Catalog Number 62031-18

APA 6000 Alkalinity Process Analyzer

Operation Manual

Hach Company, 2001, 2002. All rights reserved. Printed in the U.S.A. dd/dp 02/02 2ed

Table of Contents
Safety Precautions .................................................................................................................................................... 3 Specifications ............................................................................................................................................................ 4

Operation ............................................................................................................................................................... 5 Section 1 Instrument Overview ........................................................................................................................ 7

1.1 How to Use the Manuals ..................................................................................................................................... 7 1.2 General Description ............................................................................................................................................ 7 1.2.1 Instrument Enclosure................................................................................................................................. 7 1.2.2 Autoburette Module ................................................................................................................................... 7 1.2.3 Colorimeter Module, Holding Coil, and Reaction Coil ............................................................................... 8 1.2.4 Rotary Valve Module ................................................................................................................................. 8 1.2.5 Mixer Module ............................................................................................................................................. 8 1.2.6 Plumbing Diagram and Tubing Lengths..................................................................................................... 8 1.2.7 Vortex Sample Conditioning Block........................................................................................................... 11 1.2.8 Alkalinity Reagents .................................................................................................................................. 11

Section 2 Theory of Operation........................................................................................................................ 13

2.1 Method of Analysis............................................................................................................................................ 13 2.2 Reagent Consumption ...................................................................................................................................... 14

Section 3 Parameter Specific Functions ...................................................................................................... 15

3.1 Calibration History............................................................................................................................................. 15 3.2 Measurement Options....................................................................................................................................... 15 3.2.1 Selecting a Measurement Type ............................................................................................................... 15 3.3 Standard Solution Scrubbers ............................................................................................................................ 16

Section 4 Sequence of Instrument Events .................................................................................................. 17 Section 5 Bench Comparison Testing .......................................................................................................... 23
5.1 Comparable Bench Methods............................................................................................................................. 23 5.2 Alkalinity Relationship Table.............................................................................................................................. 26

Section 6 Replacement Parts .......................................................................................................................... 27

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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 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 operation and/or safety information. This symbol, if noted on the product, indicates the need for protective eye wear.

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Page 3 Safety Precautions

Specifications
Specifications are subject to change without notice. See instrument-specific specifications in the APA 6000 Process Analyzer Manual, Cat. No. 62005-18.

Performance
Range: 1 to 500 mg/L for T (Total) alkalinity as calcium carbonate; 5 to 250 mg/L for P (Phenolphthalein) alkalinity as calcium carbonate Accuracy: 5% of reading or 1.0 mg/L, whichever is greater Repeatability: 3% of reading or 0.6 mg/L, whichever is greater Response Time: For single channel instruments, less than 10 minutes for 90% response to step change at sample inlet Cycle Time: 8 minutes (average) Sample Temperature Range: 5 to 50 C (41 to 122 F) Instrument Detection Limit: Less than or equal to 0.10 mg/L Operating Temperature: 5 to 50 C (41 to 122 F) Relative Humidity: 5 to 95% relative humidity, non-condensing

Sample Requirements
Sample Pressure: 0.5 to 30.0 psig (0.03 to 2.04 bar) Sample Temperature: 5 to 50 C (41 to 122 F) Sample Flow: 100 to 2000 mL/min. maximum Sample Inputs: Up to two sample streams

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Operation

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.

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.

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Section 1

Instrument Overview

1.1 How to Use the Manuals

This instrument requires two manuals for complete operating instructions. The APA 6000 Installation and Maintenance Manual (Cat. No. 62005-18) provides instructions for instrument installation, menu setup, operation, maintenance, and troubleshooting. This Parameter-specific Operation Manual (Cat. No. 62030-18) contains information related to parameter specific instrument components and software functions. Descriptions of reagents and standards and their consumption rates, method of analysis, operational sequence, and bench comparison testing are all addressed in this parameter specific manual.

