Digital Titrator Manual, Model 16900, For All Digital Titrator Test Kits
Digital Titrator Manual, Model 16900, For All Digital Titrator Test Kits
Digital Titrator
Model 16900
Hach Company, 1980-2006. Digital Titrator manufactured under U.S. patent 4,086,062.
All rights reserved.
TABLE OF CONTENTS
SPECIFICATIONS.................................................................................................................... 7
OPERATION ..........................................................................................................................9
GENERAL DESCRIPTION ...................................................................................................
1.1 Introduction .......................................................................................................................
1.1.1 Following a Procedure for the First Time................................................................
1.2 Step-By-Step .....................................................................................................................
1.3 Helpful Hints .....................................................................................................................
1.3.1 To Reuse a Partially Emptied Cartridge ..................................................................
1.3.2 To Calculate Titrant Volume Used...........................................................................
1.3.3 To Fill Your Own Titration Cartridges.....................................................................
1.3.4 Verifying Technique.................................................................................................
1.4 Adapting a Buret Titration to the Digital Titrator .............................................................
1.5 Using PermaChem Powder Pillows ................................................................................
1.6 Safety.................................................................................................................................
11
11
12
13
18
18
18
18
19
22
23
24
SPECIFICATIONS
Digital Titrator
Delivery: 800 digits/mL or 0.00125 mL/digit
Accuracy*: 1% for readings over 100 digits. (Uncertainty of
readings is 1 digit. Most samples require more than 100 digits.)
Weight: 132 g (4.7 oz.)
* Overall method accuracy includes, in addition to the Digital Titrator, other sources of error controlled
by the analyst. The other sources of error include: sampling, sample volume, dilution (if required), end
point detection, reagent quality, and interferences.
OPERATION
DANGER
Handling chemical samples, standards, and reagents can be dangerous. Review the necessary
Material Safety Data Sheets and become familiar with all safety procedures before handling
any chemicals.
DANGER
La manipulation des chantillons chimiques, talons et ractifs peut tre dangereuse. Lire les Fiches
de Donnes de Scurit des Produits (FDSP) et se familiariser avec toutes les procdures de scurit
avant de manipuler tous les produits chimiques.
PELIGRO
La manipulacin de muestras qumicas, estndares y reactivos puede ser peligrosa. Revise las fichas
de seguridad de materiales y familiarcese con los procedimientos de seguridad antes de manipular
productos qumicos.
GEFAHR
Das Arbeiten mit chemischen Proben, Standards und Reagenzien ist mit Gefahren verbunden.
Es wird dem Benutzer dieser Produkte empfohlen, sich vor der Arbeit mit sicheren Verfahrensweisen
und dem richtigen Gebrauch der Chemikalien vertraut zu machen und alle entsprechenden
Materialsicherheitsdatenbltter aufmerksam zu lesen.
PERIGO
A manipulao de amostras, padres e reagentes qumicos pode ser perigosa. Reveja a folha dos
dados de segurana do material e familiarize-se com todos os procedimentos de segurana antes
de manipular quaisquer produtos qumicos.
10
GENERAL DESCRIPTION
1.1 Introduction
Hachs Digital Titrator is a new concept in titrimetric analysis. It
is a precision dispensing device fitted with compact cartridges
that contain concentrated titrants. Accurate titrations are made
without the bulk and fragility of conventional burets.
A main drive screw in the Digital Titrator controls a plunger
which forces the concentrated titrant from a titration cartridge in a
carefully regulated flow. The titrator body is constructed of
precision-molded, heavy-duty, chemical- and impact-resistant
acetal plastic. Accuracy is rated at 1% or better for a titration of
more than 100 digits. For titrations less than 100, accuracy is 1
digit.
Titration solutions (titrants) are packaged in disposable
polypropylene or Kynar containers with Teflon-covered
neoprene seals and polyethylene resealable closures to cover the
cartridge tips. Each cartridge contains approximately 13 mL of
titrating solution, enough for 50100 average titrations. Titrant
solutions are typically controlled to 0.5% concentration with
normality and tolerances listed on the label. Titrant
concentrations are designed for titrations of 10 to 40 turns
(100 to 400 digits) of the delivery knob. For the most commonly
used concentration ranges, the digits appearing in the counter
window correspond to the sample concentration.
Figure 1
11
1.1.1
1.2 Step-By-Step
1. Select a sample volume and titration cartridge corresponding
to the expected sample concentration from the table given in
each procedure.
If the expected sample concentration is not known, start with
one of the smaller sample volumes and determine its
approximate concentration. Retest with the appropriate
sample size.
2. Slide the cartridge into the titrator receptacle and lock in
position with a slight turn. See Figure 2.
Figure 2
13
APPARATUS
Quantity Required
Per Test
Description
Unit
Cat. No.
Delivery Tubes, 90 with hook for TitraStir Stir Plate ........... 1 ............. 5/pkg.......... 41578-00
Flask, Erlenmeyer, 125 mL....................................................... 1 ...............each.............. 505-43
Flask, Erlenmeyer, 250 mL....................................................... 1 ...............each.............. 505-46
Stir Bar, 28.6 x 7.9 mm............................................................. 1 ...............each.......... 20953-52
TitraStir Stir Plate, 115 Vac.................................................... 1 ...............each.......... 19400-00
TitraStir Stir Plate, 230 Vac.................................................... 1 ...............each.......... 19400-10
5. To start titrant flowing and flush the delivery tube, hold the
tip of the cartridge up. Advance the plunger release button to
engage the piston with the cartridge (push the button in and
toward the cartridge). Do not expel solution when pushing the
piston toward the cartridge. Turn the delivery knob until air is
expelled and several drops of solution flow from the tip. As
you turn the knob a drive screw pushes a piston against the
cartridge seal and forces liquid out through the delivery tube.
Then use the counter reset knob to turn the digital counter
back to zero and wipe the tip. The tip can be rinsed with
deionized water rather than wiped, if desired.
14
Figure 5
15
16
Where:
Digits Required = the number that appeared in the digital counter
window in Step 8.
Digit Multiplier = the number from the table given in the procedure.
It takes into account the sample dilution and titrant strength.
10. After completing testing for the day, press the plunger release
button and manually retract the plunger into the body of the
titrator. Remove the cartridge. Remove the delivery tube and
reseal the cartridge with the polyethylene cap. See Figure 7.
Figure 7
17
1.3.2
1.3.3
Figure 8
18
Verifying Technique
Whenever procedures are changed or new equipment is used, it is
helpful to run a sample of known concentration. This technique
will confirm the operator is following the procedure correctly and
the new equipment is working properly. One objective important
to Hach Company is making our tests self-verifying. This means
Hach makes the tools available so the operator can check their
own work for accurate results without relying on an outside lab
or chemist.
For most of the tests in this manual, Table 1 on page 20 lists each
procedure, the suggested standard, the volume of standard
needed, the titration cartridge used, and the number of expected
digits when the test is performed correctly. The suggested
standards are Voluette or PourRite Ampules whenever
possible because of their superior accuracy and stability.
To use titration standards follow these steps:
1. Select the procedure of interest and order the appropriate
standard. Use the given catalog numbers.
2. Measure the volume of standard to be used as the sample in
the procedure using a TenSette Pipet or Class A pipet.
3. Perform the procedure as written, adding deionized water
as necessary.
4. After titrating, the required number of digits should
approximately equal the expected digits.
Call Hach Technical and Customer Service (1-800-227-4224) for
additional help.
19
Standard Description
(Cat. No.)
Volume of
Standard
(mL)
Acid-Base:
Acid
1.0
5.0
Base
0.500 N Na2CO3
(14278-10)
1.0
5.0
Acidity
0.1
1.0
Alkalinity
0.1
1.0
Calcium*:
mg/L CaCO3
0.1
1.0
G.d.h.
0.2
1.0
Carbon
Dioxide
0.2
2.0
Chloride
0.1
0.1
1.0
1.0
20
Titration Cartridge
(Cat. No.)
Expected
Digits
1.600 N NaOH
(14379-01)
8.00 N NaOH
(14381-01)
250
1.600 N H2SO4
(14389-01)
8.00 N H2SO4
(14391-01)
250
0.1600 N NaOH
(14377-01)
1.600 N NaOH
(14379-01)
250
0.1600 N H2SO4
(14388-01)
1.600 N H2SO4
(14389-01)
250
0.0800 M EDTA
(14364-01)
0.800 M EDTA
(14399-01)
100
0.1428 M EDTA
(14960-01)
0.714 M EDTA
(14959-01)
112
0.3636 N NaOH
(14378-01)
3.636 N NaOH
(14380-01)
100
0.2256 N Hg(NO3)2
(14393-01)
0.2256 N AgNO3
(14396-01)
1.128 N AgNO3
(14397-01)
2.256 N Hg(NO3)2
(921-01)
125
250
250
250
250
100
112
125
250
125
Standard Description
(Cat. No.)
Chlorine
Chromate
Hardness:
mg/L CaCO3
Volume of
Standard
(mL)
Titration Cartridge
(Cat. No.)
Expected
Digits
2.0
0.02256 N Na2S2O3
(24091-01)
varies**
0.5
0.00564 N FEAS
(22923-01)
varies***
1000 mg/L Cr
(2231 mg/L CrO4)
(14664-42)
1.0
0.2068 N Na2S2O3
(22676-01)
223
0.1
0.0800 M EDTA
(14364-01)
0.0800 M CDTA
(14402-01)
0.800 M EDTA
(14399-01)
0.800 M CDTA
(14403-01)
100
0.1428 M EDTA
(14960-01)
0.714 M EDTA
(14959-01)
112
0.0716 M TitraVer
(20817-01)
0.716 M TitraVer
(20818-01)
200
0.2000 N Na2S2O3
(22675-01)
2.00 N Na2S2O3
(14401-01)
500
0.3998 N KIO3KI
(14961-01)
250
G.d.h.
0.2
1.0
Iron
Oxygen,
Dissolved****
50 mg/L Fe
(14254-10)
1000 mg/L Fe
(2271-42)
10.0
10 mg/L as DO
(401-11)
100
10.0
200
Sulfite
1.0
100
100
100
112
100
100
* One to two drops of Magnesium Standard Solution (10 g/L as CaCO3) must be added to get a sharp
end point. These added drops will not change the results.
** The expected digits equal the volume of standard times the concentration on the certificate (e.g., 2 mL
x 50 mg/L = 100 digits).
*** The expected digits equals the volume of standard times the concentration on the certificate times the
constant, 4. (Example: 0.5 mL x 50 mg/L x 4 = 100 digits)
**** Add one Sulfamic Acid Powder Pillow to the volume of standard and follow Steps 10 to 12 in the
Dissolved Oxygen Procedure. It is not necessary to add the first two reagents.
21
Where:
Nt = Normality of buret titrant
mLt = milliliters of buret titrant required for an average titration
Nc = Normality of Digital Titrator cartridge
Because this would use excessive titrant, reduce the sample size
to one fourth its normal size to reduce the digits required to 200,
well within the recommended range.
Upon completion of the titration using the smaller sample size,
calculate the equivalent buret milliliters by the second equation
above. If 205 were the digits required:
205 8.0
Equivalent Buret Milliliters = ------------------------ = 5.13 mL
800 0.4
23
4. Pour the pillow contents into the sample. The polyfilm lining
is specially formulated to deliver all the powder necessary for
accurate results (no tapping on the vessel edge is necessary).
1.6 Safety
Safety is the responsibility of each individual when performing
analysis procedures, and the analyst must develop and maintain
good safety habits. Because many of the procedures in this
methods handbook use potentially hazardous chemicals and
apparatus, it is important that the analyst practice good laboratory
techniques to minimize accidents. The following paragraphs
present several techniques applicable to water analysis in the
laboratory and in the field. They are not all inclusive, of course,
nor do they apply only to the procedures provided in this
handbook. They are general in nature but emphasize practices
that are often key factors in personal injury incidents.
24
25
26
TITRATION PROCEDURES
27
28
Method 8200
2. Insert a clean
4. Use a graduated
volume corresponding to
the expected acid
concentration in
milliequivalents (meq)/L
or normality (N) from
Table 1.
cylinder or pipet to
measure the sample
volume from
Table 1. Transfer the
sample into a clean
250-mL Erlenmeyer
flask. Dilute to about the
100-mL mark with
deionized water, if
necessary.
one Phenolphthalein
Indicator Powder Pillow
and swirl to mix. The
solution should be
colorless.
7. Calculate:
Digits Required x
Digits Multiplier =
Milliequivalents per Liter
of Acid
Note: To determine the
normality of the sample,
divide the milliequivalents
per liter obtained by 1000.
29
ACID-BASE, continued
Table 1
Range meq/L
Range N
Sample
Volume (mL)
Titration
Cartridge
Catalog
Number
Digit
Multiplier
1-4
0.001-0.004
100
1.6 N NaOH
1.6 N H2SO4
14379-01
14389-01
0.02
4-10
0.004-0.01
50
1.6 N NaOH
1.6 N H2SO4
14379-01
14389-01
0.04
10-40
0.01-0.04
100
8 N NaOH
8 N H2SO4
8 N HCl
14381-01
14391-01
14390-01
0.1
20-80
0.02-0.08
50
8 N NaOH
8 N H2SO4
8 N HCl
14381-01
14391-01
14390-01
0.2
50-200
0.05-0.2
20
8 N NaOH
8 N H2SO4
8 N HCl
14381-01
14391-01
14390-01
0.5
100-400
0.1-0.4
10
8 N NaOH
8 N H2SO4
8 N HCl
14381-01
14391-01
14390-01
1.0
200-800
0.2-0.8
8 N NaOH
8 N H2SO4
8 N HCl
14381-01
14391-01
14390-01
2.0
500-2000
0.5-2
8 N NaOH
8 N H2SO4
8 N HCl
14381-01
14391-01
14390-01
5.0
1000-4000
1-4
8 N NaOH
8 N H2SO4
8 N HCl
14381-01
14391-01
14390-01
10.0
30
ACID-BASE, continued
Base Determination
2. Insert a clean
4. Use a graduated
volume corresponding to
the expected base
concentration in
milliequivalents/L or
normality from Table 1.
cylinder or pipet to
measure the sample
volume from Table 1.
Transfer the sample
into a clean 250-mL
Erlenmeyer flask. Dilute
to about the
100-mL mark with
deionized water,
if necessary.
7. Calculate:
one Phenolphthalein
Indicator Powder Pillow
and swirl to mix. The
solution should be a
pink color.
hydrochloric acid or
sulfuric acid until the
solution is colorless.
Record the number of
digits required.
Digits Required x
Digit Multiplier =
Milliequivalents per Liter
of Base
31
ACID-BASE, continued
Sampling and Storage
Collect samples in clean plastic or glass bottles. Fill completely
and cap tightly. Minimize agitation or prolonged exposure to air.
Sample may be stored at least 24 hours by cooling to 4 C (39 F)
or below if they cannot be analyzed immediately. Warm to room
temperature before analyzing.
Accuracy Check
Using a clean Class A 20.00 mL pipet, transfer 20.00 mL 0.100 N
NaOH Standard Solution (for base determination) or 20.00 mL
0.100 N Sulfuric Acid Standard Solution (for acid determination)
to a clean 250-mL Erlenmeyer flask. Dilute to about 100 mL with
deionized water.
Follow the procedure for base determination using 8.00 N HCl or
H2SO4 Titration Cartridge or for acid determination using 8.00 N
NaOH Titration Cartridge. About 200 digits of titrant should
be required.
Interferences
Highly colored or turbid samples may mask the color change at
the end point. Use a pH meter for these samples.
