United States Industrial Environmental Research EPA-600 8-80 015
Environmental Protection Laboratory March 1980
Agency Research Triangle Park NC 27711
Research and Development
o-EPA Laboratory Procedures:
Analysis of Sodium-based
Dual-alkali Process
Streams
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RESEARCH REPORTING SERIES
Research reports of the Office of Research and Development, U.S. Environmental
Protection Agency, have been grouped into nine series. These nine broad cate-
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environmental technology. Elimination of traditional grouping was consciously
planned to foster technology transfer and a maximum interface in related fields.
The nine series are:
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2. Environmental Protection Technology
3. Ecological Research
4. Environmental Monitoring
5. Socioeconomic Environmental Studies
€. Scientific and Technical Assessment Reports (STAR)
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This report has been assigned to the SPECIAL REPORTS series. This series is
reserved for reports which are intended to meet the technical information needs
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Typical of these reports include state-of-the-art analyses, technology assess-
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EPA REVIEW NOTICE
This report has been reviewed by the U.S. Environmental Protection Agency, and
approved for publication. Approval does not signify that the contents necessarily
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This document is available to the public through the National Technical Informa-
tion Service, Springfield, Virginia 22161.
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EPA-600/8-80-015
March 1980
Laboratory Procedures:
Analysis of Sodium-based
Dual-alkali Process Streams
by
J.R. Donnelly, D.C. Shepley, T.M. Martin,
and A.H. Abdulsattar
Bechtel National, Inc.
50 Beale Street
San Francisco, California 94119
Contract No. 68-02-2634
Program Element No. EHE624
EPA Project Officer: Norman Kaplan
Industrial Environmental Research Laboratory
Office of Environmental Engineering and Technology
Research Triangle Park, NC 27711
Prepared for
U.S. ENVIRONMENTAL PROTECTION AGENCY
Office of Research and Development
Washington, DC 20460
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ABSTRACT
A flue gas desulfurization (FGD) system utilizing the Combustion Equipment
Associates/Arthur D. Little sodium-based dual alkali (D/A) process has been
installed on Louisville Gas and Electric's Cane Run Unit No. 6. The U.S.
Environmental Protection Agency has contracted with Bechtel National, Inc.
to develop and implement a test program to characterize this FGD process.
As part of this effort, Bechtel has established a laboratory at the site
for routine chemical analyses of the pertinent process streams. The
methods used for these chemical analyses comprise this laboratory procedures
manual. The various procedures were extracted from three principle sources:
"Chemical Analysis Procedures for Dual Alkali Process Stream
Samples", Arthur D. Little, Inc., Report No. 75833, April 22,
1976.
"Laboratory Procedures Manual", Shawnee Test Facility, Paducah,
Kentucky, prepared by Bechtel National, Inc., March 1976.
Standard Methods for the Examination of Water and Wastewater,
14th Edition, (1975).
Procedures were verified by actual analyses carried out at the site in accord-
ance with the quality assurance section of the manual. In some cases, modi-
fications were made to adapt the standard procedures to the specific process
conditions and to best utilize the resources available at the site.
n
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TABLE OF CONTENTS
ABSTRACT
FOREWORD
ACKNOWLEDGMENTS
n
vl
ix
Section Page
SECTION 1 Sample Handling 1
SECTION 2 Ion Chromatography 9
SECTION 3 Wet Chemical Methods 23
Method 1 Suspended Solids 23
Method 2 Total Dissolved Solids 27
Method 3 Percent HC1 Insoluble Solids 31
Method 4 Solids in Process Filter Cake 35
Method 5 pH by pH Meter/Glass Electrode 37
Method 6 Diluted Conductivity 39
Method 7 Calcium and Magnesium by EDTA Titration 43
Method 8 Sodium by Specific Ion Electrode 47
Method 9 Chloride by Hg(N03)2 Titration 51
Method 10 Fluoride by Specific Ion Electrode 55
Method 11 Nitrate by Chromotropic Acid 57
Method 12 Total Sulfur and Sulfate by Turbidimetry 63
Method 13 Total Oxidizable Sulfur and Thiosulfate 67
by lodate/ Thiosulfate Titration
Method 14 Available Alkalinity by HC1 Titration 71
Method 15 Hydroxide by HC1 Titration 73
Method 16 Carbonate in Solids by C02 Evolution 75
ill
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Section
SECTIOH 4
Method 17 Carbonate by HC1 Titration
Method 18 Liquid Density
Method 19 Settling Test Procedure
Method 20 Particle Size Distribution
Method 21 Sodium by Flame Photometer
Method 22 Active Sodium by Titration
Method 23 Total Sulfur by LECO
Quality Assurance
Pagc-
79
83
85
91
99
107
109
115
APPEJDICES
Appendix A Ion Chromatograph Material Requisition
Appendix B Short Form Procedures
Appendix C Quality Assurance Forms
137
140
157
iv
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LIST OF TABLES AND FIGURES
TABLE 1 Analytical Methods
3-1 Effective Depth of Hydrometer Reading
3-2 Sample Preparation for Sodium Analysis
by Flame Photometer
4-1 Example Calculation of Spike Amount
Required for TOS in Solids Analysis
4-2 Example Calculation of Control Limits
for Precision and Accuracy Control Charts
for TOS in Solids Analysis
4-3 Ionic Imbalance Calculation Sheet
IX
97
104
125
128
132
FIGURE 1.1 Analytical Flow Chart
1.2 Sample Log Book Page
1.3 Daily Analytical Data Sheet
1.4 Sample Storage Tag
2.1 Ion Chromatography Flow Scheme
2.2 Normal Elution Sequence for Some Common
Ions Using Ion Chromatography
2.3 Sample Cationic Analysis Chromatogram
2.4 Sample Anionic Analysis Chromatogram
3.1 Carbonate Determination Apparatus
4.1 Example Precision Control Chart
4.2 Example Accuracy Control Chart
4
5
6
7
18
19
20
21
78
134
135
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FOREWORD
This manual has been prepared by the Air Quality Group of Bechtel National,
Inc. It is a source of analytical procedures for the analyses to be carried
out during operation of the Combustion Equipment Associates/A.D. Little,
Dual Alkali (D/A) FGD Demonstration System at the Cane Run Station of
Louisville Gas and Electric Company. The bases of the methods presented
in this manual have been extracted from three principal sources:
"Chemical Analysis Procedures for Dual Alkali Process Stream Samples,"
Arthur D. Little, Inc. Report No. 75833, 4/22/76
"Laboratory Procedures Manual", Shawnee Test Facility, Paducah,
Kentucky, Prepared by Bechtel National Inc., March 1976.
Standard Methods for the Examination of Water and Wastewater,
American Health Assoc., 14th Edition, (1975).
Some of the methods presented have been extensively modified from their
references sources. These modifications have been made to simplify the
procedures and to adapt the methods to the specific chemical process and
the laboratory equipment available at the Bechtel Dual Alkali field
laboratory. These modifications are currently being and will continue
to be verified according to procedures presented in the quality assurance
section prior to routine use in the laboratory.
It is planned to employ a Dionex Model 12 Automatic Ion Chromatograph for
many routine chemical analyses. The material requisition for the I.C. is
VI
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presented in Appendix A. Back-up methods to the Ion chromatograph and
other primary methods are included. Table 1 is a list of the primary and
backup analytical methods to be used in the D/A laboratory.
Short form procedures for many of the analytical methods presented are given
in Appendix B. These short form procedures are intended as handy references
in the laboratory and are not intended to replace analytical methods.
A comprehensive quality assurance (QA) program will be instituted in the D/A
laboratory to ensure that the precision and accuracy of the data generated
meet required limits of acceptability. Section 4 of this manual contains
details of this program. Quality Assurance forms are presented in Appendix C.
The D/A QA program is based on a QA program developed by LFE Environmental
Analysis Laboratories, Richmond, California.
This manual is not intended to be a comprehensive laboratory manual and hence
does not include routine laboratory procedures or techniques. For questions
concerning routine procedures refer to "Standard Methods for the Examination
of Water and Wastewater". For questions concerning laboratory safety, refer
to the "Guide for Safety in the Chemistry Laboratory" published by the Manu-
facturing Chemists Association. Manufacturers' operating manuals will be
the major source of information concerning individual instruments.
The manual is a working document and as such modifications to the procedures
will be developed in the field. All modifications will be tested, documented
and published. The methods presented here are those currently being used in
the field laboratory as of January 1980.
vn
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Table 1
ANALYTICAL METHODS
DETERMINATION
METHOD
Primary
Backup
Liquor Analyses
Calcium
Magnesium
Sodium
Sulfate
Total Sulfur
Chloride
Fluoride
Nitrate
Thiosulfate
Alkalinity
Hydroxide
Total Oxidizable Sulfur
Dissolved Solids
Trace Metals
EDTA Titration
EDTA Titration
Flame Photometer
Calculated
Ion Chromatograph
Ion Chromatograph
Ion Chromatograph
Ion Chromatograph
Ion Chromatograph
HC1 Titration
HC1 Titration
l2/Thio Titration
Gravimetry or Calculation
Atomic Absorption
Ion Chromatograph
Ion Chromatograph
Specific Ion Electrode
Turbidimetry"
Turbidimetry
Hg(NOo)2 Titration
Specific Ion Electrode
Chromotropic Acid
I2/Thio Titration
Ion Chromatograph
Solid Analyses
% HC1 Insol
Suspended Solids
Alkalinity
Carbonate
Hydroxide
Sulfite (TOS)
Particle Size Distribution
Calcium
Magnesium
Sodium
Total Sulfur
Nitrate
Chloride
Trace Metals
Gravimetry
Gravimetry
HCl/NaOH Titration
C02 Evolution
HCT Titration
Io/Thio Titration
Sieves/Sub-sieve analysis
EDTA Titration
EDTA Titration
Flame Photometer
LECO Sulfur Determinator
Ion Chromatograph
Ion Chromatograph
Atomic Absorption
Ion Chromatograph
Ion Chromatograph
Specific Ion Electrode
Turbidimetric
Chromotropic Acid
Hg(N03)2 Titration
viii
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ACKNOWLEDGMENTS
The authors are indebted to the EPA Project Officer, Mr. Norman
Kaplan, for his technical direction and encouragement during this
project.
The help of several other individuals in also sincerely appreciated.
Those deserving special thanks include:
R. H. Borgwardt and W. B. Kuykendal of the EPA for their review of
the initial draft; S. P. Spellenberg of Arthur D. Little, Inc., for
providing consultation on the newly developed procedures included
in the manual; C. L. DaMassa of Bechtel for technical editing and
D. Y. Kawahara and M. A. Smith, also of Bechtel, for their untiring
efforts and cheerful dispositions in typing this manuscript.
ix
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Section 1
SAMPLE HANDLING
1.1 INTRODUCTION
This section outlines requirements for the collection, verification, documen-
tation, initial preparation, storage and reporting of samples at the D/A
facility. The requirements presented here are planned to minimize problems
associated with sampling and unnecessary work analyzing non-representative
samples. Figure 1.1 is a flow chart showing the sequence of steps from sample
collection to reporting.
1.2 SAMPLE COLLECTION
Obtaining a representative sample of the D/A process streams can present
special problems. The system streams contain chemical species, which react
rapidly to affect pH changes and oxidation of sulfite to sulfate. Further-
more, some streams contain solids which can settle out and result in erroneous
suspended solids values. The following procedure presents steps to minimize
errors in sampling and to initially screen samples to minimize unnecessary
work.
1. All samples must be taken (if possible) from sample taps located
on a vertical run of pipe at the discharge side of a pump. Such
sample points allow sampling of a well-mixed, non-stratified stream.
2. Samples must be collected in clean, labeled wide-mouth sample jars.
The label must contain the name of the stream being sampled and the
sample point number. The same bottles must always be used for each
sample point.
3. The sample line must be purged prior to taking the sample; the sample
bottle must be rinsed with sample at least three times and filled to
the top to minimize entrainment of air.
-------
4. At this point the sample pH must be determined using a calibrated
portable pH meter. Record the pH value. This is the first step
in sample verification. If the sample pH is outside of control
limits then resample and determine pH again.
5. Quickly take samples to the laboratory for documentation, verifica-
tion and analyses.
1.3 SAMPLE DOCUMENTATION
Upon returning to the laboratory all samples must be logged in the sample
logbook. A daily analytical data sheet and labels for sample storage must be
prepared.
Figures 1.2 and 1.3 are examples of a sample log book page and Daily Analyt-
ical Data Sheet. Figure 1.4 is an example of the information required on the
sample storage tag.
1.4 SAMPLE VERIFICATION
The purpose of sample verification is to determine if the sample is valid
prior to separating the solids from the liquor. Sample pH, conductivity and
specific gravity (or density) are used to quickly determine sample validity.
The pH is taken at the sampling port, conductivity and specific gravity
are determined after the sample has been logged. If any of these analyses
give values outside of the set control limits, then it is necessary to take
another sample and/or check with operations to determine if they are operating
at off-normal conditions. If the plant is operating at off-normal conditions,
the onsite manager will decide whether to continue with analysis of the
sample.
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1.5 SAMPLE PREPARATION
Sample preparation consists of separating solids from liquor and drying
the solids. Liquor analysis is initiated immediately following separation
and liquor samples are stored in labeled plastic bottles. Portions of dried
solids samples are dissolved, analyzed, and placed in labeled resealable
plastic bags.
1.6 SAMPLE REPORTING
All routine analytical results must be entered in the Daily Analytical Data
Sheet (see Figure 1.3). Percent ionic imbalance must be calculated for both
liquor and solid sample analyses. In liquors which are analyzed for the
individual sulfur species present, the Total Sulfur concentration (TS) must
be calculated based on the individual sulfur species and compared to measured
TS values. Any unusual circumstances concerning the sample must be noted at
the bottom of the data sheet. When the sample has been analyzed, a record
of analyses completed must be entered in the log book.
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SAMPLE *
COLLECTION
-L
LOG SAMPLE
PROCESS
FILTER CAKE
WATER LEACH
% SOLIDS
FOR ANALYTICAL PROCEDURES, SEE PRIMARY
ANALYTICAL METHODS LISTED IN TABLE I.
SOLID SAMPLES
(E.G., LIME,
SODA ASH)
DETERMINE
CONDUCTIVITY
SPECIF 1C GRAVITY
(DENSITY)
DRY
MOISTURE
SLURRY
SAMPLES
1
LIQUOR
SAMPLES
FILTER
SUSPENDED
SOLIDS
SOLIDS
_L
FILTRATE
_L
FILTRATE
HCI DISSOLUTION
% HCI INSOLUBLE
1:500 DILUTION
J-
DILUTION
FILTRATE
_L
DETERMINE
SODIUM
CHLORIDE
NITRATE
DETERMINE
TOTAL
OXIDIZABLE
SULFUR
TOTAL SULFUR
CARBONATE
HYDROXIDE
ALKALINITY
PARTICLE SIZE
DISTRIBUTION
DETERMINE
CALCIUM
MAGNESIUM
SODIUM
TRACE METALS
DETERMINE
CONDUCTIVITY
SODIUM
DETERMINE
TOTAL SULFUR
CHLORIDE
FLUORIDE
NITRATE
CALCULATED VALUES REPORTED
1. % IONIC IMBALANCE
2. CALCULATED TDS
* DETERMINE pH AND TEMPERATURE
OF SLURRY AND LIQUOR SAMPLES
DETERMINE
DISSOLVED
SOLIDS
CALCIUM
MAGNESIUM
ALKALINITY
TOTAL
OXIDIZABLE
SULFUR
HYDROXIDE
CARBONATE
THIOSULFATE
TRACE METALS
ACTIVE SODIUM
Figure 1.1 ANALYTICAL FLOW CHART
-------
Paqe f
DATE
TIME
SAMPLE PT #
ANALYSES
COMPLETE/REMARKS
ANALYST
Figure 1.2
SAMPLE LOG BOOK PAGE
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D/A LABORATORY
DAILY ANALYTICAL DATA SHEET
Date
Time
Sample Pt#
pH
Conductivity
S.G. (Density)
LIQUOR ANALYSIS
Ca"""
Mg^
Na+
F~
Cl~
S03~
ND^
SOj /TS
TDS
Alkalinity
CH~
co-j-
TOS*
% Ionic Imbalances
TDS (Calculated)
Other
SOLIDS ANALYSIS
Ca^
Mq"
Nq+
F~"
Cl~
SO-,~
ND^:
SOjVTS
Suspended Solids
Alkalinity
or
°°3~
Toi
% HC1 Insol. (PIS)
Moisture
% Ionic Imbalance
Other
REMARKS
.
FIGURE 1.3
6
CHEMIST
-------
Sample No: Date:
Sample Pt: Time:
Comments:
Chemist
FIGURE 1.4
SAMPLE STORAGE TAG
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Section 2
ION CHROMATOGRAPHY
2.1 INTRODUCTION
This section covers the use of Ion Chromatography (I.C.) for routine
analytical determination of ions in dual alkali process streams. The I.C.
is highly specific, rapid, requires small sample volumes, and has the
ability to analyze a wide range of concentrations of several ions in a
single run.
Figure 2.1 shows the flow schemes for Ion Chromatography. I.C. combines
the separation capabilities of ion exchange resins with conductimetric
detection. Conductimetric detection has relatively universal and linear
response to solutions of ions and is therefore a good technique to monitor
ion exchange separations. A suppressor column in series v/ith the analytical
column eliminates eluent background conductance and allows the use of conduc-
tivity detection. A Dionex Model 12 automatic Ion Chromatograph has been
purchased for use in the D/A laboratory.
The- remainder of this section presents a brief description of the Dionex
Model 12 I.C. and the general run conditions for routine anionic and cationic
analyses. For further information and operating instructions refer to the
manufacturer's operating and maintenance manual.
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2.2 MODEL 12 DESCRIPTION
2.2.1 General
The Dionex Model 12 Ion Chromatograph uses an Ion exchange separator column
to separate mixtures of ions, followed by an ion exchange suppressor column
to remove the background eluting ions from the separator effluent while
converting the sample ions to a common form. After sample species sepa-
ration and eluent suppression, the effluent stream passes through a conduc-
tivity cell, which is connected to a meter and recorder for continuous
monitoring of the conductivity of the sample ions. The Model 12 consists
of a programmable controller unit, a conductimetric detector and meter,
an eluent pump, a regenerant pump (which is used to restore the suppressor
column capacity) and reservoirs for liquid storage. A system of valves
directs liquid flow through the instrument.
Figure 2.2 shows the flow schemes for an anionic and for a cationic analysis
systems. Only one system can be operated at one time with the Model 12.
Changing from one system to the other requires changing the columns,
eluents, and regenerant.
2.2.2 Dionex Model 12 Automatic Ion Chromatograph Specifications
Analytical System
• Four eluent reservoirs (including one for DI HoO which is also
used during regeneration), each a 4-liter, collapsible polyethylene
bottle with quick disconnect fittings. 20-liter polyethylene bot-
tles are used for eluent and DI H20 storage for the Dual Alkali
instrument.
• Constant volume pump, flow rates adjustable 40-460 ml/hr., 0.3%
accuracy above 100 psi
10
-------
• Programmable Controller allows automatic or manual selection of
operating parameters. Total of 16 available controller programs
with 15 steps each.
t Sample capacity of 99
Sample Injection
t Sample injection valve with 0.1 ml sample loop
Column System
• Accepts one separator and one suppressor column up to 500 mm in
length and 12 mm OD. A pre-column is used in the Dual Alkali sys-
tem to prolong separator column life.
Conductimetric Detector
• Offset: calibrated 0-1000 ^mho/cm
Output: 0-1 v full scale
Two modes of operation:
Manual
• Range: linear, 0.1, 0.3, 1.0, 3.0, 10, 30, 100, 300, 1000,
jumho/cm full scale, logarithmic: 1-10,000 A
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Regeneration System
Regenerant pump, water reservoir, regenerant reservoir. Manual or
automatic control.
Dimensions and Weight
• 30"H x 24"W x 22"D, 140 Ibs
Utilities
• 115 VAC 60 Hz/20 amperes
• 80-120 psi air supplied from a compressed air storage bottle
Accessories
• Sample Changer: stores and sequentially loads for analysis up to
99 discrete samples
• Recorder: Dual pen recorder provides a permanent chromatograph
trace of each analysis. One pen provides a trace with lOx the
sensitivity of the other pen.
Appendix A contains the material requisition for the Model 12 I.e. purchased
for the D/A laboratory.
2.3 ANALYTICAL METHODS
2.3.1 Cation Anaylses (Na+, Kg"1"1", Ca++)
Discussion
Samples of scrubbing liquor (or solids after dissolution) are diluted with
deionized water and injected into the Model 12 I.e. The eluent used is
0.001M m-phenylenediamine dihydrochloride. Identification and quantisation
are performed by comparison of retention times and peak heights respectively
with those of standard solutions. Figure 2.3 shows a typical chromatogram
and instrumental conditions for this analysis.
12
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Apparatus
a. Model 12 I.C. with auto sampler and dual pen recorder
b. 6x250 mm Alkaline Earth Separator column
c. 9x250 rnm Alkaline Earth Suppressor column
d. 3x150 mm Cation pre-column
Reagents
a. m-Phenylenediamine Dihydrochloride (0.001M) Eluent.
Dissolve 0.724 grams m-pher?ylenediamine dihydrochloride with
8 ml of IN HN03 in 4 liters deionized water. Prepare fresh
eluent weekly. Note: the addition of HNOo to the eluent has
been found to give better resolution of the magnesium peak.
b. Cation Pre-Column Cleaning Eluent (3N HC1).
Dilute 775 ml concentrated hydrochloric acid in 4 liters deionized
water. This eluent is used to remove substances from the resin bed
which adversely affect its capacity. One 15 minutes flush followed
by 1 5-10 hour deionized water rinse constitutes one cleaning cycle.
c. Regeneration Solution (0.5N NaOH).
Dissolve 80 grams of NaOH in 4.0 liters deionized water.
d. Calcium Standard Solution (1000 mg/liter).
Dissolve 2.500 grams of dried CaC03 by dropwise addition of concen-
trated HC1 then dilute to one liter with deionized water.
e. Magnesium Standard Solution (1000 mg/liter).
Dissolve 10.136 grams undried MgSO^*7HoO in one liter of deionized
water. Determine exact concentration by EDTA titration.
f. Potassium Standard Solution (1000 mg/liter}.
Dissolve 1.907 grams dried KC1 in one liter deionized water.
g. Sodium Standard Solution (1000 mg/liter).
Dissolve 2.542 grams dried NaCl in one liter deionized water.
h. Mixed Cation Standard Solution.
(5 mg/1 Ca4+, 5 mg/1 Mg++, 5 mg/1 Na+).