1.2 General Description

The APA 6000 Alkalinity Process analyzer is a microprocessor-controlled process analyzer designed to continuously monitor a sample water stream for alkalinity. The analyzer displays total, phenolphthalein, hydroxide, carbonate, and bicarbonate alkalinity in the sample. Typical samples include drinking water and boiler water. The analyzer uses a colorimetric titration method to determine concentration. Data retrieval and communication with the instrument is done through the AquaTrend Interface keypad and display, mounted in the door of the analyzer. The reagent containers are sized to provide reagents for 30 days of continuous operation. All reagent containers are factory-filled to 1000 mL and meet Hachs quality standards. Reagents and standards are plumbed from the reagent enclosures on the side of the instrument. All tubing enters the instrument at the ports at the bottom of the instrument bezel.

1.2.1 Instrument Enclosure

The instrument enclosure houses various modules, the instruments power supply, and control circuitry. Within the enclosure, a module panel separates sensitive electrical components from the wetted parts. All openings to the module panel are gasketed to protect against leakage. The module panel folds out to allow access to the electrical connections at the back of the instrument. The internal instrument temperature is factory set at 50 C (122 F). The design of the analyzer door and instrument panel provides a small, insulated space ensuring temperature control for accurate analysis. In order for the temperature control system to function properly, the instrument door must remain closed and latched during operation.

1.2.2 Autoburette Module

The analyzer uses a positive-displacement autoburette to measure and move fluids through the various analytical components in the instrument. The autoburette module consists of a clear acrylic block which houses a ceramic piston, a double seal for the piston, a linear actuator, a two-way solenoid valve, and control circuitry. The burette has an overall volume of 1.6 mL and can move in either direction to aspirate or dispense fluids over a 0.1 to 8.0 mL/minute range.

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Section 1
1.2.3 Colorimeter Module, Holding Coil, and Reaction Coil
Samples are measured in a temperature-controlled single-wavelength flow cell. Light from an LED in the colorimeter passes through a 600 nm bandpass filter. The path length is 8.75 mm (0.344 inches). The temperature is controlled at 50 C (122 F). The holding coil is a length of 0.030 inch ID Tefzel tubing arranged to minimize mixing. The holding coil allows low volumes of representative sample to be measured each cycle. The holding coil also effectively brings the sample and reagents to the temperature control point. Without the holding coil, old sample would need to be flushed from the burette. This would require at least 10x greater volume, longer analysis times, higher wastes, more sample conditioning, more standard consumption, etc. This parameter also utilizes a 700 L reaction coil. The reaction coil allows reproducible dispersion (or spreading) of the sample/indicator with the titrant (acid). As the two fluids disperse, a full range of concentrations result. This range begins with all sample/indicator then transitions to a greater concentration of titrant. Eventually, a maximum concentration of titrant is reached and as the transition continues, the titrant strength drops until only sample/indicator is present again. The reaction coil is placed between the valve and detector. After the dispersion described above occurs, the response is measured as fluids pass through the detector.

1.2.4 Rotary Valve Module

The rotary valve directs fluids to various components in the instrument. The valve is a selection valve with a common port at the center. An internal rotor turns to align a grove between the center port and any one of the ten available ports around the perimeter. The valve has a face sealing design. All tubing is factory-assembled and labeled for each individual chemistry.

1.2.5 Mixer Module

The mixer module mixes reagents with the sample or standards. Fluid enters through the bottom and is emptied out the top. The vent line is connected to the drain block. The mixer is made of acrylic and has an approximate volume of 3.0 mL. The mixer is filled, emptied, and rinsed during a typical measurement cycle. Mixing and excess air removal is accomplished via a magnetic stir bar.

1.2.6 Plumbing Diagram and Tubing Lengths

Figure 1 shows the user-replaceable tubing on the analyzer and Table 1 describes the terminal end size of each tube. The tubing is 0.030 inch ID Tefzel. The small diameter allows for low-volume and high-flow rates. The higher flow rate, along with properly applied sample conditioning, prevents the tubing from plugging. General information for replacing the tubing is presented in the APA 6000 Installation and Maintenance Manual (Cat. No. 62005-18).