Summary of Method
A measured amount of sample is treated with a colorimetric
indicator and then titrated with a strong acid or base. The amount
of titrant used is directly proportional to the milliequivalents of
acid or base in the sample. These titrations also can be performed
using a pH meter instead of a colorimetric indicator. In this case,
titrate to pH 7 or to the pH required.
REQUIRED REAGENTS
(varies with sample characteristics)
Description
Cat. No.
32
ACID-BASE, continued
REQUIRED REAGENTS, continued
Description
Unit
Cat. No.
REQUIRED APPARATUS
Digital Titrator................................................................................................each .......16900-01
Flask, Erlenmeyer, 250-mL............................................................................each .......... 505-46
Select one or more based on sample concentration:
OPTIONAL REAGENTS
Phenolphthalein Indicator Solution, 5 g/L ............................................. 100 mL* ...........162-32
Sodium Hydroxide Standard Solution, 0.100 N..................................... 1000 mL ...........191-53
Sulfuric Acid Standard Solution, 0.100 N............................................. 1000 mL* ...........202-53
OPTIONAL APPARATUS
Bottle, wash, poly, 500-mL ............................................................................each ...........620-11
Clamp, 2-prong, extension, 38-mm................................................................each .......21145-00
Clamp Holder .................................................................................................each ...........326-00
Demineralizer Assembly, 473-mL .................................................................each .......21846-00
Delivery Tubes, with 180 hook...................................................................5/pkg .......17205-00
Delivery Tubes, 90 with hook for TitraStir Stir Plate ..............................5/pkg .......41578-00
Pipet, volumetric, Class A, 1-mL ...................................................................each .......14515-35
Pipet, volumetric, Class A, 2-mL ...................................................................each .......14515-36
Pipet, volumetric, Class A, 5-mL ...................................................................each .......14515-37
Pipet, volumetric, Class A, 10-mL .................................................................each .......14515-38
Pipet, volumetric, Class A, 20-mL .................................................................each .......14515-20
Pipet, volumetric, Class A, 50-mL .................................................................each .......14515-41
Pipet, volumetric, Class A, 100-mL ...............................................................each .......14515-42
Support Ring Stand ........................................................................................each ...........563-00
TitraStir Stir Plate, 115 Vac .........................................................................each .......19400-00
TitraStir Stir Plate, 230 Vac .........................................................................each .......19400-10
* Contact Hach for larger sizes.
33
34
Method 8201
1. Select a sample
2. Insert a clean
4. Use a graduated
cylinder or pipet to
measure the sample
volume from Table 1.
Transfer the sample
into a clean 250-mL
Erlenmeyer flask. Dilute
to about the
100-mL mark with
deionized water, if
necessary.
Table 1
Range
(mg/L as CaCO3)
Sample
Volume
(mL)
Titration
Cartridge
(N NaOH)
Catalog
Number
Digit
Multiplier
10-40
40-160
100-400
200-800
500-2000
1000-4000
100
25
100
50
20
10
0.1600
0.1600
1.600
1.600
1.600
1.600
14377-01
14377-01
14379-01
14379-01
14379-01
14379-01
0.1
0.4
1.0
2.0
5.0
10.0
35
ACIDITY, continued
7. Calculate:
Digits Required x
Digit Multiplier =
mg/L as CaCO3
Methyl Orange Acidity
36
ACIDITY, continued
Phenolphthalein (Total) Method
1. Measure a second
portion of the sample
selected from step 1 on
page 35 into a clean
250-mL Erlenmeyer
flask. Dilute to about the
100-mL mark with
deionized water, if
necessary.
Method 8202
4. Calculate:
Digits Required x
Digit Multiplier =
mg/L as CaCO3
Phenolphthalein Acidity
Accuracy Check
Standard Additions Method
This accuracy check should be performed when interferences are
suspected or to verify analytical technique.
1. Snap the neck off an Acidity Voluette Ampule Standard,
0.500 N.
37
ACIDITY, continued
2. Use a TenSette Pipet to add 0.1 mL of standard to the sample
titrated in step 6 for methyl orange acidity or step 3 for
phenolphthalein acidity. Resume titration back to the same
end point. Note the number of digits required.
3. Repeat using two more additions of 0.1 mL. Titrate to the end
point after each addition.
4. Each 0.1 mL addition of standard should require 25 additional
digits of 1.600 N titrant or 250 digits of 0.1600 N titrant. If
these uniform increases do not occur, refer to Appendix A,
Accuracy Check and Standard Additions.
Interferences
Summary of Method
Bromphenol blue (pH 3.7) or phenolphthalein (pH 8.3) indicator
is used to titrate the sample with sodium hydroxide to a
38
ACIDITY, continued
colorimetric end point. Bromphenol blue gives a better end point
than methyl orange indicator. Titration to pH 3.7 determines
strong mineral acidity (also referred to as methyl orange acidity),
whereas the pH 8.3 phenolphthalein end point includes weaker
acid species as well, and represents the total acidity. The results
are expressed in mg/L as calcium carbonate (CaCO3) at a
specified pH.
REQUIRED REAGENTS
(varies with sample characteristics)
Description
Unit
Cat. No.
REQUIRED APPARATUS
Digital Titrator................................................................................................each .......16900-01
Flask, Erlenmeyer, 250-mL............................................................................each ...........505-46
Select one or more based on sample concentration:
OPTIONAL REAGENTS
Acidity Standard Solution, Voluette Ampules,
0.500 N H2SO4, 10 mL ...........................................................................16/pkg .......14330-10
Bromphenol Blue Indicator Solution ............................................. 100 mL MDB .......14552-32
Buffer Powder Pillows, pH 3.7...................................................................25/pkg .......14551-68
Buffer Powder Pillows, pH 8.3...................................................................25/pkg ...........898-68
Hydrogen Peroxide Solution, 30%................................................. 200 mL MDB ...........144-45
Phenolphthalein Indicator Solution, 5 g/L ................................... 100 mL MDB* ...........162-32
Sodium Thiosulfate Standard Solution, 0.1 N.............................. 100 mL MDB* ...........323-32
* Contact Hach for larger sizes.
39
ACIDITY, continued
OPTIONAL APPARATUS
Description
Unit
Cat. No.
40
Method 8203
2. Insert a clean
4. Use a graduated
cylinder or pipet to
measure the sample
volume from Table 1.
Transfer the sample
into a clean 250-mL
Erlenmeyer flask. Dilute
to about the
100-mL mark with
deionized water, if
necessary.
Table 1
Range
(mg/L as CaCO3)
Sample
Volume (mL)
Titration
Cartridge
(H2SO4)
Catalog
Number
Digit
Multiplier
10-40
40-160
100-400
200-800
500-2000
1000-4000
100
25
100
50
20
10
0.1600
0.1600
1.600
1.600
1.600
1.600
14388-01
14388-01
14389-01
14389-01
14389-01
14389-01
0.1
0.4
1.0
2.0
5.0
10.0
41
ALKALINITY, continued
42
ALKALINITY, continued
9. Continue the
titration with sulfuric
acid to a light greenish
blue-gray (pH 5.1), a
light violet-gray (pH
4.8), or a light pink (pH
4.5) color, as required by
the sample composition;
see Table 2. Record the
number of digits
required.
10. Calculate:
Total Digits Required x
Digit Multiplier =
mg/L as CaCO3 Total
(T or M) Alkalinity
Note: Carbonate,
bicarbonate and hydroxide
concentrations may be
expressed individually
using the relationships
shown in Table 3.
Table 2
Sample Composition
Alkalinity about 30 mg/L
Alkalinity about 150 mg/L
Alkalinity about 500 mg/L
Silicates or Phosphates present
Industrial waste or complex system
43
End
Point
pH 4.9
pH 4.6
pH 4.3
pH 4.5
pH 4.5
ALKALINITY, continued
Sampling and Storage
Collect samples in clean plastic or glass bottles. Fill completely
and cap tightly. Avoid excessive agitation or prolonged exposure
to air. Samples should be analyzed as soon as possible after
collection but can be stored at least 24 hours by cooling to 4 C
(39 F) or below. Warm to room temperature before analyzing.
Carbonate Alkalinity
is equal to:
Phenolphthalein
Alkalinity = 0
Total
Alkalinity
Phenolphthalein
Alkalinity equal to Total
Alkalinity
Total Alkalinity
Phenolphthalein
Alkalinity less than one
half of Total
Alkalinity
2 times the
Phenolphthalein
Alkalinity
Phenolphthalein
Alkalinity equal to one
half of Total Alkalinity
Total Alkalinity
Phenolphthalein
Alkalinity greater than
one half of Total
Alkalinity
2 times the
Phenolphthalein
minus Total
Alkalinity
2 times the
difference between
Total and
Phenolphthalein
Alkalinity
Row
Result of Titration
Bicarbonate
Alkalinity
is equal to:
44
ALKALINITY, continued
c. Multiply the phenolphthalein alkalinity by 2.
d. Select Row 3, 4, or 5 based on comparing the result of
step c with the total alkalinity.
e. Perform the required calculations in the appropriate row,
if any.
f.
For example:
A sample has 170 mg/L as CaCO3 phenolphthalein alkalinity and
250 mg/L as CaCO3 total alkalinity. What is the concentration of
hydroxide, carbonate and bicarbonate alkalinities?
The phenolphthalein alkalinity does not equal 0 (it is 170 mg/L),
see step a.
The phenolphthalein alkalinity does not equal total alkalinity
(170 mg/L vs. 250 mg/L), see step b.
The phenolphthalein alkalinity multiplied by 2 = 340 mg/L, see
step c.
Because 340 mg/L is greater than 250 mg/L, select Row 5, see
step d.
The hydroxide alkalinity is equal to: (see step e).
340 250 = 90 mg/L hydroxide alkalinity
The above answer is correct; the sum of each type equals the total
alkalinity.
45
ALKALINITY, continued
Accuracy Check
Standard Additions Method
This accuracy check should be performed when interferences are
suspected or to verify analytical technique.
1. Snap the neck off an Alkalinity Standard Solution Voluette
Ampule, 0.500 N.
2. Use a TenSette Pipet to add 0.1 mL of standard to the
sample titrated in Steps 6 or 9. Resume titration back to the
same end point. Record the number of digits needed.
3. Repeat, using two more additions of 0.1 mL. Titrate to the
end point after each addition.
4. Each 0.1 mL addition of standard should require 25
additional digits of 1.600 N titrant or 250 digits of 0.1600 N
titrant. If these uniform increases do not occur, refer to
Appendix A, Accuracy Check and Standard Additions.
Interferences
Summary of Method
The sample is titrated with sulfuric acid to a colorimetric end
point corresponding to a specific pH. Phenolphthalein alkalinity
is determined by titration to a pH of 8.3, as evidenced by the color
change of phenolphthalein indicator, and indicates the total
hydroxide and one half the carbonate present. M (methyl orange)
or T (total) alkalinity is determined by titration to a pH between
3.7 and 5.1, and includes all carbonate, bicarbonate
and hydroxide.
46
ALKALINITY, continued
REQUIRED REAGENTS
(varies with sample characteristics)
Description
Unit
Cat. No
REQUIRED APPARATUS
Digital Titrator................................................................................................each .......16900-01
Flask, Erlenmeyer, 250-mL............................................................................each ...........505-46
Select one or more based on sample concentration:
OPTIONAL REAGENTS
Alkalinity Standard Solution Voluette Ampules,
0.500 N Na2CO3, 10-mL ........................................................................16/pkg .......14278-10
Bromcresol Green-Methyl Red Indicator Solution ........................ 100 mL MDB .......23292-32
Bromphenol Blue Indicator Solution ............................................. 100 mL MDB .......14552-32
Bromphenol Blue Powder Pillows ...........................................................100/pkg .......14550-99
Buffer Powder Pillows, pH 3.7...................................................................25/pkg .......14551-68
Buffer Powder Pillows, pH 4.5...................................................................25/pkg ...........895-68
Buffer Powder Pillows, pH 4.8...................................................................25/pkg ...........896-68
Buffer Powder Pillows, pH 5.1...................................................................25/pkg ...........897-68
Buffer Powder Pillows, pH 8.3...................................................................25/pkg ...........898-68
Methyl Purple Indicator Solution................................................... 100 mL MDB .......21934-32
Phenolphthalein Indicator Solution, 5 g/L ................................... 100 mL MDB* ...........162-32
Sodium Thiosulfate Standard Solution, 0.1 N................................ 100 mL MDB ...........323-32
47
ALKALINITY, continued
OPTIONAL APPARATUS
Description
Unit
Cat. No
48
Method 10222
Hach recommends that reagent accuracy and analyst technique be checked using a
standard solution. Use the Ammonium Hydroxide solution listed on page 53 and follow
the procedure in the Accuracy Check section on page 52.
Ammonia Titration Procedure
To ensure accurate results, read carefully before proceeding.
Select sample
volume
1. Insert a clean
delivery tube into the
8.00 N Sulfuric Acid
Titration Cartridge.
Attach the cartridge to
the titrator body.
Note: See section 1.2 on
page 13 for assembly
instructions.
49
4. Select a sample
volume for the expected
concentration range
from Table 1Table 4 on
page 51.
Note: See Sampling and
Storage following these
steps.
Find Digit
Multiplier
11. Calculate:
Digits Used x
Digits Multiplier =
concentration.
Note: See example on
page 51.
50
Digit Multiplier
515
1035
0.5
0.2
0.034
0.085
Digit Multiplier
50150
100350
0.5
0.2
0.34
0.85
Digit Multiplier
515
1030
2560
1
0.5
0.2
0.035
0.070
0.175
Digit Multiplier
50150
100300
250600
1
0.5
0.2
0.35
0.70
1.75
51
Interferences
Other strong bases such as sodium hydroxide and potassium
hydroxide will cause a positive interference in the test. Other
alkaline substances, such as carbonates, will also react with the
strong acid titrant. The amounts of these compounds should be
insignificant in aqua ammonia solutions, however, and will not
affect test results. High levels of alkalinity in the dilution water
will cause high results. Be sure to use deionized water in step 3.
Accuracy Check
1. Fill an Erlenmeyer flask with approximately 75 mL of
deionized water.
2. Use a Class A 1.0-mL pipet to transfer 1.0 mL of a
10% ammonium hydroxide solution to the flask.
3. Add 1 mL (one full dropper) of Wide Range pH Indicator
Solution to the flask. The solution will turn a purple color.
4. Titrate the sample using the Digital Titrator to the red-orange
endpoint with 8.00 N sulfuric acid. The titration should use
270300 digits of 8.00 N sulfuric acid to reach the endpoint.
Note: If the number of digits used to reach the endpoint does not fall
within the 270300 digit range, make sure that the dilution water
does not contain excess alkalinity and that the 1.0 mL of ammonium
hydroxide is measured accurately. Ammonium hydroxide solutions
that are left open to the atmosphere will lose ammonia over time and
will give low results. Store the solutions in tightly-capped bottles.
Precision
In a single laboratory using an ammonium hydroxide solution of
9.71%, a single operator obtained a standard deviation of
0.1% as NH4OH.
52
REQUIRED REAGENTS
Description
Cat. No.
REQUIRED APPARATUS
Digital Titrator Assembly...............................................................................each .......16900-01
Delivery Tubes, J hook.................................................................................5/pkg .......17205-00
Flask, Erlenmeyer, 125-mL............................................................................each .......... 505-43
Pipettor, 100 L..............................................................................................each .......22753-00
Pipettor Tips, for 22753-00 ........................................................................10/pkg .......22754-10
53
54
Method 8205
4. Collect a water
knob to eject a few drops sample directly into the
of titrant. Reset the
titration flask by filling
counter to zero and wipe to the appropriate mark.
the tip.
