155 !C), the
instrument can be used for digestion of other samples that require
different digestion temperatures. A 2-hour timer is incorporated
for applications where timed digestion is desired. When this
feature is used, the bell will sound and the unit will shut off at
the end of the selected time period. The timer also can be used
without the shut-off feature when operating in the infinity mode.
1.1.2 THM Reactor
The Model 49100 THM Reactor is a 10-well, dry bath incubator
that provides the 100 C temperature environment required in
Hachs test system for Trihalomethanes (THM) Plus
determination. In addition to the THM requirements, this model
provides features for timed operation and temperature
adjustment. In the THM digestion mode, the temperature switch
is set in the 100 position and the temperature is constantly
maintained within 2 C. Verify the heater block temperature by
placing the thermometer supplied with the instrument in the
temperature well in the block.
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SECTION 1, continued
1.1.3 Additional Features
The instrument can be switched to operate on either 115 or
230 Vac. Accessories supplied with the COD Reactor and THM
Reactor include a dial gauge thermometer, power cord, the
appropriate fuses, and instruction manual with quick reference
card. Optional accessories offered are a safety shield and a special
heater block with wells sized to hold twenty-one 16-mm tubes
and four 22-mm tubes. Refer to OPTIONAL ACCESSORIES on
page 27.
The optional safety shield is 15-inch high,
3
/16-inch thick
polycarbonate attached to a heavy steel base. It is placed on the
laboratory bench in front of the COD Reactor or THM Reactor to
protect the operator from splattered reagent in the unlikely event
that a reagent vial should break.
Figure 1 Model 45600 COD Reactor
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SECTION 1, continued
1.2 Operation
DANGER
This instrument is used to
incubate test samples that
may contain hazardous
materials. Protective
clothing, including
gloves and goggles or face
mask, should be worn.
Any spills should be wiped
up immediately and if
skin is contacted, rinse
the affected area
thoroughly with water.
Please read all Material
Safety Data Sheets
(MSDS) for complete
chemical information.
GEFAHR
Dieses Gert dient zur Inkubation von Testproben mit eventuell
gefhrlichen Stoffen. Sie sollten bei der Handhabung unbedingt
Schutzkleidung, wie Handschuhe und Schutzbrille oder eine
Gesichtmaske tragen. Verschttetes Produkt ist unverzglich
aufzuwischen. Bei Kontakt mit der Haut mu die betroffene Stelle
sofort grndlichst mit Wasser gesplt werden. Bitte lesen Sie die
kompletten chemischen Informationen und Daten aller Datenbltter
mit den Material Sicherheitsanweisungen (IDDMS).
PELIGRO
Este instrumento se utiliza para incubar muestras de prueba que
pueden contener materiales peligrosos. Por lo tanto, es necesario usar
ropa de proteccin incluso guantes y antiparras o mscara facial. Los
derrames deben limpiarse de inmediato y, en caso de contacto con la
piel, lave la zona afectada con abundante agua. Para la informacin
completa sobre los productos quimicos, lea todas las Hojas de Datos
sobre Seguridad de Materiales (HDSM).
DANGER
Cet appareil sert l'incubation d'chantillons contenant des matires
dangereuses. Pour la manipulation, nous recommandons le port de
vtements de protection, de gants et de lunettes ou d'un masque. Si le
produit est renvers, il doit tre essuy immdiatement. En cas de
contact accidentel avec la peau, la zone concerne doit tre
abondamment rince l'eau. Prire de lire attentivement les fiches
produits avec les donnes de scurit (FPDS) contenant des
informations chimiques compltes.
PERIGO
Este instrumento usado para a incubao de espcimes de que
podem conter. Roupa protetora, incluindo luvas e culos de proteo
ou protetor facial, deve ser usada. Qualquer material entornado deve
ser imediatamente limpo e, no caso de contato com a pele, a rea
afetada dever ser bem lavada com gua. Leia as Folhas de Informao
de Segurana do Material (FISM) para obter os dados qumicos
completos.
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SECTION 1, continued
1.3 Operating Controls and Indicators
(See Figure 2)
Power Indicatorlights when line power is turned on.
If instrument is in the Timer Mode, there must be time showing
on the Timer for the POWER indicator to be lit.
Temperature Mode Switchselects constant 150 !C operation for
the COD Reactor and 100 C operation for the THM Reactor,
or the adjustable temperature operating mode whereby an
alternative temperature can be selected with the 100 to 155 !C
ADJUST control on the back panel for the COD reactor or the 50
to 105 !C ADJUST control for the THM reactor.
Timerused to select digestion time in minutes. Indicator knob
shows digestion time remaining.
Timer Switchused in conjunction with timer to operate the
reactor in a timed digestion when set to TIMER position. The
reactor will shut off at the end of the elapsed time. When the
timer switch is in the Infinity position, the timer can be off or
used as an audible alarm to track the digestion time. The heater
block will remain at the selected temperature as long as the
instrument power is on.
Heating Indicatorlights only when heater is operating. The
heater cycles on and off while maintaining a stable temperature.
Power Entry Moduleincludes a power switch, power receptacle
and line fuses.
Voltage Select Switchadapts instrument for 115-volt or 230-volt
operation. Factory set for 115 V ac.
Temperature Controlused to select alternative incubation
temperature when temperature switch is in the ADJ position.
Clockwise rotation of the control increases the temperature.
Temperature is adjustable between 100 and 155 !C for the COD
Reactor and between 50 and 105 C for the THM Reactor.
150 !C Mode Temperature Control (COD Reactor)used in the
150 !C temperature mode to adjust the temperature setting to a
constant 150 !C. Refer to Section 2.1 on page 19.
15
SECTION 1, continued
100 !C Mode Temperature Control (THM Reactor)used in the
100 !C temperature mode to adjust the temperature setting to a
constant 100 !C. Refer to Section 2.2 on page 20.
Figure 2 COD Reactor Controls, Indicators and Connectors
1.4 Line Voltage Selection
Note: Misapplication of AC line power to this instrument can cause
serious damage to the instrument. Prior to connection, verify
that the Voltage Select Switch is set for the proper AC line
requirement.
This instrument is factory set and properly fused for 115 V ac line
requirements. To convert the instrument for 230 V ac line
requirements, proceed as follows:
1. Disconnect power cord from power entry module receptacle.
2. Rotate the indicator slot on the Voltage Select Switch to the
230 position.
Heating
Indicator
Timer Switch
Timer
Temperature
Switch
Power
Indicator
Power Entry
Module
Power Switch
Fuse Holder
Power
Receptacle
150 C Mode
Temperature
Control
Temperature
Control
Voltage Select
Switch
16
SECTION 1, continued
3. Remove the two 3-amp fuses and replace them with two
1.6-amp fuses. Refer to Section 2.3 on page 20.
4. Restore the power cord connection.
1.5 Reactor Preparation, 150 !C or 100 C Mode
Set the Power switch to I (on) and the Temperature switch to
either 150 !C for the COD Reactor or 100 C for the THM
Reactor. Verify that the Timer switch is set to infinity. Allow a
warm-up period of approximately 30 minutes. When the Heating
Indicator begins to cycle on and off, the block temperature is
stable. The proper temperature can be verified by placing a
thermometer into the small well provided in the heater block.
The instrument is now ready for digesting samples. If the timer is
to be used to turn the reactor off at the end of the digestion, set the
timer switch to the TIMER position and rotate the timer knob
clockwise to the desired digestion time.
1.6 Reactor Preparation, Temperature Adjust Mode
1. Set the Power switch to I (on) and set the Temperature switch
to ADJ. Verify that the timer switch is set to infinity.
2. Place a thermometer in the heater block thermometer well
and allow the temperature reading to stabilize.
Note: Use care when adjusting the temperature control. This control is a
single-turn potentiometer and can be permanently damaged if too
much torque is applied at the end of adjustment travel. At the first
sign of resistance to rotation, stop applying torque. If over-
adjustment does occur and the potentiometer is damaged, contact a
Hach Service Center. Refer to Repair Service on page 30.
3. Using a non-conducting screwdriver or trimmer pot
adjustment tool, turn the temperature adjust control slightly
counterclockwise if the temperature must be lowered or
clockwise if the temperature must be raised. Allow the
thermometer reading to stabilize to determine if further
adjustment is needed. Repeat this step until the thermometer
reading stabilizes at the desired temperature. If the optional
glass thermometer is used, remove the thermometer.
17
SECTION 1, continued
1.7 Operational Notes
Do not place the COD Reactor or THM Reactor in a draft, in
direct sunlight or near equipment that emits heat or cold.
Temperature stability could be affected.
Use of the optional safety shield is strongly recommended.
Use of an optional glass thermometer is recommended only
for checking the heater block temperature during instrument
preparation. Because the thermometer is breakable, it is
advisable to remove the thermometer during normal
operation of the reactor.
Use vial and tube sizes that match the heater block wells for
best results.
During operation, the temperature of the empty block will
differ slightly from the temperature of the block full of vials.
Also, loading the block with cold tubes will lower the block
temperature several degrees and require a few minutes to
recover as the tubes warm. If the temperature does not
recover completely, the appropriate temperature control can
be adjusted to compensate. See Section 2.1 150 C
Temperature Adjustment on page 19 or Section 2.2 100 C
Temperature Adjustment on page 20.
The dial thermometer supplied with the COD Reactor can
be recalibrated by placing the stem into an ice-water bath,
allowing it to come to equilibrium and adjusting the nut
beneath the dial to obtain a reading of zero !C.
Note: In the event of an accidental spill into the heater block, disconnect
power to the instrument and allow it to cool. After the instrument has
cooled, remove all reagent tubes and remove the heater block for
cleaning. Refer to Section 2.4 Block Removal and Installation
(Cleaning the COD Reactor) on page 22. If the spill was severe and
not contained on or in the heater block, damage may have occurred
to the instruments electrical components. Contact the appropriate
service center. Refer to Repair Service on page 30.
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19
SECTION 2 MAINTENANCE
There are no scheduled maintenance requirements for this
instrument. It should be kept clean, and reagent spills should be
wiped up promptly. The temperature setting for the 150 !C mode