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Section 1
CAUTION To familiarize yourself with handling precautions, dangers and emergency procedures, always review the Material Safety Data Sheets prior to handling containers, reservoirs, and delivery systems that contain chemical reagents and standards. Protective eye wear is always recommended when contact with chemicals is possible. PRUDENCE Pour se familiariser avec les prcautions prendre lors de la manipulation, les dangers et les procdures d'urgence, toujours lire les Fiches de Donnes de Scurit des Produits avant de manipuler les rcipients, les rservoirs et les systmes de distribution contenant les ractifs chimiques et les solutions talons. Il est toujours recommand de porter des lunettes de protection lorsqu'un contact avec les produits chimiques est possible. CUIDADO Para familiarizarse con las precauciones de manipulacin, los peligros y los procedimientos de emergencia, siempre estudie las Hojas de Datos de Seguridad de los Materiales antes de manipular recipientes, depsitos y sistemas de entrega que contengan reactivos y patrones qumicos. Siempre se recomienda el uso de protectores oculares cuando sea posible el contacto con productos qumicos. VORISCHT Es wird dringend empfohlen, die Sicherheitsdatenbltter vor der Handhabung von Behltern, Tanks und Zufuhrsystemen, die chemische Reagenzien und Standardsubstanzen enthalten, aufmerksam durchzulesen, damit Sie sich mit den beim Umgang mit diesen Chemikalien notwendigen Vorsichtsmanahmen, Risiken und Notfallschutzmanahmen vertraut machen, Es wird empfohlen, in allen Situationen, in denen mit einem Kontakt mit Chemikalien zu rechnen ist, eine Schutzbrille zu tragen. ATTENZIONE Per familiarizzare con misure di precauzione di controllo manuale, con procedure pericolose e di emergenza, rileggere sempre le schede di sicurezza del materiale prima di maneggiare contenitori, imballaggi per spedizione che contengono reagenti chimici e standards. Si consiglia di indossare sempre gli occhiali protettivi quando possibile un contatto con agenti chimici.

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Section 1
Figure 1 Plumbing Diagram for an Alkalinity Analyzer

Table 1 Replacement Tubing Lengths for Figure 1

Item 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 Description Reaction Coilpart of Temperature Control Block Tefzel tubing, 0.03 ID x0.062 OD Blank port Blank port Tefzel tubing, 0.03 ID x 0.062 OD Tefzel tubing, 0.03 ID x 0.062 OD Tefzel tubing, 0.03 ID x 0.062 OD Tefzel tubing, 0.03 ID x 0.062 OD Tefzel tubing, 0.03 ID x 0.062 OD Tefzel tubing, 0.03 ID x 0.062 OD Tefzel tubing, 0.03 ID x 0.062 OD Tefzel tubing, 0.03 ID x 0.062 OD Tefzel tubing, 0.03 ID x 0.062 OD Tefzel tubing, 0.03 ID x 0.062 OD Tefzel tubing, 0.03 ID x 0.062 OD Holding Coil Common Port Line Length 8.3 in. (21 cm) 24 in. (60 cm) 53 in. (135 cm) 66 in. (167 cm) 60 in. (152.5 cm) 66 in. (167 cm) 8.5 in. (21.3 cm) 31.5 in. (80 cm) 29.5 in. (75 cm) 9 in. (22.5 cm) 6.3 in. (16 cm) 12 in. (30.5 cm) 5 in. (12 cm) Call Hach Service 6.7 (17 cm) From... Port 1 Port 2 Port 5 Port 6 Port 7 Port 8 Port 9 Port 10 Mixer module out Two-way NC Two-way out Seal wash bottom Reaction coil Colorimeter out Center port To... Reaction coil Sample 1 Standard 1 Standard 2 Reagent 1 Reagent 2 Mixer in Waste Mixer drain Wash solution Autoburette bottom Autoburette top Colorimeter in Drain Holding coil

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Section 1
1.2.7 Vortex Sample Conditioning Block
The sample conditioning block consists of a 0.5 m ceramic filter held within a flow block. Unfiltered sample flows around the outside of the filter and serves to continuously self-clean the filter element. Sample is drawn through the filter on demand. Regular maintenance of the sample conditioning is required for proper operation. Hach recommends replacing the filter every four weeks in clean water applications and every two weeks in dirty water applications.