Table 1
Range
(mg/L as CO2)
Sample
Volume (mL)
Titration
Cartridge
(N NaOH)
Catalog
Number
Digit
Multiplier
10-50
20-100
100-400
200-1000
200
100
200
100
0.3636
0.3636
3.636
3.636
14378-01
14378-01
14380-01
14380-01
0.1
0.2
1.0
2.0
55
Accuracy Check
Standard Additions Method
This accuracy check should be performed when interferences are
suspected or to verify analytical technique.
1. Snap the neck off a Carbon Dioxide Standard Solution
Voluette Ampule, 10,000 mg/L CO2.
56
Interferences
Summary of Method
Acidity due to carbon dioxide in a sample is titrated with sodium
hydroxide to a phenolphthalein end point. Strong acids are
assumed to be absent or of insignificant concentration. Request
Hachs Water Analysis Handbook, Publication 8376, to obtain
additional information on carbon dioxide determinations.
57
Unit
Cat. No.
REQUIRED APPARATUS
Digital Titrator ............................................................................................... each....... 16900-01
Select one or more based on sample concentration:
OPTIONAL REAGENTS
Carbon Dioxide Standard Solution Voluette Ampules,
10,000 mg/L as CO2, 10 mL .................................................................. 16/pkg....... 14275-10
Phenolphthalein Indicator Solution, 5 g/L....................................100 mL MDB*.......... 162-32
Potassium Acid Phthalate Standard Solution, 100 mg/L as CO2 .............100 mL.......... 2261-42
Potassium Acid Phthalate Standard Solution, 400 mg/L as CO2 .............500 mL......... 1885-49
OPTIONAL APPARATUS
Clamp, 2-prong extension, 38 mm ................................................................ each....... 21145-00
Clamp Holder................................................................................................. each........... 326-00
Delivery Tubes, with 180 hook .................................................................. 5/pkg....... 17205-00
Delivery Tubes, 90 with hook for TitraStir Stir Plate .............................. 5/pkg....... 41578-00
Pipet, TenSette, 0.1 to 1.0 mL ..................................................................... each....... 19700-01
Pipet Tips for 19700-01 TenSette Pipet................................................... 50/pkg....... 21856-96
Pipet Filler, safety bulb .................................................................................. each....... 14651-00
sension1 Basic Portable pH Meter with electrode ................................... each....... 51700-10
Support Ring Stand........................................................................................ each........... 563-00
TitraStir Stir Plate, 115 Vac......................................................................... each....... 19400-00
TitraStir Stir Plate, 230 Vac......................................................................... each....... 19400-10
Voluette Ampule Breaker Kit ...................................................................... each....... 21968-00
58
Method 8352
1. Insert a clean
3. Use a graduated
59
one ManVer 2
Hardness Indicator
Powder Pillow to the
flask and swirl to mix. If
the solution turns blue,
free chelant is present.
Proceed to step 6. If the
solution turns red, a
deficiency of chelant
exists.
7. Calculate:
Digits Required x 0.10
= mg/L Free Chelant
(as CaCO3)
Note: The results may be
expressed as mg/L tetrasodium EDTA (digits
required x 0.38 = mg/L as
Na4 EDTA).
Accuracy Check
Standard Additions Method
This accuracy check should be performed when interferences are
suspected or to verify analytical technique.
1. Use a TenSette Pipet to add 0.4 mL of 0.035 N EDTA
Standard Solution to the solution titrated in step 6. Resume
titration back to the same end point. Record the number of
digits required.
2. Each 0.4 mL addition of standard should require 70
additional digits of 0.0800 M titrant. If this increase does not
occur, refer to Appendix A, Accuracy Check and Standard
Additions.
60
Summary of Method
Chelant residual is determined by titration with a standard
solution of magnesium chloride at pH 10. The end point is
determined by a color change from blue to red-violet.
61
Unit
Cat. No.
REQUIRED APPARATUS
Cylinder, graduated, 100-mL......................................................................each.............. 508-42
Digital Titrator ............................................................................................each.......... 16900-01
Flask, Erlenmeyer, 125 mL.........................................................................each.............. 505-43
OPTIONAL REAGENTS
EDTA Standard Solution, 0.035 N ............................................. 100 mL MDB.......... 23499-32
ManVer 2 Hardness Indicator Powder.................................................... 113 g.............. 280-14
ManVer 2 Hardness Indicator Solution ...................................100 mL MDB* .............. 425-32
Phenolphthalein Indicator Solution, 5 g/L................................. 100 mL MDB* ............. 162-32
Sulfuric Acid Standard Solution, 5.25 N .................................... 100 mL MDB............ 2449-32
Water, deionized............................................................................................4 L.............. 272-56
OPTIONAL APPARATUS
Clamp, 2-prong extension, 38 mm..............................................................each.......... 21145-00
Clamp Holder..............................................................................................each.............. 326-00
Clippers (shears), 7.25 inch ........................................................................each.......... 23694-00
Delivery Tubes, with 180 hook ............................................................... 5/pkg.......... 17205-00
Delivery Tubes, 90 with hook for TitraStir Stir Plate ........................... 5/pkg.......... 41578-00
Filter Paper, folded, 12.5 cm................................................................. 100/pkg............ 1894-57
Flask, Erlenmeyer, 250 mL.........................................................................each.............. 505-46
Funnel, analytical, poly, 65 mm..................................................................each............ 1083-67
Pipet, TenSette, 0.1 to 1.0 mL ..................................................................each.......... 19700-01
Pipet Tips for 19700-01 TenSette Pipet................................................ 50/pkg.......... 21856-96
Spoon, measuring, 0.5 gram .......................................................................each.............. 907-00
Support Ring Stand.....................................................................................each.............. 563-00
TitraStir Stir Plate, 115 Vac......................................................................each.......... 19400-00
TitraStir Stir Plate, 230 Vac......................................................................each.......... 19400-10
62
Method 8350
1. Insert a clean
3. Use a graduated
63
concentration:
Digits Required x 0.188
= Total Chelant (as mg/L
Na4EDTA)
Interferences
Interference from ferric iron (Fe3+) is minimized by adding
ascorbic acid. The end point should by approached slowly in
samples containing ferric iron because the iron decreases the
sharpness of the color change.
Summary of Method
Total chelant is determined by titrating an acid sample with
bismuth nitrate the presence of methylthymol blue indicator. The
end point is signaled by a color change from yellow to
blue-green.
64
Unit
Cat. No.
REQUIRED APPARATUS
Cylinder, graduated, poly, 100 mL............................................................. each ............1081-42
Delivery Tubes, 90 with hook for TitraStir Stir Plate ...........................5/pkg ..........41578-00
Digital Titrator............................................................................................ each ..........16900-01
Flask, Erlenmeyer, 125 mL ........................................................................ each ..............505-43
Stir Bar, analytical, Teflon-coated, 50 mm................................................. each ..........20953-55
TitraStir Stir Plate, 115 Vac ..................................................................... each ..........19400-00
TitraStir Stir Plate, 230 Vac ..................................................................... each ..........19400-10
OPTIONAL REAGENTS
Water, deionized ........................................................................................... 4 L ..............272-56
OPTIONAL APPARATUS
Clamp, 2-prong extension, 38 mm ............................................................ each ..........21145-00
Clamp Holder ............................................................................................. each ..............326-00
Clippers (shears), 7.25 inch........................................................................ each ..........23694-00
Delivery Tubes, with 180 hook................................................................5/pkg ..........17205-00
Filter paper, folded, 12.5 cm .................................................................100/pkg ............1894-57
Flask, Erlenmeyer, 250 mL ........................................................................ each ..............505-46
Funnel, analytical, poly, 65 mm ................................................................. each ............1083-67
65
66
CHLORIDE
Mercuric Nitrate and Silver Nitrate Methods
Mercuric Nitrate Method (10 to 8000 mg/L as Cl)
Method 8206
2. Insert a clean
4. Use a graduated
cylinder or pipet to
measure the sample
volume from Table 1.
Transfer the sample into
a clean 250-mL
Erlenmeyer flask. Dilute
to about the 100-mL
mark with deionized
water, if necessary.
Table 1
Range
(mg/L as
Cl-)
10-40
40-160
100-400
200-800
500-2000
1000-4000
2000-8000
Sample
Volume
(mL)
Titration
Cartridge
(N Hg(NO3)2)
Catalog
Number
Digit
Multiplier
100
25
100
50
20
10
5
0.2256
0.2256
2.256
2.256
2.256
2.256
2.256
14393-01
14393-01
921-01
921-01
921-01
921-01
921-01
0.1
0.4
1.0
2.0
5.0
10.0
20.00
67
CHLORIDE, continued
7. Calculate:
Digits Required x
Digit Multiplier =
mg/L Chloride
Note: Results may be
expressed as mg/L
sodium chloride by
multiplying the mg/L
chloride by 1.65.
Note: meq/L Chloride =
mg/L Cl- 35.45.
Method 8207
2. Insert a clean
4. Use a graduated
cylinder or pipet to
measure the sample
volume from Table 2.
Transfer the sample into
a clean 250-mL
Erlenmeyer flask. Dilute
to about the 100-mL
mark with deionized
water, if necessary.
68
CHLORIDE, continued
Table 2
Range
(mg/L as Cl-)
10-40
25-100
100-400
250-1000
1000-4000
2500-10000
Sample
Volume
(mL)
Titration
Cartridge
(N AgNO3)
Catalog
Number
Digit
Multiplier
100
40
50
20
5
2
0.2256
0.2256
1.128
1.128
1.128
1.128
14396-01
14396-01
14397-01
14397-01
14397-01
14397-01
0.1
0.25
1.0
2.5
10.0
25.0
7. Calculate:
Digits Required x
Digit Multiplier =
mg/L Chloride
Note: Results may be
expressed as mg/L
sodium chloride by
multiplying the mg/L
chloride by 1.65.
Note: meq/L Chloride =
mg/L Cl- 35.45.
69
CHLORIDE, continued
Accuracy Check
Standard Additions Method
This accuracy check should be performed when interferences are
suspected or to verify analytical technique.
1. Snap the neck off a Chloride Standard Solution Voluette
Ampule, 12,500 mg/L Cl.
2. Use a TenSette Pipet to add 0.1 mL of standard to the
sample after titration in step 6. Resume titration back to the
same end point. Record the number of digits required.
3. Repeat, using additions of 0.2 and 0.3 mL. Titrate to the end
point after each addition.
4. Each 0.1 mL addition of standard should require 12.5
additional digits of 2.256 N titrant, 25 digits of 1.128 N
titrant, or 125 digits of 0.2256 N titrant. If these uniform
increases do not occur, refer to Appendix A, Accuracy Check
and Standard Additions.
70
CHLORIDE, continued
Interferences Using the Silver Nitrate Method
CHLORIDE, continued
REQUIRED REAGENTS FOR THE MERCURIC NITRATE METHOD
Description
Unit
Cat. No.
Mercuric Nitrate Chloride Reagent Set (about 100 tests) ............................................ 22726-00
Includes: (2) 836-46, (1) 921-01, (1) 14393-01
Diphenylcarbazone Reagent Powder Pillows .......................................... 100/pkg........... 836-99
Mercuric Nitrate Titration Cartridge, 0.2256 N............................................. each....... 14393-01
Mercuric Nitrate Titration Cartridge, 2.256 N............................................... each........... 921-01
Water, deionized............................................................................................... 4 L........... 272-56
OPTIONAL REAGENTS
Chloride Standard Solution, 1000 mg/L Cl- .............................................500 mL........... 183-49
Chloride Standard Solution Voluette Ampules,
12,500 mg/L Cl-, 10-mL......................................................................... 16/pkg....... 14250-10
Hydrogen Peroxide, 30%, ACS ................................................................200 mL........... 144-45
Sodium Hydroxide Standard Solution, 5.0 N .................................100 mL MDB......... 2450-32
Sulfide Inhibitor Powder Pillows............................................................. 100/pkg......... 2418-99
Sulfuric Acid Standard Solution, 5.25 N ........................................100 mL MDB......... 2449-32
72
CHLORIDE, continued
OPTIONAL APPARATUS
Description
Unit
Cat. No.
73
74
Method 8210
1. Insert a clean
delivery tube into a
0.00564 N Ferrous
Ethylenediammonium
Sulfate (FEAS) Titration
Cartridge. Attach the
cartridge to the titrator
body. See General
Description, Step-byStep, for assembly
instructions, if necessary.
3. Pipet 25.0 mL of
knob to eject a few drops sample into a 50-mL
of titrant. Reset the
Erlenmeyer flask.
counter to zero and wipe
the tip.
6. Calculate:
tube tip into the solution
Digits Required x 0.01 =
and swirl the flask while
mg/L Free Chlorine
immediately titrating
with FEAS to a colorless
end point. Record the
number of digits
required.
75
Accuracy Check
Standard Additions Method
This accuracy check should be performed when the analyst
suspects interferences or to verify analytical technique.
1. Snap the neck off a Chlorine Standard Solution
PourRite Ampule.
2. Use a TenSette Pipet to add 0.10 mL, 0.20 and 0.30 mL of
standard, respectively, to three 25-mL samples. Mix
each well.
3. Analyze each sample as described in the procedure.
4. Each 0.1-mL addition of standard should require
approximately 20 digits. Check the certificate enclosed with
the PourRite Ampules to obtain the exact concentration. To
determine the exact number of digits required for each
0.2-mL addition, multiply the exact concentration times the
volume of the addition in mL times four. (Example: 50 mg/L
x 0.1 mL x 4 = 20 digits.) If these uniform increases do not
occur, refer to Appendix A, Accuracy Check and
Standard Additions.
Interferences
Higher room temperatures tend to lead to higher free chlorine
residual due to reaction of chloramines. Higher room
temperatures also result in increased color fading. If the sample
contains more than 250 mg/L alkalinity or 150 mg/L acidity as
CaCO3, the sample may not develop the full amount of color or it
may instantly fade. To overcome this interference, adjust the pH
of a separate 25-mL sample to a 6 to 7 pH by adding 1 N Sulfuric
Acid Standard Solution or 1 N Sodium Hydroxide Standard
Solution in small increments and using a pH meter. Record the
amount of acid or base required. Add this amount of acid or base
to the sample to be tested and proceed with step 4.
76
Summary of Method
The DPD-FEAS method provides a titrimetric procedure for
determining free available chlorine and for estimating free and
combined chlorine fractions present together. The magenta
species, resulting from the oxidation of DPD by chlorine, is
destroyed quantitatively by titration with ferrous
ethylenediammonium sulfate and the volume of titrant required to
reach a colorless end point is proportional to the chlorine
concentration. Total residual chlorine may also be determined by
this test.
77
Unit
Cat. No.