or the 100 C mode can be adjusted as described below if
necessary. If your reactor does not perform properly, please
contact a Hach Service Center for instructions. Refer to Repair
Service on page 30.
2.1 150 !C Temperature Adjustment
The 150 !C temperature setting may need readjustment in time
due to component aging. Best accuracy will be obtained if the
setting is made while the block is full of vials. Proceed
as follows:
1. Place COD Digestion Reagent Vials in all the tube wells and
insert the thermometer into the temperature well.
2. Set the timer switch to infinity, the temperature mode switch
to 150 !C and the power switch to I (on). Allow the block
temperature to stabilize.
3. Observe the thermometer reading when the temperature
has stabilized.
Note: Use care when adjusting the temperature control. This control is a
single-turn potentiometer and can be permanently damaged if too
much torque is applied at the end of adjustment travel. At the first
sign of resistance to rotation, stop applying torque. If over-
adjustment does occur and the potentiometer is damaged, contact a
Hach Service Center. Refer to Repair Service on page 30.
4. Remove the plug from the 150 !C Temperature Control
opening. See Figure 2 on page 15. Using a non-conducting
screwdriver or trimmer pot adjustment tool, slightly adjust
the 150 !C control clockwise to increase the block
temperature or counterclockwise to decrease it, allowing time
for the temperature to stabilize between adjustments. Repeat
as necessary until the thermometer reading stabilizes at the
proper temperature. Replace the plug in the back
panel opening.
20
SECTION 2, continued
2.2 100 C Temperature Adjustment
The 100 !C temperature setting may need readjustment in time
due to component aging. Best accuracy will be obtained if the
setting is made while the block is full of vials. Proceed
as follows:
1. Place THM Plus Reagent Vials in all the tube wells and
insert the thermometer into the temperature well.
2. Set the Timer switch to infinity, the Temperature Mode
switch to 100 !C and the Power switch to I (on). Allow the
block temperature to stabilize.
3. Observe the thermometer reading when the temperature
has stabilized.
Note: Use care when adjusting the temperature control. This control is a
single-turn potentiometer and can be permanently damaged if too
much torque is applied at the end of adjustment travel. At the first
sign of resistance to rotation, stop applying torque. If over-
adjustment does occur and the potentiometer is damaged, contact a
Hach Service Center. Refer to Repair Service on page 30.
4. Remove the plug from the 100 !C Temperature Control
opening. See Figure 2 on page 15. Using a non-conducting
screwdriver or trimmer pot adjustment tool, slightly adjust
the 100 !C control clockwise to increase the block
temperature or counterclockwise to decrease it, allowing time
for the temperature to stabilize between adjustments. Repeat
as necessary until the thermometer reading stabilizes at the
proper temperature. Replace the plug in the back
panel opening.
2.3 Fuse Replacement
DANGER
For continued protection
against fire, replace fuses
only with fuses of
specified type and current
rating.
GEFAHR
Zur Wahrung des kontinuierlichen Brandschutzes drfen die
Sicherungen nur mit Sicherungen des gleichen Typs und mit gleichen
Stromkennwerten verwendet werden.
PELIGRO
Para una continua proteccin contra incendios, reemplace los fusibles
nicamente por los del tipo y capacidad recomendados.
21
SECTION 2, continued
DANGER
Pour assurer la protection contre les incendies, remplacez les fusibles
uniquement avec des fusibles du mme type et pour la mme tension.
PERIGO
Para proteo continiua contra fogo, troque os fusveis somente por
fusveis do tipo especificado para a fora da corrente.
The fuse holder is located on the back panel within the power
entry module. See Figure 3.
1. Disconnect the power cord from the instrument before
removing the fuse holder.
2. Remove the fuse holder by inserting a small screwdriver or
other pointed tool in the small opening and prying out the
holder. Both sides of the power line are fused.
3. Replace the fuses with two 3A fuses for 115-volt
operation or two 1.6A fuses for 230-volt operation. Refer
to REPLACEMENT PARTS on page 27 for the proper fuse
description and catalog number. Spare fuses can be stored
in the two slide-out clips in the fuse holder.
4. Replace the holder and reconnect the power cord.
Figure 3 Fuse Replacement
Power Entry
Module
Power
Switch
Fuse
(Typical of 2)
Fuse
Holder
Fuse Holder
(Reverse View)
Spare Fuse
Storage
22
SECTION 2, continued
2.4 Block Removal and Installation (Cleaning the COD Reactor)
DANGER
Do not touch the heater
block without hand
protection unless you are
certain it has cooled. A
severe burn could result.
GEFAHR
Heitzeinheit nicht mit bloen Hnden berhren, wenn sie nicht mit
Sicherheit ausgekhlt ist. Vorsicht: Sie riskieren schwere
Verbrennungen.
PELIGRO
No toque el bloque calefactor con la mano desprotegida, a menos que
est seguro de que se haya enfriado. En caso contrario, pueden
ocurrir quemaduras graves.
DANGER
Pour viter les brlures graves, ne jamais toucher le bloc chauffant
sans protection aux mains moins d'tre sr qu'il s'est refroidi.
PERIGRO
No toque no bloco do aquecedor sem proteger a mo, a menos que
esteja certo que ele j esfriou.
Place the removable heater block in the instrument with the same
orientation each time to avoid confusion in test documentation.
When viewed from the front of the instrument, readability of the
well designations is best with the numbers running from left to
right and the letters from front to back.
Before attempting to remove the block, turn the instrument off
and allow the block to cool. Remove all the vials. Remove the
block as follows:
1. The heater block is secured in place with two socket-head
machine screws that are accessible from the top of the block.
Using the hexagonal wrench supplied with the COD Block
Replacement Kit, loosen and remove the two socket-head
screws. The block will adhere to the heater plate beneath it
because of the thermal compound applied on the bottom
surface. Use side-to-side and/or front-to-back rocking
motions to free the block and lift it from the instrument.
2. If there has been a reagent spill in one of the wells, rinse
under a water tap to remove any residue. Remove the thermal
compound from the bottom of the block and the heater plate.
Use the applicator supplied with the COD Block Installation
Kit to scrape the block and plate to remove the old
23
SECTION 2, continued
compound. Dampen a cloth with isopropyl alcohol and wipe
the block and plate clean.
Note: If the old thermal compound is not removed, poor thermal
conductance can occur, resulting in slower block warm-up and
response times.
3. Prepare the block to be installed by applying a coat of thermal
compound to the bottom surface. Use the compound and
applicator supplied in the COD Block Replacement Kit.
Use the saw-toothed edge of the applicator to apply a layer
of uniform thickness that covers the bottom of the
block completely.
4. Place the block into the instrument with the well numbers
from left to right across the back and the well letters along the
left side. Install the two socket-head screws and tighten with
the hexagonal wrench.
5. Restore power to the instrument and install the thermometer
in the small well. Check the temperature of the block when it
becomes stable. If necessary, adjust the temperature setting as
described in Sections 2.1 and 2.2. If the optional glass
thermometer is used, remove the thermometer before use.
2.5 Cleaning the THM Reactor
Turn the instrument off, unplug the instrument, and allow the
block to cool. Remove all the vials. Use a damp cloth to wipe the
block clean.
24
25
At Hach Company, customer service is an
important part of every product we make.
With that in mind, we have compiled the
following information for your convenience.
GENERAL INFORMATION
26
27
REPLACEMENT PARTS
REQUIRED APPARATUS
Description Cat. No.
COD Block Replacement Kit ........................................................................................45649-00
Includes:
Screw, 8x32 socket-head (2)
Thermal Compound, 2-oz jar
Thermal Compound Applicator
Wrench, hexagonal, 9/64 inch
Instruction Sheet
COD Reactor Replacement Block Kit, 25 16-mm wells
(includes COD Block Replacement Kit) ................................................................45609-01
Fuse, 3A, 250 V, Slow-Blo (T), for 115 Vac operation (UL, CSA approved)
(2 needed) (supplied with 45600-00 instruments) ..................................................45640-00
Fuse, 1.6A, 250 V, Slow-Blo (T), for 230 Vac operation (UL, CSA approved)
(2 needed) (supplied with 45600-02 instruments) ..................................................30307-00
Fuse, 1.6A, 250 V, Slow-Blo (T), for 230 Vac operation (IEC type, VDE approved)
(2 needed) (supplied with 45600-02 instruments) ..................................................30306-00
Manual, Instruction .......................................................................................................45600-18
Power Cord, UL, CSA approved for 115 Vac operation...............................................18010-00
Power Cord, VDE approved for European 230 Vac operation......................................46836-00
Quick Reference Card...................................................................................................45600-44
Thermometer, dial gauge, 0 to 200 !C ..........................................................................45655-00
OPTIONAL ACCESSORIES
COD Accessory Block Kit, 21 16-mm wells and 4 22-mm wells,
(includes COD Block Replacement Kit) ................................................................45717-01
Isopropyl Alcohol, tech. grade, 100 mL........................................................................12276-42
Gloves, Heat Resistant ..................................................................................................21788-00
Safety Goggles ..............................................................................................................20972-00
Safety Shield .................................................................................................................23810-00
Trimmer Pot Adjustment Tool.......................................................................................18933-00
28
29
How To Order
Information Required
Technical and Customer Service (U.S.A. only)
Hach Technical and Customer Service Department personnel
are eager to answer questions about our products and their use.
Specialists in analytical methods, they are happy to put their
talents to work for you.
Call 1-800-227-4224 or E-mail [email protected].
International Customers
Hach maintains a worldwide network of dealers and distributors.
To locate the representative nearest you, send E-mail to
intl@hach. com or contact:
In Canada, Latin America, Africa, Asia, Pacific Rim:
Telephone: (970) 669-3050; FAX: (970) 669-2932
In Europe, the Middle East, or Mediterranean Africa:
HACH Company, c/o
Dr. Bruno Lange GmbH