1.2.8 Alkalinity Reagents

The APA 6000 Alkalinity Process analyzer uses five reagents each of which is supplied in a 1-L bottle designed to provide reagents for 30 days of continuous use. APA Alkalinity Reagent 1 is an acid titrant that reacts with the alkalinity in the sample. APA Alkalinity Reagent 2 is a indicator used to determine the endpoints of the titration. APA Alkalinity Standards 1 and 2 are used together to perform a multiplepoint calibration. Standard 1 is a 0-mg/L as CaCO3 sodium carbonate solution. Standard 2 is a 500-mg/L as CaCO3 sodium carbonate solution. Both require a CO2 scrubber for the air inlet, which is assembled and shipped already attached to the reagent enclosure wall. The fifth reagent, APA Alkalinity Cleaning Solution, cleans the system during the Prime and Instrument Clean functions. Initially, a different cleaning solution (Cat. No. 26974-53) may be used to make sure all parts are wetted.

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Section 2

Theory of Operation
The APA 6000 Alkalinity Process Analyzer is designed to provide reproducible results through consistent solution handling. Every step in an analysis is performed the same way each time, ensuring accurate results. Accuracy can be verified and established by measuring grab samples with a known concentration of analyte. The analyzer works as follows: 1. The instrument aspirates a representative sample and a small amount of pH indicator. 2. The sample and indicator are pre-mixed in the mixing chamber. 3. Another representative sample is aspirated and delivered to the detector to obtain a reference measurement. 4. The sample/indicator mixture is aspirated from the mixer, followed by a slug of acid. 5. The mixture is delivered to the detector through a reaction coil, dispersing the acid through the mixture and providing a characteristic titration profile.

2.1 Method of Analysis

The analyzer aspirates and mixes the sample with a combination pH indicator solution in the mixing chamber. The indicator changes color according to the sample pH. The analyzer then aspirates more sample and delivers it to the detector to obtain a reference measurement. This compensates for small amounts of color or turbidity in the sample. Some of the sample/indicator mixture is then aspirated from the mixer and delivered to the detector, replacing the previous clear fluid. The remainder of the mixture is aspirated from the mixer, followed by a slug of acid. This acidified mixture is delivered to the detector via the reaction coil. As it travels through the reaction coil, the acid becomes dispersed through the sample/indicator mixture on both sides of the acid slug, forming a pH gradient. There will be an small volume (band) of fluid on both sides of the acid peak where the acid exactly neutralizes the alkalinity present in the sample, and the pH indicator changes color. As the fluid flows through the detector, the absorbance at 600 nm is recorded, producing a characteristic titration peak. The peak width is determined at two specific absorbance values. One width is determined at the absorbance representing pH 8.3, and the other at the absorbance representing pH 4.5. The first width represents the phenolphthalein alkalinity and the second width represents the total alkalinity of the sample. The instrument automatically calibrates using two standards (0 and 500 mg/L as CaCO3). A multi-point calibration curve is constructed by blending these standards to make intermediate calibration standards. The APA 6000 requires calibration to ensure instrument specifications are met. The analyzer monitors the response, and that response must be within a given range to assure the reagents are functional and the proper standards are in use. Consecutive runs must be repeatable. Repeatable runs increase confidence that the right value is used from the calibration. If these two criteria

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Section 2
are not met, an error will result and in many cases the analyzer will not use the values obtained from the "failed" calibration. During normal operation, the 10-port Rotary Valve rotates to various positions to move sample and reagents through the analyzer. Table 2 lists the port numbers and their function. Table 2 Port Functions For Alkalinity Analysis
Port # Function 1 2 3 4 5 Detector Sample 1 Sample 2 Not used Standard 1 Port # Function 6 7 8 9 10 Standard 2 Reagent 1 Reagent 2 (indicator) Mixer Waste

2.2 Reagent Consumption

The rate of reagent use depends on many factors, including the number of times the instrument cycles, calibration frequency, and the number of clean cycles. The following table provides the approximate volumes (in mL) of the reagents consumed with each type of function per cycle. Table 3 Reagent Consumption
Solution Sample Reagent 1 Reagent 2 Standard 1 Standard 2 Cleaning Solution Measurement 8.4 0.05 0.04 0 0 0.1 Calibration 0 0.6 0.4 57.4 36.2 1.2 Cleaning 0 0 0 0 0 11.2

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Section 3
3.1 Calibration History

