Tip Log # 88

Applications Tip of the Week

Double Known Addition (DKA) Method

DKA is useful for the following situations:
 Small numbers of samples (no calibration required)
 Samples w/ concentrated backgrounds
 Samples w/ variable backgrounds
 When greater precision is desired (than direct readings)

Required conditions:
 An estimate of the sample concentration is known within an order of magnitude
 Complexing agents are absent or in excess (>1000x the ion of interest). If unknown, assume not present.
 Sample concentration is in the linear range (or pre-dose required)
 Minimize interferences by use of special reagents, where available.*

DKA Method Details

Double Known Addition Method (DKA) is the addition of two aliquots of standard to a sample, and from the
observed changes in potential, the slope and sample concentration are determined. DKA determines the
electrode slope directly in the sample, which results in greater accuracy for samples with complex matrices.
The Orion Dual Star meter has a meter function for DKA, which walks the user through the process and
automatically calculates sample results. Other Orion meters can be used for the DKA method using an excel
spreadsheet.

Testing by DKA on the Orion DUAL STARTM meter:

1. See the Orion Dual Star user guide for details to set up DKA testing. (Application Note Log #73
“Sodium in Potato Chips” can be used as an example).
2. Estimate the sample concentration.
3. Choose a standard solution, which is approximately 100 times the estimated sample concentration.
4. Accurately measure 100 mL of a prepared sample in the analysis beaker.
5. Add the ionic strength adjustor to the sample in ratio recommended by the electrode User Guide.
6. Place electrode and stirrer in the prepared sample.
7. Press the Start key to initiate the analysis.
8. Follow the directions on the meter screen to enter values:
 Sample volume = 100 mL
 Total volume = 100 mL + ISA mL
 Standard concentration
 First standard increment = 1 mL
 Second standard increment = 10 mL
9. When done, the result of the analysis and the electrode slope will be displayed. Press the Log/Print key
to print the result and save it in the Data Log.

.
* See Appendix (following) for more details and information.

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 Tip Log # 88

Appendix for DKA Method

Activity and Concentration: Ion selective electrodes (ISE) measure the activity of ions in solution. Activity
depends on the ionic strength (IS) of the solution and is virtually equivalent (close) to the concentration when
in very dilute solutions. In more concentrated solutions with high IS, the activity decreases and will differ
from the concentration. Differences in IS between standard and samples can cause errors in the ISE
measurement.

Use of ISA or Special ISA Reagent: To minimize this difference, an Ionic Strength Adjustor (IS A) solution
is added to samples and standard solutions before measurement, so that the IS is similar in all. In addition to
IS adjustment, ISA reagents can contain pH adjustors, decomplexing agents, or species that remove
interferences. Examples of special ISA’s are TISAB II (Orion 940909) for fluoride measurement, NISS
(Orion 930710) for nitrate analysis, CISA (Orion 941709) for chloride, SAOB (Orion 941609) for sulfide
analysis, and pH adjusting ISA (951211) for ammonia. Information about ISA for each electrode can be
found in the electrode User Guide.

Strong Sample Backgrounds: Most ISAs increase the IS to about 0.1M; however, this strength may not be
sufficient to match the background of samples with very high IS, such as seawater, brines, strong acids,
strong bases, foods, beverages, etc. and won’t give a uniform IS in samples and standards. Depending on the
composition and properties of the high ionic strength samples, certain measurement techniques are
recommended, such as DKA, sample dilution, etc. See Application Note Log 74 “Testing for Ions in Strong
Background Samples” for details.

Notes on Necessary Conditions for DKA analysis

 Complexing agents should be absent or in excess (at least 1000 times the sample species concentration).
o The ratio of free species to complexed species must remain constant throughout the additions
of standard.
o Indication that a complexing agent is present, but not in a great enough quantity to maintain a
constant free/complexed ratio, is an abnormally high or low slope. In this case, an excess of
complexing or decomplexing agent may be added to the sample prior to analysis.
o If you do not know whether complexing agents are present, assume that they are not present.
 Electrode interference should be minimized, because the effect of interference may change as the
concentration of species of interest changes.
o This may result in loss of precision, high, or low slope. Use of special ionic strength adjustors
that remove interference is recommended.
o See above section on special ISA reagents and consult the appropriate electrode user guide for
specific information.

Measurement Hints for Double Known Addition Method

1) Any sample size may be used depending on availability and expected sample concentration. If sample is
a liquid, recommended sample volume should be 100 mL or 50 mL. If the sample is a solid, dilute a
weight of 1-3 grams to a known volume with DI water.
2) The first standard addition should approximately double the initial sample concentration. For a 100 mL
sample size, this can be done by adding 1 mL of a standard that is about 100 times higher than the
expected sample concentration (or 0.5 mL for a 50 mL sample volume).
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 Tip Log # 88

Appendix for DKA Method (continued)

3) Alternately, calculate the volume of standard required to double the initial sample concentration using
this formula:

Vfi = (Csample * Vsample)/Cstandard,

Where:
o Vfi – volume of first increment, mL
o Csample – expected sample concentration
o Vsample – sample volume in the analysis beaker
o Cstandard – standard concentration.

For example, if your samples are estimated to be near 10 ppm, use a spiking solution about 100
times higher (e.g. 1000 ppm) and calculate the first standard addition as follows:

Vfi = (10 ppm sample * 100 mL sample) / 1000 ppm standard = 1 mL first addition

4) The volume of the second addition should be ten times the first spike, e.g. 10 mL, if first spike is 1 mL.
5) The total volume of the added standard should not be more than 11% of the initial sample volume to
avoid significant dilution effects.

Troubleshooting DKA Testing

 Use logged slope and mV values to troubleshoot DKA testing, if results are not as expected.
 If the first spike volume does double the concentration as expected, then the observed change in potential
from the initial reading will be about 16-18 mV for monovalent ions and about 8 – 9 mV for divalent
ions.
o If not, try adjusting the spike amount higher or lower to be closer to this range.
 The observed change in potential between the first and second spike should be about 46 mV for
monovalent ions and about 23 mV for divalent ions (if the first addition did about double the sample
concentration).
 If the calculated slope value is much higher or lower than expected, there may be interference.
o Spike a sample and run DKA on the spiked sample. Is the recovery of the spike as expected?
o If not, there may be an interference or a complexing agent present. See the electrode user
guide to determine appropriate methods for removing interference and for known complexing
and decomplexing agents.

This document and other WAI Application Tips of the Week can be found in the WAI Online Library at
http://www.revbase.com/tagteam/client/login.asp?dbid=1492. Select Type = “Application Notes” and browse.
Alternately, run search on keyword of interest.

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