Willsttterstr. 11
D-40549 Dsseldorf
Germany
Telephone: +49/[0]211.52.88.0
Fax: +49/[0]211.52.88.231
By Telephone: By Mail:
6:30 a.m. to 5:00 p.m. MST
Monday through Friday
(800) 227-HACH
(800-227-4224)
By FAX: (970) 669-2932
Hach Company
P.O. Box 389
Loveland, CO 80539-0389
U.S.A.
Ordering information by E-mail: [email protected]
Hach account number (if available) Billing address
Your name and phone number Shipping address
Purchase order number Catalog number
Brief description or model number Quantity
30
Repair Service
Authorization must be obtained from Hach Company before
sending any items for repair. Please contact the HACH Service
Center serving your location.
In the United States:
Hach Company
100 Dayton Avenue
Ames, Iowa 50010
(800) 227-4224 (U.S.A. only)
Telephone: (515) 232-2533
FAX: (515) 232-1276
In Canada:
Hach Sales & Service Canada Ltd.
1313 Border Street, Unit 34
Winnipeg, Manitoba
R3H 0X4
(800) 665-7635 (Canada only)
Telephone: (204) 632-5598
FAX: (204) 694-5134
E-mail: [email protected]
In Latin America, the Caribbean, the Far East, the
Indian Subcontinent, Africa, Europe, or the Middle East:
Hach Company World Headquarters
P.O. Box 389
Loveland, Colorado, 80539-0389
U.S.A.
Telephone: (970) 669-3050
FAX: (970) 669-2932
E-mail: [email protected]
31
Warranty
Hach warrants most products against defective materials or
workmanship for at least one year from the date of shipment;
longer warranties may apply to some items.
HACH WARRANTS TO THE ORIGINAL BUYER THAT HACH
PRODUCTS WILL CONFORM TO ANY EXPRESS WRITTEN
WARRANTY GIVEN BY HACH TO THE BUYER. EXCEPT AS
EXPRESSLY SET FORTH IN THE PRECEDING SENTENCE,
HACH MAKES NO WARRANTY OF ANY KIND WHATSOEVER
WITH RESPECT TO ANY PRODUCTS. HACH EXPRESSLY
DISCLAIMS ANY WARRANTIES IMPLIED BY LAW,
INCLUDING BUT NOT BINDING TO ANY WARRANTY OF
MERCHANTABILITY OR FITNESS FOR A PARTICULAR
PURPOSE.
LIMITATION OF REMEDIES: Hach shall, at its option, replace or
repair nonconforming products or refund all amounts paid by the
buyer. THIS IS THE EXCLUSIVE REMEDY FOR ANY BREACH
OF WARRANTY.
LIMITATION OF DAMAGES: IN NO EVENT SHALL HACH BE
LIABLE FOR ANY INCIDENTAL OR CONSEQUENTIAL
DAMAGES OF ANY KIND FOR BREACH OF ANY WARRANTY,
NEGLIGENCE, ON THE BASIS OF STRICT LIABILITY, OR
OTHERWISE.
This warranty applies only to Hach products purchased and
delivered in the United States.
Catalog descriptions, pictures and specification, although
accurate to the best of our knowledge, are not a guarantee
or warranty.
For a complete description of Hach Companys warranty policy,
request a copy of our Terms and Conditions of Sale for U.S. Sales
from our Customer Service Department.
32
CERTIFICATION
Hach Company certifies this instrument was tested thoroughly,
inspected and found to meet its published specifications when it
was shipped from the factory.
The COD and THM Reactors have been tested and are certified as
indicated to the following instrumentation standards:
Product Safety
UL 1262 (ETL Listing # H0492805390), 115V model, 45900-00
CSA C22.2 No. 1010.1 (ETLc Certification # H0492805390),
115V model, 45900-00
Certified by Hach to EN 61010-1 (IEC1010-1) per 73/23/EEC,
supporting test records by Dash, Straus & Goodhue (now Intertek
Testing Services), 230V model, 45900-02.
Immunity
EN 61326:1998 (EMC Requirements for Electrical Equipment
for Measurement, Control and Laboratory Use) per 89/336/EEC
EMC: Supporting test records by Hach Company, certified
compliance by Hach Company.
Standards include:
IEC 1000-4-2:1995 (EN 61000-4-2:1995) Electrostatic Discharge
Immunity (Criteria B)
IEC 1000-4-3:1995 (EN 61000-4-3:1996) Radiated RF
Electromagnetic Field Immunity (Criteria A)
IEC 1000-4-4:1995 (EN 61000-4-4:1995) Electrical Fast
Transients/Burst (Criteria B)
IEC 1000-4-5:1995 (EN 61000-4-5:1995) Surge (Criteria B)
IEC 1000-4-6:1996 (EN 61000-4-6:1996) Conducted
Disturbances Induced by RF Fields (Criteria A)
IEC 1000-4-11:1994 (EN 61000-4-11:1994) Voltage Dip/Short
Interruptions (Criteria B)
Additional immunity Standard/s include:
ENV 50204:1996 Radiated Electromagnetic Field from Digital
Telephones (Criteria A)
33
CERTIFICATION, continued
Emissions
Per 89/336/EEC EMC: EN 61326:1998 (Electrical Equipment
for measurement, control and laboratory use-EMC requirements):
Supporting test records by Hach Co.
Required Standard/s include:
EN 55014 (CISPR 14) Emissions, Testing by ETL/Dash, Straus
& Goodhue (now Intertek Testing Services) NVLAP # 0270,
EN 55022 (CISPR 22) Emissions, Class B Limits Testing by
Hach Company
Additional Standard/s include:
EN 61000-3-2 (IEC 1000-3-2) Harmonic Disturbances Caused by
Electrical Equipment
EN 61000-3-3 (IEC 1000-3-3) Voltage Fluctuation (Flicker)
Disturbances Caused by Electrical Equipment
CANADIAN RADIO INTERFERENCE- REGULATION,
1374, Class A: Supporting test records by Hach Company and
ETL/Dash, Straus & Goodhue (now Intertek Testing Services)
NVLAP # 0270, certified compliance by Hach Company.
This Class A digital apparatus meets all requirements of the
Canadian Interference- Causing Equipment Regulations.
Cet appareil numrique de la classe A respecte toutes les
exigences du Rglement sur le matriel brouilleur du Canada.
FCC PART 15, Class "A" Limits: Supporting test records by
Hach Company and Dash, Straus & Goodhue (now Intertek
Testing Services) NVLAP # 0270, certified compliance by Hach
Company.
This device complies with Part 15 of the FCC Rules. Operation is
subject to the following two conditions:
(1) this device may not cause harmful interference, and (2) this
device must accept any interference received, including
interference that may cause undesired operation.
34
CERTIFICATION, continued
Changes or modifications to this unit not expressly approved by
the party responsible for compliance could void the user's
authority to operate the equipment.
This equipment has been tested and found to comply with the
limits for a Class A digital device, pursuant to Part 15 of the FCC
Rules. These limits are designed to provide reasonable protection
against harmful interference when the equipment is operated in a
commercial environment. This equipment generates, uses, and
can radiate radio frequency energy and, if not installed and used
in accordance with the instruction manual, may cause harmful
interference to radio communications. Operation of this
equipment in a residential area is likely to cause harmful
interference, in which case the user will be required to correct the
interference at his own expense. The following techniques of
reducing the interference problems are applied easily.
1. Disconnect the COD or THM Reactor from it's power source
to verify that it is or is not the source of the interference.
2. If the COD or THM Reactor is connected into the same outlet
as the device with which it is interfering, try another outlet.
3. Move the COD or THM Reactor away from the device
receiving the interference.
4. Reposition the receiving antenna for the device receiving the
interference.
5. Try combinations of the above.
35
APPENDIX A: Hach COD Methods
Dichromate Reactor Digestion Method
USEPA Approved
Digestion
Colorimetric Measurement
Titrimetric Measurement
36
37
Method 8000
OXYGEN DEMAND, CHEMICAL For water, wastewater and seawater
Dichromate Reactor Digestion Method*
USEPA approved for reporting wastewater analysis**
Introduction
The Chemical Oxygen Demand (COD) test is used widely to
estimate the amount of organic matter in wastewater. It is a
measurement of the oxygen equivalent of the materials present in
the wastewater that are subject to oxidation by a strong chemical
oxidant, in this case dichromate. When wastewater contains only
readily available organic bacterial food and no toxic matter, the
COD test results provide a good estimate of Biochemical Oxygen
Demand (BOD) values.
In the Dichromate Reactor Digestion Method test, the COD
procedure is simpler than Dichromate Reflux Method. Small
volumes of the water sample are pipetted into vials containing the
premeasured reagents, including catalysts and chloride
compensator. The vials are incubated until digestion is complete
and then cooled. The COD measurement is made either with the
spectrophotometer (accepted for reporting by the U.S.
Environmental Protection Agency) or by titration.
Material Safety Data Sheets and Labels
Material Safety Data Sheets (MSDS) are supplied with all
reagents. It is good laboratory practice to read the MSDS and the
reagent container labels to familiarize yourself with the reagents
used in this procedure.
* Jirka, A.M.; Carter, M.J. Analytical Chemistry, 1975, 47(8): 1397.
** Federal Register, April 21, 1980, 45(78): 26811-26812. The Ultra Low Range (0 to 40 mg/L) COD
Vials are not USEPA approved. High Range Plus (0 to 15,000 mg/L) COD Vials are not USEPA
approved. Titrimetric measurement is not USEPA approved.
38
OXYGEN DEMAND, CHEMICAL, continued
Analysis Procedure
Both the titrimetric measurement and the colorimetric
measurement for determining Dichromate Chemical Oxygen
Demand (COD) are detailed in this procedure. Sample digestion
is required for both methods, with the choice of the final
measurement method left to the analyst. Colorimetric
measurement is the simpler and quicker of the two and is
USEPA approved. Hach's titrimetric measurement should be
used if turbidity or colored species remain after digestion; it is
not USEPA approved.
Waste Management
Final samples will contain mercury, silver, and chromium at
concentration levels regulated as hazardous waste by the Federal
RCRA. Contact your governing local, state, or federal agency for
further information on proper disposal of these materials.
39
OXYGEN DEMAND, CHEMICAL, continued
Digestion Method 8000
1. Homogenize 100 mL
of sample for 30 seconds
in a blender.
Note: Mix the sample
prior to homogenization.
To improve accuracy and
reproducibility, pour the
homogenized sample into
a 250 mL beaker and
gently stir with a magnetic
stir plate. For samples
containing large amounts
of solids, increase the
homogenization time.
Note: Some of the
chemicals and apparatus
used in this procedure
may be hazardous to the
health and safety of the
user if inappropriately
handled or accidentally
misused. Please read all
warnings and the safety
section of this manual.
Wear appropriate eye
protection and clothing for
adequate user protection.
If contact occurs, flush the
affected area with running
water. Follow instructions
carefully.
2. Turn on the COD
Reactor. Preheat to
150 !C. Place the plastic
shield in front of the
reactor.
Note: Ensure safety
devices are in place to
protect analyst from
splattering should reagent
leaking occur.
3. Remove the cap of a
COD Digestion Reagent
Vial for the appropriate
range:
Note: The reagent mixture
is light-sensitive. Keep
unused vials in the
opaque shipping
container, in a refrigerator
if possible. The light
striking the vials during
the test will not affect
results.
4. Hold the vial at a
45-degree angle. Pipet
2.00 mL (0.2 mL for the
0 to 15,000 mg/L range)
of sample into the vial.
Note: For the 015,000
mg/L range, pipet only
0.20 mL of sample, not
2.00 mL of sample, using
a TenSette