Parameter Specific Functions

This option allows you to review past calibration data. 1. Press the MENU key to start from the Main Menu. 2. Select Sensor Menu and press ENTER. 3. Select the sensor by name and press ENTER. 4. Select Calibration and press ENTER. 5. Select Cal History and press ENTER. 6. A pop-up box will appear with the calibration date and time of the seven most recent calibrations. Select Review Next Cal to step through the pages of the calibration history. After the last calibration, press ENTER to return to the previous menu. To exit the Cal History Menu, press EXIT. Data displayed for the 7 most recent calibrations will include the concentration of the lowest P- and T-alkalinity standards in the first column and the highest P- and T-alkalinity standards in the second column. The values are based on the previous calibration curve and applied to the standards on the current calibration.

3.2 Measurement Options

The analyzer allows several options for the display of concentration values. The units can be changed. Available options are mg/L, ppm, and grains per gallon.
Note: If a Digital Display Module (DDM) is used, select SENSOR to DISPLAY in the Network Menu to set the output of the DDM. Important Note: Changing the displayed units will cause all stored data, for the AquaTrend channel on which the units were changed, to be erased.

3.2.1 Selecting a Measurement Type

When analyzing one sample stream, the analyzer determines all five types of alkalinity values listed below. To display each value, assign the measurement type to a channel on the AquaTrend Interface; see the Measurement to Channel section in the APA 6000 Installation and Maintenance Manual, Cat. No. 62005-18. Values will not be displayed unless they are assigned to a channel. Analyzing two sample streams creates more than eight values that can be displayed. Since the AquaTrend interface only has eight channels, the operator must choose which eight values should be displayed. For each sample stream, the choices are: Total (T) alkalinity Phenolphthalein (P) alkalinity Hydroxide alkalinity Carbonate alkalinity Bicarbonate alkalinity

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Section 3
To select the type of alkalinity measurement: 1. Press the MENU key to start at the MAIN MENU. 2. Select the SENSOR MENU and press ENTER. 3. Select the sensor by name and press ENTER. 4. Select MEASUREMENT OPTIONS. 5. Select DISPLAY. 6. Use the arrow keys to scroll to the desired measurement type and press ENTER. This measurement may then be connected to a channel on the AquaTrend Interface.

3.3 Standard Solution Scrubbers

Note: Wear synthetic gloves while working with the soda lime.

Carbon dioxide reacts with the standard and causes a concentration change. Standard 1 and Standard 2 bottles require a soda lime scrubber to remove CO2 from the air entering the reagent bottle. Replace exhausted soda lime when it turns purple. See Section 6 Replacement Parts on page 27 for catalog numbers and descriptions.

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Section 4

Sequence of Instrument Events

Table 4 Initialization

Valve Position Mixer Between ports Waste Mixer Between ports Waste Mixer Between ports Waste Between ports Detector

Volume (L) 1500 100 1600 1500 100 1600 500 100 600 1600 1600

Autoburette Action Aspirate Aspirate Dispense Aspirate Aspirate Dispense Aspirate Aspirate Dispense Aspirate Dispense

Table 5 Measurement Mode

Valve Position Sample Mixer Between ports Waste Sample Mixer Mixer Waste Sample Mixer Mixer Waste Sample Mixer Mixer Waste Sample Mixer Indicator Mixer Waste Sample Mixer Detector Waste Mixer Mixer Mixer Volume (L) 300 300 100 700 1200 600 800 1400 1450 0 950 500 1450 0 950 500 1374 0 76 900 550 1600 0 1600 0 400 400 800 Autoburette Action Aspirate Aspirate Aspirate Dispense Aspirate Dispense Aspirate Dispense Aspirate Depressurize Dispense Dispense Aspirate Depressurize Dispense Dispense Aspirate Depressurize Aspirate Dispense Dispense Aspirate Depressurize Dispense Depressurize Aspirate Aspirate Aspirate

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Section 4
Table 5 Measurement Mode (Continued)
Valve Position Detector Waste Mixer Titrant Detector Detector Volume (L) 1150 0 1106 44 0 1600 Autoburette Action Dispense Depressurize Aspirate Aspirate Depressurize Dispense