Add in a 1 liter volumetric flask and dilute to one liter with
deionized water the following quantities of 1000 mg/1 standard
solutions.
Calcium solution : 5 mis
Magnesium solution : 5 mis
Sodium solution : 5 mis
13
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Procedure
a. Place 5-10 mis of the diluted scrubbing liquor or dissolved
solids solution into the auto sampler test tubes. Record sample
numbers and order of position in the sampler rack.
b. Before the first sample and after every 10 samples, place a test
tube of cation standard solution, a duplicate sample and a sample
spiked with a known amount of standards. Record rack positions.
c. Set-up the Model 12 I.e. for alkaline earth cation analysis.
Insure that the proper columns are installed, the proper eluents
and regenerant are in the instrument, and that the analytical
system has been flushed well with deionized water.
d. Check eluent flow rate, inspect system for leaks, and zero conduc-
tivity meter.
e. After a steady baseline has been obtained, initiate automatic
operation by programming the controller memory and pushing the
start/step button. Refer to the Dionex "Operating and Maintenance
Manual" for programming instructions.
f. After ten samples have been analyzed (or at least once per day)
regenerate the suppressor column and flush the system with deionized
water.
g. Identify and quantitate the sample ions by comparing the chroma-
tograms of the samples with those of the standards (retention
times and peak heights).
Reference
Analysis of Ions in Flue Gas Scrubber Solutions, Application Notes #12,
Dionex Corporation, September 1, 1978.
2.3.2 Anion Analyses (F", Cl", N03~, S03=, S04=)
Discussion
Samples of scrubbing liquor (or solids after dissolution) are oxidized
with \\2®2 and diluted with deionized water then injected into the Model
12 I.C. The eluent used is 0.003M NaHC03/0.0024M Na2C03. Identification
14
-------
and quantitation of the sample ions are performed by comparison of retention
times and peak heights respectively with those of standard solutions.
Figure 2.4 shows a typical chromatogram and instrumental conditions for
this analysis.
Apparatus
a. Model 12 I.C. with autosampler and dual pen recorder.
b. 3x500 mm Anion Separator column
c. 6x250 mm Anion Suppressor column
d. 3x150 mm Anion pre-column
Reagents
a. Sodium carbonate-bicarbonate eluent (0.003M NaHC03/0.0024M Na2C03).
Dissolve 1.008 grams dried NaHC03 and 1.018 grams dried Na2C03 in 4
liters deionized water.
b. Anion Precolumn Cleaning Eluent (0.1M Na2C03).
Dissolve 42.400 grams dried Na2C03 in deiomzed water.
c. Regeneration Solution (IN
Carefully add 111 mis concentrated H2SO^ to 3 liters deionized
water and dilute to 4 liters.
d. Fluoride Standard Solution (1000 mg/liter).
Dissolve 2.210 grams dried NaF in 1 liter of deionized water.
e. Chloride Standard Solution (1000 mg/liter).
Dissolve 1.648 grams dried NaCl in 1 liter deionized water.
f. Nitrate Standard Solution (1000 mg/liter).
Dissolve 1.371 grams dried NaN03 in 1 liter deionized water.
g. Sulfite Standard Solution (1000 mg/liter).
Dissolve 1.300 grams of dried NaHS03 in approximately 100 ml
deionized water, add approximately 300 ml formal dahyde solution
(37%) and dilute to 1 liter with deionized water.
h. Sulfate Standard Solution (1000 mg/liter).
Dissolve 1.814 grams dried K2S04 in 1 liter deionized water.
15
-------
i. Mixed Anion Standard Solution
(3 mg/1 F", 4 mg/1 Cl~, 30 rag/1 N03", 50 mg/1 S03=, 50 mg/1 S04~)
Add in a 1 liter volumetric flask containing approximately 300 ml
formaldahyde solution (37%) and dilute to one liter with deionized
water the following quantitities of 1000 mg/1 standard solutions:
Fluoride solution : 3 mis
Chloride solution : 4 mis
Nitrate solution : 30 mis
Sulfite solution : 50 mis
Sulfate solution : 50 mis
Procedure
a. Place 5-10 mis of the diluted scrubbing liquor or dissolved
solids solution into the autosampler test tubes. Record sample
numbers and order of position in the sampler rack.
b. Before the first sample and after every 10 samples place a test
tube of anion standard, a duplicate sample and a sample spiked
with a known amount of standards. Record position of each.
c. Set-up the Model 12 I.C. for anion analysis. Insure that the
proper columns have been installed and allowed to equilibrate,
the proper eluents and regenerant are in the instrument, and
that the analytical system has been flushed well with deionized
water and then eluent.
d. Check eluent flow rates, inspect system for leaks and zero
conductivity meter.
e. After a steady baseline has been obtained, initiate automatic
operation by programming the controller memory and pushing the
START/STEP button.
f. After ten samples have been analyzed (or at least once a day)
regenerate the suppressor column and flush the system with deion-
ized water.
g. Identify and quantitate the sample ions by comparison of the
chromatograms of the samples and standards (retention times and
peak heights).
16
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References
a. Analysis of Ions in Flue Gas Scrubber Solutions, Application Notes #12,
Dionex Corporation, September 1978.
b. Dionex Auto Ion System 12 Analyzer Instrument Manual, Dionex Corporation,
Sunnyvale, California.
17
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SAMPLE
00
i
NaHCO3 j HCL
ANIONIC CATIONIC
SYSTEM SYSTEM
PUMP
1
INJECTION
VALVE
R-H+
STRONG ACID
CATION EXCHANGE
SEPARATOR
RESIN SEPARATES
SAMPLE CATIONS
IN A BACKGROUND
OF HCI ELUENT
SEPARATOR
COLUMN
STRONG BASE
SUPRESSOR RESIN
REMOVES HOE I UENT
AND CONVERTS SAMPLE
CATIONS TO THEfR
HYDROXIDES WHICH
PASSUNRETARDED
THROUGH THE
SUPPRESSOR COLUMN.
SUPPRESSOR
COLUMN
CONDUCTIVITY METER
QUAN1IHES CAIION
HYDROXIUfcS IN A
BACKGROUND OF
DEIONIZEDHjO
CONDUCTIVITY METER
AND RECORDER
CONDUCTIVITY METER
QUANTIFIES ANION ACIDS
(SAMPLE IONS) IN A BACK-
GROUND OF DILUTE
CARBONIC ACID.
WASTE
FLUENT
R^HCO"
STRONG BASE
ANION EXCHANGE
SEPARATOR
RESIN SEPARATFS
SAMPLE ANIONS
IN A BACKGROUND
OF NaHCO3 ELUENT.
STRONG ACID
SUPPRESSOR RESIN
REMOVES NaHCO,
E LUENT AND CONVERTS
SAMPLE ANIONS TO
THfclH ACIDS WHICH
PASSUNRETARDED
THROUGH THE
SUPPRESSOR COLUMN
(REGENERATED PERIODICAL LY
TO REMOVE UNWANTED ELUENT IONS)
Figure 2.1 ION CHROMATOGRAPHY FLOW SCHEME
-------
ANIONS
t
THIOSULFATE~2
o
DC
N0
I-
z
o
CATIONS
J
oc
UJ
O
O
OC
Ca+2
Na
UJ
O
UJ
oc
UJ
oc
o
X
CO
f
Figure 2.2 NORMAL ELUTION SEQUENCE FOR SOME COMMON
IONS USING ION CHROMATOGRAPHY
19
-------
CONCENTRATION (ppm)
Mg?* 1
CA" 5 2
Na
K
CONDITIONS
Eluent 0001 M
p-phenylene di-
amine • 2 HCI
138 ml hr
6 • 250 mm Alkaline
Earth Separator
Flow Rate
Separator
Column
Suppressor
Column
Injection
Volume
Meter Full
Scale Setting
9 • 250 mm Alkaline
Earth Suppressor
100 wl
10
12
MINUTES
Figure 2.3 Sample Cationic Analysis Chromatogram
20
-------
CONDITIONS
0 003 M
N.v-lCCV
a 002-s u
N.I CO
IW Rate
138 ml h:
Sr.pii'iKOr C. lunin
3 • 500 mm
Arnon SetMralnt
Suppressor Column
6 • 250 mm Anion
Suppressor
Injection Volume 100 ..
Meier Full Scale Setting
30 t,MHO cm
0 4
MINUTES
12 16 20
Figure 2.4 Sample Anionic Analysts Chromatogram
-------
Suspended Solids
Section 3
WET CHEMICAL METHODS
Method 1
Suspended Solids
1. Discussion
Suspended solids in a solution or slurry sample are filtered and then
dried to a constant weight in a microwave oven. Alternately, the sample
may be dried for 3-4 hours at 83-85°C in a conventional oven. The resultant
solids may be used for solids analysis.
Note: SAMPLE PREPARATION AND SEPARATION
Solids taken from slurries are used as a measure of suspended
solids content in the slurry as well as for solids composition
determinations. When liquor analyses are also required from the
slurry sample, two samples should be collected because sample volume
requirements for suspended solids measurement and for liquor analyses
are not compatible.
2. Apparatus
a. Membrane filter apparatus
b. Drying oven, 84 _+ 1°C or microwave oven
c. Vacuum pump with trap
d. Resealable plastic storage bags
e. Glass fiber filter discs, Whatman GFC, 4.25 cm diameter
f. Plastic weighing boats
g. Desiccator
h. Bottles, wide-mouth, polyethylene, 16 oz, 4 oz and 1 oz
23
-------
Suspended Solids
Reagents
a. Calcium sulfate solution, saturated; add 3 g calcium sulfate
dihydrate (gypsum) to 1 liter tap water at room temperature,
mix well and allow solids to settle out before using supernate
as wash solution.
b. Isopropyl alcohol, reagent grade
4. Procedure
All weighings should be made to 0.001 g.
4.1 Suspended Solids in Slurries
a. Weigh a clean, dry 1 oz bottle with cap and record weight as
Bl.
b. Collect slurry sample in bottle then cap the bottle.
c. Rinse solids off of bottle, dry then weigh and record weight
as B2.
d. Weigh a weighing boat containing a dry filter disc. Record
the weight as B3.
e. Assemble the filtration apparatus with the weighed filter disc.
Do not turn on vacuum.
f. Wash the slurry sample out of the bottle and into the filter
with about 25 ml of saturated CaS04 solution. Apply vacuum to
the filter. In order to avoid possible channeling and inef-
ficient washing, it is extremely important that the liquid
level not be allowed to go beneath the surface of the solids
in this step and the next.
g. Rinse the bottle with another 25 ml of CaSO^ wash solution and
then transfer to the filter just as the liquid level in the
filter reaches the top of the solids bed.
h. Wash the solids with about 25 ml of isopropyl alcohol.
i. Transfer the filter disc and solids to the weighing boat which
has been weighed with the filter disc in it. Transfer any
solids clinging to the filter apparatus to the boat.
24
-------
Suspended Sol ids
j. Dry the sample, filter disc and boat to constant weight in the
microwave oven at HI setting (usually 3 minutes) or in a
conventional oven at 84 +_ 1°C.
k. Remove the boat, let cool in a desiccator for 2 minutes and
weigh. Record weight as B4.
m. Transfer solids to a labeled plastic bag for storage.
4.2 Suspended Solids in Solutions
a. Weigh a weighing boat containing a dry filter disc.
b. Collect sample in a 16 oz bottle.
c. Thoroughly mix the sample by shaking.
d. Quickly pour out 250 ml of well-mixed sample into a 250 ml
graduated cylinder.
e. Assemble the filtration apparatus with the weighed filter disc
and apply vacuum.
f. Pour the cylinder contents into the filter being careful not to
let the filter go dry.
g. Continue with steps 4.1.f. through k. except wash the graduated
cylinder with each portion of wash water used in steps 4.1.f and g.
4.3 Liquor from Slurries
a. Collect sample in a 4 oz bottle.
b. Assemble the filtration apparatus with a filter disc and a
clean filter flask.
c. Decant about 20 ml of liquor into the filter and apply vacuum.
Turn off vacuum and disassemble the filter apparatus.
d. Swirl filtrate in filter flask then discard.
e. Reassemble filter apparatus with a new filter disc.
f. Decant remainder of the sample liquor into the filter and
apply vacuum. Do not wash.
g. Transfer filtrate to a clean, dry plastic bottle and label.
25
-------
Suspended Solids
5. Calculations
5.1 Suspended Solids in Slurries
Suspended Solids (wt%) = It^-B x 100%
DC. - Oi
where:
Bl = Weight of empty sample bottle, g
82 = Weight of sample bottle containing sample, g
B3 = Weight of weighing boat plus filter disc, g
B4 = Weight of weighing boat plus filter disc plus
dried solids, g
5.2 Suspended Solids in Solutions
Suspended Solids (mg/1) = ,B4 y B,3 x 106
where:
B3 = Weight of weighing boat plus filter disc, g
84 = Weight of weighing boat plus filter disc plus
dried solids, g
V = Volume of sample used in step 4.2d., ml
10^ = Factor to convert g to mg and ml to 1
6. References
a. Shawnee Test Facility, Laboratory Procedures Manual, March 1976,
% Solids in Slurry and Drying Solids, with microwave oven,
unpublished.
b. "Chemical Analysis Procedures for Dual Alkali Process Stream
Samples," Arthur D. Little, Inc., No. 75833, 4/22/76, Methods
1 and 2.
26
-------
IDS
Method 2
Total Dissolved Solids
1. Discussion
Total dissolved solids may be defined as that material capable of passing
through a standard glass fiber filter and dried to constant weight in
a microwave oven. Alternatively, the filtered sample may be dried at 84°C
in a conventional oven. Preservation of the sample is not recommended;
analysis of the sample should begin as soon as possible.
Liquor may contain calcium, magnesium, chloride, sulfite and sulfate. Salts
of these species may be hygroscopic and will require prolonged drying,
desiccation and rapid weighing.
Too much residue in the evaporating dish will crust over and entrap water
that will not be driven off during drying.
2. Apparatus
a. Glass fiber filter discs, Whatman GFC, 4.25 cm diameter
b. Membrane filter apparatus
c. Evaporating dish, glass or porcelain, small
d. Steam bath
e. Drying oven, 84 _+ 1°C or microwave oven
f. Desiccator
g. Vacuum pump with trap
27
-------
IDS
3. Procedure
a. Preparation of glass fiber filter disc: Place the disc on the
membrane filter apparatus. While vacuum is applied, wash the disc
with three successive 20 ml volumes of distilled water.
b. Remove all traces of water by continuing to apply vacuum after water
has passed through. Discard washings.
c. Preparation of evaporating dishes: Dry the clean dish for 3 minutes
at HI in the microwave oven. Cool in desiccator and store until
needed. Weigh immediately before use.
d. Assemble the filtering apparatus with a clean, dry filter flask and
begin suction. Shake the sample vigorously and rapidly transfer
about 50 ml to the funnel.
e. Filter the sample through the filter disc and continue to apply
vacuum for about 3 minutes after filtration is complete to remove
as much water as possible.
f. Pipet 5.00 ml (or a larger volume) of the filtrate to a weighed
evaporating dish and evaporate to dryness on a steam bath.
g. Dry the evaporated sample to constant weight at HI in the microwave
oven or at 84 _+ 1°C. Cool in a desiccator and weigh. Repeat the
drying cycle until a constant weight is obtained or until weight
loss is less than 1 mg.
Calculation
IDS mg/1 = (A - B) x 1000
IT
where:
A = Weight of dried residue + dish, mg
B = Weight of dish, mg
C = Volume of filtrate used, ml
1000 = Factor to convert ml to 1
28
-------
IDS
5. Reference
U.S. Environmental Protection Agency "Methods for Chemical Analysis of
Water and Wastes", EPA-625/6-74-003a (1976).
29
-------
% I.S.
Method 3
Percent HC1 Insoluble Solids
1. Discussion
This method is used to determine the HC1 insoluble fraction of slurry solids,
process filter cake and scale samples and to prepare the samples for further
chemical analyses.
Samples are dissolved in acid and separated from undissolved material by
filtration. An analytical mill is employed for scale samples to insure
that all HC1 solubles are dissolved.
Solids samples are normally analyzed for Ca and Mg subsequent to this
procedure.
This method may also be used to prepare process filter cake samples for
sodium analysis (see Method 4 discussion).
2. Apparatus
a. Membrane filter apparatus
b. Glass fiber filter discs, Whatman GFC, 4.25 cm diameter
c. Analytical mill
d. Magnetic stirrer
e. Drying oven, 84 _+ 1°C or microwave oven
f. Vacuum pump with trap
g. Desiccator
h. Hotplate
31
-------
% I.S.
i. Watchglasses, about 25 mm and 65 mm diameters
j. Plastic weighing boats
3. Reagents
a. Hydrochloric Acid, IN; dilute 85 ml concentrated HC1 to one
liter with deionized water.
4. Procedure
a. Scale samples should be milled according to laboratory practice
prior to further treatment. This step is not required for
slurry solids or process filter cake samples.
b. Dry sample in a weighing boat to constant weight at HI in a micro-
wave oven (usually 3 minutes) or at 84 j+ 1°C in a conventional
oven and cool in a desiccator. Process filter cake samples must
be dried in a preweighed weigh boat. Weigh the boat plus filter
cake sample before and after drying to determine moisture content.
c. Weigh approximately 0.2 g of sample to 0.001 g and transfer to
a 250 ml Erlenmyer flask containing about 50 ml of deionized
water and a magnetic stirring bar.
d. Slowly add 30 ml of IN HC1 while stirring. Cover with a small
watchglass and boil for about 1 minute on a hotplate then remove
from hotplate and stir for an additional 30 minutes (see Note).
e. Filter through a preweighed filter disc into a clean filter flask.
Rinse Erlenmyer into filter with deionized water making sure that
all solids are transferred to the membrane.
f. Dry the filter disc on a watchglass to a constant weight in a
microwave oven (3 minutes at HI) or at 84 +_ 1°C, cool in a desic-
cator and weigh.
g. Quantitatively transfer the contents of the filter flask into a
100 ml volumetric flask using a fume;!.
h. Dilute to the mark with deionized water, mix by irversion, transfer
to a clean, dry plastic bottle and label.
32
-------
I.S,
5. Calculation
5.1 HC1 Insoluble Solids
HC1 Insoluble Solids (wt%) = B - A x
W
where:
A = Weight of filter disc, g
B = Weight of filter disc plus dried residue, g, from 4.f.
W = Weight of sample, g, from 4.c.
5.2 Moisture in Process Filter Cake
Moisture (wt%) = ( 1 - B1 - B ) x 100%
B2 - B
where:
B = Weight of weigh boat, g
Bl = Weight of weigh boat plus dry sample, g
B2 = Weight of weigh boat plus sample as received, g
6. Note: If solids sample is to be analyzed for total sulfur by
Turbidimetry (Method 12) add 10 ml H202 and stir 15 min
prior to step d.
Reference
Shawnee Test Facility, "Laboratory Procedures Manual", March 1976,
Method 4.
33
-------
Cake Solids
Method 4
Solids in Process Filter Cake
1. Discussion
Process filter cake, as collected, is slurried with deionized water,
filtered and washed. The solids are dried and weighed to obtain % solids
in the original cake. The dried cake and the filtrate are saved for later
analyses.
If there is a question about the completeness of removal of sodium by this
procedure then the process filter cake should be dried without slurrying
with deionized water then prepared for sodium analysis by HC1 dissolution
(Method 3). Moisture content must be determined in this case.
2. Apparatus
a. Membrane filter apparatus
b. Glass fiber filter discs, Whatman GFC, 4.25 cm diameter
c. Vacuum pump with trap
d. Drying oven, 84 +_ 1°C or microwave oven
e. Plastic weighing boats
f. Resealable plastic bags
g. Desiccator
h. Magnetic stirrer
3. Procedure
a. Weigh a plastic weighing boat containing a dry filter disc.
35
-------
Cake Solids
b. Weigh 5 to 10 g of wet filter cake (as collected) to 0.001 g
and place in a 100 ml beaker.
c. Slurry with about 25 ml of deionized water.
d. Assemble the filter apparatus with a clean filter flask and the
weighed filter disc. Apply vacuum then quickly pour the slurry
into the filter. In order to avoid channeling and inefficient
washing, it is extremely important that the liquid level not be
allowed to go beneath the surface of the solids.
e. Rinse the beaker with an additional 25 ml of deionized water and
pour into the filter just as the liquid level in the filter
reaches the top of the solids bed.
f. Repeat the wash in step e. once.
g. Transfer the filter disc with solids to the weighing boat. Be
sure that any solids clinging to the filter apparatus are trans-
fered to the boat.
h. Dry the weighing boat to constant weight in the microwave oven
at HI or in a conventional oven at 84 +_ 1°C.
i. Cool in a desiccator then weigh to 0.001 g.
j. Transfer to a labeled resealable plastic bag for storage.
k. Transfer the filtrate quantitatively to a 100 ml volumetric flask
and dilute to volume with deionized water. Mix by inversion
then transfer to a plastic bottle and label.
4. Calculation
Solids in Cake (wt%) = B1 " B x 100%
where:
B * Weight of weigh boat plus filter disc, g, from 3.a.
Bl * Weight of weigh boat plus filter disc plus dried solids,
g, from 3.i.
W = Weight of sample as collected, g, from 3.a.
5. Reference
"Chemical Analysis Procedures for Dual Alkali Process Stream Samples,"
Arthur D. Little, Inc., No. 75833, 4/22/76, Methods 4 and 81.
36
-------
pH
Method 5
pH by pH Meter/Glass Electrode
1. Discussion
A pH meter with a combination glass electrode is used to measure solution
and slurry pH. Sample pH values are measured at the time and point of
sampling after calibrating pH meter at sample temperature.
2. Apparatus
a. pH meter
b. Combination electrode, Broadley-James
c. Thermometer
3. Reagents
a. Standard buffer solutions, pH 4, 7, 10
b. Storage solution, 2M KC1; dissolve 15 g of KC1 in 100 ml of
deionized water.
c. Reference electrode filling solution
4. Procedure
a. Calibrate pH meter with electrode in hot (40°C) pH 7 buffer with
the pH meter temperature compensator set to buffer temperature.
b. Use the slope control to set pH meter with a hot (40°C) buffer
at a pH near the system pH. Allow sufficient electrode immersion
time to obtain a steady pH reading whether reading slurry,
solution or buffer pH.
Use the buffer pH value for 40°C as listed in the table on the
buffer bottle rather than the pH at 25°C.