Free and Total Chlorine Reagent Set (about 100 tests) ................................................ 24453-00
Includes: (1) 14064-99, (1) 14070-99, (1) 22923-01
DPD Free Chlorine Powder Pillows, 25 mL......................................... 100/pkg.......... 14070-99
DPD Total Chlorine Powder Pillows, 25 mL........................................ 100/pkg.......... 14064-99
Ferrous Ethylenediammonium Sulfate Titration Cartridge, 0.00564 N .....each.......... 22923-01
REQUIRED APPARATUS
Digital Titrator ............................................................................................each.......... 16900-01
Flask, Erlenmeyer, 50-mL ..........................................................................each.............. 505-41
Pipet, volumetric, Class A, 25-mL .............................................................each.......... 14515-40
Pipet Filler, safety bulb ...............................................................................each.......... 14651-00
OPTIONAL REAGENTS
Chlorine Standard Solution, PourRite Ampules,
50-75 mg/L Cl2, 2-mL......................................................................... 20/pkg.......... 14268-20
Potassium Iodide Solution .......................................................... 100 mL MDB.............. 343-32
Sulfuric Acid Standard Solution, 1.000 N .................................. 100 mL MDB............ 1270-32
Sodium Hydroxide Standard Solution, 1.000 N ......................... 100 mL MDB............ 1045-32
Sodium Arsenite Solution........................................................... 100 mL MDB............ 1047-32
OPTIONAL APPARATUS
Clamp, 2-prong, extension..........................................................................each.......... 21145-00
Clamp Holder..............................................................................................each.............. 326-00
Delivery Tubes, with 180 hook ............................................................... 5/pkg.......... 17205-00
Delivery Tubes, 90 with hook for TitraStir Stir Plate ........................... 5/pkg.......... 41578-00
Pipet, TenSette, 0.1 to 1.0 mL ..................................................................each.......... 19700-01
Pipet Tips for 19700-01 TenSette Pipet................................................ 50/pkg.......... 21856-96
PourRite Ampule Breaker.......................................................................each.......... 24846-00
Support Ring Stand.....................................................................................each.............. 563-00
TitraStir Stir Plate, 115 Vac......................................................................each.......... 19400-00
TitraStir Stir Plate, 230 Vac......................................................................each.......... 19400-10
78
Method 8209
CHLORINE, TOTAL
Iodometric Method (1 to 400 mg/L as Cl2 Using Sodium Thiosulfate)
2. Insert a clean
4. Use a clean
graduated cylinder to
take a water sample.
Pour sample into a clean
125- or 250-mL
Erlenmeyer flask. Dilute
to about the 100-mL
mark with deionized
water.
Table 1
Range
(mg/L Cl2)
Sample
Volume (mL)
Titration
Cartridge
(N Na2S2O3)
Catalog
Number
Digit
Multiplier
1-4
2-8
5-20
10-40
20-80
50-200
100-400
100
50
20
10
5
2
1
0.02256
0.02256
0.02256
0.02256
0.02256
0.02256
0.02256
24091-01
24091-01
24091-01
24091-01
24091-01
24091-01
24091-01
0.01
0.02
0.05
0.10
0.20
0.50
1.00
79
5. Add 2 Droppers
9. Continue the
titration until the
solution changes from
dark blue to colorless.
Record the number of
digits required.
10. Calculate:
Digits Required x Digit
Multiplier = mg/L Total
Chlorine (Cl2)
Note: These procedures
can be used to check
iodine and bromine
concentrations if chlorine
is not present. Multiply the
test result (in mg/L
chlorine) by 3.58 or 2.25,
respectively, to accurately
express the iodine or
bromine content of your
sample.
80
Accuracy Check
Standard Additions Method
Perform this accuracy check when you suspect interferences or to
verify analytical technique.
1. Snap the neck off a Chlorine Standard Solution
PourRite Ampule.
2. Use a TenSette Pipet to add 0.2 mL, 0.4 mL, and 0.6 mL of
standard to three aliquots of sample of the same volume as
used in the procedure.
3. Analyze each sample as described in the procedure.
4. Each 0.2-mL addition of standard should require
approximately 10 digits of the titration cartridge solution.
Check the certificate enclosed with the PourRite Ampules to
obtain the exact concentration. To determine the exact
number of digits required for each 0.2-mL addition, multiply
the exact concentration times the volume of the addition in
mL. (Example: 50 mg/L x 0.2 mL = 10 digits.) If these
uniform increases do not occur, refer to Appendix A,
Accuracy Check and Standard Additions.
81
2. Insert a clean
4. Use a pipet or
graduated cylinder to
measure the sample
volume from Table 2.
Transfer the sample into
a 125-mL Erlenmeyer
flask and dilute to about
the 50-mL mark with
deionized water.
Table 2
Range
(mg/L Cl2)
Sample
Volume (mL)
Titration
Cartridge
(N Na2S2O3)
Catalog
Number
Digit
Multiplier
20-80
50-200
100-400
250-1000
500-2000
2000-9000
(0.2-0.9%)
5000-18,000
(0.5-1.8%)
10,000-35,000
(1.0-3.5%)
20,000-70,000
(2.0-7.0%)
25
10
5
2
1
4
0.113
0.113
0.113
0.113
0.113
2.00
22673-01
22673-01
22673-01
22673-01
22673-01
14401-01
0.2
0.5
1
2.5
5
22.2
2.00
14401-01
44.3
2.00
14401-01
88.7
0.5
2.00
14401-01
177
82
of starch indicator
solution and swirl to
mix. A dark blue color
will develop.
contents of one
Potassium Iodide
Powder Pillow (Cat. No.
1077-99) to the flask and
swirl to mix.
9. Continue the
titration until the
solution changes from
dark blue to colorless.
Record the number of
digits required.
10. Calculate:
Digits Required x Digits
Multiplier = mg/L Total
Chlorine (Cl2)
83
Summary of Method
Total chlorine concentration equals the concentration of the free
and the combined forms of chlorine. Free chlorine reacts readily
with ammonia to form combined chlorine such as
monochloramines. When potassium iodide is added to a sample
containing chlorine at a pH less than 8, free iodine is liberated in
direct proportion to the amount of total chlorine present. The
iodine is then titrated with sodium thiosulfate.
84
Unit
Cat. No.
REQUIRED APPARATUS
Clippers, for opening pillows .........................................................................each ...........968-00
Digital Titrator................................................................................................each .......16900-01
Flask, Erlenmeyer, 125 mL ............................................................................each ...........505-43
Pipet Filler, 3-valve ........................................................................................each .......12189-00
Select one or more based on sample concentration:
85
Unit
Cat. No.
OPTIONAL APPARATUS
Clamp, 2-prong, extension, 38 mm................................................................ each....... 21145-00
Clamp Holder................................................................................................. each........... 326-00
Cylinder, graduated, 5 mL ............................................................................. each........... 508-37
Cylinder, graduated, 10 mL ........................................................................... each........... 508-38
Cylinder, graduated, 25 mL ........................................................................... each........... 508-40
Delivery Tubes, with 180 hook .................................................................. 5/pkg....... 17205-00
Delivery Tubes, 90 with hook for TitraStir Stir Plate .............................. 5/pkg....... 41578-00
Pipet, TenSette, 0.1 to 1.0 mL ..................................................................... each....... 19700-01
Pipet Tips for 19700-01 TenSette Pipet................................................... 50/pkg....... 21856-96
pH Paper, 1-11 pH ............................................................................... 5 rolls/pkg........... 391-33
PourRite Ampule Breaker.......................................................................... each....... 24846-00
sension1 Basic Portable pH Meter with electrode ................................... each....... 51700-10
Support Ring Stand........................................................................................ each........... 563-00
TitraStir Stir Plate, 115 Vac......................................................................... each....... 19400-00
TitraStir Stir Plate, 230 Vac......................................................................... each....... 19400-10
86
Method 10024
CHLORINE, FREE
1. Assemble the
4. Add 1 mL of
Amperometric Digital
Titrator System
according to the
instructions in the
Amperometric Titrator
Instruction Manual.
Phenylarsine Oxide
(PAO) cartridge. Flush
the Digital Titrator
delivery tube by turning
the delivery knob to
eject a few drops of
titrant. Reset the counter
to zero and wipe the tip.
agitation, measure
200 mL of sample with a
clean graduated cylinder.
Transfer the sample to a
clean 250-mL beaker
containing the 50-mm
stirring bar supplied
with the system.
pH 7 Phosphate
Buffer Solution.
* Procedure is equivalent to Standard Methods for the Examination of Water and Wastewater (18th ed.)
4500 Cl D for drinking water.
87
reading on the
Amperometric Titrator.
Unlock the BIAS control
and adjust the BIAS
control knob until a
reading between 0.500.60 is obtained. Lock
the BIAS control.
the titration is
approached, record the
LED readings along
with the corresponding
digits displayed on the
Digital Titrator counter.
Note: If the chlorine
Near the titration end
content of the sample is
high, add titrant at a faster point, add 2 to 5 digits of
rate; only the end point of titrant; wait a few
Note: The bias adjustment
the titration and the
seconds for a stable
controls the slope of the
volume of titrant used at
reading and record.
titration curve. The actual
instrument reading is not
important; but rather the
change in the readings as
the titration proceeds. The
adjustment need not be
precise.
88
Meter Reading
End
Point
Digits
9. Continue the
titration, recording at
least three points on the
downward sloping curve
and at least three points
after the end point has
been reached. The latter
points will have little
change in the LED
readings.
free chlorine:
Digits at End Point x 1.25
= g/L free chlorine as
Cl2
Meter Reading
Figure 1
Sample Plot
End
Point
Digits
89
Where:
Cu = measured concentration of sample, in mg/L (g/L divided by 1000)
Vu = volume of sample in mL
Cs = concentration of chlorine standard (mg/L, certificate value)
Vs = volume of standard added in mL
Example:
Sample result (Cu) = 120 g/L or 0.120 mg/L
Spiked sample result = 185 g/L or 0.185 mg/L
Volume Sample (Vu) = 200 mL
Volume Standard (Vs) = 0.2 mL
Chlorine Standard (Cs) = 68.1 mg/L
(0.120 200) + (68.1 0.2)
Theoretical concentration = ------------------------------------------------------------------------ = 0.188 mg/L
200 + 0.2
0.185 mg/L
% Spike recovery = ------------------------------ 100 = 98%
0.188 mg/L
90
Detection Limit
With good operator technique, the estimated detectable
concentration is approximately 15 g/L chlorine using
0.00564 N PAO.
Interferences
Summary of Method
In the amperometric forward titration procedure for free chlorine,
a small electrical current is applied across two identical platinum
electrodes. No current can flow between the electrodes unless a
91
REQUIRED REAGENTS
Description
Unit
Cat. No.
Phenylarsine Oxide Solution, 0.00564 N Digital Titrator Cartridge ............. each......... 1999-01
Phosphate Buffer Solution, pH 7 ....................................................100 mL MDB....... 21553-32
REQUIRED APPARATUS
Amperometric Titrator Assembly .................................................................. each....... 19299-00
Digital Titrator ............................................................................................... each....... 16900-01
Beaker, low-form, 250 mL............................................................................. each........... 500-46
Cylinder, graduated, 250 mL ......................................................................... each........... 508-46
Delivery Tubes, 90 with hook .................................................................... 5/pkg....... 41578-00
Probe Assembly, Amperometric Titrator ....................................................... each....... 19390-00
Stir Bar, octagonal, Teflon-coated, 50.8 x 7.9 mm ........................................ each....... 20953-55
TitraStir Stir Plate, 115 Vac......................................................................... each....... 19400-00
TitraStir Stir Plate, 230 Vac......................................................................... each....... 19400-10
OPTIONAL REAGENTS
Chlorine Standard Solution PourRite Ampules,
50-75 mg/L Cl2, 2 mL ............................................................................ 20/pkg....... 14268-20
Water, deionized............................................................................................... 4 L........... 272-56
OPTIONAL APPARATUS
Pipet, TenSette 0.1 to 1.0 mL ...................................................................... each....... 19700-01
Pipet Tips for 19700-01 TenSette Pipet................................................... 50/pkg....... 21856-96
PourRite Ampule Breaker.......................................................................... each....... 24846-00
Standard Methods for the Examination of Water
and Wastewater, 19th edition...................................................................... each....... 22708-00
92
CHLORINE, TOTAL
Method 10025
For wastewater
1. Assemble the
Amperometric Digital
Titrator System
according to the
instructions in the
Amperometric Titrator
Instruction Manual.
3. Using a graduated
4. Add 1 mL of pH 4
cylinder, measure 200
Acetate Buffer and the
mL of deionized water
contents of one
into a clean 250-mL
Potassium Iodide Pillow.
beaker. Place the
50-mm stirring bar
supplied with the system
into the beaker.
* Procedure is equivalent to USEPA method 330.2 and Standard Methods for the Examination of Water
and Wastewater (17th ed.) 4500-Cl C for wastewater.
93
reading on the
Amperometric Titrator.
Unlock the BIAS control
and adjust the BIAS
control knob until a
stable reading between
0.50-0.60 is obtained.
Lock the BIAS control.
1. Set-up the
2. Using a graduated
3. Using a Class A
4. Add 1 mL of pH 4
Amperometric Digital
Titrator System as in
Phase 1: Adjusting the
Electrode Response
Slope if it has not
already been done. Reset
the Digital Titrator
counter to zero and wipe
the tip.
94
8. Continue dispensing
reading on the
Amperometric Titrator.
It should read 0.00
0.05. DO NOT adjust
the BIAS control.
Titrator delivery
knob, dispense 100
digits of Standard Iodine
Titrant Solution and note
the LED reading.
95
Meter Reading
End Point
Digits
appropriate multiplier
based on the standard
end point in Table 1 on
page 99. The multiplier
is used in Phase 3:
Titration of Sample for
Note: The iodine titrant
Total Residual Chlorine.
concentration is
Interpolation between
approximately 0.0282 N,
which relates to 160 digits values in the table is not
needed to titrate 1.00 mL necessary.
of 0.00564 N Thiosulfate.
If the calculated end point
is greater than 160 digits,
this indicates the Standard
Iodine Titrant is weaker
than when packaged.
Discard the Standard
Iodine Titrant cartridge if
the calculated
standardization end point
is greater than 200 digits.
Figure 1
Back Amperometric
Titration Graph
96
1. Set-up the
Amperometric Digital
Titrator System as in
Phase 1: Adjusting the
Electrode Response
Slope if it has not
already been done. Reset
the Digital Titrator
counter to zero and wipe
the tip.
agitation, measure
200 mL sample with a
clean graduated cylinder
and transfer the sample
to the beaker. Swirl to
mix the reagents with
sample.
97
reading on the
Amperometric Titrator.
It should read 0.00
0.05. DO NOT adjust
the BIAS control.
of the titration is
reached, record the
increasing LED readings
along with the
corresponding digits
displayed on the Digital
Titrator counter. Add
5-10 digits of titrant;
wait a few seconds for a
stable reading and
record. Stop the titrant
addition when the LED
readings exceed 0.60.
Note: LED readings
above 0.60 will be
excessively noisy. With
samples containing
excess de-chlorinating
agents, such as sulfur
dioxide, sulfite or bisulfite,
the titration end point
(number of digits) will be
greater than the number of
digits obtained during the
standardization. It is not
necessary to continue the
titrant addition if the
number of digits used in
the sample titration
exceeds that calculated
for the standardization end
point. This indicates that
no free or combined
chlorine is present in the
sample.
98
total chlorine:
Table 1
99
Digits
(standard end point)
Multiplier
160
6.25
165
6.06
170
5.88
175
5.71
180
5.56
185
5.40
190
5.26
195
5.13
200
5.00
Accuracy Check
Standard Additions Method*
Snap the top off a Chlorine Standard Solution PourRite
Ampule. Note the certificate value of the standard in mg/L.
1. Split a fresh sample into two 200-mL portions.
2. Using a TenSette Pipet, add from 0.1 to 0.5 mL of the
standard to one portion and swirl to mix. This is the
spiked sample.
3. Analyze each sample as described above and record the
chlorine concentrations.
4. Calculate the theoretical concentration of the spiked sample:
( Cu Vu ) + ( Cs Vs )
Theoretical concentration = ----------------------------------------------------------Vu + Vs
Where:
Cu = measured concentration of sample, in mg/L (g/L divided by 1000)
Vu = volume of sample in mL
Cs = concentration of chlorine standard (mg/L, certificate value)
Vs = volume of standard added in mL
* Standard additions is not applicable for samples containing excess reducing agents such as sulfur
dioxide, sulfite, or bisulfite.