Table 6 Clean Mode

Valve Position Between ports Waste Between ports Waste Between ports Mixer Between ports Sample Between ports Sample Between ports Waste Mixer Sample Sample Waste Sample Waste Sample Waste Sample Waste Sample Mixer Mixer Waste Volume (L) 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 1600 Autoburette Action Aspirate Dispense Aspirate Dispense Aspirate Dispense Aspirate Dispense Aspirate Dispense Aspirate Dispense Aspirate Dispense Aspirate Dispense Aspirate Dispense Aspirate Dispense Aspirate Dispense Aspirate Dispense Aspirate Dispense

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Section 4
Table 7 Prime All
Valve Position Between ports Waste Between ports Titrant Waste Between ports Detector Waste Standard 2 Waste Standard 1 Waste Between ports Detector Volume (L) 1600 1600 400 1200 600 1600 1600 0 1600 1600 1600 1600 1600 1600 Autoburette Action Aspirate Dispense Aspirate Aspirate Dispense Aspirate Dispense Depressurize Aspirate Dispense Aspirate Dispense Aspirate Dispense

Table 8 Calibration
Valve Position STEP 1 Mixer Standard 2 Mixer Between ports Waste Standard 2 Mixer Mixer Waste Standard 2 Waste Mixer Waste Standard 2 Waste Indicator Mixer Waste Standard 2 Waste Mixer Waste Standard 2 Waste Mixer 0 300 300 100 700 1200 600 800 1400 1450 0 800 650 1374 0 76 564 886 1450 0 950 500 1450 0 484 Depressurize Aspirate Aspirate Aspirate Dispense Aspirate Dispense Aspirate Dispense Aspirate Depressurize Dispense Dispense Aspirate Depressurize Aspirate Dispense Dispense Aspirate Depressurize Dispense Dispense Aspirate Depressurize Dispense Page 19 Sequence of Instrument Events Volume (L) Autoburette Action

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Section 4
Table 8 Calibration (Continued)
Valve Position Waste Standard 1 Mixer Detector Waste Mixer Detector Waste Mixer Titrant Detector STEP 2 Mixer Standard 1 Mixer Between ports Waste Standard 1 Mixer Mixer Waste Standard 1 Indicator Mixer Waste Standard 1 Standard 2 Mixer Waste Standard 1 Waste Mixer Waste Standard 1 Mixer Detector Waste Mixer Detector Waste Mixer Titrant Detector 0 300 300 100 700 1200 600 800 1400 1526 74 1200 400 480 1120 1200 400 1200 0 400 800 1600 0 1600 0 1600 1150 0 1106 44 1600 Depressurize Aspirate Aspirate Aspirate Dispense Aspirate Dispense Aspirate Dispense Aspirate Aspirate Dispense Dispense Aspirate Aspirate Dispense Dispense Aspirate Depressurize Dispense Dispense Aspirate Depressurize Dispense Depressurize Aspirate Dispense Depressurize Aspirate Aspirate Aspirate Volume (L) 966 1600 0 1600 0 1600 1150 0 1106 44 1600 Autoburette Action Dispense Aspirate Depressurize Dispense Depressurize Aspirate Dispense Depressurize Aspirate Aspirate Aspirate

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Section 4
Table 8 Calibration (Continued)
Valve Position STEP 3 Waste Standard 1 Mixer Between ports Waste Standard 1 Mixer Mixer Waste Standard 1 Mixer Indicator Mixer Waste Standard 1 Standard 2 Standard 1 Waste Mixer Waste Standard 1 Waste Mixer Waste Standard 1 Mixer Detector Waste Mixer Detector Waste Mixer Titrant Detector 0 300 300 100 700 1200 600 800 1400 1526 0 74 1200 400 1388 112 100 0 1200 400 1200 0 400 800 1600 0 1600 0 1600 1150 0 1106 44 1600 Depressurize Aspirate Aspirate Aspirate Dispense Aspirate Dispense Aspirate Dispense Aspirate Depressurize Aspirate Dispense Dispense Aspirate Aspirate Aspirate Depressurize Dispense Dispense Aspirate Depressurize Dispense Dispense Aspirate Depressurize Dispense Depressurize Aspirate Dispense Depressurize Aspirate Aspirate Aspirate Volume (L) Autoburette Action