37
-------
pH
c. As soon as possible after sampling add enough sample to a beaker
to cover the lower portion of the glass electrode. Measure the
sample temperature and set the pH meter temperature compensator
to the sample temperature. Read the pH.
d. Rinse the electrode with deionized water after each reading.
e. Replace buffer solution with fresh buffer at the beginning of
each day.
5. Glass electrode performance evaluation
A glass electrode is considered unreliable and should be replaced if either
of the following tests are failed:
a. If the pH meter cannot be set to the correct buffer pH value by
turning the standardization control.
b. If a pH value is radically different from previous values or from
an in-line meter value, the electrode should be compared with two
"lab-standard" electrodes that are known to be reliable. If the
pH value obtained with the questionable electrode is different by
more than 0.2 pH units from the values obtained with the standard
electrodes in a slurry sample, the questionable electrode should
be discarded. Note that a defective electrode will sometimes give
an accurate answer in a buffer but not in a slurry.
6. Reference
"pH Study at the Shawnee Test Facility," Air Quality Group, Research
and Engineering, Bechtel Corporation, September 1976.
38
-------
Conductivity
Method 6
Diluted Conductivity
1. Discussion
The specific conductance of a scrubber liquor sample diluted 1:500 is
measured. This value is used as a check of analytical results. The
diluted sample is saved for further analyses.
2. Apparatus
a. Conductivity meter, YSI Model 31
b. Thermometer
3. Reagents
Potassium Chloride; make up concentrations shown in the following table as
needed for checking conductivity meter. Use deionized water with conduc-
tivity _< 1 Mmho/cm for dilutions:
Concentrations In:
Molarity
0.001
0.005
0.01
0.02
0.05
0.10
0.20
Grams/Liter
0.074
0.373
0.745
1.491
3.727
7.455
14.910
Specific Conductance @ 25°C
Mmho/cm
147.0
717.8
1,413
2,767
6,668
12,900
24,820
Procedure
a. Pi pet 1.00 ml of absorber solution or freshly filtered slurry
liquor into a 500 ml volumetric flask, dilute to volume with deion-
39
-------
Conductivity
ized water with conductivity <. 1 Mmho/cm and mix by inversion.
b. Set Function switch to Line. Allow 5 minutes for warm-up.
c. Rinse conductivity cell, and place in sample solution. Tap the
cell, and dip it two or three times to remove trapped air (see
Notes).
d. Set "Sensitivity" control to minimum by turning knob as far
as possible counterclockwise.
e. Rotate "Range Switch" to obtain maximum shadow. "Shadow" is
the area of the electron tube not lighted. Turn "Drive" to
obtain maximum shadow. If dial indication is above 20.0 or
below 2.0, turn "Range Switch" to next higher or lower setting.
f. Set "Sensitivity" to maximum (turn fully clockwise).
g. Turn "Drive" to obtain maximum shadow. If you cannot obtain a
clear, well defined shadow, set the "Function" switch to 1 KHz.
h. Read the conductance by multiplying the reading on the dial by
multiplier. Multiply this result by 500.
i. Save sample for sodium analysis.
5. Standardization
Standardize the conductivity meter daily with 0.001M or 0.005M KC1 stan-
dard. The meter should indicate the specific conductance listed in the
table +_ 5%. If the variation is greater than _+ 5% and is consistently
either high or low, a factor should be used in determining actual conduc-
tivities. Calculate the factor as follows:
Conductivity of KC1 Theoretical
factor = C = Conductivity of KC1 Measured
at 25°C or temperature compensated
Multiply this factor times conductivity reading to get corrected result.
40
-------
Conductivity
6. Notes
a. The cell must be clean before making any measurement. The cell
should be rinsed with deionized water after each sample and
before storing.
b. When taking a measurement, the cell's vent slots should be
submerged. The electrode chamber should be free of any
trapped air.
c. The cell should be at least 1/4" away from any other object,
including the walls or bottom of the solution container.
d. Electric fields present from stirrer motors, heaters, etc.,
may affect readings.
e. If pH of the diluted solution is between 6 and 9 there should be
a consistent relationship between conductivity and total dissolved
solids for each sample type. Variation indicates analytical
problems.
f. The conductivity should be approximately equal to the summation
of the anion concentrations in meq/1 x 100, if pH of the diluted
sample is between 6 and 9. Presence of hydroxyl ion raises the
conductivity relative to anion concentrations. Variation from
this relationship indicates analytical problems.
g. Other KC1 standard solutions should be checked when working with
samples with higher conductivities.
7. Reference
Standard Methods for the Examination of Water and Wastewater, 14th
Edition, pp. 35-36, 71-75, (1975).
41
-------
Calcium/Magnesium
Method 7
Calcium and Magnesium by EDTA Titration
1. Discussion
Calcium in solution is titrated with a complexing agent, EDTA, at a high
pH. An indicator changes color when all calcium has been complexed.
Calcium plus magnesium is titrated with EDTA at pH 10. In liquor samples,
magnesium concentration can be calculated by subtracting the calcium concen-
tration (meq/1) from the calcium plus magnesium (hardness) concentration
(meq/1) since the two concentrations are comparable. This is not the
case in D/A solids samples where the concentration of magnesium is very
low compared to the calcium concentration. Magnesium concentration in
solids must be measured by I.C. or atomic absorption.
2. Apparatus
a. Buret, automatic, 10 ml
b. Measuring spoon (scoop), 0.1 g
c. Magnetic stirrer
3. Reagents
a. Ethylenediamine tetra-acetic acid, disodium salt (EDTA), standard
solution, 0.02N
b. Potassium Hydroxide, 8N; carefully dissolve 45 g of KOH then
dilute to 100 ml with deionized water in a volumetric flask
while cooling under a stream of tap water.
c. Calcium Indicator, Hach Chemical Co. CalVer II, Cat. #852-99
d. Calcium standard solution, 1,000 mg/1
43
-------
Calcium/Magnesium
e. Buffer solution; carefully add 55 ml cone HC1 to 400 ml deionized
water and then, slowly and with stirring, add 310 ml 2-aminoethanol
Add 5.0 g of the magnesium salt of EDTA and dilute to 1 liter with
deionized water.
f. Hardness Indicator; mix 0.5 g Eriochrome Black T with 100 g NaCl.
g. Magnesium Chloride solution, 1%; dissolve 1 g of MgClo and dilute
to 100 ml.
4. Procedure
4.1 Calcium in Liquor
a. Pipet 20.0 ml of slurry filtrate into a 250 ml Erlenmyer flask.
b. Dilute to about 100 ml with deionized water and start stirring.
c. Add 1 ml of 8N KOH. Immediately continue with next two steps.
d. Add 0.1 g of CalVer II with a scoop.
e. Titrate with 0.02N EDTA, slowing the titration near the endpoint,
until the color just changes to pure blue.
4.2 Calcium in Solids
a. Pipet 5.00 ml of HC1 dissolved solids from Method 3 into a 250
ml Erlenmyer flask. A solution of lime or limestone prepared as
in Method 3 can be used in place of dissolved slurry solids
except use 2.00 ml of dissolved lime solution instead of 5.00 ml.
b. Proceed with steps 4.1.b. through e. of this method.
4.3 Hardness in Liquor
a. Carry out steps 4.1.a. and 4.1.b.
b. Add 1 ml of hardness buffer. See note c.
c. Add O.lg of hardness indicator.
d. Carry out step 4.I.e.
44
-------
Calci um/Magnesi urn
5. Calculation
5.1 Calcium (mg/1) in liquor = 400 x V = 20V for SI = 20 ml
SI
where:
V = volume of 0.02N EDTA, ml, from 4.I.e.
SI = volume of liquor, ml, from 4.1.a.
5.2 Calcium (wt%) in solids = 4 x V = 0.8 x V for S2 = 5 ml
W x S2 W
where:
V = volume of 0.02N EDTA, ml, from 4.I.e.
W = weight of solids dissolved, g, from Method 3, step 4.c.
S2 = volume of solids solution, ml, from 4.2.a.
5.3 Magnesium (mg/1) in liquor = 243 x (Vt - V) = 12.2 x (Vt - V) for SI = 20 ml
SI
where:
V = volume of 0.02N EDTA, ml, from 4.I.e.
Vt = volume of 0.02N EDTA, ml, from 4.3.d.
SI = volume of liquor, ml, from 4.3.a.
and aliquots for the calcium and total hardness analyses are
the same volume.
6. Notes
a. If an endpoint is indistinct, interferences may be present. Use
a smaller aliquot and add more water before titrating.
b. Magnesium must be present for a sharp endpoint with CalVer II.
If endpoint is not sharp, add a drop of 1% MgCl2 in step 4.1.b.
c. If pH in step 4.3.b. is not 10 _+ 0.1, repeat step 4.3.a. then
adjust pH to about 10 with HC1 or NaOH before adding hardness
buffer.
45
-------
Calcium/Magnesium
7. Reference
Standard Methods for the Examination of Water and Wastewater, 14th
Edition, pp. 189-190 and 202-206, (1975).
46
-------
Sodium
Method 8
Sodium by Specific Ion Electrode
1. Discussion
A sample of 1:500 diluted liquor is mixed with conditioning solution and
sodium concentration is measured directly with a specific ion meter. There
are no known intereferences to this method in D/A samples diluted 1:500.
2. Apparatus
a. Specific ion meter, Orion Model 407 A/F
b. Sodium electrode, Orion Model 94-11-00
c. Single junction reference electrode, Orion Model 90-01-00
d. Magnetic stirrer
e. Beakers, plastic, 100 ml
f. Drying oven, 140°C or microwave oven
3. Reagents
a. Sodium Chloride, standard solution, 100 ppm sodium, Orion 94-11-07
or dissolve 254.2 mg NaCl dried in a microwave oven or at 140°C
and dilute to 1,000 ml with doubly deionized water.
b. Ionic Strength Adjuster (ISA); dissolve 20 g NH4C1 in 50 ml doubly
deionized water, add 5.0 ml concentrated NH4OH and dilute to 100 ml
c. Filling Solution, for reference electrode, Orion 90-00-19.
d. Electrode rinse stock solution, 1M ammonium bifluoride; dissolve
5.7 g of reagent grade NH4F*HF in 100 ml deionized water. Store
in a plastic bottle.
47
-------
Sodium
4. Procedure
a. Pi pet 5.00 ml of 100 ppm sodium standard into a 100 ml plastic
beaker. Add 45 ml of doubly deiom'zed water and a clean stirring
bar. Place on an asbestos mat on a magnetic stirrer.
b. Add 1.0 ml of ISA and start stirring slowly.
c. Turn Function Switch to X+, wait for the reading to stabilize and
adjust the meter needle to "1" (center scale) on the red logarithmic
scale with the "CALIB" control.
d. Rinse electrodes, blot dry and place in a second plastic beaker
containing 50 ml of 100 ppm sodium standard, 1.0 ml of ISA and a
clean stirring bar. Start stirring slowly.
e. After reading is stable, turn the "Temp °C" knob until the meter
needle reads "10" (full-scale right) on the red, logarithmic
scale. Turn the clear "% Slope" dial until the white arrow on
the "Temp "C" points to the temperature of the standards. If
the slope is not in the range of 90 to 100%, consult trouble
shooting check list in the electrode manual.
f. Transfer 50 ml of slurry liquor diluted 1:500 from Method 6 to
another plastic beaker, add 1.0 ml ISA and a clean stirring bar.
g. Rinse electrodes, blot dry and place in sample. Stir thoroughly
and read ppm sodium by multiplying meter reading on logarithmic
scale by 10. See note a.
5. Calculations
mg/1 Na in liquor = 500 x ppm Na in test solution
6. Notes
If the needle goes off-scale right in step 4.g., rinse electrodes,
blot dry and place in the beaker containing 100 ppm sodium stan-
dard. Adjust the "CALIB" control until the needle points to "1"
(center scale) on the red logarithmic scale. Rinse the electrode,
blot dry and replace in sample. Multiply meter reading for sample
by 100.
b. Store electrodes upright in a beaker containing a dilute sodium
solution.
48
-------
Sodium
c. Never touch the membrane of the sodium electrode or the ground
surface of the reference electrode.
d. The sodium electrode response may become slow due to hydration
of the membrane. If this occurs, transfer 10 ml of electrode
rinse stock solution into a 150 ml beaker, add about 100 ml of
deionized water and place the tip of the sodium electrode in
the solution. Swirl for about 30 seconds. Rinse well.and soak
in deionized water for an hour.
e. Problems with the reference electrode may be due either to
improper flow of electrolyte or contamination of the filling
solution. These problems may be handled as follows:
t The Filling Solution level in the electrode should be at
least one inch above the level of the solution being
measured.
• Push back the reference electrode sleeve so that a drop of
Filling Solution collects at the tip of the electrode then
release sleeve. Do this before every series of measurements.
• Whenever electrode response becomes erratic, change the
reference electrode Filling Solution. Flush several times
with Filling Solution before finally filling the electrode.
7. Verification
a. Pipet 5.0 ml of 100 ppm sodium standard, 1.0 ml of ISA and 45 ml of
1:500 diluted slurry liquor into a 100 ml plastic beaker and stir
slowly.
b. New reading should be 0.9 times reading obtained in step 4g. plus
10.0 ppm.
c. If interference is suspected, repeat analysis using Method of Known
Addition as outlined in electrode manual.
8. Reference
Instruction Manual for Sodium Electrode, Orion Research, Inc.
Cambridge, Massachusetts.
49
-------
Chloride
Method 9
Chloride by Hg(N03)2 Titration
1. Discussion
Chloride ions are titrated with mercuric nitrate to form soluble, slightly
dissociated mercuric chloride at a pH near 2.5. Diphenylcarbazone forms a
purple complex with excess mercuric ions to indicate the endpoint of the
titration. Sulfite interference is removed by oxidation with hydrogen
peroxide.
2. Apparatus
a. Buret, automatic, 10 ml
b. Magnetic stirrer
3. Reagents
a. Phenolphthalein indicator solution, 0.1% in alcohol.
b. Sodium hydroxide solution, IN.
c. Hydrogen peroxide solution, 30%.
d. Manganese chloride solution, 10 mg/1; dissolve 0.04 g
*4H0 in 1000 ml of distilled water.
e. Bromocresol green indicator solution, 0.4% in alcohol, neutralized.
f. Nitric acid IN; dilute 64 ml of 70-72% nitric acid to 1 liter.
g. Sodium hydroxide solution, IN; carefully dissolve 40 g of NaOH and
dilute to one liter with deionized water.
h. Diphenylcarbazone Buffer powder pillows, Hach Cat. #836-99
i. Mercuric nitrate solutions 0.141N and 0.0141N
51
-------
Chloride
Chloride Standard Solution, 1,000 ppm; dissolve 1.648 g of Nad
(dried at 140°C) in chloride-free deionized water and dilute to
1,000 ml in a volumetric flask.
4. Procedure
4.1 Liquor
a. Pi pet a 2.00 ml aliquot of sample into a 250 ml Erlenmeyer flask.
Add 20 ml of deionized water.
b. Add 2 drops of phenol phthalein indicator solution and sufficient
IN NaOH to give a red color.
c. Add 2 ml 30% ^2, mix and let stand for 10 minutes.
d. Add 1 ml of 10 mg/1 manganese solution. (The amount of chloride
added is neglible, equivalent to only 4 x 10"bM chloride in the
sample.)
e. Heat solution and boil gently for approximately 15 minutes to
destroy the peroxide, adding more deionized water if necessary
to maintain liquid level. Absence of peroxide is indicated by a
change in the boiling (gas evolution) character.
f. Cool the solution to room temperature, add 3-4 drops of bromocresol
green indicator and bring just to the green color with IN
g. Add contents of a diphenylcarbazone buffer powder pillow and
titrate with 0.141N HgfNOj^ solution until color just changes
to a permanent light pink.
4.2 Lime, Limestone or Soda Ash
a. Weigh out 0.2 to 0.3 g (weighed to +_ 0.001 g) of dry, well-mixed
sample, and transfer into a 250 ml Erlenmyer flask containing
50 ml of deionized water plus 3-4 drops of bromocresol green
indicator solution. Start magnetic stirring.
b. Add IN HNOo acid (4-8 ml) to dissolve all solids, and continue
dropwise addition of the acid until the indicator turns green.
c. Adjust the indicator color to yellow-green by dropwise addition
of IN HN03 or IN NaOH.
d. Add contents of a diphenycarbazone indicator buffer powder pillow
and titrate with 0.0141N Hg(N03)2 solution until color just
changes to a stable light pink.
52
-------
Chloride
5. Calculation
5.1 Chloride (moles/1) in liquor = V x N
S
where:
V = volume of Hg(N03)2 titrant used, ml
N = normality of Hg(N03)2 titrant
S = volume of sample used, ml, from 4.1.a.
5.2 Chloride (millimole/g) in lime or limestone = V_x N
W
where:
W = weight of sample used, g, from 4.1.a.
6. Titrant Standardization
Titrate a 25 ml aliquot of 1,000 ppm CT solution, for 0.141N Hg(N03)2
titrant using the procedure outlined above. Use 2 ml of 1000 ppm Cl~
solution to standardize O.OH1N HgN03.
N of titrant = 0.0282 x j>
V
where:
V = volume of Hg(N03)2 titrant used, ml
S = volume of 1000 ppm Cl" solution used, ml
53
-------
Chloride
7. Notes
a. A small amount of undissolved indicator/buffer powder remaining
in a sample will not affect results.
b. To analyze chloride in slurry solids, perform steps 4.2.a. and
4.2.b. then steps 4.1.b. through 4.1.f. and finally step 4.2.d.
Calculations are the same as for chloride in lime or limestone.
8. References
a. "Chemical Analysis Procedures for Dual Alkali Process Stream
Samples," Arthur D. Little, Inc., No. 75833, 4/22/76, Methods
19, 61, 63 and 69.
b. Standard Methods for the Examination of Water and Wastewater,
14th edition, pp 304-306, (1975).
54
-------
Fluoride
Method 10
Fluoride by Specific Ion Electrode
1. Discussion
A sample of slurry liquor is mixed with conditioning solution and fluoride
concentration is read directly with a specific ion meter. Interferences
are removed in the procedure.
2. Apparatus
a. Specific Ion Meter, Orion Model 407 A/F
b. Fluoride Electrode, Orion Model 94-09-00
c. Single Junction Reference Electrode, Orion Model 90-01-00
d. Magnetic Stirrer
e. Beakers, plastic, 100 ml
f. Micropipet
3. Reagents
a. Fluoride Standard Solution, 100 ppm, Orion 94-09-07 or dissolve
221.0 mg NaF and dilute to 1,000 ml with deionized water
b. Total Ionic Strength Adjustment Buffer, Orion 94-09-11 diluted
with deionized water as indicated on bottle
c. Filling Solution, for reference electrode, Orion 90-00-01
d. Hydrochloric Acid, concentrated
4. Procedure
a. Transfer 49.5 ml deionized water into a beaker and add 0.50 ml of
100 ppm fluoride standard with a micropipet.
55
-------
Fluoride
b. Pipet 5.0 ml of TISAB into the beaker and stir slowly with magnetic
mixer.
c. Turn Function Switch to X-, wait for reading to stabilize and adjust
the meter needle to "1" (center scale) on the red logarithmic scale.
d. Rinse electrodes, blot dry and place in a second beaker containing
5.0 ml of fluoride standard, 5.0 ml of TISAB and 45.0 ml of deionized
water. Start stirring slowly.
e. After reading is stable, turn the Temperature Compensator Knob until
the meter needle reads "10" (full-scale right) on the red logarithmic
scale.
f. Transfer 50 ml of decanted slurry liquor to another beaker, add 5.0
ml TISAB and start stirring slowly.
g. Rinse and blot dry pH meter electrode then place in sample. If pH is
not £ 5.5, adjust pH to <5.5 with measured, dropwise addition of con-
centrated HC1. Remove pH electrode without rinsing into sample.
h. Rinse fluoride and reference electrodes, blot dry and place in sample.
Read fluoride concentration directly. If HC1 addition^ 0.5 ml, cor-
rect results by multiplying:
55 + ml HC1 x (meter reading)
55
5. Verification
a. Transfer 0.50 ml of 100 ppm fluoride standard with a syringe into the
sample measured in step 4h.
b. New reading should be exactly 1.0 ppm higher than reading for sample
alone.
c. If interference is suspected, repeat analysis using Method of Known
Addition as outlined in electrode manual.
6. References
a. Instruction Manual for Fluoride Electrode, Orion Research, Inc.,
Cambridge, Massachusetts.
b. Standard Methods for the Examination of Water and Wastewater,
14th Edition, pp 391-393, (1975).
56
-------
Nitrate
Method 11
Nitrate by Chromotropic Acid
1. Discussion
Solutions containing nitrate are first treated to eliminate interfering
ions. A yellow reaction product is then formed with chromotropic acid and
the nitrate concentration is determined spectrophotometrically. As written,
the procedure measures only nitrate nitrogen; see note for including ammonia
and nitrite nitrogen in the determination. Concentration range is 0.1 to
5 mg/1 nitrate nitrogen (N03-N).
2. Apparatus
a. Spectrophotometer for use at 410 nm with 1 cm or longer light path
b. 1 cm cells for use in Spectrophotometer
c. Magnetic stirrer
d. Hotplate
3. " Reagents
a. Stock Nitrate Solution; dissolve 721.8 mg dried anhydrous potassium
nitrate _or 606.9 mg dried anhydrous sodium nitrate and dilute to
1000 ml with doubly-deionized water in a volumetric flask.
1 ml = 0.1 mg N03-N.
b. Standard Nitrate Solution; pipet 50.0 ml of stock nitrate solution
into a 500 ml volumetric flask and dilute to the mark with doubly-
deionized water. 1 ml = 10 Mg NO
c. Antimony Reagent; heat 500 ml antimony metal in 80 ml cone HpS04
until all the metal has dissolved. Cool and cautiously add 20 ml
of doubly-deionized water which has been cooled to near 0°C in an
ice bath. If crystals separate upon standing overnight, redissolve
them by heating.
57
-------
Nitrate
f.
9-
Chromotropic acid reagent: Purify the chromotropic acid (4,
5-dihydroxy-2,7-naphthalene disulfonic acid disodium salt) in the
following manner. Boil 125 ml deionized water in a beaker and
gradually add 15 g 4,5-dihydroxy-2,7-naphthalene disulfonic acid
disodium salt with constant stirring. To the solution add 5 g
activated decolorizing charcoal. Boil the mixture for about 10
minutes. Add deionized water to make up the loss due to evapora-
tion. Filter the hot solution through cotton wool. Add 5 g acti-
vated charcoal to the filtrate and boil for 10 more minutes.