Pipet.
For greater accuracy a
minimum of three
replicates should be
analyzed and the results
averaged.
Note: Spilled reagent will
affect test accuracy and is
hazardous to skin and
other materials. Do not
run tests with vials that
have been spilled. If vials
spill, wash them with
running water.
Sample
Conc.
Range
(mg/L)
COD
Digestion
Reagent Vial
Type
0 to 40 Ultra Low
Range
0 to 150 Low Range
0 to 1500 High Range
0 to 15,000 High Range
Plus
40
OXYGEN DEMAND, CHEMICAL, continued
5. Replace the vial cap
tightly. Rinse the outside
of the COD vial with
deionized water and
wipe the vial clean with
a paper towel.
6. Hold the vial by the
cap and over a sink.
Invert gently several
times to mix the
contents. Place the vial
in the preheated COD
Reactor.
Note: The vial will become
very hot during mixing.
7. Prepare a blank by
repeating steps 3 to 6,
substituting 2.00 mL
(0.2 mL for the 0 to
15,000 mg/L range)
deionized water for the
sample.
Note: Be sure the pipet
is clean.
Note: One blank must be
run with each set of
samples. Run samples
and blanks with the same
lot of vials.
8. Heat the vials for
2 hours.
Note: Many samples are
digested completely in
less than 2 hours. If
desired, measure the
concentration (while still
hot) at 15 minute intervals
until the reading remains
unchanged. Cool the vials
to room temperature for
final measurement.
HRS MIN SEC HRS MIN SEC
Heat for 2 hours
41
OXYGEN DEMAND, CHEMICAL, continued
9. Turn the reactor off.
Wait about 20 minutes
for the vials to cool to
120 !C or less.
10. Invert each vial
several times while still
warm. Place the vials
into a rack. Wait until
the vials have cooled to
room temperature.
Note: If a pure green color
appears in the reacted
sample, measure the
COD and, if necessary,
repeat the test with a
diluted sample.
11. Use one of the
following techniques to
measure the COD:
Colorimetric method,
040 mg/L COD
Colorimetric method,
0150 mg/L COD
Colorimetric method,
01500 mg/L COD
Colorimetric method,
015,000 mg/L COD
Titrimetric method,
0150, 01500,
015,000 mg/L COD
Choose a range.
42
OXYGEN DEMAND, CHEMICAL, continued
Colorimetric Measurement, 0 to 40 mg/L COD* Method 8328
* Ultra Low Range Reagent Vials are not USEPA approved and may be used only with spectrophotometers with
350-nm capability.
1. If using the DR/4000
Spectrophotometer,
press the soft key under
HACH PROGRAM.
Select the stored
program number for ultra
low range COD by
pressing 2700 with the
numeric keys.
Press: ENTER
2. The display will
show:
HACH PROGRAM:
2700 COD, ULR
The wavelength ($),
350 nm, is automatically
selected.
3. Insert the Test Tube
Adapter into the sample
cell module by sliding it
under the thumb screw
and into the alignment
grooves. Fasten with the
thumb screw.
Note: The DR/4000 Test
Tube Adapter is NOT
designed to allow
readings on hot vials
(150 !C).
4. Clean the outside of
the blank with a towel.
Note: Wiping with a
damp towel, followed by
a dry one will remove
fingerprints or other
marks.
HACH
PROGRAM
ENTER
7 0 0 2
HACH PROGRAM:
2700 COD, ULR
43
OXYGEN DEMAND, CHEMICAL, continued
5. Place the blank into
the adapter with the
Hach logo facing the
front of the instrument.
Close the light shield.
Note: Preparation of the
blank is described in the
digestion procedure.
Note: The blank is stable
when stored in the dark;
see Blanks for
Colorimetric Measurement
on page 51.
6. Press the soft key
under ZERO.
The display will show:
0.0 mg/L COD
Note: For alternate
concentration units press
the OPTIONS soft key.
Then press the soft key
under UNITS to scroll
through the available
options. Press ENTER to
return to the read screen.
7. Clean the outside of
the sample vial with a
towel.
8. Place the sample vial
into the adapter with the
Hach logo facing the
front of the instrument.
Close the light shield.
Results in mg/L COD
(or chosen units) will be
displayed.
Note: Results may be
expressed as mg/L COD
or mg/L O
2
. Press the soft
key under OPTIONS and
then press FORM: to scroll
through the available
choices.
Note: If the display shows
45 mg/L COD and/or
OVER!, the upper limit of
the range has been
exceeded. Repeat the test
with a dilute sample or use
a Low Range or High
Range COD Reagent Vial.
ZERO
44
OXYGEN DEMAND, CHEMICAL, continued
Colorimetric Measurement, 0 to 150 mg/L COD Method 8000
1. Enter the stored
program number for
chemical oxygen
demand (COD),
low range.
Press: 4 3 0 ENTER
The display will show:
Dial nm to 420
2. Rotate the
wavelength dial until the
small display shows:
420 nm
When the correct
wavelength is dialed in,
the display will quickly
show: Zero Sample
then: mg/L COD LR
Note: Approach the
wavelength setting from
the higher to lower values.
3. Place the COD Vial
Adapter into the cell
holder with the marker
to the right.
4. Clean the outside of
the blank with a towel.
Note: Wiping with a
damp towel, followed by
a dry one, will remove
fingerprints or other
marks.
420 nm
45
OXYGEN DEMAND, CHEMICAL, continued
5. Place the blank into
the adapter with the
Hach logo facing the
front of the instrument.
Place the cover on the
adapter.
Note: The blank is stable
when stored in the dark;
see Blanks for
Colorimetric
Determination following
these procedures.
6. Press: ZERO
The display will show:
Zeroing. . . .
then: 0. mg/L COD LR
7. Clean the outside of
the sample vial with a
towel.
8. Place the sample vial
into the adapter with the
Hach logo facing the
front of the instrument.
Place the cover on the
adapter.
9. Press: READ
The display will show:
Reading. . . .
then the result in mg/L
COD will be displayed.
Note: For most accurate
results with samples near
150 mg/L COD, repeat the
analysis with a diluted
sample.
46
OXYGEN DEMAND, CHEMICAL, continued
Colorimetric Measurement, 0 to 1500 and 0 to 15,000 mg/L COD* Method 8000
* The High Range Plus (0 to 15,000 mg/L) COD Vials are not USEPA approved.
1. Enter the stored
program number for
chemical oxygen
demand, high range.
Press: 4 3 5 ENTER
The display will show:
Dial nm to 620
2. Rotate the
wavelength dial until the
small display shows:
620 nm
When the correct
wavelength is dialed in,
the display will quickly
show:
Zero Sample
then: mg/L COD HR
3. Place the COD Vial
Adapter into the cell
holder with the marker
to the right.
4. Clean the outside of
the blank with a towel.
Note: Wiping with a damp
towel followed by a dry
one will remove
fingerprints or other
marks.
620 nm
47
OXYGEN DEMAND, CHEMICAL, continued
5. Place the blank into
the adapter with the
Hach logo facing the
front of the instrument.
Place the cover on the
adapter.
Note: The blank is stable
when stored in the dark.
See Blanks for
Colorimetric Measurement
following these
procedures.
6. Press: ZERO
The display will show:
Zeroing. . . .
then: 0. mg/L COD HR
7. Clean the outside of
the sample vial with
a towel.
8. Place the sample vial
in the adapter with the
Hach logo facing
the front of the
instrument. Place the
cover on the adapter.
9. Press: READ
The display will show:
Reading. . . .
then the result in mg/L
COD will be displayed.
Note: When using High
Range Plus COD
Digestion Reagent Vials
multiply the reading by 10.
Note: For most accurate
results with samples near
1500 or 15,000 mg/L
COD, repeat the analysis
with a diluted sample.
48
OXYGEN DEMAND, CHEMICAL, continued
Titrimetric Measurement, 0 to 150, 0 to 1500, and 0 to 15,000 mg/L COD* Method 8231
* Titrimetric measurement of reactor-digested samples is not USEPA approved.
1. Carefully remove the
cap of a digested vial.
Rinse the inside walls
with less than 1 mL of
deionized water.
2. Add a small Teflon-
coated stirring bar and
one drop of the
appropriate Ferroin
Indicator Solution.
When using the Low
Range COD Digestion
Vials, use Low Range
Ferroin Indicator
Solution. When using
the High Range or High
Range Plus COD
Digestion Reagent Vials,
use High Range Ferroin
Indicator Solution.
Note: If the color of the
prepared sample changes
from blue-green to
orange-brown, the COD
value is out of range.
Dilute the sample and
repeat the digestion.
3. Place the vial on the
titration stand. Turn on
the magnetic stirrer.
4. Titrate with the
appropriate Ferrous
Ammonium Sulfate
Standard Solution (FAS)
until the sample color
changes sharply from