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Page 21 Sequence of Instrument Events

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Section 5

Bench Comparison Testing

5.1 Comparable Bench Methods

The precision of the APA 6000 analyzer is specified at 3%, however the precision of the bench method is estimated to be 10%. This may lead to apparent discrepancies between measurements obtained on the instrument and with the bench procedure. Contact with carbon dioxide in the air reduces the sample P alkalinity with time. While the measurements given by the APA analyzer are representative of the sample P alkalinity where it is sampled, the results from the bench method may only be representative of the sample P alkalinity after some of it, over time, has reacted with carbon dioxide in the air. Also note that alkalinity measurements on the instrument are made at 50 C, while the bench method is performed at room temperature. Depending on the sample matrix, this may contribute to apparent differences between instrument and bench method results.

Select sample size.

1. Select the sample

volume and Sulfuric Acid (H2SO4) Titration Cartridge corresponding to the expected alkalinity concentration as mg/L calcium carbonate (CaCO3) from Table 9.

2. Insert a clean delivery tube into the titration cartridge. Attach the cartridge to the titrator body.
Note: See General Description, Step-by-Step in the Digital Titrator Manual for assembly instructions, if necessary.

3. Turn the delivery knob to eject a few drops of titrant. Reset the counter to zero and wipe the tip.
Note: For added convenience use the TitraStir Stir Plate. See General Description Digital Titrator Manual, Step 3 in Step-by-Step.

4. Use a volumetric pipet to measure the sample volume from Table 9. Transfer the sample into a clean 250-mL Erlenmeyer flask. Dilute to about the 100-mL mark with deionized water, if necessary.

Table 9
Range (mg/L as CaCO3) 10-50 50-100 100-500 500-1000 Sample Volume (mL) 100 50 100 50 Titration Cartridge (H2SO4) 0.1600 N 0.1600 N 1.600 N 1.600 N Catalog Number 14388-01 14388-01 14389-01 14389-01 Digit Multiplier 0.1 0.2 1.0 2.0

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Section 5

5. Add the contents of

one Phenolphthalein Indicator Powder Pillow and swirl to mix.
Note: A solution of one pH 8.3 Buffer Powder Pillow and one Phenolphthalein Powder Pillow in 50 mL of deionized water is recommended as a comparison for determining the proper end-point color. Note: Four drops of Phenolphthalein Indicator Solution may be substituted for the Phenolphthalein Indicator Powder Pillow.

6. If the solution turns pink, titrate to a colorless end point. Place the delivery tube tip into the solution and swirl the flask while titrating with sulfuric acid. Record the number of digits required.
Note: If the solution is colorless before titrating with sulfuric acid, the Phenolphthalein (P) Alkalinity is zero; proceed with Step 8.

7. Calculate:
Digits Required x Digit Multiplier = mg/L CaCO3 P Alkalinity

8. Add the contents of one

Bromcresol Green-Methyl Red Indicator Powder Pillow to the flask and swirl to mix.
Note: Four drops of Methyl Purple Indicator Solution may be substituted for the Bromcresol Green-Methyl Red Indicator Powder Pillow. Titrate from green to a gray end point (pH 5.1). Note: Four drops of Bromcresol Green-Methyl Red Indicator Solution may be substituted for the Bromcresol Green-Methyl Red Indicator Powder Pillow.

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Section 5

9. Continue the titration

with sulfuric acid to a light greenish blue-gray (pH 5.1), a light violet-gray (pH 4.8), or a light pink (pH 4.5) color, as required by the sample composition; see Table 10. Record the number of digits required.
Note: A solution of one Bromcresol Green-Methyl Red Powder Pillow and one pillow of the appropriate pH buffer in 50 mL of deionized water is recommended as a comparison for judging the proper end-point color. If the pH 3.7 end point is used, use a Bromphenol Blue Powder Pillow instead of a Bromcresol Green-Methyl Red and titrate to a green end point.