Filter, first through cotton wool and then through a filter paper,
to remove the charcoal completely. Cool the solution and slowly
add 10 ml nitrate-free cone F^SO*. Boil the solution until about
100 ml are left in the beaker. Allow the solution to stand over-
night. Transfer the crystals of chromotropic acid to a Buchner
funnel and wash thoroughly with 95% alcohol until the crystals
are white. Dry the crystals at 80°C.
Dissolve 100 mg purified chromotropic acid in 100 ml cone H^O^
and store in a brown bottle. Prepare every 2 weeks. A colorless
reagent solution signifies the absence of nitrate contamination
from the sulfuric acid.
Urea reagent; dissolve 5 g urea in doubly-deionized water and dilute
to 100 ml.
NaOH, 0.1N; carefully dissolve 4 g of NaOH pellets and dilute to
1 liter with doubly-dionized water.
H2S04, 0.1N; carefully add 2.8 ml of cone H2S04 to doubly-deionized
water and dilute to 1 liter.
h. MnCl2, 10 mg Mn/1; dissolve 0.04 g MnCl2*4H20 in 1000 ml of deionized
water.
i. AgNOg, 1.4N; dissolve 24 g AgNOg in deionized water and dilute to
100 ml. 1 ml is equivalent to about 50 mg Cl. Store in a brown
bottle.
j. Phenolphthalein Indicator Solution; 0.1% in alcohol.
k. H202, 30%
1. f^SO^, concentrated, nitrate-free
m. Source of air or nitrogen for sparging
4.
Procedure
a. Pipet 25.0 ml of sample into a 125 ml Erlenmyer flask,
58
-------
Nitrate
b. Add a drop of phenolphthalein solution and if the solution is pink,
add sufficient 0.1N H^SO^ to make the solution colorless plus an
additional ml.
c. Add 0.5 ml of AgNO^ solution for every 1,000 mg/1 Cl in the sample
as determined in Method 9. Mix. See note C.
d. Add a few drops more of phenolphthalein and sufficient 0.1N NaOH to
make the solution pink.
e. Sparge the solution with a stream of air or N2 while gently boiling
to remove NH^. Add doubly-deionized water to keep volume near 2.5
ml. Sparging is complete when a piece of pH indicator paper, dampened
with deionized water and held in the fumes from the flask, indicates
a neutral pH. Cool solution to near room temperature.
f. Add 2 ml of 30% H202, mix and allow to react for 10 minutes.
g. Add a ml of 10 mg/1 manganese solution and boil for about 15 minutes
to destroy the peroxide. Absence of peroxide is indicated by a
change in the boiling (gas evolution) character. During this
period, allow the volume to be reduced to about 10 ml but do not
allow the solution to go to dryness. Add additional doubly-deionized
water during boiling, if needed.
h. Cool, then quantitatively transfer the contents of the flask to a
25 ml volumetric flask using doubly-deionized water to rinse and
dilute to volume. Mix by inversion.
i. Filter with a filter funnel into a clean test tube. Do not rinse.
j. Pipet 2.5 ml of the filtrate into a dry 10 ml volumetric flask.
k. Add 1 drop of urea reagent.
1. Place the flask in a small beaker containing cold (10 to 20°C)
water and carefully add 2 ml antimony reagent. Swirl the flask
during addition of each reagent. Leave the flask in the bath for
about 4 minutes before continuing.
m. Add 1 ml chromotropic acid reagent and swirl flask again. Leave
the flask in the bath for an additional 3 minutes.
n. Add cone H2S04 to the mark, stopper and mix by inverting four times.
o. Allow the flask to stand for 45 minutes at room temperature then
again adjust the volume to the 10 ml with cone H^SO^. Mix by
inversion very gently to avoid introducing gas bubbles.
Set zero on the spectrophotometer at 410 nm using deionized water
in a 1 cm cell.
59
-------
Nitrate
q. Rinse the sample cell with sample solution then fill carefully, to
avoid trapping bubbles, by holding the cell in a slanting position
and pouring the solution very slowly down the side of the cell. Be
careful not to get any of the solution on fingers or clothes and
neutralize any spills with sodium bicarbonate and water.
r. Read the absorbance at 410 nm 15 minutes or more after the last
volume adjustment.
s. Determine the corresponding Mg N03-N from the standard curve.
5. Standard N03-N Curve Preparation
a. Pipet into marked, 100 ml volumetric flasks 0, 1.0, 5.0, 15, 25,
35 and 50 ml of standard nitrate solution and dilute to the mark
with doubly-deionized water. Mix. These flasks contain 0, 10,
50, 150, 250, 350 and 500 g N03-N respectively.
b. Pipet 25.0 ml of each standard into Tabled 125 ml Erlenmyer flask
and add 1 ml 0.1 N H2S04 and 0.5 ml of AgN03 solution to each.
c. Carry out steps d., f. through h. and j. through r. of the above
procedure for each.
d. Plot absorbance on the ordinate against mg N on the abscissa for
each standard.
6. Calculation
mg/1 nitrate N = Mg nitrate N
ml sample (from step 4.j.)
mg/1 N03 = mg/1 nitrate N x 4.43
7. Notes
a. The procedure as written determines only nitrate N. To include
nitrite N, delete step 4.k. To include ammonia N, delete step 4.e.
b. If sample contains more than 5 mg/1 N03-N, make an appropriate
dilution of the sample before starting procedure. Dilution factor
must then be included in the calculation.
60
-------
Nitrate
c. If sample chloride concentration is less than 2,000 mg/1 steps 4.b., c.
and i. may be deleted.
8. References
a. "Chemical Analysis Procedures for Dual Alkali Process Stream Samples",
Arthur D. Little, Inc. No. 75833, Method 21, 4/22/76.
b. Standard Methods for the Examination of Water and Wastewater, 14th
Edition, pp 429-431, (1975).
61
-------
Total Sulfur and Sulfate
Method 12
Total Sulfur and Sulfate by Turbidimetry
1. Discussion
Sulfate (or sulfate plus sulfite which has been oxidized by H202 to
the sulfate form) is converted to a uniform barium sulfate suspension.
The resulting turbidity is measured spectrophotometrically and com-
pared to a standard curve.
2. Apparatus
a. Spectrophotometer, for use at 420 nm, with 25 mm light path
b. Matched 1" test tubes for use in spectrophotometer
c. Vortex type test tube stirrer
d. Hotplate
3. Reagents
a. Hydrogen peroxide, 30%
b. Standard sulfate solution, 50 mg/1, Hach Cat #2578-11 or dissolve
147.9 mg dried anhydrous sodium sulfate, Na2SO^, in deionized
water and_dilute to 1,000 ml in a volumetric flask (1.00 ml =
100 mg SO*). Dilute 50 ml to 100 ml in a volumetric flask
for 50 mg/1.
c. SulfaVer IV powder pillows, Hach Cat. #12065-99
4. Procedure
4.1 Preparation of Standard Absorption Curve
a. Pipet 2.0, 5.0, 10.0, 15.0, 20.0 and 25.0 ml of 50 mg/1 standard
sulfate solution into matched test tubes. This represents 0.10,
63
-------
Total Sulfur and Sulfate
0.25, 0.50, 0.75, 1.00 and 1.25 mg of SOj ion.
b. Dilute each solution to 25.0 ml with deionized water.
c. Add 25 ml of deionized water to another matched test tube for
a blank.
d. Empty one SulfaVer IV powder pillow into each test tube and
mix on a vortex mixer for 15 seconds.
e. At least 5 minutes but before 10 minutes after mixing, set zero
on the spectrophotometer at 420 nm with the blank, then read the
absorbance for each test tube.
f. Prepare a standard absorption curve by plotting absorbance
against mg S0^~ for each reading.
4.2 Total Sulfur in Liquor
a. Pipet 20.0 ml of 1:500 diluted slurry filtrate from Method 6
into a 100 ml volumetric flask.
b. Add 1 ml of 30% ^2^2* ^eat 9ent^ and swirl for 3 minutes.
c. Cool, then dilute to 100 ml with deionized water and mix by
inversion.
d. Transfer 25 ml of this solution into a matched test tube.
e. Pipet 10.0 ml of 50 mg/1 standard sulfate solution into
another matched test tube and dilute to exactly 25.0 ml
with deionized water.
f. Add 25 ml of deionized water to another matched test tube
for a blank.
g. Empty one SulfaVer IV powder pillow into each test tube and
mix on a vortex-mixer for 15 seconds.
h. At least five minutes but before 10 minutes after mixing, set
zero on the spectrophotometer at 420 nm with the blank, then
read the absorbance for each test tube. See Note b.
4.3 Total Sulfur in Solids
a. Pipet 2.0 ml of HC1/H202 dissolved solids solution from Method 3
step 4.h. into a 100 ml volumetric flask.
b. Dilute to 100 ml with deionized water and mix by inversion.
c. Transfer 25 ml of this solution into a matched test tube.
64
-------
Total Sulfur and Sulfate
d. Proceed with steps 4.2.e. through 1. of this Method.
4.4 Sulfate in Liquor
a. Pipet 5.00 ml of freshly prepared 1:500 diluted slurry filtrate
from Method 6 into a matched test tube. Dilute to 25.0 ml.
b. Proceed with steps 4.2.e. through i. of this Method.
4.5 Sulfate in Solids
a. Pipet 5.00 ml of slurry solids solution from Method 3 into a
matched test tube. Dilute to 25.0 ml.
b. Proceed with steps 4.2.e. through i. of this Method.
5. Calculation
5.1 Total Sulfur (as g/1 SOj) in liquor = mg SO/f (from curve) x 2 x 103
A
where:
A = ml of 1:500 diluted filtrate used in 4.2.a.
2 x 103 = dilution factor for A:500 dilution and 25:100 dilution
5.2 Total sulfur (in millimoles/g) in solids = mg SO/f (from curve) x 4>17
B x Wj
where:
B = ml of solution used in 4.3.a.
Wi = weight of solids used in step 4.c. of Method 3
4.17 = dilution factor for B:100 dilution and 25:100 dilution/MW (S04)
5.3 Sulfate (in g/1) in liquor = mg SO/f (from curve) Y K25 x 10
V->
where:
C = ml of 1:500 diluted filtrate used in 4.4.a.
1.25 x 104 = dilution factor for 1:500 dilution and C:25 dilution
65
-------
Total Sulfur and Sulfate
5.4 Sulfate (in millimoles/g) in solids = nig SO^ (from curve) j 04
D x W2
where:
D = ml of solution used in 4.5.a.
W2 = weight of solids used in step 4.c. of Method 3
(Solids Dissolution), g
1.04 = dilution factor for D:100 dilution/MW (S04)
6.
Notes
If the result for the standard sulfate solution is not 0.50 mg
S04= ± °'°25 mg, then the standard absorption curve should be
checked and the analysis repeated, if necessary.
If the absorbance value measured is not within the range of 0.05
to 0.8, the analysis must be repeated using a suitably adjusted
aliquot in step 4.2.a. for liquor or 4.3.c. for solids.
The matched test tubes must be washed shortly after each set
of analyses to prevent the deposition of a white film on the
inside of the tubes.
7. References
a. Shawnee Test Facility, Turbidimetric Determination of Total Sulfur,
unpublished.
b. Methods for Chemical Analysis of Water and Wastes, EPA-625-16-
74-003, p 277, (1974).
c. Standard Methods for the Examination of Water and Wastewater,
14th Edition, pp 496-498, (1975).
66
-------
TOS
Method 13
Total Oxidizable Sulfur and Thiosulfate by lodate/Thiosulfate Titration
1. Discussion
Excess iodate is added to a sample, then the sample is acidified and excess
iodine is backtitrated with thiosulfate. To determine thiosulfate, sulfite
is complexed with formaldehyde so that only thiosulfate is free to react
with added iodate.
2. Apparatus
a. Buret, automatic, 10 ml
b. Magnetic stirrer
3. Reagents
a. Sodium Thiosulfate, 0.1N, standardize daily against 0.1N lodide-
lodate
b. lodide-Iodate solution, 0.1N, dissolve 3.566 g KI03 (dried for
two hours at 120°C), 2.5 g NaHC03 and 34.8 g KI in about 500 ml
of deionized water then dilute to 1,000 ml in a volumetric flask.
c. Starch solution, 0.5%
d. Hydrochloric Acid, 10% or IN
e. Formaldehyde, 37%
4. Procedure
4.1 Total Oxidizable Sulfur
a. Pipet 2.00 ml of freshly filtered slurry liquor into a 250 ml
67
-------
TOS
Erlenmyer flask or place 0.1 to 0.12 g slurry solids dried to
constant weight in a microwave oven (or at 84 _+ 1°C in a conven-
tional oven), cooled and weighed to 0.001 g, in a flask. Add
about 50 ml of deionized water to the flask.
b. Start magnetic stirring, then pipet in iodate solution. Use
10.0 ml of 0.1N iodate solution for a liquor sample or 20.0 ml
of 0.1N iodate solution for a solids sample.
c. Add 10 ml of IN HC1.
d. Titrate with 0.1N thiosulfate until a pale yellow color is
evident then add a ml of starch solution and continue titrating
slowly until the solution just turns from blue to colorless.
e. Run a blank repeating steps 4.1.a. through d. using 10.00 ml of
0.1N iodate solution and no sample.
4.2 Thiosulfate
a. Use a graduated cylinder to measure 50.0 ml of freshly filtered
slurry liquor into a 250 ml Erlenmyer flask or place 1.0 g of
dry (75°C or microwave), finely-ground slurry solids, weighed to
0.001 g, and 50 ml of deionized water in the flask.
b. Place flask in a mixture of ice and water contained in a large
beaker on top of a magnetic stirrer.
c. Start stirring. Add 10 ml of formaldehyde and cool solution to
below 15°C. Remainder of analysis must be carried out with
solution temperature < 15°C to maintain bisulfite-formaldehyde
complex.
d. Add 10.0 ml of 0.1N iodate solution with a pipet.
e. Proceed with steps 4.I.e. through 4.I.e.
5. Calculation
5.1 N = -|&- x N I03
where:
N = normality of thiosulfate titrant
B = volume of thiosulfate titrant used for blank, ml, from 4.I.e.
N lOg = normality of thiosulfate titrant used for blank, ml, from 4.I.e.
68
-------
TOS
5.2 TOS as mg SO-T/1 in liquor = (B - S) x N x (40.000)
VI
where:
S = volume of thiosulfate titrant used for sample, ml, from 4.1.d.
VI = volume of liquor sample used, ml, from 4.1.a.
40,000 = JH2_ SOo x 1000 El
meq J 1
5.3 TOS in meq/g in solids = (B - S) x N
Wl
where:
Wl = weight of solids sample used, g, from 4.1.a.
5.4 Thiosulfate in mg/1 in liquor = (B - S) x N x (112,000)
V2
where:
V2 = volume of liquor sample used, ml, from 4.2.a.
112,000 = Ei_ SoOo x 1000 m1
meg ^ J
5.5 Thiosulfate in ppm in solids = (B - S) x N x (112.000)
W2
where:
W2 = weight of solids sample used, g, from 4.2.a.
6. Note
To minimize errors associated with sulfite oxidation in the sample,
sample bottles should be filled to overflowing then capped and
analysis should be performed within an hour of sample collection.
7. References
a. "Chemical Analysis Procedures for Dual Alkali Process Stream Samples,"
Arthur D. Little, Inc., No. 75833, 4/22/76, Methods 11 and 51.
b. Snell, F.D., Biffen, P.M., Commercial Methods of Analysis, McGraw-Hill
Book Co., Inc., New York, pp. 174-175, (1944).
69
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Alkalinity
Method 14
Available Alkalinity by HC1 Titration
1. Discussion
The available alkalinity in lime or limestone is determined by titration
with HC1 to the phenolphthalein endpoint. The value found for lime is
available alkalinity but the value found for limestone must be doubled for
available alkalinity.
2. Apparatus
a. Buret, automatic
b. Magnetic stirrer
3. Reagents
a. Hydrochloric acid, standard 0.1N
b. Phenolpnthalein indicator solution, 0.1% in alcohol
c. Drying oven, 105°C or microwave oven
d. Desiccator
4. Procedure
a. Dry lime or limestone sample to constant weight and cool in a
desiccator. Weigh out about 0.4 g of sample to 0.001 g and
transfer to a 250 ml Erlenmeyer flask containing about 100 ml of
deionized water.
Alternatively, thoroughly mix a lime slurry sample by shaking
the sample bottle then quickly pour out about 2 g of lime slurry
into a preweighed sample boat. A lime slurry sample is then
treated in the same manner as a dry sample.
71
-------
Alkalinity
b. Add a drop of phenolphthalein indicator solution and titrate
with 0.1N HC1 to the permanent disappearance of the pink color.
The solution should remain colorless for at least 3 minutes
while stirring is continued to dissolve all the solids.
5. Calculation
5.1 Lime
Total Alkalinity (millimoles OH/g) = (ml HC1) x (N of HC1)
g sample
Alkalinity (as wt* Ca(OH)2 = (ml HC1) x (N of HC1) x (3.7)
g sample
where:
3.7 = 37 m9 Ca(OH)2 x innlg x 100%
meq ' 1000 mg
5.2 Limestone
Total Alkalinity (mi 11 into! es OH/g) = (ml HC1) x (N of HC1) x (2)
g sample
Alkalinity (as wt% CaC03) = (ml HC1) (N of HC1) (10)
g sample
*« 10 = 2 x CaC03 x -. x 100%
6. Reference
"Chemical Analysis Procedures for Dual Alkali Process Stream Samples",
Arthur D. Little, Inc., No. 75833, Methods 58 and 65, 4/22/76.
72
-------
Hydroxide
Method 15
Hydroxide by HC1 Titration
1. Discussion
Hydroxide concentration is determined directly by titration with hydrochloric
acid, using thymolphthalein as an indicator.
2. Apparatus
a. Buret, automatic
b. Magnetic stirrer
3. Reagents
a. Calcium chloride solution; dissolve 2.5 g of CaCl2*2H20 in 100 ml
deionized water
b. Thymolphthalein indicator solution, 0.05% in ethanol
c. Hydrochloric acid, standard solution, 0.1N
4. Procedure
a. Pi pet 10.0 ml of solution sample into a 250 ml Erlenmyer flask
or place about 0.5 g of dried solids, weighed to 0.001 g, in the
flask.
b. Add about 50 ml of deionized water, 10 ml of CaCl2 solution and
3-4 drops of thymolphthalein solution.
c. If solution is not blue, report _< 0.001 moles OH"/1 in a solution
sample or _< 0.02 millimoles OH'/g in a solids sample.
d. If solution is blue, titrate with HC1 to the disappearance of the
blue color. If the blue color reappears on continued stirring,
continue titration until blue color is absent for at least one
minute. See Note a.
73
-------
Hydroxide
5. Calculation
Hydroxide in solution (moles/1) = (ml HC1) x (N HC1)
10
Hydroxide in solids (nrillimoles/g) = (ml HC1) x (N HC1)
g sample
6. Notes
a. If too much indicator has been added, the endpoint is seen as a
marked decrease in the intensity of the blue color.
b. For increased sensitivity (lower detection limit) use a larger
aliquot or less concentrated HC1 titrant.
7. Reference
"Chemical Analysis Procedures for Dual Alkali Process Stream Samples",
Arthur D. Little, Inc., No. 75833, Methods 13 and 53, 4/22/76.
74
-------
Carbonate in Solids
Method 16
Carbonate in Solids by C02 Evolution
1. Discussion
Sample is made alkaline and S03= is oxidized with H202. It is then acidified
in an air tight system and the volume of C02 evolved is measured.
2. Apparatus (see Figure 3.1)
a. Leveling bulb (250 ml)
b. Tygon tubing
c. Gas buret (100 ml)
d. T-connector
e. Stopcock
f. Reaction flask (250 ml Erlenmeyer) with two hole stopper
g. Buret
h. 2 Ring stands with clamps
i. Magnetic stirrer
j. Asbestos mat
3. Reagents
a. Sodium Hydroxide, 0.1N
b. Hydrochloric Acid, concentrated
c. Hydrogen Peroxide, 30%
d. Phenolphthalein Indicator Solution
e. 10% H2S04 + methyl red indicator
75
-------
Carbonate in Solids
4. Procedure
a. Set up the apparatus as shown in Figure 3.1, except do not stopper.
The leveling bulb and gas buret contain 10% I^SO^ Buret g should
be filled with concentrated HC1.
b. Transfer about 1.5 g of dry slurry solids or lime (weighed to 0.001
g) into the reaction flask. Use about 0.1 g of limestone or soda
ash.
c. Add 10 ml of deionized water, and a magnetic stirring bar. Steps
d. and e. should be omitted for lime and limestone samples.
d. Add 2 drops of phenolphthalein solution and then add 0.1N NaOH
dropwise while stirring until a permanent faint pink color is seen
in solution.
e. Add 5 ml of 30% F^Og, st°PPer tne flask and stir for at least ten
minutes.
f. Stop stirring, and check that the flask is tightly stoppered.
g. With stopcock open, lower leveling bulb 20-30 cm and raise until
both liquid levels are at the zero reading. Close stopcock.
h. Again lower the leveling bulb as before and raise to the zero mark
to check for possible leaks in the system. Repeat until a zero
reading is maintained.
i. Start stirring again then add exactly 1.00 ml HC1 from buret g.
As the COp is evolved, keep the leveling bulb below the liquid
level in the buret to lower pressure and allow the ($2 to escape
freely.
j. Measure the volume of gas liberated by raising the leveling bulb
to the point where liquid levels are equal. Repeat until a
constant value is obtained. Read the volume of gas collected,
subtract 1.00 ml for the volume of HC1 added and record this
value as the volume of gas evolved.
5. Calibration
Place 0.100 g of reagent grade, dry CaC03 into the reaction flask with
10 ml of deionized water. Continue with steps f. through j. of the procedure.
It is essential that the time allowed for C02 evolution in step i. be the
same for the standard as for the sample in order to avoid errors from
76
-------
Carbonate in Solids
temperature effects on gas volume due to heat of reaction.
6. Calculations
Carbonate (mmol/g) = Vs
Vst x W
where:
Vs = volume of gas evolved from sample, ml
Vst = volume of gas evolved from 0.100 g of CaCOg, ml
W = weight of sample used in analysis, g
0.100 g of CaC03 standard = 1.00 mmol
weight % Carbonate as CaCOo Vs x J^
Vst W
where:
= 10° m9 CaC0 x 1g x 100%
10 = 3
mmol 1000 mg
7. Reference
"Methods of Soil Analysis," American Society of Agronomy, Inc., Madison,
Wisconsin, Method 91-6, 1965.
77
-------
I , . —Jf-
b d
jCL,
Ml
c
h
/"^ i '
i
^
9
\
J
TT
>
7
:
!