100
Precision
In a single laboratory, using a standard solution of 120 g/L
chlorine, a single operator obtained a standard deviation of
19 g/L chlorine.
Detection Limit
The estimated detectable concentration is equivalent to one digit
of 0.0282 N Standard Iodine Titrant Solution or approximately
6 g/L chlorine.
Interferences
101
Summary of Method
The back titration procedure minimizes errors caused by
liberating the full concentration of iodine in the sample and is the
preferred method for amperometric measurement for total
chlorine in wastewaters. In the back titration procedure, the end
point signal is reversed because the remaining thiosulfate (or
phenylarsine oxide) added to the sample is titrated with standard
iodine. The end point of the back titration is reached just when
free iodine exists in the sample resulting in a measurable
polarization current. The end point is estimated by continued
addition of titrant, recording of the current at each titrant addition,
and graphing the data points. Where the best line between the
data points intersects with the null current, the number of digits
(from the Digital Titrator) at the end point can be determined and
the concentration of chlorine calculated.
It is necessary to adjust the electrode sensitivity by using the bias
control prior to performing the analysis. The bias adjustment is
set by adding a known amount of standard iodine titrant to
deionized water and adjusting the bias control to a given value on
the display. The electrode sensitivity will vary depending on the
probe conditioning. Adjustment should be made at least daily or
before each series of samples.
Although the iodine titrant solution is formulated and packaged to
be quite stable it is recommended the iodine be routinely
standardized against standard thiosulfate or phenylarsine oxide.
The number of digits determined for the iodine standardization is
recorded and used in the calculation of the samples
chlorine concentration.
102
REQUIRED REAGENTS
Description
Unit
Cat. No.
REQUIRED APPARATUS
Amperometric Titrator Assembly .............................................................. each ..........19299-00
Beaker, low-form, 250-mL......................................................................... each ..............500-46
Cylinder, graduated, 250-mL ..................................................................... each ..............508-46
Digital Titrator............................................................................................ each ..........16900-01
Delivery Tubes, 90 with hook..................................................................5/pkg ..........41578-00
Pipet, volumetric, Class A, 1-mL ............................................................... each ..........14515-35
Probe Assembly, Amperometric Titrator ................................................... each ..........19390-00
Stir Bar, octagonal, Teflon-coated, 50.8 x 7.9 mm..................................... each ..........20953-55
TitraStir Stir Plate, 115 Vac ..................................................................... each ..........19400-00
TitraStir Stir Plate, 230 Vac ..................................................................... each ..........19400-10
OPTIONAL REAGENTS
Chlorine Standard Solution PourRite Ampules,
50-75 mg/L Cl2, 2-mL .........................................................................20/pkg ..........14268-20
Phenylarsine Oxide Solution, 0.00564 N .............................................. 100 mL ............1999-42
Water, deionized ........................................................................................... 4 L ..............272-56
OPTIONAL APPARATUS
Bottle, BOD, 300-mL................................................................................. each ..............621-00
Pipet, TenSette, 0.1 to 1.0 mL.................................................................. each ..........19700-01
Pipet Tips for 19700-01 TenSette Pipet ................................................50/pkg ..........21856-96
PourRite Ampule Breaker ...................................................................... each ..........24846-00
103
104
Method 10026
1. Assemble the
2. Install the
Amperometric Digital
Titrator System
according to the
instructions in the
Amperometric Titrator
Instruction Manual.
Phenylarsine Oxide
(PAO), 0.00564 N
Cartridge. Flush the
Digital Titrator delivery
tube by turning the
delivery knob to eject a
few drops of titrant.
Reset the counter to zero
and wipe the tip.
3. With minimum
* Procedure is equivalent to USEPA method 330.1 and 330.3, Standard Methods for the Examination of
Water and Wastewater (18th ed.) 4500-Cl D for drinking water and Standard Methods (17th ed.) 4500Cl D for wastewater.
105
5. Add 1 mL of pH 4
reading on the
Amperometric Titrator.
Unlock the BIAS control
and adjust the BIAS
control knob until a
reading between 0.500.60 is obtained. Lock
the BIAS control.
106
Meter Reading
End
Point
Digits
the titration is
approached, record the
LED readings along
with the corresponding
digits displayed on the
Digital Titrator counter.
Near the titration end
point, add 2 to 5 digits of
titrant; wait a few
seconds for a stable
reading and record.
titration, recording at
least three points on the
downward sloping curve
and at least three points
after the end point has
been reached. The latter
points will have little
change in the LED
readings.
Meter Reading
Figure 1
Sample Plot
End
Point
Digits
107
total chlorine:
Digits at End Point X
1.25 = g/L total chlorine
as Cl2
Where:
Cu = measured concentration of sample, in mg/L (g/L divided by 1000)
Vu = volume of sample in mL
Cs = concentration of chlorine standard (mg/L, certificate value)
Vs = volume of standard added in mL
Example:
Sample result (Cu) = 120 g/L or 0.120 mg/L
Spiked sample result = 185 g/L or 0.185 mg/L
Volume Sample (Vu) = 200 mL
Volume Standard (Vs) = 0.2 mL
Chlorine Standard (Cs) = 68.1 mg/L
* The standard additions technique is not applicable for samples containing excess reducing agents such
as sulfur dioxide, sulfite, or bisulfite.
108
Precision
In a single laboratory, using a standard solution of 347 g/L
chlorine, a single operator obtained a standard deviation of
3.2 g/L chlorine.
Detection Limit
With good operator technique, the estimated detectable
concentration is approximately 15 g/L chlorine using
0.00564 N PAO.
Interferences
110
Unit
Cat. No.
REQUIRED APPARATUS
Amperometric Titrator Assembly .............................................................. each ..........19299-00
Digital Titrator............................................................................................ each ..........16900-01
Beaker, low-form, 250-mL......................................................................... each ............. 500-46
Cylinder, graduated, 250-mL ..................................................................... each ............. 508-46
Delivery Tubes, 90 with hook..................................................................5/pkg ..........41578-00
Probe Assembly, Amperometric Titrator ................................................... each ..........19390-00
Stir Bar, octagonal, Teflon-coated, 50.8 x 7.9 mm..................................... each ..........20953-55
TitraStir Stir Plate, 115 Vac ..................................................................... each ..........19400-00
TitraStir Stir Plate, 230 Vac ..................................................................... each ..........19400-10
OPTIONAL REAGENTS
Chlorine Standard Solution PourRite Ampules,
50-75 mg/L Cl2, 2-mL .........................................................................20/pkg ..........14268-20
Water, deionized ........................................................................................... 4 L ............. 272-56
OPTIONAL APPARATUS
Pipet, TenSette, 0.1 to 1.0 mL.................................................................. each ..........19700-01
Pipet Tips for 19700-01 TenSette Pipet ................................................50/pkg ..........21856-96
PourRite Ampule Breaker ...................................................................... each ..........24846-00
Standard Methods for the Examination of Water
and Wastewater, 19th edition .................................................................. each ..........22708-00
111
112
Method 8211
1. Insert a clean
3. Select a sample
4. Use a graduated
volume corresponding to
the expected chromate
(CrO42) concentration
from Table 1.
cylinder or pipet to
measure the sample
volume from Table 1.
Transfer the sample
to a clean 125-mL
Erlenmeyer flask. Dilute
to about the
50-mL mark with
deionized water.
Table 1
Range
(mg/L as CrO42-)
Sample
Volume
(mL)
Titration
Cartridge
(N Na2S2O3)
Catalog
Number
Digit
Multiplier
20-80
50-200
100-400
> 400
50
20
10
5
0.2068 N
0.2068 N
0.2068 N
0.2068 N
22676-01
22676-01
22676-01
22676-01
0.2
0.5
1.0
2.0
113
CHROMATE, continued
Starch Indicator
Solution and swirl to
mix.
9. Continue titrating
until the solution turns
from blue to colorless.
Record the number of
digits required.
10. Calculate:
Total Digits Required x
Digit Multiplier = mg/L
chromate
(CrO42)
Note: Results may be
expressed as mg/L sodium
chromate (Na2CrO4) or
chromium (Cr) by
multiplying the
mg/L chromate by 1.4 or
0.448, respectively.
114
CHROMATE, continued
Sampling and Storage
Collect 200 to 300 mL of sample in an acid-washed glass or
polyethylene container. If sample cannot be analyzed
immediately add 1 mL concentrated sulfuric acid and swirl
to mix.
Accuracy Check
Standard Additions Method
This accuracy check should be performed when interferences are
suspected or to verify analytical technique.
1. Use a TenSette Pipet to add 0.1 mL, 0.2 mL and 0.3 mL of
Hexavalent Chromium Standard Solution, 1000 mg/L to three
samples of the same volume as that titrated in the procedure.
2. Analyze each as described in the procedure.
3. Each 0.1 mL addition of standard should require 22
additional digits of titrant. If these uniform increases do not
occur, refer to Appendix A, Accuracy Check and
Standard Additions.
Standard Preparation
A standard solution equivalent to 67 mg/L chromate (30 mg/L Cr)
can be prepared by diluting 3.0 mL of Hexavalent Chromium
Standard Solution, 1000 mg/L Cr to 100 mL in a volumetric
flask. Titrate a 20-mL or 50-mL sample as described in
the procedure.
Interferences
Substances capable of oxidizing iodide to iodine under acidic
conditions (such as ferric iron and copper) will interfere to give
high results. The effects of iron and copper may be masked by
dissolving a Magnesium CDTA Powder Pillow, followed by two
1.0-gram measuring spoons of Sodium Acetate in the sample
between steps 6 and 7.
Summary of Method
Chromate in the sample reacts with iodide under acidic
conditions to form iodine as triiodide. Addition of starch
115
CHROMATE, continued
indicator produces a blue color complex with the iodine. This
complex is titrated with sodium thiosulfate to a colorless end
point. The volume of titrant used is proportional to the
chromate concentration.
REQUIRED REAGENTS
Description
Unit
Cat. No.
REQUIRED APPARATUS
Clippers, for opening pillows......................................................................each.............. 968-00
Digital Titrator ............................................................................................each.......... 16900-01
Flask, Erlenmeyer, 125-mL ........................................................................each.............. 505-43
Select one or more based on sample concentration:
OPTIONAL REAGENTS
Chromium, Hexavalent, Standard Solution, 1000 mg/L........................100 mL.......... 14664-42
Magnesium CDTA Powder Pillows ...................................................... 100/pkg.......... 14080-99
Sodium Acetate, trihydrate, ACS.............................................................. 100 g.............. 178-26
OPTIONAL APPARATUS
Clamp, 2-prong, extension..........................................................................each.......... 21145-00
Clamp Holder..............................................................................................each.............. 326-00
Demineralizer Assembly, 473-mL..............................................................each.......... 21846-00
Delivery Tubes, with 180 hook ............................................................... 5/pkg.......... 17205-00
Delivery Tubes, 90 with hook for TitraStir Stir Plate ........................... 5/pkg.......... 41578-00
Flask, volumetric, Class B, 100 mL............................................................each.............. 547-42
Pipet, TenSette, 0.1 to 1.0 mL ..................................................................each.......... 19700-01
116
CHROMATE, continued
OPTIONAL APPARATUS, continued
Description
Unit
Cat. No.
117
118
119
120
Method 8204
4. Use a graduated
cylinder or pipet to
measure the sample
volume from Table 1 or
Table 2. Transfer the
sample into a clean
250-mL Erlenmeyer
flask. Dilute to about the
100-mL mark with
deionized water,
if necessary.
121
5. Add 2 mL of 8 N
Potassium Hydroxide
Standard Solution and
swirl to mix.
Table 1
Range (mg/L as
CaCO3)
Sample
Volume
(mL)
Titration
Cartridge
(M EDTA)
Catalog
Number
Digit
Multiplier
10-40
40-160
100-400
200-800
500-2000
1000-4000
100
25
100
50
20
10
0.0800
0.0800
0.800
0.800
0.800
0.800
14364-01
14364-01
14399-01
14399-01
14399-01
14399-01
0.1
0.4
1.0
2.0
5.0
10.0
Table 2
Range (G.d.h.)
Sample
Volume
(mL)
Titration
Cartridge
(M EDTA)
Catalog
Number
Digit
Multiplier
1-4
4-16
10-40
25-100
>100
100
25
50
20
10
0.1428
0.1428
0.714
0.714
0.714
14960-01
14960-01
14959-01
14959-01
14959-01
0.01
0.04
0.1
0.25
0.5
122
Accuracy Check
Standard Additions Method
This accuracy check should be performed when interferences are
suspected or to verify analytical technique.
1. Snap the neck off a Hardness Standard Solution Voluette
Ampule, 10,000 mg/L as CaCO3.
2. Use a TenSette Pipet to add 0.1 mL of standard to the
solution titrated in step 7. Resume titration back to the same
end point. Record the number of digits required.
3. Repeat, using two more additions of 0.1 mL. Titrate to the
end point after each addition.
4. Each 0.1 mL addition of standard should require 10
additional digits of 0.800 N titrant or 100 digits of 0.0800 N
titrant (11 digits of 0.714 M or 56 digits of 0.1428 M titrant).
If these uniform increases do not occur, refer to Appendix A,
Accuracy Check and Standard Additions.
Interferences
WARNING:
Potassium cyanide is
toxic. Always add it after
the potassium hydroxide.
Excess potassium cyanide
does not affect results. All
cyanide wastes should be
disposed of by adding an
excess of strongly alkaline
sodium hypochlorite
solution (bleach) with
stirring. Use good
ventilation. Allow to stand
for 24 hours
before disposal.
123
Max. Tolerance
Level* with KCN
Max. Tolerance
Level* without KCN
present
Cobalt
20 mg/L
none
Copper
100 mg/L
0.10 mg/L
Nickel
200 mg/L
0.5 mg/L
Zinc
100 mg/L
5 mg/L
124
Summary of Method
The sample is made alkaline (pH 12-13) with potassium
hydroxide to precipitate magnesium as magnesium hydroxide.
CalVer 2 Indicator is added and combines with any calcium to
form a pink-red color. As EDTA is added, it reacts with the free
calcium ions present. When no free calcium ions remain, the
EDTA then removes the calcium complexed with the indicator,
causing a color change to blue.
REQUIRED REAGENTS
Description
Unit
Cat. No.
REQUIRED APPARATUS
Digital Titrator............................................................................................ each ..........16900-01
Flask, Erlenmeyer, 250 mL ........................................................................ each ..............505-46
Select one or more based on sample concentration:
125
Unit
Cat. No.