greenish-blue to orange-
brown. When using the
Low Range COD
Digestion Reagent Vials,
use 0.0125 N FAS.
When using the High
Range or High Range
Plus COD Digestion
Reagent Vials, use 0.125
N FAS. Record the mL
of titrant required. The
mL required for the
prepared sample is value
B. The mL required for
the blank is value A.
Note: Mix the FAS bottle
well before using.
Note: Values A and B are
used in step 8.
Stir Bar
49
OXYGEN DEMAND, CHEMICAL, continued
5. Pipet 2.00 mL of
Potassium Dichromate
Standard Solution into
an empty vial. When
using the Low Range
COD Digestion Reagent
Vials, use a 0.025 N
solution. When using
High Range or High
Range Plus COD
Digestion Reagent Vials,
use a 0.25 N solution.
Add 3 ml of sulfuric acid
to the vial. Swirl to mix.
Wait for the solution to
cool until the vial is
comfortable to touch.
Note: Steps 5 through 7
need only be done daily
because the FAS
deteriorates over time.
6. Add one drop of
the Ferroin Indicator
Solution selected in
step 2.
7. Add a stir bar and
titrate with the Ferrous
Ammonium Sulfate
Standard Solution
selected in step 4 until
the color changes from
greenish-blue to orange-
brown. Record the
number of mL required.
This is value C in the
following equation.
Note: Mix the FAS bottle
well before using.
Note: To remove the stir
bar from the vial, tip the
vial at an angle in one
hand and hold the stir bar
retriever in the other.
Place the retriever near
the bottom of the vial on
the OUTSIDE. Move the
retriever up the wall to the
top of the vial.
8. Determine the
mg/L COD according to
the equation above.
Where:
A = mL used in titration of
reagent blank
B = mL used in titration of
prepared sample
C = mL used in titration
of standard solution in Step 7
above
M = 0.1 when using Low Range
COD Digestion Reagent Vials
M = 1 when using High Range
COD Digestion Reagent Vials
M = 10 when using High Range
Plus COD Digestion Reagent
Vials
For example, when using Low
Range COD Reagent Vials:
A= 3.95 mL
B = 2.00 mL
C = 4.00 mL
M = 0.1
(A - B)
2000
C
------------- " M = "
mg/L COD
mg/L COD
3.95 2.00 % &
2000
4.00
------------- " 0.1 " =
97.5 =
50
OXYGEN DEMAND, CHEMICAL, continued
Sampling and Storage
Collect samples in glass bottles. Use plastic bottles only if they
are known to be free of organic contamination. Test biologically
active samples as soon as possible. Homogenize samples
containing solids to assure representative samples. Samples
treated with sulfuric acid to a pH of less than 2 (about 2 mL
per liter) and refrigerated at 4 !C can be stored up to 28 days.
When significant amounts of preservatives are used, a volume
correction should be made for the extra acid by dividing the total
volume (sample + acid) by the sample volume and multiplying
this value by the final test reading.
Accuracy Check
Standard Solution Method
Check the accuracy of the 0 to 40 mg/L range with a 30 mg/L
COD standard solution. Using Class A glassware, prepare a
1000-mg/L solution by diluting 850 mg of dried (120 !C,
overnight) potassium acid phthalate (KHP) in 1000 mL of
organic-free deionized water. Prepare a 30 mg/L dilution by
diluting 3.00 mL of this solution into a 100.0 mL volumetric
flask. Dilute to volume with deionized water, stopper, and invert
10 times to mix.
Check the accuracy of the 0 to 150 mg/L range with a 100 mg/L
standard. Prepare by dissolving 85 mg of dried (120 !C,
overnight) potassium acid phthalate (KHP) in 1 liter of deionized
water. Use 2 mL as the sample volume. The expected result will
be 100 mg/L COD. Or, dilute 10 mL of 1000-mg/L COD
Standard Solution to 100 mL to produce a 100-mg/L standard.
Check the accuracy of the 0 to 1500 mg/L range by using either
a 300 mg/L or 1000 mg/L COD Standard Solution. Use 2 mL of
one of these solutions as the sample volume; the expected result
will be 300 or 1000 mg/L COD respectively.
Or, prepare a 500 mg/L standard by dissolving 425 mg of dried
(120 !C, overnight) KHP. Dilute to 1 liter with deionized water.
Check the accuracy of the 0 to 15,000 mg/L range by using a
10,000 mg/L COD standard solution. Prepare the 10,000 mg/L
solution by dissolving 8.500 g of dried (120 !C, overnight) KHP
51
OXYGEN DEMAND, CHEMICAL, continued
in 1 liter of deionized water. Use 0.2 mL of this solution as the
sample volume; the expected result will be 10,000 mg/L COD.
Preparing Organic-Free Water
To prepare organic-free water with no measurable COD:
1. Pour 1.0 liter of deionized water with low COD in a 2-liter
Erlenmeyer flask.
2. Add the contents of one Potassium Persulfate Powder Pillow
to the flask. Swirl to dissolve.
3. Suspend a UV lamp in the flask so the glass portion of the
bulb is immersed and the black bakelite portion is above the
solution. Follow the safety and operation instructions
recommended in the UV lamp kit. Safety UV goggles should
be worn for eye protection.
4. Irradiate the solution with UV light for at least 2 hours
(overnight is fine).
5. Remove the lamp from the solution. Add one level 0.05-gram
scoop of Nickel Sulfate to the solution.
6. Heat the water to a boil. Remove the flask from the hot plate
and cover it with a watch glass.
7. Let the flask cool to room temperature. The water will have
zero oxygen demand. Seal the flask top with aluminum foil to
prevent organic contamination. The water should stay free of
oxygen demand for one week if properly sealed.
Blanks for Colorimetric Measurement
The blank may be used repeatedly for measurements using
the same lot of vials. Store it in the dark. Monitor decomposition
by measuring the absorbance at the appropriate wavelength
(350, 420, or 620 nm.) Zero the instrument in the absorbance
mode, using a culture tube (see OPTIONAL APPARATUS on
page 56) containing 5 mL of deionized water. Measure the
absorbance of the blank and record the value. Prepare a blank
when the absorbance has changed by approximately 0.010
absorbance units.
52
OXYGEN DEMAND, CHEMICAL, continued
Precision For Colorimetric Measurement
In a single laboratory using standard solutions of 100 mg/L
COD and 500 mg/L COD and two lots of reagent with the
DR/2010 Spectrophotometer, a single operator obtained a
standard deviation of 2.7 mg/L COD, 18 mg/L COD and
100 mg/L COD for 0 to 150, 0 to 1500 and 0 to 15,000 mg/L
ranges, respectively.
Estimated Detection Limit (EDL)
The EDL is the calculated lowest average concentration in a
deionized water matrix that is different from zero with a 99%
level of confidence. The EDL for program 2700 is 0.2 mg/L
COD, and for program 430 is 2 mg/L COD.
The EDL for program 435 is 5 mg/L COD. For more information
on derivation and use of Hachs estimated detection limit, see
your Hach spectrophotometer instrument manual.
Interferences
Chloride is the primary interference when determining COD
concentration. Each COD vial contains mercuric sulfate, which
will eliminate chloride interference up to the level specified in
column 1 in the table below. Samples with higher chloride
concentrations should be diluted. Dilute the sample enough to
reduce the chloride concentration to the level given in column 2.
If sample dilution will cause the COD concentration to be too
low for accurate determination, add 0.50 g of mercuric sulfate
(HgSO
4
) to each COD vial before the sample is added. The
additional mercuric sulfate will raise the maximum chloride
concentration allowable to the level given in column 3.
Bromide interference will not be controlled by mercuric sulfate.
53
OXYGEN DEMAND, CHEMICAL, continued
Summary of Method
The mg/L COD results are defined as the mg of O
2
consumed
per liter of sample under conditions of this procedure. In this
procedure, the sample is heated for two hours with a strong
oxidizing agent, potassium dichromate. Oxidizable organic
compounds react, reducing the dichromate ion (Cr
2
O
7
2
) to green
chromic ion (Cr
3+
). When the 040 mg/L or 0150 mg/L
colorimetric measurement is used, the amount of Cr
6+
remaining
is determined. When the 01500 mg/L or 015,000 mg/L
colorimetric measurement is used, the amount of Cr
3+
produced
is determined. The COD reagent also contains silver and mercury
ions. Silver is a catalyst, and mercury is used to complex
chloride interferences.
Vial Type Used
Maximum Cl