•
r
•
n
b
1
i "j
V
n
FIGURE 3.1
CARBONATE DETERMINATION APPARATUS
78
-------
Carbonate
Method 17
Carbonate by HC1 Titration
1. Discussion
Carbonate in liquor samples is determined by preliminary titration with
hydrochloric acid followed by backtitration with sodium hydroxide. Sulfite
interference is removed by alkaline oxidation with hydrogen peroxide.
2. Apparatus
a. 2 Burets, automatic
b. Magnetic stirrer
c. Hotplate
3. Reagents
a. Sodium hydroxide, standard solution, 0.1N
b. Phenolphthalein indicator solution, 0.1% in alcohol
c. Hydrogen peroxide solution, 30%
d. Manganese chloride solution; dissolve 0.04 g of MnCl2*4H20 in
1000 ml distilled water
e. Hydrochloric acid, standard solution, 0.1N
f. Bromocresol green indicator solution, 0.4% in alcohol, neutralized
4. Procedure
Note- Once the determination is started, it must be carried through Step q.
(acid to bromocresol green) in order to avoid error from absorption
of atmospheric C02.
79
-------
Carbonate
a. Transfer 25 ml of 0.1N NaOH into a 250 ml Erlenmeyer flask and add
1 drop of phenolphthalein indicator solution.
b. Pi pet a 25.0 ml aliquot of sample solution into the sodium hydroxide.
Record this volume as "S".
c. If the phenolphthalein color disappears immediately, add an addi-
tional 10 ml of NaOH solution. The pink (alkaline) indicator color
should persist for at least 30 seconds.
d. Add 5 ml of 30% hydrogen peroxide, mix well and allow to stand for
10 minutes. Add 1 ml of manganese chloride solution, and boil until
effervescence ceases.
e. Cool quickly in water bath. If pink color has faded, add 1 drop
of the the phenolphthalein solution to determine if the solution
is still alkaline.
f. Titrate with 0.1N HC1 to disappearance of pink color.
Note: If too much indicator has been added, the endpoint is seen
as a marked decrease in intensity of the red color. Record
the volume (level) of 0.1N HC1 in the buret as "A".
g. Add 3-4 drops of bromocresol green indicator solution to the titra-
tion solution, and continue titration with 0.1N HC1 until a perma-
nent yellow color is seen. Then add 3 ml of titrant in excess.
Record the reading of the HC1 buret as "B".
h. Quantitatively transfer the titrated solution to a 150 ml beaker
and gently boil (uncovered) for 10 minutes.
Note: It may be necessary to add small amounts of distilled water
during the boiling in order to avoid spattering losses.
i. Cool the solution, and backtitrate with standard 0.1N NaOH to a
green endpoint. Record this volume as "C".
j. Run blank determination with all reagents.
5. Calculation
Millimoles carbonate = [(B - A) x N HC1] - [C x N NaOH]
Carbonate (moles/1) = (millimoles CO-a in sample) - (millimoles COo in blank)
L_<
where: N HC1 = normality of HC1
N NaOH = normality of NaOH (to bromocresol green endpoint)
80
-------
Carbonate
Notes
a. The size of the aliquot used in step b. should be adjusted as
necessary so that only a few ml of 0.1N HC1 (step g.) are needed
to backtitrate the 25 ml (or less) of 0.1N NaOH (step a.) for
routine samples.
b. The 0.1N NaOH used in steps a. and c. need not be a standardized
solution. The normality of the NaOH used in step i. must be known
exactly.
Reference
"Chemical Analysis Procedures for Dual Alkali Process Stream Samples",
Arthur D. Little, Inc., No. 75833, Method 15, 4/22/76.
-------
Liquid Density
Method 18
Liquid Density
1. Discussion
Liquid densities are determined by the use of a hydrometer (for clear liquors)
or by weighing a known volume (for slurries).
2. Apparatus
a. Hydrometer set, capable of measuring specific gravities between
0.900 and 2.000
b. Volumetric flask, 50 ml capacity
c. Thermometer
d. Triple beam balance 1000 g capacity, sensitive to 0.1 g
3. Procedure
3.1 Using hydrometers: For clear liquids and very slow-settling slurries
a. Use cylinder of sufficient diameter for hydrometer to float freely
without touching walls. Read value for specific gravity from the
graduated scale at the meniscus. It may be necessary to try
several hydrometers before the one most suited to the particular
sample is found.
b. Record temperature of the sample. Convert specific gravity to
density or vise versa, as shown under calculations.
3.2 Weighing a known volume: For slurries
a. Weigh a clean, dry 50 ml volumetric flask to 0.1 g. Record
weight as "F".
b. Measure temperature of sample and record as "T".
c. Mix sample thoroughly by shaking in sample bottle.
83
-------
Liquid Density
d. Quickly pour through a funnel into the volumetric flask slightly
less than 50 ml.
e. Mix sample again then quickly withdraw some sample with a medicine
dropper and transfer exactly enough sample to the flask to bring
volume to 50.0 ml.
f. Wipe outside of flask then weigh to 0.1 g. Record weight as S.
4. Calculations
Note: Report 3 significant figures for these calculations.
4.1 Density of liquids
Sp. Gr.
where:
Dj = Density of liquid at temperature T, °C, referred to water
at 4°C, g/ml
Sp. Gr. = Specific gravity read from hydrometer
4.2 Density of slurries
50
where:
S = Weight of flask plus sample, g
F = Weight of flask, g
50 = Volume of flask, ml
5. Reference
Shawnee Test Facility, "Laboratory Procedures Manual," March 1976,
Method 3.
84
-------
Sett!Ing Test
Method 19
Settling Test Procedure
1. Discussion
Well-stirred slurry or slurry dilutions are introduced into a graduated
cylinder. Liquid interface versus time data are collected. Thickener
sizing factors are calculated.
2. Special Equipment
a. Graduated cylinders, 2000 ml and 1000 ml.
b. Stop watch or,
c. Clock with second hand.
d. Yardstick; opaque cardboard background.
e. Gallon containers for slurry samples.
f. Thickening test stirrer, 0.02 rpm (Dorr-Oliver).
g. Beakers, 500 ml and 1000 ml.
h. Pi pets, 50 ml and 100 ml.
3. Procedure
3.1 Characterization of Slurry
a. Shake container of slurry well. Pour slurry into cylinder. The
test stirrer should be in operation. Observe solid/liquid inter-
face and note whether the interface is distinct or diffuse.
Observe if slurry settles fast or slowly. Cylinder size is based
on settling characteristics of the slurry.
b. Record position of solid/liquid interface at 0, 5, 10, 15, 30, and
60 minutes after pouring slurry into cylinder.
85
-------
Settling Test
3.2 Tests on Concentrated Slurry and Diluted Slurry.
a. Shake container of slurry well, pour into test cylinder and turn
on stirrer. Repeat observations as described above.
b. Decant sufficient clear liquid from the settling slurry to increase
concentration to 1.5 times original.
c. Repeat step 3.1.
d. Decant sufficient clear liquid from the settled slurry to increase
concentration to 1.5 times original.
e. Repeat step 3.1.
f. Decant sufficient clear liquid from the settled slurry to increase
concentration to 4.0 times original.
g. Repeat step 3.1.
h. Add sufficient water to bring concentration to 1/2 that of original
sample.
i. Repeat step 3.1.
3.3 Settling Tests with Coagulant Addition
Mix slurry well with the amount of coagulant prescribed by the test condi-
tions. Pour into test cylinder and observe solid/liquid interface. Test
stirrer should be in operation. Record time required for settling as
described in 3.1, above.
3.4 Tests on Slowly Settling Slurry
a. Repeat 3.1 above but allow 16 hours per set of 6 points because
of slow settling.
b. Repeat 3.3 above but allow 16 hours per set of 6 points because
of slow settling.
86
-------
Settling Test
3.5 Second Order Settling Tests for "Thin" Slurry (<1% suspended solids)
a. Arrange six 500 ml beakers and six 50 ml pipets on the laboratory
bench. Clamp the pipets so that the tips are uniformly 2" below
the liquid surface in each of the beakers. Bring the slurry to
room temperature. Beaker and pi pet sizes are determined by slurry
characteristics.
b. Mix slurry well and pour to equal heights in each of the beakers.
Use yardstick to measure exact height.
c. Withdraw slurry samples from the respective beakers sequentially
at 0, 5, 10, 15, 30, and 60 minutes. Determine and record %
solids at each settling time. Provide illumination (lamp) and
opaque background (black or white cardboard) for observation of
solid/liquid interface.
4. Alternate Laboratory Test Method
Place a measured quantity of slurry at a known density in a beaker or glass
cylinder. Attach a narrow strip of paper on one side of the container. Mix
slurry thoroughly. Draw a line on the paper at the top of the slurry and
mark "0" minutes. For five minutes, at one-minute intervals, mark the point
to which the solids have settled. This determines the free settling rate
of solids at the initial density.
Usually readings should be taken at three different densities of the slurry
corresponding approximately to densities which will exist in the various
zones in the thickener.
Decant sufficient clear water or solution to establish a slurry with inter-
mediate density. For instance, if initial slurry density was 1:4, solids to
water, the removal of one-fourth of the water would establish a density of
1:3. Mix thoroughly. Repeat readings of settlement as above.
Then decant again to obtain a slurry at the third density. The slurry just
87
-------
Settling Test
tested was at 1:3 dilution, so decanting one-third of the water will give a
1:2 dilution, solids to water. Mix thoroughly. Repeat settling measurements
at one-minute intervals for five minutes.
The settling rate per minute should be uniform during the testing at each
dilution until compression is reached, at which time the amount of settling
will decrease during each succeeding minute. Measure the settling marks
in inches, thus determining the settling rate in inches per minute for each
slurry density, and convert this to feet per hour.
Determining Final Density
Final density is then determined. Thoroughly mix the slurry remaining after
the test at 1:2 dilution and allow to settle for 19 hours. Mark the position
of settled solids and let stand for a few hours to see if final density was
reached. If the solids continue to settle mark its position at hourly inter-
vals until settling stops. Decant off all clear water or solution. Then
determine moisture content of the solids by weighing and drying.
5. Calculating Thickener Area
Thickener area required is calculated by applying above determined data in
the following formula:
A . 1.333 (F - D)
R
^ _ Thickener area in square feet per ton of dry solids thickened in
24 hours.
F = Initial density (Parts Water to Solids by weight).
88
-------
Settling Test
D = Final density at which solids will settle or density at which you
want to discharge solids from the thickener.*
R = Settling rate in feet per hour.
Calculations of indicated thickener area from each of the three settling
rates obtained in tests will indicate any change in settling rate in the
different zones of the thickener, and the largest area obtained from the
three calculations should be used.
Assume the following data was obtained from the above tests:
At 1:4 dilution R = 0.50 feet per hour
At 1:3 dilution R = 0.30 feet per hour
At 1:2 dilution R = 0.15 feet per hour
Final density D = 1.1
Applying this data to above formula, you obtain:
A = 1.33 (4-1) = 7.98 FT2/TPD
.50
A = 1.33 (3-1) = 8.86 FT2/TPD
.30
A = 1.33 (2-1) = 8.87 FT2/TPD
15
A computer program has been developed by Bechtel that reduces the data. The
output is thickener size data, in square feet of thickener area per ton/day
of solids (FT2/TPD).
* Usually it is desired to discharge solids from the thickener at its final
density as shown in the above test. However, if you want the discharge to
be more diluted than the actual final density, the density desired should
be used in above formula rather than the final density to which the solids
will settle.
89
-------
Settling Test
6. Reference
Shawnee Test Facility, "Laboratory Procedures Manual," March 1976,
Method 20.
90
-------
Particle Size
Method 20
Particle Size Distribution
1. Discussion
Slurry solids are sized with a wet screen technique for particle size
ranges greater than 37 jum. For more definition of size ranges below 75 Mm,
a sub-sieve analysis utilizing an hydrometer can be used. These procedures
are discussed in order below:
A. Wet Sieve Analysis
2. Apparatus
a. 3" O.D. x 2" high brass sieves, lid and bottom pan. Tyler screen
sizes 48, 100, 200, 325 and 400 mesh equivalent to 300, 150, 75,
45 and 37 Mm respectively.
b. Porcelain Buchner funnel, 75 mm plate with fitted rubber stopper
c. Filter paper, 7 cm dia., Whatman #1
d. Vacuum pump with water trap
e. Filter-flask, 1 liter
f. Rubber tubing, heavy-duty
g. Brush for cleaning sieves
h. Drying oven, 105°C
i. Hand-operated, pump-type spray bottle with adjustable spray for
washing particles through screens
j. Ladle, stainless steel, 1 oz. capacity
91
-------
Particle Size
3. Reagent
Calcium Sulfate solution, saturated; mix CaS04*2H20 with tap water (room
temperature) at the rate of 3 g per liter, mix well and allow solids to
settle out before using supernate.
4. Procedure
a. Weigh the dry, clean sieves, bottom pan and a 250 ml beaker.
Also weigh a dry filter paper.
b. Thoroughly mix the slurry sample by shaking and inverting the
sample bottle. Be sure that no solids remain clumped on the
bottom of the bottle.
c. Quickly pour all of the mixed sample into a large beaker.
d. Stir the slurry with the ladle and ladle out a representative
sample containing about 25 g of suspended solids into the tared,
250 ml beaker.
e. Assemble the Buchner funnel apparatus and connect to the vacuum
pump through a trap. Place tared filter paper in funnel, wet
and smooth, apply vacuum and check that there are no leaks.
f. Assemble the sieves in order of decreasing mesh size and push
the bottom sieve of the stack into the Buchner funnel.
g. Pour sample into the top sieve and carefully wash out the beaker
into the sieve with saturated CaS04 solution using the hand
sprayer.
h. Rinse top sieve with sprayer until all undersized particles are
washed through and wash water is clear. See note.
i. Remove top screen and rinse next screen, etc. until all screens
have been rinsed. Stack rinsed screens in original order on
bottom pan.
j. When all wash water has passed through the filter paper, remove
paper and transfer to bottom pan. Recover all solids remaining
in the Buchner funnel by brushing into the bottom pan, if solids
are dry, or use a stream of deiom'zed water from a wash bottle
to complete transfer.
k. Reassemble the sieves and pan in original order and dry at 105°C
to constant weight.
92
-------
Particle Size
1. Place the lid on the top screen, cool and hand-sieve by means
of a lateral and vertical motion of the sieves accompanied by a
jarring action in order to transfer remaining, under-size
material.
m. Weigh each sieve and the pan and record as gross weights.
5. Calculations
Subtract the filter paper weight from the pan weight. Determine net weight
of each fraction by subtracting the tare weight from the gross weight of each
sieve and the pan. Calculate percent passing or percent retained by each
sieve and tabulate results against screen size. The sum of the individual
fraction weights should be near net weight of beaker times percent suspended
solids divided by 100.
6. Note
In steps g. and h., control CaSO^ solution addition so that none of the sieves
or the filter funnel overflow. The process can be sped up by tapping each of
the sieves in the stack. If solids appear in the filter flask, discard the run.
B. Sub-Sieve Analysis by Hydrometer Method
2. Apparatus
a. Hydrometer, ASTM 151 H, 0.995-1.050 Specific Gravity
b. Graduated cylinder, 1,000 ml
c. Thermometer, -20 to 110°C
d. Constant temperature bath, 20°C, e.g., a styrofoam ice chest
e. Volumetric flask, 100 ml marked so as to be distinguishable from
other 100 ml flasks in lab
93
-------
Particle Size
f. Syringe, 1 ml
g. Stopwatch
h. Parafilm
3. Reagent
Calcium Sulfate solution, saturated; see A.3. above.
4. Procedure
4.1 Specific Gravity (based on ASTW D854, Test for Specific Gravity of
Soils)
a. Adjust the temperature of the water bath to 20°C with hot water
or ice.
b. Weigh out 10 to 15 g of dried slurry solids prepared as in the
procedure for Total Suspended Solids from the sample to be
sub-sieve analyzed. Record weight as Wl.
c. Transfer to the marked, 100 ml flask which has been completely
dried.
d. Add about 50 ml of saturated CaSO^ solution at 20°C and mix by
inversion.
e. Rinse down any solids adhering to the neck of the flask above
the 100 ml mark by adding additional 20°C CaS04 solution until
liquid is about 2 cm below mark.
f. Cap flask and place in 20°C bath for one hour.
g. If any air bubbles are present after one hour, remove by rolling
flask or application of vacuum.
h. Carefully dry inside of flask neck above 100 ml mark with a rolled
up filter paper or by other means.
i. Recap flask, replace in 20°C bath for 15 minutes.
j. Carefully add additional CaS04 solution to make exactly 100 ml
using the syringe.
k. Recap the flask, dry thoroughly and weigh. Record as W2.
1. Occasionally repeat steps e. through k. with no sample. In
94
-------
Particle Size
step k. record the weight as P, the weight of the flask
plus 100 ml of saturated CaS04 solution at 20°C.
4.2 Sub-Sieve Analysis (based on ASTM D422, Particle Size Analysis of Soils)
a. Thoroughly mix the slurry sample by shaking and inverting the sample
bottle. Be sure that no solids remain clumped on the bottom of the
bottle.
b. Quickly pour all the mixed sample into a large beaker.
c. Stfr the slurry with a ladle and ladle out a representative sample
containing about 50 g of suspended solids into a tared beaker.
(See note a).
d. Weigh the beaker with sample and record the difference between
the gross and tare weights of the beaker as W, the weight of the
slurry sample.
e. Transfer the sample to 1000 ml graduated cylinder rinsing with
20°C CaS04 solution.
f. Dilute to 1,000 ml with 20°C CaS04 solution.
g. Cover the cylinder mouth with Parafilm and vigorously mix the
contents by shaking and inversion. Place the cylinder in the
water bath, start the stopwatch and remove the Parafilm.
h. Take hydrometer readings at 2, 5, 10, 15, 30, 60, 120, 240, 360
and 1440 minutes (see Note a.). Read hydrometer at top of meniscus.
Insert the hydrometer 20 to 25 seconds before each reading is due
to approximately the depth it will have when the reading is taken.
After each reading is taken immediately remove the hydrometer and
place in a cylinder of 20°C CaS04 solution with a spinning motion.
Adjust temperature of water bath to 20°C about 15 minutes before
each reading is due. Record hydrometer reading and time from
start of settling period.
i. Hydrometers are graduated to be read at the bottom of the meniscus
and calculations in section 5. are based on using water with a
specific gravity of 1.000 instead of saturated CaS04 solution.
To correct for these factors, fill the 1,000 ml graduated cylinder
to 1,000 ml with CaS04 solution, adjust to 20°C in the water bath
and record the specific gravity as read at the top of the meniscus.
The correction factor is this value minus 1.000.
5. Calculations
5.1 Slurry Solid Specific Gravity = Wl
Wl - (W2 - PJ
95
-------
Particle Size
where:
Wl = weight of 105°C or microwave dried slurry sample solids
W2 = weight of the volumetric flask with CaS04 solution and
sample solids at 20°C
p = weight of the volumetric flask with CaS04 solution only
at 20°C
5.2 Solids Remaining in Suspension (%) = 100.000 x G x R
Ws G-l
where:
Ws = weight of slurry sample, W, from B.4.2.d. x % Total
Suspended Solids in sample divided by 100, g
G = slurry solids specific gravity
R = hydrometer reading minus correction factor from B.4.2.i.
5.3 Diameter of a particle corresponding to the percentage indicated by
a given hydrometer reading, D,
0.30 I
= 980 x (G - 1) x T
where:
D = diameter of particle, mm
L = distance from the surface of the suspension to the level at
which the density is being measured from Table 3-1, cm
T = interval of time from beginning of sedimentation to the taking
of the reading, minutes
G = slurry solids specific gravity
96
-------
Particle Size
Table 3-1
EFFECTIVE DEPTH OF HYDROMETER READING
Actual Hydrometer
Reading
1.000
1.002
1.004
1.006
1.008
1.010
1.012
1.014
1.016
1.018
Effective Depth.
L, cm
16.
15.
15.
14.
14.
13,
13.
12,
12.
Actual Hydrometer
Reading
11.5
1.020
1.022
1.024
1.026
1.028
1.030
1.032
1.034
1.036
1.038
Effective Depth,
L, cm
11.0
10.5
10.0
9.4
8.9
8.4
7.8
7.3
6.8
6.2
6. Reporting
Make a plot of particle diameters on a logarithmic abscissa against percent-
ages smaller than the corresponding diameter on an arithmetic ordinate.
Results can also be tabulated as for the wet-sieve analysis.
7.
Notes
a. Weight of sample used and the time intervals between hydrometer
readings can be adjusted to obtain reasonable changes in specific
gravity values between readings.
b. A computer or programmable calculator can be used to advantage for
these calculations.
c. See ASTM D422 for details of determining particle size ranges below
75 jum in dry samples or at temperatures other than 20°C.
8.
Reference
American Society for Testing and Materials, Philadelphia, Pennsylvania,
Methods D854 and D422.
97
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Sodium
Method 21
Sodium by Flame Photometer
1. Discussion
A diluted liquid sample is aspirated in an LPG/oxygen flame. Emitted light
is passed through a filter to isolate the radiation characteristic of
sodium. The intensity of the light is measured by a phototube and is approx-
imately proportional to the sodium concentration. The relationship of the
intensity measured to sodium concentration is not linear so that a standard
curve must be utilized.
The calcium to sodium concentration ratios in D/A absorber liquors and in
samples of soda ash or process filter cake dissolved in water is small and
calcium is not an interference in these samples. However, if HCl-dissolved
process filter cake samples are to be analyzed by this method, standards
must contain the same concentration of calcium as samples since the relatively
high level of calcium in the samples would otherwise be an interference.
A non-ionic surfactant is used in samples and standards to assure proper
aspiration. Samples which contain suspended solids must be filtered to pre-
vent burner clogging.
2. Apparatus
a. Flame photometer, Coleman Model 51 with accessories
b. Regulators for oxygen and LPG supply
c. Drying oven, 140°C or microwave oven
d. Micropipet, 100 microliter volume
99
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Sodium
e. Bottles, plastic, 125 ml
Reagents
a. Sodium standard solution, 1000 mg/1 Na, dissolve 2.542 g of
NaCl dried in a microwave oven (or at 140°C) in deionized
water and dilute to the mark in a one liter volumetric flask.
b. Calcium, 1,160 mg/1 Ca; place 2.896 g CaC03 in a one liter
volumetric flask, add 50 ml deionized water then dissolve
the CaC03 by dropwise addition of a minimum amount of cone
HC1. Dilute to the mark with deionized water and mix by
inversion.
c. Sterox, 1% solution.