10. Calculate:
Table 10
Total Digits Required x Digit Multiplier = mg/L as CaCO3 Total (T or M) Alkalinity Note: Carbonate, bicarbonate and hydroxide concentrations may be expressed individually using the relationships shown in Table 11. Note: meq/L Alkalinity = mg/L as CaCO3 50. Sample Composition Alkalinity about 30 mg/L Alkalinity about 150 mg/L Alkalinity about 500 mg/L Silicates or Phosphates present Industrial waste or complex system End Point pH 5.1 pH 4.8 pH 4.5 pH 4.5 pH 3.7

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Section 5
5.2 Alkalinity Relationship Table
Total alkalinity primarily includes hydroxide, carbonate and bicarbonate alkalinities. The concentration of these alkalinities in a sample may be determined when the phenolphthalein and total alkalinities are known (see Table 11). Table 11 Alkalinity Relationships
Row Result of Titration 1 2 Phenolphthalein Alkalinity = 0 Phenolphthalein Alkalinity equal to Total Alkalinity Phenolphthalein Alkalinity less than one half of Total Alkalinity Phenolphthalein Alkalinity equal to one half of Total Alkalinity Phenolphthalein Alkalinity greater than one half of Total Alkalinity Hydroxide Alkalinity is equal to: 0 Total Alkalinity Carbonate Alkalinity is equal to: 0 0 2 times the Phenolphthalein Alkalinity Total Alkalinity 2 times the difference between Total and Phenolphthalein Alkalinity Bicarbonate Alkalinity is equal to: Total Alkalinity 0 Total Alkalinity minus two times Phenolphthalein Alkalinity 0

0 2 times the Phenolphthalein minus Total Alkalinity

To use the table follow these steps: 1. Does the phenolphthalein alkalinity equal zero? If yes, use Row 1. 2. Does the phenolphthalein alkalinity equal total alkalinity? If yes, use Row 2. 3. Multiply the phenolphthalein alkalinity by 2. 4. Select Row 3, 4, or 5 based on comparing the result of Step 3 with the total alkalinity. 5. Perform the required calculations in the appropriate row, if any. 6. Check your results. The sum of the three alkalinity types will equal the total alkalinity.

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Section 6

Replacement Parts

Required Reagents for APA 6000

Reagent 1, Titrant, 0.08 N............................................................................................................ 1 L.......... 28261-53 Reagent 2, Mixed Indicator .......................................................................................................... 1 L.......... 26966-53 Standard 1, 0 mg/ml..................................................................................................................... 1 L.......... 26967-53 Standard 2, 500 mg/mL ............................................................................................................... 1 L.......... 28262-53 Wash Solution .............................................................................................................................. 1 L.......... 26970-53

Required Reagents for Bench Method

(varies with sample characteristics) Alkalinity Reagent Set (about 100 tests) ...................................................................................................... 22719-00 Includes: (1) 942-99, (1) 943-99, (1) 14388-01, (1) 14389-01
Description Unit Cat. No

Bromcresol Green-Methyl Red Powder Pillows.....................................................................100/pkg.............. 943-99 Phenolphthalein Powder Pillows ...........................................................................................100/pkg.............. 942-99 Sulfuric Acid Titration Cartridge, 1.600 N...................................................................................each.......... 14389-01 Sulfuric Acid Titration Cartridge, 0.1600 N.................................................................................each.......... 14388-01 Water, deionized .......................................................................................................................... 4 L .............. 272-56

Required Apparatus for Bench Method

Digital Titrator.............................................................................................................................each.......... 16900-01 Flask, Erlenmeyer, 250 mL ........................................................................................................each.............. 505-46 Select one or more based on sample concentration: Pipet, volumetric, Class A, 50 mL ..............................................................................................each.......... 14515-41 Pipet, volumetric, Class A,100mL ..............................................................................................each.......... 14515-42 Pipet Filler, safety bulb ...............................................................................................................each.......... 14651-00 Scrubber Kit, CO2, for standard bottles......................................................................................each.......... 51431-00 Scrubber, CO2, soda lime absorbent (desiccant)..................................................................... 500 g.......... 27476-00

Replacement Parts
Colorimeter Module ...................................................................................................................each.......... 62060-01 Colorimeter Assembly ...............................................................................................................each.......... 62058-01 Mixing Module ............................................................................................................................each.......... 51021-01 For common APA 6000 Parts and Accessories, please see the APA 6000 Process Analyzer Installation and Maintenance Manual, Cat. No. 62005-18.

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