concentration in
sample (mg/L)
Suggested Cl

concentration of
diluted sample (mg/L)
Maximum Cl

concentration in
sample with 0.5 g
HgSO
4
Added (mg/L)
Ultra Low Range 2000 1000 NA
Low Range 2000 1000 8000
High Range 2000 1000 4000
Ultra High Range 20,000 10,000 40,000
54
OXYGEN DEMAND, CHEMICAL, continued
REQUIRED REAGENTS (for colorimetric measurement)
Quantity Required
Description Per Test Unit Cat. No.
Select the appropriate COD Digestion Reagent Vial:
Ultra Low Range, 0 to 40 mg/L COD ...............................12 .....................25/pkg ... 24158-25
Low Range, 0 to 150 mg/L COD.......................................12 .....................25/pkg ... 21258-25
High Range, 0 to 1500 mg/L COD....................................12 .....................25/pkg ... 21259-25
High Range Plus, 0 to 15,000 mg/L COD.........................12 .....................25/pkg ... 24159-25
Water, deionized............................................................... varies......................... 4 L ....... 272-56
REQUIRED REAGENTS (for titrimetric measurement)*
Quantity Required
Description Per Test Unit Cat. No.
Select One or Both Potassium Dichromate Standard Solutions
0.025 N ............................................................................ 2 mL.................. 500 mL ....... 164-49
0.25 N............................................................................... 2 mL................ 1000 mL ..... 1809-53
Sulfuric Acid, ACS ......................................................... 3 mL.............. 500 mL** ....... 979-49
Water, deionized............................................................... varies......................... 4 L ....... 272-56
Select the appropriate COD Digestion Reagent Vial
Low Range ........................................................................12 ...............25/pkg*** ... 21258-25
High Range ...................................................................... 1 2...............25/pkg*** ... 21259-25
High Range Plus ...............................................................12 .....................25/pkg ... 24159-25
Select one or both Ferroin Indicator Solutions
Low Range .................................................................. 1 2 drops ..........29 mL DB ... 20551-33
High Range ..................................................................12 drops ....29 mL DB*** ..... 1812-33
Select one or both Ferrous Ammonium Sulfate Standard Solutions***
0.0125 N .......................................................................... varies ................ 1000 mL ... 14237-53
0.125 N ............................................................................ varies .................. 500 mL ... 20548-49
* Does not include reagent or apparatus for reagent blanks or standardization.
** Contact Hach for larger sizes.
*** Ferrous Ammonium Sulfate Standard Solutions, as prepared by Hach, have a length of cadmium
wire in each bottle. The cadmium wire will help preserve the standard solution. Before filling the buret,
the bottle should be swirled to bring the upper layer of solution in contact with the wire. When titrating
these solutions, do not return unused portions from the buret to the bottle or allow solution to stand in
the buret for long periods of time. Do NOT use an automatic buret with a reservoir that holds more
solution than can be used in one day.
55
OXYGEN DEMAND, CHEMICAL, continued
REQUIRED APPARATUS (for colorimetric measurement)
Quantity Required
Description Per Test Unit Cat.
COD Reactor, 115/230 Vac, 50/60 Hz,
North American fuses and plug........................................... 1........................... each....45600-00
COD Reactor, 230 Vac, 50 Hz,
European fuses and plug ..................................................... 1........................... each....45600-02
COD Test Tube Adapter, DR/4000 ..................................... 1........................... each....48189-00
COD Vial Adapter, DR/2010 .............................................. 1........................... each....44799-00
Pipet, TenSette

, 0.1 to 1.0 mL........................................... 1........................... each....19700-01

Pipet, volumetric, Class A, 2.00 mL ................................... 1........................... each....14515-36
Pipet Filler, safety bulb........................................................ 1........................... each....14651-00
Test Tube Rack.................................................................. 12......................... each....18641-00
REQUIRED APPARATUS (for titrimetric measurement)
Quantity Required
Description Per Test Unit Cat.
Bottle, wash, 500 mL .......................................................... 1........................... each ........620-11
Buret Clamp, double ........................................................... 1........................... each ........328-00
Buret, automatic, Class A, 5.00 mL.................................... 1........................... each ....20550-37
COD Reactor, 115/230 Vac, 50/60 Hz,
North American fuses and plug........................................... 1........................... each....45600-00
COD Reactor, 230 Vac, 50 Hz,
European fuses and plug ..................................................... 1........................... each....45600-02
Pipet, volumetric, Class A, 2.00 mL ................................... 1........................... each ....14515-36
Pipet, Mohr, 5.00 mL .......................................................... 1........................... each ....20934-37
Pipet Filler, safety bulb........................................................ 1.......................... each ....14651-00
Safety Shield, laboratory bench .......................................... 1........................... each ....23810-00
Stir Bar ................................................................................ 1.......................... each ....20549-59
Stir Bar Retriever................................................................. 1........................... each ....15232-00
Stirrer, magnetic, 120 Vac, 50/60 Hz .................................. 1........................... each ....23444-00
Stirrer, magnetic, 240 Vac, 50/60 Hz .................................. 1........................... each....23444-02
Support Stand...................................................................... 1........................... each ........563-00
Test Tube Rack, steel, 8 place ..........................................1 or 2 ....................... each ....18641-00
Titration Stand, test tube ..................................................... 1........................... each ....18642-00
56
OXYGEN DEMAND, CHEMICAL, continued
OPTIONAL REAGENTS
Quantity Required
Description Per Test Unit Cat. No.
COD Digestion Reagent Vials, 0 to 40 mg/L COD.....................................150/pkg ... 24158-15
COD Digestion Reagent Vials, 0 to 150 mg/L COD...................................150/pkg ... 21258-15
COD Digestion Reagent Vials, 0 to 1500 mg/L COD.................................150/pkg ... 21259-15
COD Standard Solution, 300 mg/L.............................................................. 200 mL ... 12186-29
COD Standard Solution, 1000 mg/L............................................................ 200 mL ... 22539-29
Mercuric Sulfate, ACS............................................................................ 28.3 grams ..... 1915-20
Nickel Sulfate, ACS................................................................................... 25 grams ... 11264-24
Potassium Acid Phthalate, ACS.......................................................................500 g ....... 315-34
Sulfuric Acid, ACS.................................................................................... 500 mL* ....... 979-49
Potassium Persulfate Powder Pillows ..........................................................100/pkg ... 20847-69
OPTIONAL APPARATUS
Balance, analytical, 115 Vac............................................................................. each ... 26103-00
Balance, analytical, 220 Vac............................................................................. each .. 26103-02
Beaker, 250 mL................................................................................................. each ....... 500-46
Blender, 120 Vac, 1.2-L, 2-speed...................................................................... each ... 26161-00
Blender, 220 Vac, 1.2-L, 2-speed...................................................................... each ... 26161-02
Culture Tube, 16 x 100 ....................................................................................6/pkg ... 22758-06
Culture Tube Cap.............................................................................................6/pkg ... 22411-06
Cylinder, graduated, 5 mL ................................................................................ each ....... 508-37
Electromagnetic Stirrer, 120 V ac, with electrode stand .................................. each ... 45300-01
Electromagnetic Stirrer, 230 V ac, with electrode stand .................................. each ... 45300-02
Flask, volumetric, Class A, 1000 mL ............................................................... each ... 14574-53
Flask, volumetric, Class A, 100 mL ................................................................. each ... 14574-42
pH Indicator Paper, 1 to 11 pH............................................................... 5 rolls/pkg ....... 391-33
Pipet, serological, 5 mL.................................................................................... each ....... 532-37
Pipet Tips, for 19700-01 TenSette