4. Procedure
4.1 Photometer operation
a. Turn power switch to On. Be sure "FILTER" switch is set to
sodium.
b. Run aspirator cleaning tool wire through the aspirator
capillary several times. Insert from the bottom of the
capillary—never insert from the top.
c. Start 02 flow and set regulator pressure to 13 psi, if
necessary. Shut off 02 with needle valve.
d. Open LPG tank valve and adjust regulator pressure to 6 inches
of water, if necessary. Shut off LPG with tank valve.
e. Hold down "IGNITE" button for about 5 seconds then open LPG
tank valve. When flame ignites, immediately release the
"IGNITE" button and start 02 flow by opening needle valve.
f. Allow flame and electronics to "warmup" for 10 minutes.
g. Transfer prepared samples to small plastic sample cups being
careful not to touch the inside or rim of the cups. Place
cups in the 20-position sample tray and then mount the tray
on the rotating sample holder beneath flame compartment.
Rotate each sample and standard in turn to the position be-
neath aspirator and then lift sample holder to start aspira-
tion. Sample holder will not rotate while in the raised
position.
Note: Readings must be taken while liquid level in sample
cup is between the two lines inscribed on the cup.
100
-------
Sodium
Discard cups after use.
h. Set photometer as follows:
For liquor or water dissolved samples of soda ash or process
filter cake
• Aspirate 100 mg/1 Na standard and set reading with
"CALIBRATE" control to exactly 10 on 0-10 scale.
• Aspirate 10 mg/1 Na standard (no Ca) and set reading
to exactly 1 with "ZERO" control.
• Repeat above two steps until readings are consistent--
be sure that liquid level in sample cup is above bottom
inscribed line when reading is taken.
For HCl-dissolved process filter cake samples with normal sodium
concentration
• Aspirate 50 mg/1 Na standard (Low Ca) and set reading
with "CALIBRATE" control to exactly 10 on 0-10 scale.
• Aspirate 5 mg/1 Na standard (Low Ca) and set reading to
exactly 1 with "ZERO" control.
• Repeat above two steps until readings are consistent--
be sure that liquid level in sample cup is above bottom
line inscribed on cup when reading is taken.
For HCl-dissolved process filter cake samples with low sodium
concentration
• Aspirate 50 mg/1 Na standard (High Ca) and set reading
with "CALIBRATE" control to exactly 10 on 0-10 scale.
• Aspirate 5 mg/1 Na standard (High Ca) and set reading to
exactly 2 with "ZERO" control.
• Repeat above two steps until readings are consistent--
be sure that liquid level in sample cup is above bottom
line inscribed on cup when reading is taken.
4.2 Preparation of standard curve
Prepare 100 ml Na standards for use with liquor or soda ash samples (no
calcium) as follows:
a. Label six 100 ml volumetric flasks with the Na concentra-
tion indicated for each.
b. Pipet 2.00 ml of 1% Sterox into each flask.
101
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Sodium
c. Pi pet the following amounts of 1,000 mg/1 Na standard
into the flasks.
Sodium Concentration ml of 1,000 mg/1 Na
(mg/1) Standard in 100 ml
10 1.00
20 2.00
40 4.00
60 6.00
80 8.00
100 10.0
d. Add sufficient deionized water to each flask to make
exactly 100 ml of solution then mix by inversion. Trans-
fer to clean, dry 125 ml plastic bottles and label. In-
clude on the labels the statement "No Calcium".
e. Prepare a second set of standards for HC1-dissolved process
filter cake samples by following steps a. through d. above
with the following exceptions:
t Pipet 100 ml of 1,160 mg/1 Ca solution into each flask.
t Include on the labels the statement "Low Calcium (116 mg/1)".
t Use the following table for sodium standard addition in
step c.
Sodium Concentration ml of 1,000 mg/1 Na
(mg/1) Standard in 100 ml
5 0.50
10 1.00
20 2.00
30 3.00
40 4.00
f. Prepare a third set of standards as in the step e. with the
following exceptions:
t Pipet 50.0 ml of 1,160 mg/1 Ca solution into each flask.
• Include on the labels the statement "High Calcium (580 mg/1)".
g. Set instrument according to 4.1.h. above with "No Calcium" stand-
ards then take readings of the first set of standards. Reset
instrument with "Low Calcium" standards then take readings of the
"Low Calcium" set of standards. Reset with "High Calcium" stand-
ards and take readings of the "High Calcium" set of standards.
102
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Sodium
h. Plot three standard curves, one for low calcium samples,
one for HCl-dissolved process filter cake samples with high
sodium content (>1%), and one for HCl-dissolved filter cake
with low sodium content (<1%). Plot meter reading on the
y-axis against sodium concentration (mg/1) on the x-axis
then draw a smooth curve through the points for each set of
standard readings. The standard curves containing calcium
are good only for process filter cake samples containing
about 29% Ca in the dried sample and which are prepared for
analysis as indicated in 4.3 below.
4.3 Sample Analyses
a. Prepare sample dilutions in volumetric flasks as indicated in
Table 3-1 on page 3-21-6. Label flasks with the sample log
numbers.
b. Transfer a maximum of 10 diluted samples plus a duplicate and
a spike of one sample to sample cups then place the cups in the
sample tray and record the tray location for each sample. Do
not place samples containing differing concentrations of calcium
in the same batch of sodium analyses.
c. Transfer a low sodium concentration standard and a high sodium
concentration standard in sample cups to the tray for setting
the instrument. Use the standards with calcium concentrations
appropriate to the samples being analyzed as indicated by in
Table 3-1.
d. Analyze samples as directed in 4.1 and record the reading obtained
for each sample.
e. Use the standard curve appropriate to the calcium concentration
to determine the sodium concentration in mg/1 corresponding to
the reading obtained for each sample.
5. Calculations
5.1 Sodium in Liquor
Sodium (g/1) = C x 1g x 100 ml
1000 mg O.lml
= C
where:
C = Na concentration from standard curve, mg/1
103
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Table 3-2
SAMPLE PREPARATION FOR SODIUM ANALYSIS BY FLAME PHOTOMETER
Sample Type
Initial Dilution
for Solids Sample
Dissolution
Additional D1lu- Volume of 1%
tlon RequMed for Sterox RequMred
Na Analysis 1n Na Dilution
Ma Standards Used
for Water-For HC1-
D1ssl 'd Samps DIssTd Samps
Liquor (Absorber,
Secondary Reactor,
Thickener)
Soda Ash
~5 g:250 ml
0.1 ml:100 ml
0.1 ml:25 ml
2.00 ml
0.5 ml
No Ca
No Ca
Process Filter
Cake (> 1% Na
1n cFy cake)
~0.5 g:100 ml
2 ml:25 ml
0.5 ml
No Ca
*Low Ca
Process Filter
Cake (< 1% Na
1n dry cake)
'0.5 g:100 ml
10 ml:25ml
0.5 ml
No Ca
*H1gh Ca
*Note: The standards Indicated may be used for sodium analysis of HCl-d1ssolved process filter cake
containing between 28 and 30 wt% calcium 1n the dry cake. If sample calcium concentration
1s outside of this range, then new standards must be utilized containing [Ca]/29 times the
amount of 1,160 mg/1 calcium solution (in 100 ml of standard) Indicated in Section 4.2 for
low or high calcium standard preparation where [Ca] = Calcium concentration (wt%) in the
dry process filter cake sample.
CO
o
CL
_j.
c
-------
Sodium
5.2 Sodium in Solids
Sodium (wt% in dry solids) = C x _V x _V_L x lg x 11 x 100%
W AF 1000 mg 1000 ml
= C x _V x VF x 10'4
W AF
where:
C = Na concentration from standard curve, mg/1
V = Volume of dissolved solids sample, ml
W = Weight of solids in dissolved sample, g
VF = Volume of final dilution, ml
AF = Aliquot volume of dissolved solids sample used in
final dilution, ml
6. References
a. Coleman Model 51 Flame Photometer Instrument Manual, Coleman Instru-
ments Division of Perkin Elmer Corporation, Maywood, Illinois.
b. Standard Methods for the Examination of Water and Wastewater, 14th
Edition, pp. 250-253, (1975).
105
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Active Sodium
Method 22
Active Sodium by Titration
1. Description
This is a tentative method proposed by Arthur D. Little, Inc. for analysis of
active sodium in Dual Alkali absorber liquor.
Total active sodium concentration is defined as follows:
[Na+]active = 2 x ([Na2S03] + [Na2C03]) + [NaHS03] + [NaOH] + [NaHC03]
In this procedure the anions associated with active sodium are titrated with
standard acid to the bromocresol green endpoint.
The sample is boiled with excess acid, during the analysis, to expel S02 and
C02. Other cations than sodium could be an interference (actually, the alka-
line anions associated with these cations) if present in significant concentra-
tions but in D/A absorber streams their concentrations are very small compared
to the concentration of sodium. Sulfate and chloride do not interfere.
2. Apparatus
a. Burets, automatic
b. Magnetic stirrer
c. Hotplate
3. Reagents
a. Hydrochloric acid, standard solution, 0.1N
b. Sodium hydroxide, standard solution, 0.1N
c. Bromocresol green indicator solution, 0.4% in alcohol, neutralized
107
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Active Sodium
4. Procedure
a. Pipet 2.00 ml of filtered sample into an Erlenmyer flask.
b. Add about 50 ml of deionized water and 2-3 drops of bromocresol
green indicator solution.
c. Titrate with 0.1N HC1 to a yellow endpoint and add 5 ml excess
acid. Record the exact total volume added.
d. Bring solution to a boil on a hotplate and continue to boil for
10 minutes. Add additional deionized water, as necessary, to
maintain volume. See note.
e. Cool flask then titrate to a green endpoint with 0.1N NaOH.
5. Calculations
Active sodium (moles/1) =AxNHCl -BxN NaOH
V
where:
A = Volume of HC1 added in 4.C., ml
B = Volume of NaOH added in 4.e., ml
V = Volume of sample used in 4.a., ml
N HC1 = Normality of HC1
N NaOH = Normality of NaOH
6. Note
If sample turns green while boiling in 4.d., start analysis with a new sample
aliquot and add 10 ml excess HC1 in 4.c.
7. Reference
Letter, S. P. Spellenberg {A. D. Little) to C. Hardt (Louisville Gas &
Electric), dated May 31, 1979.
108
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TS
Method 23
Total Sulfur by LECO
1. Discussion
A solids sample is burned at high temperature in a stream of oxygen to
convert sulfur to Sf^. Iron and tin accelerators are added to the sample
before combustion to provide required inductive mass. The combustion
products are carried into a dilute acid solution containing iodate, iodide
and starch indicator. As the blue iodine/starch complex is bleached by S02,
more iodate solution is added to return the solution color to the original
intensity. The color intensity is measured by a lamp and photocell with
output displayed on a microammeter.
Since the conversion of sulfur to SC^ is not complete j a "furnace factor"
is developed by analyzing sulfur standards. The amount of standard iodate
consumed during a sample combustion is used with the furnace factor to
compute total sulfur in the sample as wt% sulfate.
2. " Apparatus
LECO Sulfur Determinator including oxygen purifying train, induction
furnace and semi-automatic titrator.
3. Reagents
a. Iodate solution; add 4.44 g KI03, 5 g KI and 6 pellets of KOH to
about 500 ml of deionized water in a 1 liter volumetric flask.
Dissolve the salts then dilute to the mark with deionized water
and mix by inversion.
109
-------
TS
b. Hydrochloric acid; carefully add 15 ml of concentrated HC1 to
about 500 ml of deionized water in a 1 liter graduated cylinder.
Dilute to 1,000 ml with deionized water and mix.
c. Starch solution; use commercially prepared stabilized, starch
indicator solution and add 10 g of KI per liter. Dissolve and
mix. Replace when endpoint produced is not a distinct blue
with no reddish tinge.
d. Tin metal accelerator; LECO Cat. #501-076.
e. Iron powder accelerator; LECO Cat #501-077.
4. Procedure
a. Turn on filament voltage (located beneath the green indicator light
on the lower right side of the induction furnace).
b. Turn on titrator power switch (located in the lower right side of
the titrator face).
c. Allow 5 minutes for warmup.
d. Accurately weigh about 0.07 grains of dried sample into a porous cup
and record exact weight of sample.
e. Add to the cup in the following order:
(1) One glass scoop of tin metal accelerator.
Note: Shake the tin metal into the cup so that the sample
is covered by the tin.
Caution: Three scoops or two heavily heaped scoops of
iron powder may over-load the furnace result-
ing in a circuit breaker trip on the furnace.
If this occurs, remove the cup and set up again
using less iron. Reset the breaker and restart
the procedure.
(2) Two slightly rounded glass scoops of iron powder accelerator
(see note under [1]). Place porous cover on cup.
The sample is ready for analysis.
f. Drain the reaction vessel by opening the glass stopcock at the
bottom of the reaction vessel on the titrator.
g. Close the stopcock.
no
-------
TS
h. Place a finger over the hole on the manifold button located on the
lower left side of the titrator and press the button down. Squeeze
the rubber bulb until the fluid level in the reaction chamber reaches
the bottom black line on the reservoir.
i. Add 3-4 drops of starch solution to the reaction vessel.
j. Raise the porous cup holder (without porous cup) into the glass
reaction chamber on the induction furnace and lock into place.
k. Open the valve on the oxygen bottle and set the flow rate at
1 liter/minute (flow rate is controlled by needle valve on the
left side of oxygen purifying train and by the regulator control
on the oxygen tank).
1. Briefly press the "FINE" button on the lower right side of titrator.
Note: At this point, a blue color will develop in the titration
vessel.
m. Cover the hole of the manifold button on the left side of the ti-
trator (do not press down), then squeeze the rubber bulb till the
buret is filled. Uncover the hole and the buret will self-zero.
n. Set microammeter pointer to 10 with "CALIBRATE" knob.
o. Lower the cup holder on the induction furnace and place porous
sample cup with sample in position.
p. Turn on the high voltage switch (located below the red indicator
light on the lower left side of the induction furnace).
q. Return cup holder and sample cup to operating position.
r. Check to see if bubbles of gas are being evolved from the titration
reaction vessel. If not, lower cup holder and check to see if
sample cup is in proper position.
s. When S0? is evolved the microammeter reading will decrease. Keep
the reading between 10 and 12 by depressing the "COARSE" and "FINE"
buttons as required. When reading no longer changes, adjust reading
to exactly 10 with "FINE" button. Titration is complete.
Things that should occur during combustion:
(1) An orange light will appear over the sample cup.
(2) After about 2 minutes the sample cup will begin to emit
orange light.
(3) A white gas will be evolved from the titration vessel until
near the end of the titration.
Ill
-------
TS
(4) The plate current will increase until all S02 in evolved, then
decrease.
(5) The grid current will decrease as the plate current increases.
t. Carefully lower the cup holder.
u. Read and record the buret reading.
v. Drain the titration vessel and refill as before the further analyses.
w. Remove the sample cup with tongs or test tube holder.
5. Furnace Factor Determination:
a. Obtain a sample of known sulfur concentration, dry to constant
weight.
b. Weigh at least 3 samples of the known into 3 sample cups. Record
the weights.
c. Run the samples as described for routine samples.
6. Calculations
6.1 Total Sulfur
Total Sulfur (wt% as S04=) = 30 x V x FF
W
Where:
V = volume of iodate titrant used, ml
W = weight of solids sample, g
FF = furnace factor
30 = conversion factor for S0^= equivalent weight and percent
6.2 Furnace Factor
FF = S x W
30V
where:
FF = Furnace Factor
S = Sulfur content of standard, wt% as S0^=
V = volume of iodate titrant used, ml
Use the average furnace factor found with the replicate standard analyses.
112
-------
TS
7. Note
The volume of titrant added by pushing the "FINE" button may be adjusted
with the "SENSITIVITY" control on the rear of the titrator unit.
8. Reference
LECO Semi-Automatic Sulfur Determinator Instruction Manuals,
LECO Corporation, St. Joseph, Michigan.
113
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Section 4
QUALITY ASSURANCE PROGRAM
4.1 INTRODUCTION
This quality assurance program details procedures for establishing a laboratory
quality control (QC) program and also gives the quality assurance procedures
which will be used for monitoring the QC program. The purpose of the QC
program is to systematically insure that the precision and accuracy of all
analytical data meet required limits of acceptability for proper evaluation
of project results. The QC program will monitor and document the quality of
data produced by both the on-site laboratory and subcontractors. Quality
assurance procedures will be used to ensure the effectiveness of the QC
program.
The quality assurance program will consist of three phases. During Phase I,
the project Quality Control Coordinator will ensure that the QC program is
established. During Phase II he will ensure the QC program is being imple-
mented effectively. Round robin samples prepared by an outside laboratory
will be utilized and a quality assurance audit will be carried out. In Phase
III, after completion of project field activities, a written evaluation of the
project quality control effectiveness will be prepared.
115
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4.2 ORGANIZATION
The organizational structure shown in Appendix C on page 158 illustrates
the basic QC functions of the project personnel.
The project Quality Control Coordinator (QCC) will coordinate the quality
control program and quality assurance procedures with operations personnel
to insure that the quality control program is properly functioning through-
out the project. In addition to responsibility for the overall functioning
of the QC program, specific duties of the QCC will include performance of
the QC audit(s) and maintenance of the round-robin reference sample program.
The QCC will report to the project manager.
4.3 QUALITY ASSURANCE PLAN
The quality control for the project will be developed and executed under a
three phase QA program.
Phase I
Phase I consists of an initial period of laboratory start-up and on-site
evaluation of instruments and methods for precision and accuracy. QC
charts will be prepared for each analytical procedure. Instructions for
constructing these charts are listed in Section 4.7.1, Development of
Quality Control Charts. A QC notebook will be initiated at this time.
Contents of the QC notebook will include the following:
Item Reference
QC Charts Section 4.7
QC Memos Appendix C, page 159
116
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Item Reference
Lab Notebook Audits Appendix C, pages 160 and 161
Copies of calibration
curves with check
standard values and
acceptance limits
Other log books and notebooks that will be initiated during Phase I include:
Item Reference
Analytical Balance Appendix C, page 162
QC Log
Sample Log Book Section 4.6
Instrument Service Section 4.4
and Repair Notebook
Reagent Log Book Section 4.4
Lab Notebook for each analyst Appendix C, pages 160 and 161
Description of these items may be found under the associated references.
Some of the items may be combined into a single notebook.
Phase II
Phase II covers routine laboratory operation. During routine operations, at
least one duplicate and one spiked sample (if appropriate) will be determined
per day for each analysis run. If samples in a batch exceed 10 in number, a
second duplicate and spike will be included for every multiple of 10 samples.
These duplicate and spike results will be monitored with modified Shewart
charts as specified in Section 4.7, Quality Control Data Aquisition and Data
Handling. Samples will be logged in accordance with the procedure outlined
in Section 4.6, Sample Handling, Shipping, and Storage. Any samples which
are submitted to a subcontractor for analyses will be handled as described
in Section 4.6. Modified Shewhart charts will be used to monitor the
117
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quality of data obtained from subcontractors by documenting the results
obtained on blind duplicates and spiked samples or standards. Whenever
results from either the site laboratory or a subcontractor exceed control
limits, results of that analytical run will be considered invalid. The
investigation into the problem and the remedies instituted will be the
responsibility of the laboratory supervisor. He will document the inves-
tigation with a Quality Control Memo (Appendix C, page 159) which will be
submitted to the QCC for final review.
Also during phase II, the overall effectiveness and performance of the data
aquisition and handling system will be continually evaluated. Standards
will be routinely submitted to the on-site laboratory and to outside labora-
tories for analyses and the analytical results will be documented. A major
audit by the Quality Control Coordinator will be performed on the quality
control system. As part of the audit, notebooks and logs will be evaluated
utilizing the notebook audit sheet (Appendix C, pages 160 and 161).
Phase III
At the completion of the project a comprehensive quality assurance report
including the documents, memo's, and charts generated during the project
will be prepared. Any evaluations and suggestions for improvement that
develop from the system audit(s) will be included.
4.4 CALIBRATION AND CONTROL
Instruments
An Instrument Service and Repair Notebook will be maintained by the on-site
118
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laboratory supervisor. All major analytical instruments will be described
including accessories. For example, a pH meter will be identified by manu-
facturer, model, serial number, and number and type of electrodes. The date
the instrument and/or accessory is put into service will be recorded. Any
routine maintenance and calibration procedures required will be documented
along with a schedule and check-off sheet to indicate that the work has
been completed. Service and repair performed by authorized repairmen will
be documented by inserting copies of their reports in the notebook.
Instruments will be calibrated according to manufacturer recommendations or
as described in the written procedures in Section 3 of this manual.
The analytical balance calibration will be verified weekly and any time the
balance is moved or subjected to rough handling. If at any time, standard
Class S weights cannot be weighed to +_ I mg of their stated value, the
balance will be recalibrated by a service engineer. A form for weekly
verification of the analytical balance calibration is shown in Appendix C,
page 162. A daily calibration of each pH meter will be made and recorded
in the Instrument Service and Repair Notebook. A daily reading of a
conductivity standard will likewise be recorded for the conductivity meter.
Reagents
All reagent chemicals will be dated upon receipt and stored properly in
accordance with safety regulations. A "first-in, first-out" storage
procedure will be used.
A reagent log-book will be maintained in the laboratory. Entries will
document the manufacturer and lot number of the reagent or stock solution,
119
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date of preparation, technician, the concentration of the solution, and
the expiration date (if appropriate). A label containing this information
will be affixed to the reagent bottle.
4.5 DOCUMENT CONTROL
All written analytical procedures will state the date at which the procedure
becomes effective and any subsequent revision will be given an effective
date. Procedure revisions will be sent to all affected parties.
Instrument manuals will be stored in specified locations convenient to the
respective instruments. All notebooks and logs will be stored in specified
locations within the laboratory.
4.6 SAMPLE HANDLING, SHIPPING, AND STORAGE
The following outline describes in chronological order the QC procedures
to be followed for sample handling, storing, and shipping. More specific
sampling instructions are given in Section 1 of this manual.
1. When samples are received in the lab, they will be identified
with a numbering code.
2. This information will be recorded in a sample log along with date,
sampling location, and other related information (see Figure 1.2).
3. Samples will be preserved when required.
4. Samples will next be segregated into those to be analyzed at the
site laboratory and those to be sent to outside labs.
5. Those analyses such as sulfite which require immediate attention
will be started at this point.
6. All shipped samples will be packaged consistent with the physical
abuse they may receive during shipment. Samples will be shipped
120
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and packed in a manner which insures that the required preservation-
handling requirements are met and maintained during the entire
period of shipment.