Calcium Chloride Standard Solution, 1000 mg/L as CaCO3 ..............1000 mL.............. 121-53
CalVer 2 Calcium Indicator Powder....................................................... 113 g.............. 281-14
Calcium Standard Solution Voluette Ampules,
10,000 mg/L as CaCO3, 10-mL........................................................... 16/pkg............ 2187-10
Magnesium Standard Solution, 10 g/L CaCO3............................ 29 mL SCDB............ 1022-33
Nitric Acid, ACS....................................................................................500 mL.............. 152-49
Nitric Acid Solution, 1:1........................................................................500 mL............ 2540-49
Potassium Cyanide, ACS .......................................................................... 125 g.............. 767-14
OPTIONAL APPARATUS
Bottle, wash, poly, 500-mL.........................................................................each.............. 620-11
Clamp, 2-prong, extension, 38-mm ............................................................each.......... 21145-00
Clamp Holder..............................................................................................each.............. 326-00
Demineralizer Assembly, 473 mL ..............................................................each.......... 21846-00
Delivery Tubes, with 180 hook ............................................................... 5/pkg.......... 17205-00
Delivery Tubes, 90 with hook ................................................................. 5/pkg.......... 41578-00
pH Paper, 1.0 to 11 pH...................................................................... 5 rolls/pkg.............. 391-33
Pipet, TenSette, 0.1 to 1.0 mL ..................................................................each.......... 19700-01
Pipet Tips for 19700-01 TenSette Pipet................................................ 50/pkg.......... 21856-96
Pipet, volumetric, Class A, 10-mL .............................................................each.......... 14515-38
Pipet, volumetric, Class A, 20-mL .............................................................each.......... 14515-20
Pipet, volumetric, Class A, 25-mL .............................................................each.......... 14515-40
Pipet, volumetric, Class A, 50-mL .............................................................each.......... 14515-41
Pipet, volumetric, Class A, 100-mL ...........................................................each.......... 14515-42
Pipet Filler, safety bulb ...............................................................................each.......... 14651-00
sension1 Basic Portable pH Meter with electrode ................................each.......... 51700-10
Spoon, measuring, 0.1-gram .......................................................................each.............. 511-00
Spoon, measuring, 0.5-gram .......................................................................each.............. 907-00
Support Ring Stand.....................................................................................each.............. 563-00
TitraStir Stir Plate, 115 Vac......................................................................each.......... 19400-00
TitraStir Stir Plate, 230 Vac......................................................................each.......... 19400-10
Voluette Ampule Breaker Kit ...................................................................each.......... 21968-00
126
Method 8213
4. Use a graduated
cylinder or pipet to
measure the sample
volume from Table 1 or
Table 2. Transfer the
sample into a clean
250-mL Erlenmeyer
flask. Dilute to about the
100-mL mark with
deionized water,
if necessary.
127
5. Add 2 mL of
Hardness 1 Buffer
Solution and swirl
to mix.
one ManVer 2
Hardness Indicator
Powder Pillow (Cat. No.
851-99) and swirl to
mix.
Table 1
Range
(mg/L as CaCO3)
Sample
Volume
(mL)
Titration
Cartridge
(M EDTA)
Catalog
Number
Digit
Multiplier
10-40
40-160
100-400
200-800
500-2000
1000-4000
100
25
100
50
20
10
0.0800
0.0800
0.800
0.800
0.800
0.800
14364-01
14364-01
14399-01
14399-01
14399-01
14399-01
0.1
0.4
1.0
2.0
5.0
10.0
Table 2
Range (G.d.h.)
Sample
Volume
(mL)
Titration
Cartridge
(M EDTA)
Catalog
Number
Digit
Multiplier
1-4
4-16
10-40
25-100
>100
100
25
50
20
10
0.1428
0.1428
0.714
0.714
0.714
14960-01
14960-01
14959-01
14959-01
14959-01
0.01
0.04
0.1
0.25
0.5
128
Accuracy Check
Standard Additions Method
To verify analytical technique, use 20 mL of the Calcium
Standard Solution, 1000 mg/L as CaCO3. Perform the procedure
as described above. This solution will read 1000 mg/L or
55.9 G.d.h.
Perform this accuracy check when interferences are suspected.
1. Snap the neck off a Hardness Standard Solution Voluette
Ampule, 10,000 mg/L as CaCO3.
2. Use a TenSette Pipet to add 0.1 mL of standard to the
sample titrated in step 7. Resume titration back to the same
end point. Record the number of digits required.
3. Repeat, using two more additions of 0.1 mL. Titrate to the
end point after each addition.
4. Each 0.1 mL addition of standard should require 10
additional digits of 0.800 M titrant, 100 digits of 0.0800 M
titrant, 11 digits of 0.714 M, or 56 digits of 0.1428 M titrant.
If these uniform increases do not occur, refer to Appendix A,
Accuracy Check and Standard Additions.
Interferences
WARNING
Potassium cyanide is
toxic. Always add it after
the potassium hydroxide.
Excess potassium cyanide
does not affect results. All
cyanide wastes should be
disposed of by adding an
excess of strongly alkaline
sodium hypochlorite
solution (bleach) with
stirring. Use good
ventilation. Allow to stand
for 24 hours
before disposal.
Aluminum
50 mg/L
Cobalt
200 mg/L
Copper
100 mg/L
Iron
100 mg/L
Manganese
200 mg/L
Nickel
400 mg/L
Zinc
300 mg/L
130
Metal
Aluminum
3.710
Barium
0.729
Cobalt
1.698
Copper
1.575
Iron
1.792
Manganese
1.822
Nickel
1.705
Strontium
1.142
Zinc
1.531
Summary of Method
After the sample is buffered to pH 10.1, ManVer 2 Hardness
Indicator is added, and forms a red complex with a portion of the
calcium and magnesium in the sample. EDTA titrant reacts first
with the free calcium and magnesium ions, then with those bound
to the indicator, causing it to change to a blue color at the
end point.
131
Unit
Cat. No.
REQUIRED APPARATUS
Digital Titrator ............................................................................................each.......... 16900-01
Flask, Erlenmeyer, 250-mL ........................................................................each.............. 505-46
Select one or more based on sample concentration:
OPTIONAL REAGENTS
Ammonium Hydroxide, 10%.................................................... 100 mL MDB*.......... 14736-32
Calcium Chloride Standard Solution, 1000 mg/L as CaCO3 ..............1000 mL.............. 121-53
CDTA Magnesium Salt Powder Pillows............................................... 100/pkg.......... 14080-99
CDTA Titration Cartridge, 0.0800 M .........................................................each.......... 14402-01
CDTA Titration Cartridge, 0.800 M ...........................................................each.......... 14403-01
Calcium Standard Solution Voluette Ampules,
10,000 mg/L as CaCO3, 10-mL........................................................... 16/pkg............ 2187-10
Hydroxylamine Hydrochloride, Monohydrate, ACS................................ 113 g.............. 246-14
ManVer 2 Hardness Indicator Powder.................................................... 113 g.............. 280-14
ManVer Hardness Indicator Solution ..................................... 100 mL MDB*.............. 425-32
Nitric Acid Solution, 1:1........................................................................500 mL............ 2540-49
Nitric Acid, ACS....................................................................................500 mL.............. 152-49
Potassium Cyanide, ACS .......................................................................... 125 g.............. 767-14
132
Unit
Cat. No.
133
134
Method 8329
(10 to 4000 mg/L as CaCO3)
4. Use a graduated
cylinder or pipet to
measure the sample
volume from
Table 1 or Table 2.
Transfer the sample
into a clean 250-mL
Erlenmeyer flask. Dilute
to about the 100-mL
mark with deionized
water, if necessary.
Table 1
Range (mg/L as
CaCO3)
Sample
Volume
(mL)
Titration Cartridge
(M EDTA)
Catalog
Number
Digit
Multiplier
10-40
40-160
100-400
200-800
500-2000
1000-4000
100
25
100
50
20
10
0.0800
0.0800
0.800
0.800
0.800
0.800
14364-01
14364-01
14399-01
14399-01
14399-01
14399-01
0.1
0.4
1.0
2.0
5.0
10.0
Table 2
Range (G.d.h.)
Sample
Volume
(mL)
Titration Cartridge
(M EDTA)
Catalog
Number
Digit
Multiplier
1-4
4-16
10-40
25-100
>100
100
25
50
20
10
0.1428
0.1428
0.714
0.714
0.714
14960-01
14960-01
14959-01
14959-01
14959-01
0.01
0.04
0.1
0.25
0.5
135
5. Add 2 mL of 8 N
Potassium Hydroxide
Standard Solution and
swirl to mix.
concentration of calcium
hardness by using one of
the formulas below:
one ManVer 2
Hardness Indicator
Powder Pillow (Cat. No.
928-99) or 4 drops of
Hardness 2 Test Solution
(Cat. No. 425-32). Swirl
to mix.
136
Hardness Relationships
mg/L Mg Hardness as CaCO3
= mg/L Total Hardness as CaCO 3 mg/L Ca Hardness as CaCO 3
mg/L MgCO 3 = mg/L Mg Hardness as CaCO 3 0.842
mg/L Mg = mg/L MgCO 3 0.29
Interferences
WARNING:
Do not use potassium cyanide to eliminate interferences because it
will generate deadly hydrogen cyanide gas when the sulfuric acid
solution is added in step 9.
138
Aluminum
50 mg/L
Cobalt
200 mg/L
Copper
100 mg/L
Iron
100 mg/L
Manganese
200 mg/L
Nickel
400 mg/L
Zinc
300 mg/L
Table 4
Metal
Aluminum
3.710
Barium
0.729
Cobalt
1.698
Copper
1.575
Iron
1.792
Manganese
1.822
Nickel
1.705
Strontium
1.142
Zinc
1.531
139
Unit
Cat. No.
REQUIRED APPARATUS
Digital Titrator ............................................................................................each.......... 16900-01
Flask, Erlenmeyer, 250 mL.........................................................................each.............. 505-46
Select one or more based on sample concentration:
OPTIONAL REAGENTS
CDTA Magnesium Salt Powder Pillows............................................... 100/pkg.......... 14080-99
CDTA Titration Cartridge, 0.08 M .............................................................each.......... 14402-01
CDTA Titration Cartridge, 0.8 M ...............................................................each.......... 14403-01
Hardness 2 Test Solution ............................................................ 100 mL MDB.............. 425-32
Hardness Standard Solution, Voluette Ampules,
10,000 mg/L as CaCO3, 10 mL ........................................................... 16/pkg............ 2187-10
Hydroxylamine Hydrochloride ................................................................. 113 g.............. 246-14
Nitric Acid, 70% ....................................................................................500 mL.............. 152-49
* Other reagents and apparatus are listed with the specific procedure.
** Marked Dropper Bottle (MDB). Contact Hach for larger sizes.
140
Unit
Cat. No.
141
142
HYPOCHLORITE (Bleach)
Method 10100
(50 to 150 g/L [5 to 15%] as Cl2)
Iodometric Method*
Scope and Application: For testing concentrated liquid bleach (sodium hypochlorite, soda bleach) used
as a disinfectant in drinking water or wastewater treatment.
1. Insert a clean
3. Fill a 125-mL
Erlenmeyer flask to
about the 75-mL mark
with deionized or
tap water.
8. Swirl to mix.
dispense 0.2 mL of
bleach sample below the
solution level in
the flask.
143
Note: Proceed
immediately with Step 9.
g/L Chlorine
as Cl2 =
Digits at End Point
x 0.5
Starch Indicator
Solution to the flask and
swirl to mix. A dark blue
or green color will
develop.
chlorine:
Accuracy Check
Standard Solution Method
Hach strongly recommends that, for optimum test results, reagent
accuracy be checked with each new lot of reagents. The strength
of the Thiosulfate Standard Solution can be checked using
Potassium Iodide-Iodate Standard Solution:
1. Use a Class A pipet to transfer 50.00 mL of 0.0125 N
Potassium Iodide-Iodate Standard Solution to a clean 125-mL
Erlenmeyer flask.
2. Add the contents of one Potassium Iodide Powder Pillow to
the flask and swirl to mix.
3. Add the contents of three Acid Reagent Powder Pillows to
the flask and swirl to mix. Swirl until all powder is dissolved.
144
Interferences
The iodometric method is relatively free of interferences. The test
will determine chlorite ion (ClO2) in addition to the hypochlorite
ion (ClO). However, the amount of chlorite in commercial
bleach is insignificant (typically less than 0.2%).
A large excess of caustic in the bleach sample may lead to low
results. After adding the Acid Reagent Powder Pillow (step 5),
check the pH of the solution with pH paper. The pH should be
less than 3. If not, add additional Acid Reagent, one pillow at a
time, until the pH drops below 3.
For most accurate results, the temperature of the dilution water
(step 3) should be less than 20 C (68 F).
Precision
In a single laboratory, using a commercial bleach sample of
91.2 g/L (9.12%) Cl2, a single operator obtained a standard
deviation of 1.5 g/L ( 0.15%) Cl2.
Summary of Method
Under acidic conditions, hypochlorite reacts with iodide to
produce an equivalent amount of triiodide (I3). The released I3
is titrated with standard thiosulfate solution to a colorless end
point. The number of digits of thiosulfate required is proportional
to the hypochlorite concentration in the original bleach sample.
145
Unit
Cat. No.
REQUIRED APPARATUS
Clippers, large .............................................................................................each.............. 968-00
Delivery Tubes, 180 ................................................................................ 5/pkg.......... 17205-00
Digital Titrator Assembly ...........................................................................each.......... 16900-02
Flask, Erlenmeyer, 125-mL ........................................................................each.............. 505-43
Pipet, TenSette, 0.11.0 mL .....................................................................each.......... 19700-01
Pipet Tips for 19700-01 TenSette Pipet ............................................... 50/pkg.......... 21856-96
OPTIONAL REAGENTS
Potassium Iodide-Iodate Standard Solution, 0.0125 N.................................1 L.......... 14001-53
OPTIONAL APPARATUS
pH Paper, 111.......................................................................................... 5/pkg.............. 391-33
Pipet, volumetric, Class A, 50.00 mL.........................................................each.......... 14515-41
146
Method 8214
IRON
1. Select a sample
2. Insert a clean
4. Use a graduated
Table 1
Range
(mg/L as Fe)
Sample
Volume (mL)
Titration
Cartridge
(M TitraVer)
Catalog
Number
Digit
Multiplier
10-40
25-100
100-400
250-1000
50
20
50
20
0.0716
0.0716
0.716
0.716
20817-01
20817-01
20818-01
20818-01
0.1
0.25
1.0
2.5
147
IRON, continued
9. Calculate:
Digits Required x Digit
Multiplier = mg/L Iron
(Fe)
148
IRON, continued
Accuracy Check
This accuracy check should be performed when interferences are
suspected or to verify analytical technique.
1. Use a TenSette Pipet to add 0.5 mL of 1000 mg/L as Fe
standard to the sample in step 7. Resume titration back to the
same end point. Record the number of additional
digits required.
2. Repeat, using two more additions of 0.5 mL. Titrate to the
end point after each addition.
3. Each 0.5-mL addition of standard should require 10
additional digits of 0.716 M titrant or 100 digits of 0.0716 M
titrant. If these uniform increases do not occur, refer to
Appendix A, Accuracy Check and Standard Additions.
Summary of Method
Iron (Fe2+) is oxidized by sodium periodate to the ferric ion
(Fe3+). When sulfosalicylic acid is present, the ferric ion forms a
red complex, coloring the solution. The red complex is destroyed
by titration with EDTA. Citric acid is used to buffer the solution
and to stabilize the ferric ion in solution.
149
IRON, continued
REQUIRED REAGENTS
(varies with sample characteristics)
Iron Reagent Sets (about 100 tests)
10-100 mg/L includes: (1) 984-99, (1) 20815-99, (1) 20816-69, (1) 20817-01 ....... 24492-00
100-1000 mg/L includes: (1) 984-99, (1) 20815-99, (1) 20816-69, (1) 20818-01 ...... 24493-00
Description
Unit
Cat. No.