Pipet ......................................................50/pkg ... 21856-96

Pipet, volumetric, Class A, 10 mL.................................................................... each ... 14515-38
Safety Shield for COD Reactor ........................................................................ each ... 23810-00
Spoon, measuring, 0.5 g.................................................................................... each ....... 907-00
Stir Bar, 22.2 x 4.76 mm................................................................................... each ... 45315-00
Stir Bar Retriever .............................................................................................. each ... 15232-00
UV Lamp Kit, 115 Vac ..................................................................................... each ... 20828-00
UV Lamp Kit, 230 Vac ..................................................................................... each ... 20828-02
For Technical Assistance, Price and Ordering, see GENERAL INFORMATION.
In the U.S.A.Call 800-227-4224
Outside the U.S.A.Contact the Hach office or distributor serving you.
* Contact Hach for larger sizes.
57
APPENDIX B: Hach COD Methods
Manganese III COD Method
Digestion
Colorimetric Measurement
58
59
Method 10067
OXYGEN DEMAND, CHEMICAL (20 to 1000 mg/L) For water and wastewater
Manganese III Reactor Digestion Method * (with optional chloride removal)
1. Enter the stored user
program number for
Manganese III COD.
Press: 4 3 2 ENTER
The display will show:
Dial nm to 510
Note: If samples cannot
be analyzed immediately,
see Sampling and Storage
on page 64.
Note: Preheat the COD
Reactor to 150 !C for use
later in the procedure.
2. Rotate the
wavelength dial until the
small display shows:
510 nm
When the correct
wavelength is dialed in,
the display will quickly
show: Zero Sample
then:
mg/L COD Mn III
Note: Approach
wavelength settings from
higher to lower values.
3. Homogenize
100 mL of sample for
30 seconds in a blender.
Note: Blending promotes
even distribution of solids
and improves accuracy
and reproducibility.
Note: Continue mixing the
sample while pipetting if
suspended solids are
present.
4. If the sample
contains chloride, go to
step 6 and follow the
chloride removal
procedure.
If chloride is not present
in significant amounts,
pipet 0.50 mL of
homogenized sample
into a Mn III COD vial.
Cap and invert several
times to mix.
Note: If the sample
COD value is not between
20 to 1000 mg/L and the
chloride removal
procedure is not
necessary, dilute the
sample with deionized
water to obtain a range of
20 to 1000 mg/L COD.
Multiply the final result by
the dilution factor.
To determine if chloride
will interfere, run the
sample with and without
the chloride removal
procedure and compare
the results.
* U.S. patent 5,556,787.
510 nm
IF SAMPLE
CONTAINS
CHLORIDE, GO
TO STEP 6
60
OXYGEN DEMAND, CHEMICAL, continued
5. Prepare a blank (see
note) by substituting
0.50 mL of deionized
water for the sample.
Continue with step 19 of
this procedure.
Note: The reagent blank
is stable and can be
reused. Verify reagent
blank quality by measuring
the absorbance of the
blank vs. a clean COD vial
filled with deionized water.
The absorbance range
should be about
1.451.51.
Chloride Removal
Procedure (Steps 618)
6. Using a TenSette

Pipet or a pipet and
safety bulb, pipet 9.0 mL
of homogenized sample
into an empty glass
mixing cell. If the
sample COD exceeds
1000 mg/L, dilute the
sample as described in
Table 1.
Note: If suspended solids
are present, continue
mixing the sample while
pipetting.
7. Using an automatic
dispenser or TenSette
Pipet, add 1.0 mL of
concentrated sulfuric
acid to the mixing cell.
Note: Mixing concentrated
sulfuric acid and water is
not additive. Adding 1.0
mL of concentrated
sulfuric acid to 9.0 mL of
sample does not result in
a final volume of 10.0 mL.
This factor is built into the
calibration curve.
8. Cap the cell tightly
and invert it several
times. The solution will
become hot. Cool to
room temperature before
proceeding.
Note: Acidified samples
are stable for several
months when refrigerated
at 4 !C.
Table 1 Dilution Table (for use with Chloride Removal Procedure only)
PREPARE BLANK
All dilutions require that the ratio of sample to sulfuric acid remain at 9:1. For other dilutions that are not listed in Table 1, simply add the
sample volume + deionized water and divide by the sample volume to obtain the multiplication factor.
Example:
Dilute the sample to a range of 904500 mg/L COD
Sample Volume (2.0 mL) + Deionized water (7.0 mL) = Total Volume (9.0 mL)
Standard test range is 201000 mg/L COD.
It is best to use 0.5 mL or more of sample for diluting. If sample values exceed 18,000 mg/L COD, use a separate sample dilution before
the sample chloride removal procedure.
Sample (mL) Deionized Water (mL) Range (mg/L COD) Multiplication Factor
6.0 3.0 301500 1.5
3.0 6.0 603000 3
1.0 8.0 1809000 9
0.5 8.5 36018,000 18
Multiplication Factor
Total Volume
Sample Volume
------------------------------------------
9.0 mL
2.0 mL
------------------ 4.5 = = =
Example Test Range 4.5 (20) to 4.5 (1000) 90-4500 mg/L COD = =
61
OXYGEN DEMAND, CHEMICAL, continued
9. Prepare a blank (see
note) by repeating steps
68, substituting 9.0 mL
of deionized water for
the sample.
Note: The reagent blank
is stable and can be
reused. Verify reagent
blank quality by measuring
the absorbance of the
blank vs. a clean COD vial
filled with deionized water.
The absorbance range,
when using chloride
removal, should be about
1.421.47.
Note: Use a clean pipet or
rinse it thoroughly.
Note: One blank must be
run with each lot of
reagents. Run all samples
and blanks with the same
lot of vials (lot number is
on the container label).
10. If not already on,
turn on the COD Reactor
and heat to 150 !C.
Place the shield in front
of the reactor.
Note: Ensure safety
devices are in place to
protect the analyst from
splattering if leaks occur.
Spilled reagent will affect
test accuracy and is
hazardous. Do not run
tests with vials which have
been spilled.
11. Label each Mn III
COD vial and remove
the cap. Place the vial in
one of the numbered
holes in the Vacuum
Pretreatment Device
(VPD)* base.
Note: The VPD must be
attached to a vacuum
pump (not an aspirator-
type vacuum) that can
create a vacuum of 20 to
25 inches of mercury.
*Patent pending.
12. Place the VPD top
on the base. Insert a
fresh Chloride Removal
Cartridge (CRC)**
directly above each Mn
III COD Reagent Vial.
Plug any open holes in
the VPD top using the
stoppers provided.
** U.S. patents
5,667,754 and
5,663,914.
PREPARE BLANK
62
OXYGEN DEMAND, CHEMICAL, continued
13. Turn the vacuum
pump on and adjust the
vacuum regulator valve
on top of the VPD until
the internal gauge reads
20 inches of water.
Note: The optimum
setting allows the sample
to flow through the CRC in
about 30 to 45 seconds.
14. Pipet 0.60 mL of
acidified sample (made
in steps 68) into the
CRC. Pipet 0.60 mL
of acidified blank
into another CRC.
It should take about
3045 seconds to draw
the liquid through the
CRC into each vial.
Note: If the sample does
not flow through the CRC,
increase the vacuum until
flow starts, then reduce
the vacuum to 20 inches
of water. Proceed as
usual.
15. Close the vacuum
regulator valve
completely to achieve
full vacuum. After
1 minute under full
vacuum, slide the VPD
back and forth several
times to dislodge any
drops clinging to the
cartridge.
Note: The maximum
range of the VPD vacuum
gauge is 40 inches of
water. It will not indicate
the full vacuum level
obtained. Full vacuum is
2025 inches of mercury,
measured at the vacuum
pump with a gauge
calibrated for inches of
mercury.
16. Open the VPD
regulator valve to release
the vacuum. Turn the
pump off. Remove the
VPD top and set it
beside the base.
63
OXYGEN DEMAND, CHEMICAL, continued
17. Use forceps to
remove the filter from
the top of each CRC.
Place each filter in the
corresponding Mn III
COD Vial (use the
numbers on the VPD as
a guide).
Note: To avoid cross
contamination, clean
forcep tips between
samples by wiping with a
clean towel or rinsing with
deionized water.
Note: If the sample does
not contain suspended
solids, it is not necessary
to transfer the filter to the
digestion vial.
18. Remove the Mn III
COD vial from the
vacuum chamber and
replace the original cap.
Screw the cap on tightly.
Invert several times to
mix.
Note: Dispose of the used
Chloride Removal
Cartridge. Do not reuse it.
19. Place the vials in
the COD Reactor that is
preheated to 150 !C.
Digest for 1 hour.
Note: Boiling sample in
the vials during digestion
indicates the vial is not
properly sealed; test
results will be invalid.
Note: Samples can be
digested up to 4 hours to
oxidize more resistant
organics. The prepared
blank must be treated in
the same manner.
20. Remove the vials
and place them in a
cooling rack for
2 minutes to air cool.
Then cool the vials to
room temperature in a
cool water bath or
running tap water. This
usually takes about
3 minutes.
Note: Occasionally a vial
will develop a colorless
upper layer and a purple
lower layer. Invert the vial
several times to mix and
proceed. This will not
affect test results.
21. Remove the vials
from the water and wipe
with a clean, dry paper
towel.
Invert the vials several
times to mix.
22. Place the COD
Vial Adapter into the
cell holder.
23. Place the blank into
the sample cell adapter.
Place the cover on the
adapter.
24. Press: ZERO
The display will show:
Zeroing. . .
then:
0 mg/L COD Mn III
3:00 minutes
64
OXYGEN DEMAND, CHEMICAL, continued
Sampling and Storage
Collect samples in clean glass bottles. Use plastic bottles only
if they are known to be free of organic contamination. Test
biologically active samples as soon as possible. Homogenize
samples containing solids to assure representative samples.
Samples treated with concentrated sulfuric acid to a pH of less
than 2 (about 2 mL per liter) and refrigerated at 4 !C may be
stored up to 28 days. Correct results for volume additions; see
your Hach spectrophotometer manual for more information.
Accuracy Check
Standard Solution Method
Prepare an 800 mg/L COD standard solution by adding 0.6808 g
of dried (103 !C, overnight) potassium acid phthalate (KHP) to
1 liter of deionized water. Use 0.50 mL of this solution (0.60 mL
for the chloride removal procedure) as the sample volume. The
result should be 800 26 mg/L COD. An 800 mg/L COD
solution can also be purchased directly from Hach (see
OPTIONAL REAGENTS AND APPARATUS on page 67).
25. If the chloride
removal was done, make
sure the filter disc is not
suspended in the middle
of the vial; it can
interfere with the
instrument reading.
Move it with gentle
swirling or by lightly
tapping the vial on the
table top.
26. Place the sample in
the sample cell adapter.
Place the cover on the
adapter.
27. Press: READ
The display will show:
Reading. . .
then the results in mg/L
COD will be displayed.
Note: Adjust the result for
any sample dilution in
steps 4 or 6.
65
OXYGEN DEMAND, CHEMICAL, continued
Method Performance
(for Manganic III COD without the chloride removal procedure)
Precision
In a single laboratory, using a standard solution of 800 mg/L
COD and two representative lots of reagent with the DR/2010
Spectrophotometer, a single operator obtained a standard
deviation of ' 20 mg/L COD.
Estimated Detection Limit (EDL)
The EDL for program 432 is 4 mg/L COD. The EDL is the
calculated lowest average concentration in a deionized water
matrix that is different from zero with a 99% level of confidence.
For more information on derivation and use of Hachs estimated
detection limit, see your Hach spectrophotometer manual.
Interferences
Inorganic materials may also be oxidized by trivalent manganese
and constitute a positive interference when present in significant
amounts. Chloride is the most common interference and is
removed by sample pretreatment with the Chloride Removal
Cartridge. If chloride is known to be absent or present in
insignificant levels, the pretreatment can be omitted. A simple
way to determine if chloride will affect test results is to run
routine samples with and without the chloride removal, then
compare results.
Other inorganic interferences (i.e., nitrite, ferrous iron, sulfide)
are not usually present in significant amounts. To correct for these
interferences, determine their concentrations separately. Then
perform the COD test on a standard solution made up to match
those concentrations, and subtract that COD value from the
sample COD test result.
Ammonia nitrogen is known to interfere in the presence of
chloride; it does not interfere if chloride is absent.
Summary of Method
Chemical oxygen demand (COD) is defined as ... a measure of
the oxygen equivalent of the organic matter content of a sample
that is susceptible to oxidation by a strong chemical oxidant
66
OXYGEN DEMAND, CHEMICAL, continued
(APHA Standard Methods, 19th ed., 1995). Trivalent manganese
is a strong, non-carcinogenic chemical oxidant that changes
quantitatively from purple to colorless when it reacts with organic
matter. It typically oxidizes about 80% of the organic compounds.
Studies have shown that the reactions are highly reproducible and
test results correlate closely to Biochemical Oxygen Demand
(BOD) values and hexavalent chromium COD tests. None
of the oxygen demand tests provide 100% oxidation of all organic
compounds.
A calibration is provided which is based on the oxidation of
Potassium Acid Phthalate (KHP). A different response may be
seen in analyzing various wastewaters. The KHP calibration is
adequate for most applications. The highest degree of accuracy is
obtained when test results are correlated to a standard reference
method such as BOD or one of the chromium COD methods.
Special waste streams or classes will require a separate
calibration to obtain a direct mg/L COD reading or to generate a
correction factor for the precalibrated KHP response. The sample
digestion time can be extended up to 4 hours for samples which
are difficult to oxidize.
REQUIRED REAGENTS
Quantity Required
Description Per Test Unit Cat. No.
Chloride Removal Cartridges (CRC)...................................... 1 ...... 25/pkg ................ 26618-25
Chloride Removal Cartridges (CRC)...................................... 1 .... 150/pkg ................ 26618-15
Manganese III COD Reagent Vials,
20 to 1000 mg/L COD............................................................ 1 ...... 25/pkg ................ 26234-25
Manganese III COD Reagent Vials,
20 to 1000 mg/L COD............................................................ 1 .... 150/pkg ................ 26234-15
Sulfuric Acid, concentrated, ACS........................................1 mL........4 kg .................... 979-09
Water, deionized.................................................................. varies ........ 4 L .................... 272-56
67
OXYGEN DEMAND, CHEMICAL, continued
REQUIRED APPARATUS
Quantity Required
Description Per Test Unit Cat. No.
Adapter, COD, DR/2010........................................................ 1........... each.................44799-00
Blender, Osterizer, 120 Vac, 14-speed ................................... 1........... each.................26747-00
Blender Container, 50250 mL.............................................. 1......... 2/pkg.................26748-00
Cap, with inert Teflon liner, for mixing bottle ....................... 1....... 12/pkg.................24018-12
COD Reactor, 115/230 Vac, 50/60 Hz,
North American fuses and plug.............................................. 1........... each.................45600-00
or
COD Reactor, 230 Vac, 50 Hz,
European fuses and plug ........................................................ 1........... each.................45600-02
Forceps, extra fine point ......................................................... 1........... each.................26696-00
Mixing Bottle, glass, for sample + acid ................................. 1........... each.................24347-06
Pipet, TenSette