7. An inventory of the samples by I.D. number and analyses required
will be recorded in the Sample Shipment Letter. A separate form
will be prepared for each shipping container. One copy of the
Sample Shipment Letter will be included in the shipping box, one
copy will be sent to the project manager and one to the shipment
destination. The original will be maintained at the field facility.
8. Upon delivery for shipment, field personnel will telephone the
outside laboratory and inform them of the estimated time of arrival
of the samples, the carrier, the number of shipping containers, and
whether the samples will be held for pick-up or will be delivered.
9. When the outside laboratory receives the shipment, they will sign
and date the letter, note any discrepancies on it and forward a
copy of the letter to the Project Manager.
4.7 QUALITY CONTROL DATA AQUISITION AND DATA HANDLING
The procedures discussed in Sections 4.4 through 4.6 are designed to enable
the laboratory to produce reliable analytical data. Analytical data quality
is monitored by a continuing statistical evaluation of analytical precision
and accuracy.
Analytical precision and accuracy are defined in the following paragraphs and
then a listing of the procedures to be followed for monitoring these parameters
is given.
Precision
Precision refers to the reproducibility of replicate analyses. If an analysis
is performed many times on the same sample, results will not be the same but will
vary around an average value. The width of this group of results is a property
of the given procedure. The narrower the grouping, the closer each individual
121
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measurement is to the average, the more precise the method is said to be.
Conversely, the more disperse the grouping, the less precise it is.
In a properly designed analytical procedure, this scatter of results is due
to the accumulated effects of all the indeterminate random errors associated
with the procedure. The width of this grouping is specified by a parameter
called the standard deviation. The distribution of individual results of
a properly designed analysis are specified by knowledge of the mean and
the standard deviation provided the distribution law is known. This speci-
fication allows the establishment of consistent criteria for the acceptance
or rejection of data.
Precision control charts based on these acceptance criteria are used to
establish and monitor the reproducibility of analytical procedures.
Accuracy
Accuracy refers to the agreement between a determined constituent concen-
tration and the true or known concentration. Accuracy in the laboratory
is established and monitored with accuracy control charts which are similar
in construction to precision control charts.
Poor accuracy is caused by systematic errors. These errors are always in one
direction, either high or low relative to the "true" value, and are determinate.
This deviation is often called laboratory bias.
It is much more difficult to monitor accuracy than it is to monitor precision.
Analyses of samples with an unknown matrix, containing an unknown quantity
of some substance which may be in an unknown form cannot always be judged to
have high accuracy when an added amount of "spike" gives a good yield.
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Unusual matrices must be carefully monitored and accuracy data for unusual
samples should generally be evaluated separately from established control
charts. For example, a +_ 10% accuracy control limit for water sample analyses
cannot be expected to apply to analyses of fly ash.
Consideration must also be given to whether or not the spike addition will
respond in the same manner as the element in question already in the sample
will respond. The spike will be free and available to treatment in most
cases, while the naturally occurring element may be found in the matrix or
may be present in a volatile or insoluble form, etc.
4.7.1 Development Of Quality Control Charts
The data necessary for establishment of both precision and accuracy control
charts will be generated simultaneously. To develop this data for an analytical
procedure, the following steps will be followed.
1. Select twenty samples which are similar to the routine
laboratory samples which will be analyzed with the analytical
procedure.
2. Analyze each sample in duplicate.
3. Add known amounts of standard ("spike") to an aliquot of each
sample. The final concentration in each spiked sample aliquot
must be within the concentration range of the analytical
procedure and should be within the middle one-third of the range.
For each sample aliquot, use the following equation to determine
the amount of spike to be added (see Table 4-1 for an example).
Amts = Amtos (Cncss - Cncos)
Cncs - Cncss
where: Amts = Amount of standard to be added
Amtos = Original sample aliquot size
123
-------
Cncss = Constituent concentration required in spiked sample
Cncos = Average constituent concentration found in original
sample
Cncs = Constituent concentration in standard
Note: Amounts (Amts and Amtos) are expressed in ml for liquid
samples and in grams for solids samples.
Concentrations (Cncss, Cncos and Cncs) are expressed in mg/1
for liquid samples and in weight % for solid samples.
4. Analyze each of the spiked samples.
124
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TABLE 4-1
EXAMPLE CALCULATION OF SPIKE AMOUNT REQUIRED
FOR TOS IN SOLIDS ANALYSIS
TOS Concentration (wt% as
Sample
1
2
3
Dupl icate
Al
A2
Al
A2
Al
A2
Found
47.72
47.12
45.68
45.98
47.01
46.59
Average
(Cncos)
47.42
45.83
46.80
Required
(Cncss)
50.0
47.5
52.0
Amts*
0.211
0.113
0.507
Al 43.78 43.95 46.0 0.126
A2 44.13
*Amts = Amtos (Cncss - Cncos)
Cncs - Cncss
Amts = Amount of Na2S03 to be added, g
Amtos = Original sample aliquot size = 1.000 g (or as required)
Cncss = S0| concentration required in spiked sample, wt%
Cncos = Ave. $03 concentration found in original sample, wt%
Cncs = SOj concentration in standard Na2S03, wt%
MWSOo x 100% x PNa2S03 = 80.06 x 100% x .980 = 62.25 wt%
MWNa2S03 126.04
PNaoSOo = NaoSOo Purity = 98.0% = .980 (for this example)
*• 6 • * 100%
for « *c - 1.000 9 x (50.0 wt% - 47.42 wt%) = 0.211 g
Sample 1: AmtS 62.25 wt% - bU.O wt%
Notes- 1. The required SO? concentration values are arbitrarily selected within
the normal working concentration range.
2 The amount of spike required depends on the original sample aliquot
size ToOO g was arbitrarily used for the original sample aliquot
size in this example.
125
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Precision Control Charts
Data obtained from the duplicate analyses of the 20 unspiked samples are
used to calculate the control limit for an analytical precision control
chart. The following procedure is used (see Table 4-2 for an example).
1. Calculate the precision statistic, I, for each pair of
duplicates:
where: Al = Analytical result for first duplicate
A2 = Analytical result for second duplicate
/Al - A2/ = Absolute value of the difference between
Al and A2
2. Calculate the average value, I, of the I statistic:
I =
n
where: £1 = Sum of I values
n = Number of I values
3. Calculate the precision upper control limit:
Upper Control Limit, UCL = 3.271
4. At least SOX of the I values used to calculate the UCL must
be _< UCL/3 and none of these I values may exceed the UCL.
Data that do not meet these criteria cannot be used for
establishing control charts.
5. Prepare the precision control chart as shown in Figure 4-1.
126
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Accuracy Control Charts
Data obtained from analyses of the 20 samples before and after spiking are
used to calculate control limits for an analytical accuracy control chart.
The following procedure is used:
1. Calculate the yield, Y, for each spiked sample:
Y = _ x 100%
Cncss
where: Cncf = Constituent concentration found in spiked sample
Cncss = Theoretical constituent concentration in spiked
sample
2. Calculate the average yield, Y, and the standard deviation of the
yield, aY:
-IT
n - 1
where: 2Y = Sum of Y values
n = Number of Y values
3. At least 50% of the Y values must fall within the range of Y +_ ay
and all Y values must fall within the range of Y +_ 3 oy. Data
that do not meet these criteria cannot be used for establishing
control charts.
4. Calculate the accuracy control limits:
Upper Control Limit, UCL = Y + 3oy
Lower Control Limit, LCL = Y - 3oY
5. Prepare the accuracy control chart as shown in Figure 4-2.
127
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Table 4-2
EXAMPLE CALCULATION OF CONTROL LIMITS
FOR PRECISION AND ACCURACY CONTROL CHARTS
FOR TOS IN SOLIDS ANALYSIS
TOS Concentration (wt% as
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
Original Sample
Dupl
Al
47.72
45.68
47.01
47.76
45.88
46.53
47.00
47.96
48.40
46.45
45.44
47.48
46.68
47.48
50.96
47.08
48.02
39.86
43.01
43.78
icate
A2
47.12
45.98
46.59
47.04
46.27
45.44
46.83
47.00
48.08
46.72
46.40
47.52
46.12
47.82
51.13
46.80
49.08
40.51
43.50
44.13
Precision Control
Average
(Cncos)
47.42
45.83
46.80
47.40
46.08
45.99
46.92
47.48
48.24
46.59
45.92
47.50
46.40
47.65
51.05
46.94
48.55
40.19
43.26
43.96
Limit
Spiked
Calc.
(Cncss)
50.00
47.50
52.00
49.25
48.35
50.05
48.85
49.80
52.55
48.75
47.80
49.20
48.60
51.25
55.50
49.65
51.00
42.25
44.65
46.00
Sample
Found
(Cncf
48.42
47.23
50.95
49.48
47.02
50.10
48.32
48.21
51.38
48.56
48.02
46.76
48.59
51.41
54.87
50.02
50.30
41.45
43.57
46.26
I = _JJ_ = 5.48
n
Al + A2
6.33
3.27
4.49
59
23
11.85
1.81
10.11
3.32
2.90
10.45
0.42
6.03
3.57
1.67
2.98
10.92
8.09
5.66
3.98
10
Cncs
*100%)
96.84
99.43
97.98
100.47
97.25
100.10
98.92
96.81
97.77
99.61
100.46
95.04
99.98
100.31
98.86
100.74
98.63
98.10
97.58
100.57
Accuracy Control Limits
Y = -AL = 98.77%
n
Upper Control Limit, UCL = 3.271 = 17.9
Upper Control Limit, UCL = Y + 3oy = 103.5*
Lower Control Limit, LCL = Y - 3ay = 94.0%
128
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4.7.2 Use of Quality Control Charts
After quality control charts have been established for each method, they
will be used for routine monitoring of analytical precision and accuracy.
The following procedures will be used for monitoring the analytical data.
1. Each set of analyses must include at least one duplicate and
one spiked sample (or standard). If the set includes more than
10 samples, then at least one duplicate and one spike must be
run for each multiple of 10 samples. If this is not possible,
a notation should be made in the analyst's laboratory notebook
explaining the conditions that make it impossible (e.g.,
"Duplicates could not be run due to insufficient volume of
sample").
2. After calculating concentrations in the normal manner, compute
the precision statistic, T = /A1-A2/ x 103 where Al is the
A1+A2
first duplicate result and A2 is the second.
3. Record the calculated value along with the date, sample identi-
fication, initials, matrix, etc., in the appropriate section of
the Quality Control Notebook.
4. Plot the I statistic value on the appropriate precision graph.
Page 163 of Appendix C can be photocopied to provide blank
QC charts.
5. Calculate the yield, Y = £ncf x 100%, where Cncss is the calcu-
Cncss
lated concentration of the spiked sample or standard, and Cncf
is the concentration found.
6. Repeat step 3. for spiked samples then plot the Y statistic values
on the appropriate accuracy graph.
7. If any I or Y value falls outside the associated control limit
or if any seven successive Y values fall on :the same side of
the average Y value line then notify the Laboratory Supervisor.
Analytical results determined since the last in-control check
was made are suspect and should not be reported until verified.
Further analyses using the method in question must be suspended
until the problem is identified and resolved. A Quality Control
Memo should be used to document the investigation. A Quality
Control Memo form is shown in Appendix C, page 159.
8. After all the QC data has been transferred to the QC chart, the
analyst should write "QC" at the top of his lab notebook page. If
no QC data appears on the page, "No QC" is written at the top of
the page.
129
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4.7.3 Other Methods For Monitoring Analytical Quality
Following are some additional procedures which will be used for monitoring
the quality of sample analyses.
Ionic Imbalance
The ionic imbalance of a complete sample analysis can be computed
as shown on the calculation form in Table 4-3. The ionic imbalance
is calculated here as the difference between the total cation and
anion concentrations divided by the average of the cation and anion
concentrations and multiplied by 10W when analytical results for
liquors are expressed in mi Hi equivalents/liter (meq/1) and for
solids in mi Hi equivalents/gram (meq/g).
Since the sulfate plus total oxidizable sulfur concentrations
together make up the total sulfur determined in the total sulfur
analysis, the sulfate plus total oxidizable sulfur concentrations
j>r the total sulfur concentration can be used in calculating the
sum of anion concentrations for a sample analysis.
When thiosulfate is present in a liquor sample, the thiosulfate
concentration in mg/1 is multiplied by 0.0089 and this value is
added to the total oxidizable sulfur (TOS) concentration (meq/1)
when calculating the sum of the anions (SAnions). This is required
because two equivalents of thiosulfate, in terms of ionic strength,
represent only one equivalent in terms of reaction with iodine in
the TOS analysis.
All TOS is present as thiosulfate in the quality assurance liquor
standard used. For these samples, the TOS concentration should be
doubled (and the thiosulfate concentration ignored) when calculating
SAnions. That is, for quality assurance Liquor standards only,
2Anions = 2 x [TOS] + [SOJJ] + [CT] + [Total Alkalinity]
where [ ] is the concentration in rneq/1.
For solids samples containing thiosulfate, the thiosulfate concen-
tration in wtX (10*4 x ppm thiosulfate) is added to the TOS
concentration (meq/g) when calculating SAnions.
If it is desired to compute SAnions using the total sulfur concen-
tration instead of the total oxidizable sulfur plus sulfate concen-
trations, a related adjustment must be used. Here, one equivalent
of thiosulfate in terms of ionic strength represent two equivalents
in terms of oxidation to sulfate in the total sulfur analysis.
Therefore, the meq/1 or meq/g of thiosulfate calculated as described
above is subtracted from the total sulfur concentration when calcu-
lating SAnions with the total sulfur concentration.
130
-------
To summarize, SAnions can be calculated in either of two ways:
SAnions = [TOS] + [SOj] + [Cl~] + [OH'] + [C0§]
+ Thiosulfate cone
or sAnions = [TS] + [Cl~] + [OH"] + [C03] - Thiosulfate cone
where [ ] is concentration in meq/1 for liquors or in meq/g for
solids and thiosulfate concentration is in mmol/1 for liquors or in
mmol/g for solids. Use the Ionic Imbalance Calculation Sheet shown
in Table 4-3 for these calculations.
Ionic imbalances should be monitored with control charts similar to
the accuracy control charts described in Section 4.7.1. The value
for the ionic imbalance itself is used in place of the Y value for
the control chart. Twenty solids analysis ionic imbalance results
are used to calculate control limits which are then used to construct
a solids analysis ionic imbalance control chart as described under
Accuracy Control Charts in Section 4.7.1. Twenty liquor analysis ionic
imbalance values are used to construct a liquor analysis ionic imbal-
ance control chart. Ionic imbalance results are then plotted on the
appropriate chart for every complete analysis performed and if an ionic
imbalance exceeds a control limit or if seven consecutive values fall
on one side of the average ionic imbalance line then the laboratory
supervisor will be notified.
An ionic imbalance will be calculated whenever a complete analysis is
made on a solids or liquor sample. Results will not be reported for any
sample analysis with an ionic imbalance outside of the control limits.
Sulfur Analyses Balance
The sum of the sulfur concentrations found in the sulfate and total
oxidizable sulfur analyses must be equivalent to the sulfur found
in the total sulfur analysis. If there is not an equivalency, the
analytical problem must be found and corrected.
The total oxidizable sulfur plus sulfate concentrations may be
converted to the equivalent total sulfur concentration as follows:
TSE = SO/, + TOS x 96.1 + S203 x 96.1
4 80TT 112.1
= S04 + 1.2 x TOS + 0.86 x S203
where: TSE = Total Sulfur Equivalent (as S04)
S04 = Sulfate (as S04)
TOb = Total Oxidizable Sulfur (as S03)
S203 = Thiosulfate (as S203)
all liquor concentrations are in mg/1 and
all solids concentrations are in wt%
(wt% = ppm x 10"4)
131
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TABLE 4-3
IONIC IMBALANCE CALCULATION SHEET
Liquor Sample Solids Sample
mg/1 x factor = meg/1 wt% x factor = meg/g
Na 0.0435 0.435
Ca 0.0499 0.499
Mg 0.0823 0.823
SCations
TOS (as SOo) _ 0.0250* _ _ 0.250
SO, - 0.0208 _ 0.208
d4 0.0282 _ _ 0.282
OH 0.0588 _ _ 0.588
CO, 0.0333 _ _ 0.333
Total Alk _
ZAnions _
Ionic Imbalance _ _
*>«
* In the case of quality assurance liquor standards this factor should be
0.0500 instead of 0.0250. See 4.7.3, Ionic Imbalance.
132
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pH and Conductivity Screening
The pH measured at the sample point (see Section 1.2) and undiluted
conductivity found for slurry and liquor samples with Methods 5 and 6
should be used to screen samples brought to the laboratory for analyses.
Routine samples collected at the same sample point should have similar
pH values and conductivities from day to day. If the pH or conductivity
has changed significantly and the reason is unknown, it is possible
that the sample was improperly taken, or taken from the wrong sample
point. Another possibility is an upset in process conditions.
When a pH or conductivity value is outside of the expected range, a
new sample should be taken immediately.
5. Reference
Handbook for Analytical Quality Control in Water and Wastewater Labora-
tories, EPA-600/4-79-019 (March 1979).
133
-------
ANALYSIS SOLIDS TOS
CONTROL CHART DATE
THESE ARE SAMPLES USED FOR CALCULATION OF TOS PRECISION CONTROL LIMITS
AGF-1
P.37
X
1
I
2
X
I
3
I
" X "
4
I
5
*
6
X
&GF-1
P.38
7
— x-
8
V
9
X
10
—
•
I x
11
—
—
— X-—
--—
12
r
r-
17
X
18
— x
AGF-1
P.40
19
— U(
X
—
20
:L^d
-j
NOTE
REF.
DATE
I.D.
+25
+20
+ 15
+10
+5
0
co
FIGURE 4.1 EXAMPLE PRECISION CONTROL CHART
-------
ANALYSIS SOLIDS TOS
ACCURACY CONTROL CHART DATE 9/28/79
DTE
EF.
VTE
I.D.
110
108
106
104
102
100
98
96
94
92
90
THESE ARE SAMPLES USED FOR CALCULATION OF TOS ACCURACY CONTROL LIMITS
AGF-1
P.37
/
1
2
X
3
4
5
.„
6
AGF-1
P.38
7
8
v/
A
9
X
10
11
12
X
AGF-1
P.39
13
14
X
15
w
16
v
A
17
18
y
AGF-1
P.40
19
-~
20
LICL _
X
Y
LC1
GO
cn
FIGURE 4.2 EXAMPLE ACCURACY CONTROL CHART
-------
APPENDIX A
ION CHROMATOGRAPH MATERIAL REQUISITION
137
-------
APPENDIX A
ION CHROMATOGRAPH MATERIAL REQUISITION
Item #
1.
Quantity
1
2.
3.
5.
2
1
6.
Description Catalog #
Auto Ion System 12 Analyzer complete 030002
with provision for one Separator/
Suppressor column system, loop-type
sample injection valve, high sensiti-
vity conductimetric detector, eluent
reservoirs, quick disconnect fittings,
two constant volume pumps with adjust-
able flowrates, solid state programmable
controller, and all other necessary
accessories.
Autosampler - Holds 99+, 15 ml samples, 030009
manufactured by Gil son.
Master Starter Kit - Contains flanging 030190
tool, various tubing fittings, extra-
buffer bottles and injection syringes
and Milton-Roy Pump rebuild kit.
3x250 2% Brine Separator Columns 030364
Anion/Cation Column Kit Ca, Mg, Na 030011
Includes 3x150 mm, 3x250 mm, 3x500 mm
Anion Separator Columns, 6x250 Anion
Separator, 3x150 mm, 6x250 mm Cation
Separator and 9x250 mm Cation Suppressor.
Honeywell Dual Pen Recorder - AFB 030012
200A1015 1 pen input selectable, variable
speed.
138
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APPENDIX B
SHORT FORM PROCEDURES
139
-------
D/A Liquid Analyses
Sequence
1. Start anion system on 1C to obtain steady baseline.
2. Weigh a 1-oz bottle for % SS, and label this bottle and a 4-02 bottle
for each sample.
3. Collect samples. See Method 1 for amount of sample to collect in
the 1-oz bottle; fill the 4-oz bottle. Measure pH at sample point.
4. Log in samples, and place assigned numbers on each bottle.
5. Measure density, temperature, and conductivity on each sample in
4-oz bottle before filtration.
6. Filter the 4-oz samples without washing.
7. As soon as possible, run Total Oxidizable Sulfur on the unoxidized*
filtrate.
8. To a 250 volumetric flask, add 1 ml of unoxidized filtrate from #6
above, and then add 1 ml of 30% H20o; mix well to oxidize sulfite
to sulfate (Total Sulfur). Dilute the Total Sulfur sample to 250 ml
exactly.
9. Run the oxidized sample through the 1C on auto mode. If you get a
peak for S03, notify lab manager immediately.
10. While the 1C is running, complete the % suspended solids samples.
11. Next, run calcium and magnesium (plus hydroxide and thiosulfate, if
required) on the unoxidized filtrate from #6 above.
12. Dilute some of the remaining unoxidized liquid (filtrate) 1:500 for
- diluted conductivity and Na analysis by flame photometer.
13. Complete calculations for concentrations and ionic imbalance as
presented in Sections 3 and 4 of the Laboratory Manual.
*Unoxidized = filtrate without H20o addition
Oxidized = filtrate with H202 added
141
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Anion Analysis with Auto-Ion 12 Analyzer
Initial Startup
1. Check that:
a. "Program Select" is set to 1.
b. Eluent pump (front pump) vernier is set to 30.0.
c. Detector Range switch is set to 5.
d. "Gauge" switch is up.
e. "B Samples/Cycle" is set to 99.
f. "MANUAL AUTO" is set to AUTO.
2. Switch "PGM Auto Manual" to Manual.
3. Flip up "HoO", "ELU", "SEP", and "3" (RECORDER) switches. Turn
"Eluent Selection to Ei. Flip down "RGN" and "INJ" switches,
then push "Write" button and hold down momentarily.
4. Flip "Pump" switch to ON. If gauge indicates greater than 700
psi or if maximum reading does not fall to 650 psi or less after
5 minutes, flip "Pump" switch off and notify lab supervisor.
5. Push and hold down "METER ZERO" button while setting blue and
red pens to zero with the "BLUE" and "RED" recorder knobs.
6. When blue pen draws a steady line, unlock "OFFSET" control (side
lever up) and set blue pen on zero with "OFFSET"; relock "OFFSET*
Sample Setup
1. Dilute each sample and an equal volume of 30% H202 1:250 with
deionized water (e.g., add 1 ml sample + 1 ml H^ to a 250
volumetric flask and dilute to volume with deionized water).
Mix well. Note that other dilutions may be required to obtain
peaks within the working range.