REQUIRED APPARATUS
Clippers, for opening pillows......................................................................each.............. 968-00
Digital Titrator ............................................................................................each.......... 16900-01
Flask, Erlenmeyer, 125 mL.........................................................................each.............. 505-43
Select one or more based on sample concentration:
OPTIONAL REAGENTS
Iron Standard Solution, 1000 mg/L as Fe ..............................................100 mL............ 2271-42
OPTIONAL APPARATUS
Bottle, wash, poly, 500 mL .........................................................................each.............. 620-11
Clamp, 2-prong, extension, 38 mm.............................................................each.......... 21145-00
Clamp Holder..............................................................................................each.............. 326-00
Demineralizer Assembly, 473 mL ..............................................................each.......... 21846-00
Delivery Tubes, with 180 hook ............................................................... 5/pkg.......... 17205-00
Delivery Tubes, 90 with hook ................................................................. 5/pkg.......... 41578-00
Pipet, TenSette, 0.1 to 1.0 mL ..................................................................each.......... 19700-01
Pipet Tips for 19700-01 TenSette Pipet................................................ 50/pkg.......... 21856-96
Pipet, volumetric, Class A, 25.0 mL...........................................................each.......... 14515-40
Pipet, volumetric, Class A, 50.0 mL...........................................................each.......... 14515-41
Pipet Filler, safety bulb ...............................................................................each.......... 14651-00
Support Ring Stand.....................................................................................each.............. 563-00
TitraStir Stir Plate, 115 Vac......................................................................each.......... 19400-00
TitraStir Stir Plate, 230 Vac......................................................................each.......... 19400-10
150
Method 8351
NITRITE
2. Insert a clean
4. Use a graduated
cylinder or pipet to
measure the sample
volume from Table 1.
Transfer the sample to a
clean 125-mL
Erlenmeyer flask. Add
deionized water to about
the 75-mL mark, if
necessary.
Note: A pipet is
recommended for sample
volumes less than 10 mL.
151
NITRITE, continued
Table 1
Expected Sample
Concentration
(as NaNO2)
Digit Multiplier
100-400
400-800
800-1500
1500-2500
25
10
5
2
0.86
2.15
4.31
10.78
NITRITE, continued
digits required. This step should require about 400-450 digits
of titrant.
9. Add one drop of Ferroin Indicator Solution. Swirl to mix.
The solution will turn a faint blue.
10. Continue titrating the Ceric Standard Solution (using the 0.20
Sodium Thiosulfate Titration Cartridge) from a faint blue to
orange color. Record the number of digits required.
11. Calculate the correction factor:
Digits Required
Correction Factor = ----------------------------------------500
12. Multiply the mg/L sodium nitrite from step 8 of the nitrite
titration procedure by the correction factor to obtain the
correct sodium nitrite concentration.
Accuracy Check
Dissolve 1.000 gram of fresh sodium nitrite in 100 mL of
deionized water. Dilute to 1000 mL with deionized water to
prepare a 1000 mg/L sodium nitrite standard solution. Use a 5.0
sample of the standard solution and start with step 4 of the
titration procedure. The analysis should yield 1000 mg/L for
step 8 of the titration procedure.
Summary of Method
Sodium nitrite is titrated with tetravalent cerium ion, a strong
oxidant, in the presence of ferroin indicator. After the cerium
oxidizes the nitrite, it oxidizes the indicator, causing a color
change from orange to pale blue. The concentration of sodium
nitrite is proportional to the amount of titrant used.
153
NITRITE, continued
REQUIRED REAGENTS
Description
Unit
Cat. No.
REQUIRED APPARATUS
Digital Titrator ............................................................................................each.......... 16900-01
Flask, Erlenmeyer, 125 mL.........................................................................each.............. 505-43
Select one or more based on sample volume:
OPTIONAL REAGENTS
Sodium Thiosulfate Titration Cartridge, 0.200 N .......................................each.......... 22675-01
Sodium Nitrite, ACS................................................................................. 454 g............ 2452-01
Sulfuric Acid Standard Solution, 19.2 N ...............................................100 mL............ 2038-32
Water, deionized............................................................................................4 L.............. 272-56
OPTIONAL APPARATUS
Balance, electronic, analytical ....................................................................each.......... 22310-00
Flask, volumetric, Class A, 50 mL .............................................................each.......... 14547-41
154
OXYGEN, DISSOLVED
1. Collect a water
Method 8215
3. Immediately insert
sample in a clean
300-mL BOD Bottle.
7. Insert a clean
155
9. Use a graduated
droppers of Starch
Indicator Solution and
swirl to mix.
titration to a colorless
end point. Record the
number of digits
required.
13. Calculate:
Digits Required x Digit
Multiplier = mg/L
Dissolved Oxygen
Table 1
Range
Sample
(mg/L D.O.) Volume (mL)
1-5
2-10
>10
200
100
200
Titration
Cartridge
(N Na2S2O3)
Catalog
Number
Digit
Multiplier
0.200
0.200
2.000
22675-01
22675-01
14401-01
0.01
0.02
0.1
156
Method 8332
1. Collect a water
3. Immediately insert
20 mL of the prepared
sample and transfer it to
a 125-mL Erlenmeyer
flask.
straight-stem delivery
tube to a 0.2000 N
Sodium Thiosulfate
Titration Cartridge.
Twist the cartridge onto
the titrator body. See
General Description,
Step-by-Step for
assembly instructions, if
necessary
157
10. Calculate:
solution with 0.2000 N
Digits required x 0.1 =
Sodium Thiosulfate until
mg/L Dissolved Oxygen
the sample changes from
yellow to colorless.
Record the number of
digits.
Accuracy Check
Check the strength of the Sodium Thiosulfate Solution by using
an Iodate-Iodide Standard Solution which is equivalent to
10 mg/L dissolved oxygen. For the 300-mL procedure, begin at
step 5 adding the Sulfamic Acid Powder Pillow. For the 60-mg/L
procedure, begin the analysis at step 5 adding the Dissolved
Oxygen 3 Powder Pillow. The titration should take 10 mL. If
158
Interferences
Nitrite interference is eliminated by the azide in the reagents.
Other reducing or oxidizing substances may interfere. If these are
present, use an alternate method, such as the High Range
Dissolved Oxygen Method (colorimetric) in this manual, or a
dissolved oxygen electrode.
Summary of Method
Samples are treated with manganous sulfate and alkaline iodideazide reagent to form an orange-brown precipitate. Upon
acidification of the sample, this floc reacts with iodide to produce
free iodine as triiodide in proportion to the oxygen concentration.
The iodine is titrated with sodium thiosulfate to a colorless
end point.
Unit
Cat. No.
159
Unit
Cat. No.
OPTIONAL REAGENTS
Iodate-Iodide Standard Solution, 10 mg/L as DO ...............................500 mL*.............. 401-49
OPTIONAL APPARATUS
Cap, BOD Bottle, plastic .......................................................................... 6/pkg............ 2419-06
Clamp Holder..............................................................................................each.............. 326-00
Clamp, 2-prong, extension, 38 mm.............................................................each.......... 21145-00
Delivery Tubes, with 180 hook ............................................................... 5/pkg.......... 17205-00
Delivery Tubes, 90 with hook ................................................................. 5/pkg.......... 41578-00
Sewage Sampler, Lab-Line .........................................................................each.............. 427-00
Support Ring Stand.....................................................................................each.............. 563-00
TitraStir Stir Plate, 115 Vac......................................................................each.......... 19400-00
TitraStir Stir Plate, 230 Vac......................................................................each.......... 19400-10
Procedures and kits for portable dissolved oxygen measurements using this method are
available from Hach.
160
Method 10073
1. Insert a clean,
straight-stem delivery
tube to a Mercuric
Nitrate Titration
Cartridge. Attach the
cartridge to the titrator
body. See General
Description, Step-byStep for assembly
instructions, if
necessary.
one Diphenylcarbazone
Reagent Powder Pillow
to the vial and mix.
161
SALINITY, continued
Summary of Method
The mercuric nitrate method of chloride analysis has become
popular due to the sharp yellow to pinkish-purple end point of
diphenylcarbazone. A single, stable powder has been developed,
combining the color indicator with an appropriate buffer to
establish the correct pH.
REQUIRED REAGENTS
Description
Unit
Cat. No.
REQUIRED APPARATUS
Vial, 2, 5, 10, 15, 20, 25-mL marks ............................................................each............ 2193-00
Syringe, 3 cc, Luer lock tip.........................................................................each.......... 43213-00
Demineralizer Assembly, 473 mL ..............................................................each.......... 21846-00
OPTIONAL APPARATUS
TitraStir Stir Plate, 115 Vac......................................................................each.......... 19400-00
TitraStir Stir Plate, 230 Vac......................................................................each.......... 19400-10
162
Method 8216
1. Select a sample
2. Insert a clean
4. Use a graduated
volume corresponding to
the expected sulfite
(SO32) concentration
from Table 1.
cylinder or pipet to
measure the sample
volume from Table 1.
Transfer the sample into
a clean 125-mL
Erlenmeyer flask. Dilute
to about the 50-mL mark
with deionized water.
Table 1
Range
(mg/L as SO32)
Sample
Volume (mL)
Titration
Cartridge
(N KIO3-KI)
Catalog
Number
Digit
Multiplier
Up to 160
100-400
200-800
>400
50
20
10
5
0.3998
0.3998
0.3998
0.3998
14961-01
14961-01
14961-01
14961-01
0.4
1.0
2.0
4.0
163
SULFITE, continued
8. Calculate:
Table 2
Form
Multiplier
1.01
1.30
1.19
1.58
Accuracy Check
Standard Additions Method
This accuracy check should be performed when interferences are
suspected or to verify analytical technique.
1. Snap the neck off a Sulfite Standard Solution Voluette
Ampule, 5,000 mg/L SO32.
164
SULFITE, continued
2. Use a TenSette Pipet to add 0.1 mL of standard to the
sample titrated in step 7. Resume titration back to the same
end point. Record the number of digits required.
3. Repeat, using additions of 0.2 and 0.3 mL, titrating to the end
point after each.
4. Each 0.1 mL addition of standard should require 25
additional digits of titrant. If these uniform increases do not
occur, refer to Appendix A, Accuracy Check and
Standard Additions.
A standard solution equivalent to 40 mg/L sulfite can be prepared
by diluting 10.0 mL of 0.025 N Sodium Thiosulfate Titrant to 250
mL in a volumetric flask. Titrate a 50 mL sample, using the
above procedure.
Interferences
Sulfide, organic matter and other oxidizable substances will cause
positive error in the titration. Nitrite will react with sulfite to
cause low results. Some metals, especially copper, catalyze the
oxidation of sulfite to sulfate. Addition of one Dissolved Oxygen
3 Powder Pillow per liter of sample immediately upon sampling
will help eliminate the effects of nitrite and copper.
Summary of Method
Sulfite ion is titrated with potassium iodate-iodide standard
solution under acidic conditions to a blue starch end point. The
volume of titrant used is proportional to the sulfite concentration.
REQUIRED REAGENTS
Sulfite Reagent Set (about 100 tests) ............................................................................22723-00
Includes: (1) 349-32, (1) 987-99, (1) 14961-01
Description
Unit
Cat. No.
165
SULFITE, continued
REQUIRED APPARATUS
Description
Unit
Cat. No.
OPTIONAL REAGENTS
Sodium Thiosulfate Standard Solution, 0.025 N .................................1000 mL.......... 24093-53
Sulfite Standard Solution, Voluette Ampules,
5,000 mg/L SO3 10 mL ....................................................................... 16/pkg.......... 14267-10
Sulfuric Acid Standard Solution, 19.2 N .................................... 100 mL MDB............ 2038-32
OPTIONAL APPARATUS
Bottle, wash poly, 500 mL ..........................................................................each.............. 620-11
Clamp, 2-prong, extension, 38 mm.............................................................each.......... 21145-00
Clamp Holder..............................................................................................each.............. 326-00
Demineralizer Assembly, 473 mL ..............................................................each.......... 21846-00
Delivery Tubes, with 180 hook ............................................................... 5/pkg.......... 17205-00
Delivery Tubes, 90 with hook ................................................................. 5/pkg.......... 41578-00
Flask, volumetric, Class B, 250 mL............................................................each.............. 547-46
Pipet, TenSette 0.1 to 1.0 mL ...................................................................each.......... 19700-01
Pipet Tips for 19700-01 TenSette Pipet................................................ 50/pkg.......... 21856-96
Pipet, volumetric, Class A, 5 mL................................................................each.......... 14515-37
Pipet, volumetric, Class A, 10 mL..............................................................each.......... 14515-38
Pipet, volumetric, Class A, 20 mL..............................................................each.......... 14515-20
Pipet, volumetric, Class A, 50 mL..............................................................each.......... 14515-41
Pipet Filler, safety bulb ...............................................................................each.......... 14651-00
Support Ring Stand.....................................................................................each.............. 563-00
TitraStir Stir Plate, 115 Vac......................................................................each.......... 19400-00
TitraStir Stir Plate, 230 Vac......................................................................each.......... 19400-10
Voluette Ampule Breaker Kit ...................................................................each.......... 21968-00
166
Method 8217
TURBIDITY STANDARDS
Preparing Turbidity-Free Water
Phase 1: Filtration Assembly
2. Using plastic
3. Cover the stem with
funnel stem to a
tweezers, position a 0.45 the filter housing.
1000-mL filtering flask. micron membrane filter
on top of the funnel
stem.
4. Attach a vacuum
of deionized water
through the filter funnel
and collect in a filter
flask. Remove vacuum
hose from sidearm and
turn off water.
167
See Table 1
Table 1
Formazin Standard
Concentration (NTU)
Number of Digits
Required
Flask Size
100
1000
50-mL
40
400
50-mL
10
100
50-mL
80
100-mL
168
Where:
Tw is the turbidity of the dilution water
Where:
TD = desired turbidity of the formazin standard
Tw = turbidity of the dilution water (this term may be dropped if it is
1% or less of the TD value)
V = volume of the flask in mL
169
Interferences
Because dirty or scratched glassware, air bubbles and color in a
sample will interfere with turbidity measurements, sample cells
must be scratch-free and samples should be colorless without
air bubbles.
Summary of Method
The measurement of turbidity is based on the scattering of light
by the suspended particles (clay, sand, bacteria) in solution. The
amount of light scattered at 90 to the incident light is directly
proportional to the turbidity.
Turbidity is measured in nephelometric turbidity units (NTUs).
These units of measurement are based on the amount of light
scattered by particles of a polymer reference standard called
170
REQUIRED REAGENTS
Description
Unit
Cat. No.
REQUIRED APPARATUS
Clippers, for opening pillows ..................................................................... each ..............968-00
Digital Titrator............................................................................................ each ..........16900-01
Filter Holder, 47 mm, magnetic base ......................................................... each ..........13529-00
Aspirator, vacuum pump, poly ................................................................... each ............2131-00
Filters, membrane, 0.45 microns...........................................................100/pkg ..........13530-00
Flask, filtering, 1000 mL............................................................................ each ..............546-53
Flask, volumetric, Class A, 50 mL............................................................. each ..........14574-41
Flask, volumetric, Class A, 100 mL........................................................... each ..........14574-42
Flask, volumetric, Class A, 500 mL........................................................... each ..........14574-49
Stopper, rubber, No. 7, one hole................................................................6/pkg ............2119-07
Tubing, rubber, 2.4 mm ID......................................................................... 12 ft ..............560-19
Tweezers, plastic ........................................................................................ each ..........14282-00
OPTIONAL APPARATUS
Bottle, wash poly, 500 mL ......................................................................... each ..............620-11
Clamp, 2-prong, extension, 38 mm ............................................................ each ..........21145-00
Clamp Holder ............................................................................................. each ..............326-00
Demineralizer Assembly, 473 mL.............................................................. each ..........21846-00
Delivery Tubes, with 180 hook................................................................5/pkg ..........17205-00
TitraStir Stir Plate, 115 Vac ..................................................................... each ..........19400-00
TitraStir Stir Plate, 230 Vac ..................................................................... each ..........19400-10
171
172
Method 8218
VOLATILE ACIDS
Using Sodium Hydroxide
2. Attach a clean
delivery tube to a
0.9274 N Sodium
Hydroxide titration
Note: Use the Volatile
Acids Procedure, Sample cartridge. Attach the
Distillation, accompanying cartridge to the titrator
body. See General
the General Purpose
Distillation Apparatus Set Description, Step-byor the distillation
Step, for assembly
procedure described in
instructions, if
Standard Methods for the
necessary.