, 1.0 to 10.0 mL ............................................ 1........... each.................19700-10

Pipet Tips, for 19700-10 TenSette

........................................ 2....... 50/pkg.................21997-96

Pipet, TenSette

, 0.1 to 1.0 mL.............................................. 1........... each.................19700-01

Pipet Tips, for 19700-01 TenSette

........................................ 2....... 50/pkg.................21856-96

Safety Shield .......................................................................... 1........... each.................23810-00
Test Tube Rack, steel, 8 place ................................................ 1........... each.................18641-00
Vacuum Pretreatment Device (VPD) ..................................... 1........... each.................49000-00
Vacuum Pump, 115 Vac ......................................................... 1........... each.................14697-00
or
Vacuum Pump, 220 Vac ......................................................... 1........... each.................14697-02
OPTIONAL REAGENTS AND APPARATUS
COD Standard Solution, 800 mg/L COD........................................200 mL.................26726-29
Dispenser, Digital, for sulfuric acid ..................................................... each.................25631-37
Pipet Tips, for 19700-10 TenSette

.............................................. 1000/pkg.................21997-28
Pipet Tips, for 19700-10 TenSette

................................................ 250/pkg.................21997-25
Potassium Acid Phthalate, ACS......................................................... 500 g.....................315-34
For Technical Assistance, Price and Ordering see GENERAL INFORMATION.
In the U.S.A.Call 800-227-4224
Outside the U.S.A.Contact the Hach office or distributor serving you.
68
69
APPENDIX C: THM Plus Method
Digestion and Colorimetric Measurement
70
71
Method 10140
THM Plus Trihalomethanes* 0200 ppb as Chloroform For drinking water
THM Reactor Method
* Patent Pending
1. Place the reactor in a
fume hood and place a
plastic shield in front of
the reactor.
Turn on the COD
Reactor. Preheat to
100 C.
2. Press the soft key
under HACH
PROGRAM. Select the
stored program number
for Trihalomethane
(THM) Plus by pressing
3560 on the numeric
keys.
Press ENTER.
Note: For the most
precise results, use
matched cells. See
Sample Cell Matching on
page 77.
3. The display will
show:
HACH PROGRAM:
3560 THM Plus
The wavelength ($),
515 nm, is automatically
selected.
4. Prepare a cooling
bath by adding 500 mL
of cold (1825 C) tap
water to an evaporating
dish.
Note: Maintain the water
temperature between 18
and 25 C.
Note: If analyzing more
than four samples, use
450 mL of water.
HACH
PROGRAM
ENTER
6 3 5 0
HACH PROGRAM:
3560 THM Plus
72
THM Plus Trihalomethanes, continued
5. Fill two sample cells
to the 10 mL mark with
sample. Label one
sample and the other
blank.
Note: Perform steps 5
through 9 rapidly so as
not to lose volatile THMs
from the sample. If you are
testing more than one
sample, complete steps 5
through 9 for one sample
before going on to the
next.
Note: If dispensing
sample with a pipette, the
pipette must dispense
quickly without causing
aeration or back pressure.
6. Add three drops of
THM Plus Reagent 1 to
each cell.
7. Cap tightly and mix
gently by swirling each
cell three times.
Note: Vigorous shaking
can cause loss of THMs.
8. Use a TenSette
pipette to add 3 mL of
THM Plus Reagent 2 to
each cell.
Note: The liquid is viscous
and a small amount may
remain in the tip after
dispensing. This will not
affect the results.
Note: The THM Plus
Reagent 2 must be at
room temperature before
use.
9. Cap tightly and mix
by shaking ten times.
Note: Thorough mixing
ensures that all of the
THM goes into the liquid
and does not accumulate
in the head space.
10. Place the sample
cell in the THM reactor
at 100 C. Set the blank
aside.
11. Press 800 START
TIMER to begin an
eight-minute reaction
period.
12. At the end of the
reaction period, remove
the cell from the reactor
and place in the cell
holder assembly.
Place the assembly in a
cooling bath.
START
TIMER
10 mL
73
THM Plus Trihalomethanes, continued
13. Press: NEXT
TIMER twice.
Note: Pressing NEXT
TIMER twice skips Timer 1,
which is used for a water
bath digestion.
14. Press: START
TIMER 2. Cool for three
minutes.
At the end of the cooling
period, remove the cell
from the cooling bath.
15. Use the Repipet Jr.
to add 1 mL of THM
Plus Reagent 3 to the
sample cell and to the
blank. Swirl to mix.
Note: The sample will
become warm
Note: The liquid is viscous
and may not be entirely
dispensed if measured
using any other pipetting
method.
16. Replace the
cooling water with fresh,
cold tap water. Place the
assembly containing the
sample and blank cells
into the cooling bath.
17. Press: START
TIMER 3 to begin a
three-minute cooling
time.
At the end of the cooling
period, remove the cells
from the cooling bath.
Note: At the end of the
cooling time, the sample
temperature should be
between 15 and 25 C.
18. Add one THM Plus
Reagent 4 Powder
Pillow each to the
sample cell and to the
blank.
19. Cap each cell
tightly and shake to
dissolve.
20. Press START
TIMER 4 to begin a
15-minute color
development time.
START
TIMER
START
TIMER
START
TIMER
74
THM Plus Trihalomethanes, continued
21. While the color is
developing, insert the
AccuVac Ampul
Adapter into instrument.
22. Wipe the reagent
blank with a damp
towel, followed by a dry
one, to remove
fingerprints or other
marks.
23. At the end of the 15
minutes, place the blank
into the cell holder and
close the light shield.
24. Press the soft key
under ZERO.
The display will show:
0 ppb CHCl
3
Note: For alternate
concentration units, press
the soft key under
OPTIONS, and then the
soft key under UNITS.
Scroll through the
available options. Press
ENTER to return to the
Read screen.
25. Wipe the sample
cell with a damp towel,
followed by a dry one, to
remove fingerprints or
other marks.
26. Place the prepared
sample into the cell
holder. Close the lid.
Results will be displayed
in ppb chloroform.
ZERO
75
THM Plus Trihalomethanes, continued
Sampling and Storage
Collect samples in 40-mL glass bottles sealed with Teflon-lined
septa caps. Use Cat. No. 27940-05 or equivalent for best results.
Fill the bottles slowly to overflowing so that no air is included
with the sample. Seal the bottles tightly and invert to check that
no air has been trapped.
Because trihalomethane compounds (THMs) are extremely
volatile, immediate analysis yields the greatest accuracy. If the
samples cannot be analyzed immediately, cool samples to 4 C.
This will slow the formation of any additional THM compounds
in chlorinated samples. Store the preserved samples at 4 C in an
atmosphere free of organic vapors. Samples should not be held
more than 48 hours. Allow the samples to equilibrate to room
temperature before analyzing.
Ascorbic acid cannot be used as a preservative with the THM
Plus method. Sodium Thiosulfate may be used as a preservative
in samples containing hardness of 100 mg/L or less as CaCO
3
.
Accuracy Check
Standard Additions Method
Prepare the standard additions sample at the same time as the
unspiked water sample. Snap the neck off a THM Standard
Ampule, 10 ppm as chloroform. Using a Wiretrol Pipet (Cat.
No. 25689-05), add 0.050 mL of the standard to 10 mL of water
sample. Immerse the tip of the pipet below the surface of the
water sample and dispense the aliquot of chloroform standard.
Cap the sample cell immediately and swirl three times to mix.
Prepare the sample and the spiked sample according to the
procedure steps 626.
a. Leave the unspiked sample in the sample compartment
after completing step 26. Verify that the units displayed
are in ppb. Select standard additions mode by pressing
the soft keys under OPTIONS, (MORE) and the STD ADD.
b. Press ENTER to accept the default sample volume
(mL), 10.0.
c. Use the keypad to enter 10000. Press ENTER.
76
THM Plus Trihalomethanes, continued
d. Press the soft key under ENTRY DONE.
e. Read the standard additions sample prepared above.
Accept the standard additions reading by pressing the
soft key under READ. The addition should reflect
80120% recovery. To view % Recovery, press the soft
key under EDIT TABLE.
See the Procedures Manual for more information.
Standard Solutions Method
Chloroform is extremely
volatile! Do not shake it
when mixing.
Prepare a 99 ppb chloroform standard by pipetting 10.0 mL of
organic-free water into a sample cell. Snap the neck off a THM
Standard Ampule, 10 ppm as chloroform. Using a Wiretrol
Pipette (Cat. No. 25689-05), transfer 0.100 mL of the chloroform
standard into the organic-free water. Immerse the end of the pipet
tip under the water to dispense the chloroform. Cap the sample
cell immediately and swirl three times to mix. Immediately
perform steps 625 of the procedure. Do not make up the
standard in advance. Use the standard immediately upon
preparation.
Method Performance
Precision
Standard: 60 ppb CHCl
3
For more information on determining precision data and method
detection limits, refer to the Procedures Manual.
Estimated Detection Limit
For more information on the derivation and use of Hachs
estimated detection limit, see the Procedures Manual. To
Program 95% Confidence Limits
3560 5664 ppm CHCl
3
Program EDL
3560 6 ppb CHCl
3
77
THM Plus Trihalomethanes, continued
determine a method detection limit (MDL) as defined by the 40
CFR part 136, appendix B, see the Procedures Manual.
Sensitivity
See the Procedures Manual for more information.
Sample Cell Matching
The THM Plus method requires that the 1" sample cells be
optically matched for best performance. Although sample cells
supplied by Hach Company are distortion-free, nicks and
scratches from handling, fingerprints, and other foreign material
on the glass surfaces may cause an optical mismatch between two
sample cells and introduce error into the test results. This type of
error may be avoided by optically matching the sample cells and
following the cell precaution statements listed in the procedure.
Procedure:
1. Turn on your instrument and select the THM Plus method.
Select the wavelength indicated in the procedure if your
instrument has not automatically done so.
2. Change the instrument to the absorbance mode.
3. Pour at least 10 mL of deionized water into each of the
samples cells to be matched.
4. Place one of the sample cells into the cell holder. Note and
mark the orientation of the cell in the cell holder. Close the
light shield. (Sample cells should be carefully wiped with a
lint free cloth to remove any fingerprints or other foreign
matter on the outside of the cell.)
5. Press: ZERO. The display will show: 0.000 Abs
6. Place the next sample cell into the cell holder. Close the light
shield.
7. Wait for the absorbance value to stabilize. Record the value.
Portion of Curve (Abs (Concentration
Entire Range 0.010 21 ppb as CHCl
3
78
THM Plus Trihalomethanes, continued
8. Turn the cell 180 degrees and repeat steps 67. Try to achieve
an absorbance value within 0.001 Abs of the first cell. Note
the orientation of the sample cell in the cell holder. This will
allow the cells to be oriented consistently in the cell holder.
Reagent Storage
Refrigerate THM Plus Reagent 2 for maximum stability. Long-
term exposure to temperatures above 35 C may cause reagent
degradation.
Interferences
The substances in the following table have been tested and found
not to interfere up to the indicated levels (in ppm):
Interferences that have no effect up to the maximum level
tested
Interference Maximum Level tested
Chlorine <10 ppm
Copper <1000 ppm
Hardness, Ca <1000 ppm as CaCO
3
May have some turbidity until Reagent 3 is added
Hardness, Mg <4000 ppm as CaCO
3
May have some turbidity until Reagent 3 is added
Iron <10 ppm
Lead <2 ppm
Mercury <10 ppm
Monochloramine <20 ppm
Nickel <10ppm
Sodium Bisulfite <100 ppm
EDTA Interferes negatively at all levels
79
THM Plus Trihalomethanes, continued
Additional disinfection by-products that react
Summary of Method
The THM Plus method reacts with the trihalogenated disinfection
by-products formed as the result of the disinfection of drinking
water with chlorine in the presence of naturally occurring organic
materials. These disinfection by-products (DBPs) may be
produced in the treatment plant or the distribution system as long
as the water is in contact with free chlorine residual. The
formation of the DBPs is influenced by chlorine contact time,
chlorine dose and residual, temperature, pH, precursor
concentration, and bromide concentration.
The predominant DBPs formed by the chlorination of drinking
water are the trihalomethanes or THMs. The four trihalogenated
compounds that form are chloroform, bromoform,
dichlorobromomethane, and dibromochloromethane. These four
compounds comprise the Total Trihalomethanes (TTHMs) group
which is regulated under the Safe Drinking Water Act. The
combined concentration of the TTHMs, reported as chloroform,
is regulated to be 100 ppb or less in drinking water samples.
Other DBPs that may be present and react under the conditions of
the THM Plus method are listed in Interferences.
In the THM Plus method, THM compounds present in the sample
react with N, N,-diethylnicotinamide under heated alkaline
conditions to form a dialdehyde intermediate. The sample is then
cooled and acidified to pH 2.5. The dialdehyde intermediate formed
is then reacted with 7-napthylamine-1,3 disulfonic acid to form a
colored Schiff base which absorbs at 515 nm. The color formed is
directly proportional to the total amount of THM compounds
present in the sample. The results are reported as ppb chloroform.
Compound Effect
1,1,1-trichloro-2-propanone Interferes positively
1,1,1-tricholoacetonitrile Interferes positively
Chloral hydrate Interferes positively
Dibromochloroacetic acid Interferes positively
Dichlorobromoacetic acid Interferes positively
Tribromoacetic acid Interferes positively
Trichloroacetic acid Interferes positively
80
THM Plus Trihalomethanes, continued
Safety
Good safety habits and laboratory techniques should be used
throughout the procedure. Consult the Material Safety Data Sheet
for information specific to the reagents used.
REQUIRED REAGENTS
Reagent Set (50 tests) ................................................................................................... 27908-00
Includes: (1) 27539-29, (1) 27540-48, (1) 27541-42, (1) 27566-99
Quantity Required
Description Per Test Unit Cat. No.
THM Plus Reagent 1.......................................................6 drops ........ 30 mL/bottle .. .27539-29
THM Plus Reagent 2........................................................ 6 mL........ 330 mL/bottle ... 27540-48
THM Plus Reagent 3........................................................ 2 mL........ 100 mL/bottle ... 27541-42
THM Plus Reagent 4..................................................... 2 pillows ......... 100 pillows ... 27566-99
REQUIRED APPARATUS
Beaker, 600-mL ................................................................................................ each ....... 500-52
Cell Holder Assembly, TTHM.............................................1 .......................... each ... 47880-00
Evaporating Dish, 125 mm x 65 mm...................................1 .......................... each ... 27647-00
Repipet Jr., 1 mL..................................................................1 .......................... each ... 21113-02
Pipet, Tensette, 110 mL .....................................................1 .......................... each ... 19700-10
Pipet tips, 110 mL (for 19700-10) ...............................................................50/pkg ... 25589-96
Sample cells, 10 mL, w/caps. ..............................................2 .........................6/box ... 24276-06
THM Reactor, Model 49100, 115 V ac ............................................................ each ... 49100-00
THM Reactor, Model 49100, 230 V ac ............................................................ each ... 49100-02
Wipers, Disposable, KimWipes ...................................................................280/pkg ... 20970-00
OPTIONAL REAGENTS
THM Standard Ampules, 10 ppm as Chloroform............................................7/pkg ... 27567-07
Water, Reagent, Organic-free....................................................................... 500 mL ... 26415-49
OPTIONAL APPARATUS
Flask, volumetric, 100 mL, class A................................................................. .each ... 14574-42
Pipet, filler, safety bulb..................................................................................... each ... 14651-00
Pipet, volumetric, class A, 10 mL..................................................................... each ... 14515-38
Pipettes, Wiretrol, 50100 L..................................................................250/pkg ... 25689-05
Vials, glass, 40-mL, with Septa cap.................................................................5/pkg ... 27940-05
For Technical Assistance, Price and Ordering, see GENERAL INFORMATION.
In the U.S.A.Call 800-227-4224
Outside the U.S.A.Contact the Hach office or distributor serving you.