2. Use the large automatic pi pet to transfer samples to the
automatic sampler sample tubes. Start with the first sample
tube to the right of the sampler suction tube. Transfer
standards and diluted samples in the following order:
a. Mid-anion Standard
b. Diluted samples, maximum of 10 (if there are more than 10
samples, repeat Steps a-d and f-k for each multiple of 10;
Step e is performed only for the final group of samples)
142
-------
c. Duplicate of the last diluted sample transferred
d. Mid-anion Standard
e. Sample of deionized water
Use the following procedure to transfer samples to sample tubes:
f. Wipe outside of the automatic pi pet syringe with a
Kim Wipe.
g. Depress pi pet button completely, then slowly suck the
sample into the syringe.
h. Dispense the syringe contents into a waste container.
i. Suck a new portion of the sample into the syringe, then
dispense into the appropriate sample tube.
j. Record the sample description, dilution and sample tube
number in your lab notebook. Leave room in notebook to
record peak heights.
k. Repeat Steps f-j for each diluted sample and standard.
3. Set "Total Samples" to the total number of sample tubes filled.
Set "A Samples/Cycle" to either 13 or to the total number of sample
tubes filled minus one, whichever number is smaller.
Start of Operation
When depressing a button in the following steps, hold the button down
momentarily to assure operation:
1. Push "Reset" button.
2. - Switch "PGM Auto Manual" to Auto.
3. Push "Sub-program Load" button.
4. Push "Start/Step" button.
Results
Record peak heights for each sample as follow:
1. There will be a red peak and a blue peak (5 divisions after
the red) for each component.
2. The order of elution in the standard is fluoride first,
then chloride, and finally sulfate. The number of divisions
143
-------
on the zero line between the injection pip and the highest
point on each of the component peaks (i.e., retention times)
must be the same for sample and standards; this is how
sample peaks are identified (i.e., F~, Cl~ or SO^").
3. For each of the three components for each sample, record
the blue peak maximum minus the blue baseline value if the
blue peak maximum is less than 100. Otherwise, subtract
the red baseline value from the red peak maximum and
record this value multiplied by 10.
4. Transfer results to 1C worksheets, and perform the indicated
calculations.
144
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Method #1
Suspended Solids
1. Pre-weigh a clean, dry, 1-oz bottle, and record as empty bottle weight.
2. Collect % SS sample from same sample point as sample for other analyses.
3. Collect enough sample to yield about 1/8" of solids when filtered
through the filter disc:
a. V-101 about 1/4" in bottle (4 to 7 g)
b. 3001 bottle full (around 30 g)
c. 3501 about 1/4" from top in bottle (around 20 g)
4. Dry the outside of the bottle, then record the weight of the sample bot-
tle plus sample. This weight minus empty bottle weight = sample weight.
5. Pre-weigh a weight boat containing a dry GFC filter disc.
6. Place the filter disc in the filter holder and assemble filter.
7. Measure two 25 ml portions of saturated CaS04 solution* into
two 30 ml beakers.
8. Transfer the slurry from the sample bottle to the filter apparatus.
9. Turn on vacuum pump.
10. Rinse the sample bottle and the filter cake twice with the 25 ml
portions of CaS04 solution as follows: Swirl the CaS04 solution
in the sample bottle, then quickly transfer to the filter just as
the liquid level in the filter reaches the top of the filter cake.
Note: In order to avoid channeling and inefficient washing, it is
Important that the liquid level not go beneath the surface of the
solids at any time before filtering and washing are completed.
11. Follow the CaS04 washings by washing down the sides of the filter
" funnel and the filter cake with 20-25 ml of isopropyl alcohol from
a squeeze bottle.
12. Carefully transfer all the filter cake and the filter disc into the
pre-weighed weigh boat.
13. Dry in microwave oven on HIGH setting for 3 minutes.
14. Remove weigh boat, and place in desiccator. Weigh when cool. This
weight minus the combined weight of filter disc and weigh boat = dry
solids weight.
15. Calculate as follows: SS (wt%) = Weight of Dry Solids x 100%
Original Sample Weight
*CaS04 solution must be free of all suspended solids. See Lab Manual,
Method #1.
145
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Method #3
% HC1 Insoluble Solids
1. Weigh about 0.2 g of dried solids samples from Method 1 and transfer to
an Erlenmyer flask. Record Weight.
2. Slowly add 30 ml of IN HC1, swirl to mix and add about 50 ml of deionized
water.
3. Boil for about one minute on a hotplate with a watchglass covering flask,
then remove from hotplate and stir 30 minutes with a magnetic stirrer.
4. Pre-weigh a dry GFC filter disc.
5. Place the filter disc in the filter holder and assemble filter apparatus
with a clean filter flask.
6. Turn on vacuum.
7. Transfer Erlenmyer contents to filter and rinse Erlenmyer into filter
with deionized water.
8. Carefully transfer all the solids to the filter disc and place on a
watchglass.
9. Dry in microwave oven on HI for 3 minutes.
10. Cool in desiccator then weigh filter disc plus solids. Record weight.
11. Transfer contents of filter flask into a 100 ml volumetric flask using a
funnel. Rinse filter flask into funnel with deionized water.
12. Dilute to volume, mix by inversion and transfer to a clean, dry plastic
bottle. Label bottle.
13. Calculate as follows:
HC1 Insoluble Solids (wt%) = (Weight of Dry Solids plus filter
disc-weight of filter disc) x 100%
Original Sample Weight
146
-------
Method #6
Diluted Conductivity
Sample Preparation
1. Use 1:500 diluted absorber solution or freshly filtered slurry liquor.
2. Measure the conductivity using the procedure described below or as
indicated in the conductivity meter instruction manual.
Conducti v i ty Measurement
1. Set "Function" switch to Line. Allow 5 minutes for warm-up.
2. Rinse Conductivity Cell, and place in sample solution. Tap the cell,
and dip it two or three times to remove trapped air (see Notes).
3. Set "Sensitivity" control to minumum by turning knob as far as poss-
ible counter-clockwise.
4. Rotate "Range Switch" to obtain maximum shadow. "Shadow" is the
area of the electron tube not lighted. Turn "Drive" to obtain maxi-
mum shadow. If dial indication is above 20.0 or below 2.0, turn
"Range Switch" to next higher or lower setting.
5. Set "Sensitivity" to maximum (turn fully clockwise).
6. Turn "Drive" to obtain maximum shadow. If you cannot obtain a clear,
well defined shadow, set the "Function" switch to 1 KHz.
7. Read the Conductance by multiplying the reading on the dial by
multiplier. Multiply this result by 500.
8. Save sample for sodium analysis.
Notes:
1. The cell must be clean before making any measurement. The cell
should be rinsed with deionized water after each sample and before
storing.
2. When taking a measurement, the cell's vent slots should be submerged.
The electrode chamber should be free of any trapped air.
3. The cell should be at least 1/4" away from any other object, includ-
ing the walls on bottom of the solution container.
4. Electric fields present from stirrer motors, heaters, etc., may
affect readings.
147
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Method #7
Calcium by EDTA Titration
1. Pipet 20.0 ml of filtered, undiluted sample (use 5.00 ml for lime
slurry) into an Erlenmeyer flask. For solids, pi pet 5.00 ml of
HC1-dissolved slurry from Method #3.
2. Dilute sample to about 50 ml with deionized water.
3. Add 1 ml of 8N KOH.
4. For solids samples, add 1 drop of 1% MgCl2 solution.
5. Add 0.1 g of CalVer II with a scoop (color will be purple).
6. Titrate with 0.02N EDTA until color just changes from purple to
pure blue.
7. Calculations
Calcium (mg/1) = 400 x V
S
where:
V = Volume of 0.02N EDTA, ml
S = Sample volume from 1. above
Calcium (wt%) = 4V
WS
where:
V = Volume of 0.02N EDTA, ml
W = Weight of solids dissolved, g
S = Sample volume
Note: 1. If endpoint is not sharp, use a smaller sample aliquot and dilute to
about 100 ml with deionized water.
148
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Method #7
Total Hardness (Magnesium) by EDTA Titration
1. Pipet 20.0 ml of sample into an Erlenmeyer flask.
2. Dilute to about 50 ml with deionized water.
3. Add 1 ml of Total Hardness Buffer.
4. Add about 0.1 g of Hardness Indicator with a scoop (color will be
pink).
5. Titrate with 0.02N EDTA until color just changes from
pink to pure blue.
6. Calculations
Magnesium (mg/1) = 243 x (V+ - V)
^
where:
V£ = Volume of 0.02N EDTA, ml
V = Volume of 0.02N EDTA, ml
used in calcium determination
S = Volume of sample, ml
Note: Calculations are based on dilutions given in Section 3.
149
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Method #8
Sodium by Specific Ion Electrode
1. Place 50 ml of the 10 ppm Na standard and 1 ml of Ionic Strength Adjuster
(ISA) in a 100 ml plastic beaker.
2. Rinse electrode, blot dry, then place in solution. Start magnetic
stirring.
3. Turn to "X+" and use "CALIBRATE" knob to adjust needle to read "1" on
the red scale.
4. Place 50 ml of the 100 ppm Na standard and 1 ml of ISA in another 100 ml
beaker. Repeat Step 2.
5. Use "TEMP°C" knob to set needle to read "10" on the red scale. Turn
outer ring to solution temperature. Slope should read between 90 and
100%.
6. Repeat 10 ppm and 100 ppm Na standards several times to assure calibra-
tion is accurate.
7. Check 30 ppm Na standard (should read "3" on the red scale) and 50 ppm
Na standard (should read "5" on red scale). Instrument is now ready for
use on unknown samples.
8. Use 50 ml of a 1:500 dilution of sample, and add 1 ml of ISA. Place
electrode in sample, and read red scale.
9. Multiply result by dilution factor to obtain sample concentration.
Notes:
a. Specific Ion instrument is left on at all times, set on X"1". Electrode
should be stored in a sample that contains sodium (not a sodium
standard).
b. Between each sample or standard that is run, the electrodes should be
rinsed with deionized water and then carefully dried with tissue.
c. Use a magnetic stirrer with an asbestos pad. Stir slowly.
d. Excessive needle drift may be stopped by cleansing the sodium electrode.
Dip electrode in ammonium bifluoride for 30 seconds, followed by rins-
ing with deionized water and drying (see electrode manual). Recalibra-
tion will be necessary.
150
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Method #9
Chloride by Hg(N03)2 Titration
1. Pipet 2.00 ml of sample into a flask or beaker and add approximately
20 ml of deionized water.
2. Add 2 drops of phenolphthalein indicator solution and exactly enough
drops of IN NaOH to give a red color.
3. Add 2 ml of 30% H202 (stored in refrigerator), mix, and let stand
for 10 minutes (solution will turn clear).
4. Add 1 dropperful of MnCl2 solution.
5. Heat solution, and boil gently for approximately 15 mintues to destroy
peroxide. Absence of peroxide is shown by a change in the boiling
character. It will not fizz as much. Add deionized water if neces-
sary for volume control.
6. Cool to room temperature (in an ice bath if desired), then add 3-4
drops of bromocresol green indicator (solution will turn blue).
7. Add IN HN03 dropwise until solution just turns pale green or yellow.
8. Add 1/4 contents of a Hach diphenylcarbazone powder pillow, and
titrate with 0.0141N Hg(N03)2 until color just changes from yellow
to light pink.
9. Calculation
Chloride (moles/1) = V_x_N
S
where:
V = Volume of Hg(N03)2 titrant, ml
N = Normality of H (N03)2
S = Volume of sample
151
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Method #13
Total Oxidizable Sulfur
1. Add about 50 ml of deionized water into a clean Erlenmeyer flask.
2. Pipet in 0.1N iodate solution. Use 10.0 ml for liquor samples
or 20.0 ml for solids samples.
3. Add 5 ml of IN HC1.
4. Pipet 2.00 ml of freshly filtered, undiluted sample into flask.
For solids, place in flask 0.100 to 0.120 g of dry solids dried
to constant weight in microwave oven (3 minutes at HI) or at 84°C
and then cool in desiccator.
5. Titrate with 0.1N thiosulfate until a pale yellow color is present
and then add several drops of starch solution (this will turn
solution very dark blue).
6. Continue titrating slowly until solution just turns from dark blue
to colorless, the final endpoint.
7. Also run a blank by using about 50 ml of deionized water and 10.0
ml of 0.1N iodate solution.
8. Calculations
TOS (mgSO-T/1) = (B - S) x N x (40.000)
j _
TOS (meq/g) = (B - S) x N
W
where:
B = Volume of titrant used for blank, ml
S = Volume of titrant used for sample, ml
N = Normality of thiosulfate
V = Volume of sample, ml
W = Weight of sample, g
Note: 1. Blank should require about 10 ml of titrant. Samples should
require less titrant. Increasing SOg concentration will result
in decreasing titrant used.
2. Calculations are based on dilutions given in Section 3.
152
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Method #13
Thiosulfate
1. Add approximately 50 ml of deionized water into a 250 ml Erlenmeyer
flask or 150 ml beaker.
2. Place container in an ice bath contained in a large beaker.
3. When temperature is below 15°C, add 10 ml of formaldehyde.
4. Add 10.0 ml of 0.1N iodate solution.
5. Add 5 ml of IN HC1.
6. Using a graduated cylinder, measure 50.0 ml of filtered sample
into the container that is in the ice bath. For solids, place in
container about 1 g (weighed to 0.001 g) of dry (84°C or microwave
for 3 minutes) sample.
7. Titrate with 0.1N Thiosulfate until color is pale yellow.
8. Add a few drops of starch solution (this will cause solution to
turn dark blue) and continue titrating slowly until solution just
turns from dark blue to colorless.
9. Run a blank using approximately 50 ml of deionized water and 10.00 ml
of 0.1N iodate solution.
10. Calculations
Thiosulfate (mg/1) = (B - S) x N x 112,000
V
Thiosulfate (ppm, solids) = (B - S) x N x 112,000
W
where:
B - Volume of titrant used for blank, ml
S = Volume of titrant used for sample, ml
N = Normality of titrant
V = Volume of sample, ml
W = Weight of sample, g
Note: Calculations are based on dilutions given in Section 3.
153
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Method #15
Hydroxide Determination by HC1 Titration
1. Pi pet 10.0 ml of solution sample, or place about 0.5 g (weighed
to 0.001 g) of dried solids, into a beaker or Erlenmeyer flask.
2. Add approximately 50 ml of deionized water.
3. Add 10 ml of CaCl2 solution.
4. Add 3-4 drops of thymolphthalein indicator solution. (Solution
should turn blue; if not, then report _< 2 mg/1 OH in a solution or
_< 0.02 millimoles OH/g in a solid sample.)
5. Titrate blue solution with 0.1N HC1 until blue color disappears
and remains clear for at least one minute.
6. Calculations
Hydroxide (moles/1) = (ml HC1) x (N HC1)
Volume sample, ml
Hydroxide (millimoles/g)= (ml HC1) x (N HC1)
Weight sample, g
154
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Method #23
Total Sulfur by LECO
1. Turn on Filament Voltage Switch. (Other two furnace switches should
be off.)
2. Add about 0.07 g of dried sample weighed to 0.001 g to a green crucible.
3. Add 1-1/2 scoops of iron accelerator chips and one scoop of tin accel-
erator chips to the green crucible. Place lid on crucible.
4. Fill Titration Vessel to approximately 1-1/2" below the HC1 inlet with
diluted HC1 (15 ml HC1/1000 ml) by pushing down on "Manifold" and
squeezing Aspirator Bulb.
5. Add 3-4 drops of starch indicator to diluted HC1 in Titration Vessel.
6. Purge gas line by inserting crucible holder (without crucible) into
furnace and opening 02 regulator. Set 02 flow rate to between 1 and 1.5
liters/minute.
7. Add several drops of titration solution with "FINE" button until the
HC1 solution turns yellow. If solution turns dark blue, an excess of
the KI-KIOo solution has been added; empty Titration Vessel by opening
stopcock beneath vessel, close stopcock, and start again at Step 4.
8. Fill the buret with KI-KIOo solution by holding finger lightly on Mani-
fold and squeezing Aspirator Bulb. Set the reading on the microammeter
to 10 by adjusting the "CALIBRATE" control knob. Lower crucible holder.
9. Turn on High Voltage Switch.
10. Place crucible with sample and lid on crucible holder, raise holder
into the furnace, and lock in place.
11. Keep the microammeter reading between 10 and 12 by depressing "COARSE"
and "FINE" buttons as required. When reading no longer changes,
adjust to exactly 10 with "FINE" button. Titration is complete.
12. Record the volume of KI-KI03 solution used, and calculate the sample
sulfur concentration.
Total Sulfur (as wt% S04) = ml of KI-KIO, sol'n x 30 x Furnace Factor
wt. sample
155
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APPENDIX C
QUALITY ASSURANCE FORMS
157
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DUAL ALKALI LABORATORY
ORGANIZATION CHART
Project Manager
Project Quality
Control Coordinator
On-Site Manager
LTL Supervisor
Bechtel Lab Supervisor
On-Site
Analysis Personnel
158
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QUALITY CONTROL MEMO
A Q.C. Review was performed on
The following items are
brought to your attention for action or information.
TAKE ACTION INDICATED
NOT LATER THAN
Return to me
See me personally
Need not be returned
Being sent for your
information
Furnish data requested
Take action indicated
Take up with
Investigate and
report to
Express your judgement
Set time when we may
discuss this
Date:
Q.C. Auditor
Reply Below This Line
Date:
By
159
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LABORATORY NOTEBOOK AUDIT
A. Neatness
1. Entries are legible.
2. Entries are not obscured or obliterated by smudges, acid holes,
etc.
3. Erroneous entries are lined out with a single horizontal line.
(Not obliterated).
4. Inappropriate pages are lined out with a single diagonal line.
5. Entries are in pen.
B. Completeness
1. There is sufficient information to reconstruct what was done
during analysis, including calculations.
2. Entries are titled.
3. Entries are dated.
4. The method used in the analysis is identified or described.
5. Standards are identified adequately.
6. Samples are identified adequately.
7. Q.C. samples are identified adequately.
8. Aliquots and dilutions are identified adequately.
9. All columns are identified adequately.
10. Proper units are identified in the final result column.
11. There are sufficient notations and explanations in the event
of unusual circumstances, i.e. interferences.
12. There are sufficient cross references (i.e., see Mud page 5
for DWF's) to permit review of calculation, etc.
13. There is either the original calibration curve graph, a cross
reference to the location of the graph, or linear regression
analysis parameters for the curve directly in the note book.
160
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14. There are notations to indicate that the Q.C. data has been
reported (Q.C. at the top of the page).
15. There are notations that the results have been transferred to
the work-in-progress book (R at top of page).
16. There are initials of analyst and calculation checker at the
bottom of the page.
17. If a standard method is referenced, any modifications or changes
in the method as it was actually performed are noted.
C. Organization
1. There is either an up to date table of contents or an up to date
index in the notebook.
2. The entries follow an easily determined pattern (i.e., the time
sequence for sequential measurements indicated by vertical
spacing).
3. Sufficient space is allotted such that analytical data are not
crowded together.
D. Quality Assurance
1. Whenever feasible, at least one duplicate and one spiked sample
are included in the analysis.
2. With larger groups of samples a duplicate and spike are included
for every multiple of 10 samples.
- 3. The Q.C. data is calculated and recorded in the Q.C. book.
E. Initiative
1. Analyst takes pride in overall appearance and quality of his work.
2. Analyst constantly works to improve procedures and performance.
3. Analyst is alert to potential problems and communicates them to the
Laboratory Supervisor.
4. Analyst records Q.C. data and indicates that data have been recorded.
161
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Balance:
ANALYTICAL BALANCE QUALITY CONTROL LOG
Class S Weights (g)
Date
Tine
10
50
Garments
Tech
Analytical Balance Quality Control Form
162
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ANALYSIS
NOTE
REF.
DATE
t.D.
en
co
CONTROL CHART D AT E
-------
TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO,
EPA-600/8-80-015
2.
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Laboratory Procedures: Analysis of Sodium-based
Dual-alkali Process Streams
5. REPORT DATE
March 1980
6. PERFORMING ORGANIZATION CODE
7. AUTHOR(S)
J.R.Donnelly, D.C.Shepley, T.M.Martin, and
A. H.Abduls attar
8. PERFORMING ORGANIZATION REPORT NO.
9. PERFORMING ORGANIZATION NAME AND ADDRESS
Bechtel National, Inc.
50 Beale Street
San Francisco, California 94119
10. PROGRAM ELEMENT NO.
EHE624
11. CONTRACT/GRANT NO.
68-02-2634
12. SPONSORING AGENCY NAME AND ADDRESS
EPA, Office of Research and Development
Industrial Environmental Research Laboratory
Research Triangle Park, NC 27711
13. TYPE OF REPORTAND PERIOD C
Procedures: f/78-1/80
COVERED
14. SPONSORING AGENCY CODE
EPA/600/13
is.SUPPLEMENTARY NOTES nsRL-RTP project officer is Norman Kaplan, Mail Drop 61, 919/
541-2556.
16. ABSTRACT
report gives procedures for chemical analysis of process streams
of a flue gas desulfurization (FGD) system (utilizing the Combustion Equipment
Associates /Arthur D. Little sodium-based dual- alkali process) at Louisville Gas
and Electric's Cane Run Unit 6. The U.S. EPA has contracted with Bechtel to
develop and implement a test program to characterize this FGD process. As part of
this effort, Bechtel has established a laboratory at the site for routine chemical
analyses of the process streams. The methods used for these chemical analyses
comprise this laboratory procedures manual. The procedures were extracted from
three principal sources: 'Chemical Analysis Procedures for Dual Alkali Process
Stream Samples,1 A.D. Little report No. 75833, 4/22/76; 'Laboratory Procedures
Manual/ Shawnee Test Facility, Paducah, KY, prepared by Bechtel, 3/76; and
'Standard Methods for the Examination of Water and Wastewater,' 14th edition, 1975.
Procedures were verified by on-site analyses in accordance with the quality assur-
ance section of this report. In some cases, modifications adapted the standard
procedures to the specific process conditions and to best utilize available resources .
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
b.lOENTIFIERS/OPEN ENDED TERMS
c. COSATI Field/Group
Pollution
Flue Gases
Desulfurization
Sodium
Tests
Analyzing
Pollution Control
Stationary Sources
Dual-alkali Process
13B
21B
07A,07D
07B
14B
8. DISTRIBUTION STATEMENT
Release to Public
19. SECURITY CLASS (ThisReport)
Unclassified
21. NO. OF PAGES
173
20. SECURITY CLASS (Thispage)
Unclassified
22. PRICE
EPA Form 2220-1 (9-73)
164
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