Examination of Water and
Wastewater.
volume corresponding to
the expected volatile
acids concentration as
acetic acid from Table 1.
Using a graduated
cylinder, transfer the
Note: For added
distillate volume into a
convenience use the
clean 250-mL
TitraStir Stir Plate. See
General Description, Step Erlenmeyer flask and
3 in Step-by-Step.
dilute to about the
150-mL mark with
deionized water.
Table 1
Range
(mg/L as CH3COOH)
Volume
(mL)
Titration
Cartridge
(N NaOH)
Catalog
Number
Digit
Multiplier
100-400
200-800
600-2400
150
75
25
0.9274
0.9274
0.9274
14842-01
14842-01
14842-01
1
2
6
173
7. Calculate:
Digits Required x
Digits Multiplier =
mg/L Volatile Acids
(as acetic acid,
CH3COOH)
Note: Approximately 70%
of the volatile acids in the
sample will be found in the
distillate. This has been
accounted for in the
calculation.
Summary of Method
A sample acidified with sulfuric acid is distilled and the distillate
titrated to the phenolphthalein end point with sodium
hydroxide standard.
REQUIRED REAGENTS
Volatile Acids Reagent Set (about 100 tests) ............................................................... 24602-00
Includes: (1) 942-99, (1) 14842-01
Description
Unit
Cat. No.
REQUIRED APPARATUS
Cylinder, graduated, 250 mL ......................................................................each.............. 508-46
Digital Titrator ............................................................................................each.......... 16900-01
Flask, Erlenmeyer, 250 mL.........................................................................each.............. 505-46
174
175
176
APPENDIX A
ACCURACY CHECK AND STANDARD ADDITIONS
Most of the procedures in this manual have an accuracy check
based on the standard additions method. Standard additions is a
widely accepted technique for checking the validity of test
results. Also known as spiking and known additions, the
technique adds a small amount of the component (parameter)
being measured to an analyzed sample and the analysis is
repeated. The increase in the test results should equal the amount
of the standard added. The results can be used to check the
performance of the reagents, the apparatus, and the procedure.
APPENDIX A, continued
Figure 1
Decision Tree
No
Are
Interferences
Present?
Are
Interferences
Present?
No
Yes
Analysis
Is Correct
Do Multiple
Standard Additions
On DI Water Give
Correct Recovery?
No
No
Is the Procedure in
Use Correct?
Yes
Yes
Yes
Do Multiple Standard
Additions On Sample
Give Uniform Increments?
No
Use Correct
Procedure and
Repeat B
No
Yes
Analysis May
be Correct
Analysis
Is Incorrect
Yes
Yes
Repeat B with
New Reagents
Yes
Standards Defective
Repeat B with New
Standards
Repair/Replace
Instrument Apparatus
and Repeat B
178
APPENDIX A, continued
Branch B
Repeat the Accuracy Check given in the procedure substituting
the same volume of deionized water for the sample. For example,
using the Chloride Procedure, Silver Nitrate Method:
1. Take a 50.0-mL sample of deionized water and follow the
Chloride Procedure, Silver Nitrate Method. Record the
number of digits required for the titration.
2. Add 0.10 mL of Chloride Standard Solution, 12,500 mg/L,
and titrate to the end point. Record the number of digits
required for the titration.
3. Repeat, using two more additions of 0.1 mL of 12,500
chloride standard, titrating to the end point after each
addition. Record the number of digits required.
4. Tabulate the date as shown below:
Table 1
Total Standard
Added (mL)
Total Number
of Digits Used
Total Standard
Added (mg/L)
Total
Parameter
Found (mg/L)
0
0.1
0.2
0.3
______
______
______
______
0
______
______
______
______
______
______
______
179
APPENDIX A, continued
deionized water as used for the sample. The addition of standard
will not change the digit multiplier.
Performing the above procedure, the completed table would look
like this:
Table 2
Total Standard
Added (mL)
Total Number
of Digits Used
Total Standard
Added (mg/L)
Total
Parameter
Found (mg/L)
0
0.1
0.2
0.3
0
25
50
75
0
25
50
75
0
25
50
75
Second Addition
0.1 + 0.1 = 0.2 mL = Total Standard Added (mL)
APPENDIX A, continued
conclude the sample contains interferences which prevent the
test reagents from operating properly.
Total Number
of Digits Used
Total Standard
Added (mg/L)
Total
Parameter
Found (mg/L)
0
______
______
______
______
______
______
______
0
______
______
______
______
______
______
______
181
APPENDIX A, continued
G. If the results are not uniform (i.e., 13, 10, and 6 mg/L),
proceed to Branch F.
For example, a sample of water was analyzed for chloride with
the result being 100 mg/L. The analyst, suspecting interferences,
made one standard addition of 0.10 mL of 12,500-mg/L chloride
standard to 50.0 mL of sample. Rather than an increase of
25 mg/L as expected, the analyst found an increase of 13 mg/L.
The analyst added a second and third addition of 0.1 mL of
standard. The titrations were made and the results tabulated. The
increments were 10 (123 minus 113) and 6 (129 minus 123)
mg/L, respectively. The analyst proceeded to Branch F.
Table 4
Total Standard
Added (mL)
Total Number
of Digits Used
Total Standard
Added (mg/L)
Total
Parameter
Found (mg/L
0
0.1
0.2
0.3
100
113
123
129
0
25
50
75
100
113
123
129
Second Addition
0.1 + 0.1 = 0.2 mL = Total Standard Added (mL)
182
APPENDIX A, continued
Branch D
Carefully check the instructions or directions for use of the
procedure, making sure the proper techniques, reagents, titrant,
sample volume, and digit multiplier were used. Verify there is no
air or liquid, other than the titrant being used, in the delivery tube
by ejecting several drops of solution. If the procedure in use is
found to be in error, repeat Branch B using the correct procedure.
If the procedure is found to be correct, proceed to Branch E.
Branch E
Check the performance of the reagents. This may be done easily
by using a known standard solution to run the test or by obtaining
a new fresh lot of the reagent. A list of known standard solutions
is given in Table 1 on page 20. If it is determined reagents are
defective, repeat Branch B with new reagents. If the reagents are
proven in good condition, proceed with Branch H.
Branch F
Examples of non-uniform increments between standard additions
on a sample are shown below in Table 5, Table 6 and Figure 2 on
page 186. These plots illustrate the effect of interferences upon
the standard addition and upon substances in the sample. The
plots were made by graphing the Total Standard Added (mg/L) on
the X axis and the Total Parameter Found (mg/L) on the Y axis as
shown in Figure 2 on page 186.
Table 5 Plot A
Total Standard
Added (mL)
Total Number
of Digits Used
Total Standard
Added (mg/L)
Total
Parameter
Found (mg/L)
0
0.1
0.2
0.3
100
113
123
129
0
25
50
75
100
113
123
129
Table 6 Plot B
Total Standard
Added (mL)
Total Number
of Digits Used
Total Standard
Added (mg/L)
Total
Parameter
Found (mg/L)
0
0.1
0.2
0.3
0
25
50
75
0
25
50
75
0
0
25
50
183
APPENDIX A, continued
Both of these plots show that the four data points do not lie on a
straight line. Plot A illustrates an interference which becomes
progressively worse as the concentration of the standard
increases. This type of interference is not common and may be
caused by an error or malfunction of the procedure, reagents or
apparatus. Perform Branch B to ensure that the supposed
interference is present.
Plot B illustrates a common chemical interference which
becomes less or even zero as the concentration of the standard
increases. The plot shows the first standard addition was
consumed by the interference and the remaining additions gave
the correct increase of 25 mg/L for each additional 0.1 mL of
standard added. The apparent interference in Plot B could be the
result of an error made in the standard addition, and the analysis
should be repeated with a fresh portion of sample.
The two examples illustrate chemical interferences which most
certainly mean the result of the first analysis of the water sample
was incorrect. When this type of interference is encountered,
review the Interference section for the procedure for corrective
steps. If this fails, the analyst should attempt to analyze the
sample with an alternate method which, if possible, uses a
different type of chemistry.
Branch G
Examples of uniform increments between standard additions on a
sample are shown below in Table 7 and Table 8 on page 185.
These plots illustrate the effect of interferences upon the standard
addition and upon substances in the sample. The plots were made
by graphing the Total Standard Added (mg/L) on the X axis and
the Total Parameter Found (mg/L) on the Y axis as shown in
Figure 2 on page 186.
Table 7 Plot C
Total Standard
Added (mL)
Total Number
of Digits Used
Total Standard
Added (mg/L)
Total
Parameter
Found (mg/L)
0
0.1
0.2
0.3
50
63
75
88
0
25
50
75
50
63
75
88
184
APPENDIX A, continued
Plot C illustrates a common interference with a uniform effect
upon the standard and the substances in the sample. The four data
points form a straight line, but the titration increments between
the additions is not correct. The straight line between the
additions may be extrapolated back through the horizontal axis.
The point of intersect of the line with the horizontal axis gives a
more accurate estimate of the concentration of the substance in
question for the sample. In the example, the first analysis of the
sample gave 50 mg/L. The result located graphically (100 mg/L)
using the accuracy check should be much closer to the correct
result. Other interference effects may also be present, or
interferences may not be consistent in all samples. Use of another
method not subject to the interference, or elimination of the
interference is preferred over extrapolation or use of the percent
recovery calculation.
Apparent interferences also may be caused by errors in the
method, a defect in the apparatus or standards. Before assuming
the interference is chemical in nature, perform Branch B.
Table 8 Plot D
Total Standard
Added (mL)
Total Number
of Digits Used
Total Standard
Added (mg/L)
Total
Parameter
Found (mg/L)
0
0.1
0.2
0.3
0
25
50
75
0
25
50
75
0
25
50
75
Plot D illustrates correct results but may hide a problem for the
analyst. The increments found are uniform and the recovery of
the standard was complete. The result of the first analysis was 0
mg/L and the plot graphs back through 0 mg/L. If interfering
species are present, the interference may be sufficient to change
the sample result but not sufficient to prevent the analyst from
finding uniform increments and complete recovery of the
additions. This would be an uncommon situation and results are
probably correct unless unusual interferences are possible. Refer
to the Interferences section in the specific procedure.
185
APPENDIX A, continued
Figure 2
Multiple Standard Additions Graph
Branch H
Check operation of the apparatus used in the performance of the
test. Verify the correct volumes of sample and standard were
used. Check glassware used in the procedure, making sure that it
is scrupulously cleaned. Dirty pipets and graduated cylinders are
a source of contamination and will not deliver the correct volume.
If a defect is found in the apparatus, repeat Branch B after repair
or replacement of apparatus. If the apparatus is found to be in
good working order, proceed with Branch I.
Branch I
After demonstrating that the procedure, reagents, and apparatus
are correct and operating properly, the only possible cause for
standard additions not functioning properly in deionized water is
the standard used in performing the standard additions. Prepare or
obtain a new set of standards and repeat Branch B.
186
APPENDIX A, continued
Branch J
If the standard addition gave the correct result, the analyst must
then determine if interfering substances are present. If interfering
substances are not present, the result of the analysis prior to the
standard addition is correct. If interfering substances are present,
proceed to Branch C.
One of the greatest aids to the analyst is knowledge of the water
samples composition. An analyst need not know the exact
composition of each sample but should be aware of potential
interferences in the method of analysis to be used. When
performing a particular method, the analyst should know if those
interferences are present or not in order to have confidence in the
accuracy of the results. Once the interferences are known, the
Interference section of each procedure describes how to correct
for many common interferences.
If the correct result is obtained with one standard addition when
no interfering species are present, the chance of an error in
sample results is very small. Possible sources of error not
revealed include: sample quality, sample quantity (unless the
sample and standard volume used is equal), and inconsistent end
point determinations.
Call Hach Technical and Customer Support (1-800-227-4224)
for additional help.
187
188
GENERAL INFORMATION
189
190
Unit
Cat. No.
Digital Titrator including delivery tubes, manual, and case....................... each ..........16900-01
Delivery Tubes, 180 hook........................................................................5/pkg ..........17205-00
Case ............................................................................................................ each ..........46602-00
Digital Titrator Manual .............................................................................. each ..........16900-08
191
192
HOW TO ORDER
By Telephone:
By Mail:
Hach Company
P.O. Box 389
Loveland, CO 80539-0389
U.S.A.
Information Required
Billing address
Shipping address
Catalog number
Quantity
International Customers
Hach maintains a worldwide network of dealers and distributors.
To locate the representative nearest you, send E-mail to
intl@hach. com or contact:
In Canada, Latin America, Africa, Asia, Pacific Rim:
Telephone: (970) 669-3050; FAX: (970) 669-2932
In Europe, the Middle East, or Mediterranean Africa:
HACH Company, c/o
Dr. Bruno Lange GmbH
Willsttterstr. 11
D-40549 Dsseldorf
Germany
Telephone: +49/[0]211.52.88.0
Fax: +49/[0]211.52.88.231
193
REPAIR SERVICE
Authorization must be obtained from Hach Company before
sending any items for repair. Please contact the HACH Service
Center serving your location.
In the United States:
Hach Company
100 Dayton Avenue
Ames, Iowa 50010
(800) 227-4224 (U.S.A. only)
Telephone: (515) 232-2533
FAX: (515) 232-1276
In Canada:
Hach Sales & Service Canada Ltd.
1313 Border Street, Unit 34
Winnipeg, Manitoba
R3H 0X4
(800) 665-7635 (Canada only)
Telephone: (204) 632-5598
FAX: (204) 694-5134
E-mail: [email protected]
In Latin America, the Caribbean, the Far East, the
Indian Subcontinent, Africa, Europe, or the Middle East:
Hach Company World Headquarters
P.O. Box 389
Loveland, Colorado, 80539-0389
U.S.A.
Telephone: (970) 669-3050
FAX: (970) 669-2932
E-mail: [email protected]
194
WARRANTY
Hach warrants most products against defective materials or
workmanship for at least one year from the date of shipment;
longer warranties may apply to some items.
HACH WARRANTS TO THE ORIGINAL BUYER THAT HACH
PRODUCTS WILL CONFORM TO ANY EXPRESS WRITTEN
WARRANTY GIVEN BY HACH TO THE BUYER. EXCEPT AS
EXPRESSLY SET FORTH IN THE PRECEDING SENTENCE,
HACH MAKES NO WARRANTY OF ANY KIND WHATSOEVER
WITH RESPECT TO ANY PRODUCTS. HACH EXPRESSLY
DISCLAIMS ANY WARRANTIES IMPLIED BY LAW,
INCLUDING BUT NOT BINDING TO ANY WARRANTY OF
MERCHANTABILITY OR FITNESS FOR A PARTICULAR
PURPOSE.
LIMITATION OF REMEDIES: Hach shall, at its option, replace or
repair nonconforming products or refund all amounts paid by the
buyer. THIS IS THE EXCLUSIVE REMEDY FOR ANY BREACH
OF WARRANTY.
LIMITATION OF DAMAGES: IN NO EVENT SHALL HACH BE
LIABLE FOR ANY INCIDENTAL OR CONSEQUENTIAL
DAMAGES OF ANY KIND FOR BREACH OF ANY WARRANTY,
NEGLIGENCE, ON THE BASIS OF STRICT LIABILITY, OR
OTHERWISE.
195