EUTECH INSTRUMENTS CARBON DIOXIDE GAS User manual

Instruction Manual Carbon Dioxide Electrode
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EUTECH INSTRUMENTS PTE LTD.
INSTRUCTION MANUAL
CARBON DIOXIDE ION ELECTRODE

Instruction Manual Carbon Dioxide Electrode
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TABLE OF CONTENTS
GENERAL INSTRUCTIONS.........................................................................................................................................3
Introduction............................................................................................................................................................. 3
Required Equipment................................................................................................................................................3
Required Solutions.................................................................................................................................................. 3
GENERAL PREPARATION..........................................................................................................................................4
Electrode Preparation.............................................................................................................................................. 4
Checking Membrane ............................................................................................................................................... 4
Changing the Membrane......................................................................................................................................... 4
Connecting the Electrode to the Meter.................................................................................................................... 4
Electrode Slope Check (with pH/mV meter)........................................................................................................... 4
Electrode Slope Check (with ion meter) ................................................................................................................. 5
MEASUREMENT............................................................................................................................................................5
Measuring Hints...................................................................................................................................................... 5
Sample Storage........................................................................................................................................................ 6
Sample Requirements.............................................................................................................................................. 6
Units of Measurement............................................................................................................................................. 6
MEASUREMENT PROCEDURE.................................................................................................................................. 7
Direct Measurement................................................................................................................................................ 7
Direct Measurement of Carbon Dioxide (using a pH/mV meter) ........................................................................... 7
Direct Measurement of Carbon Dioxide (using an ion meter)................................................................................ 8
ELECTRODE CHARACTERISTICS ........................................................................................................................... 9
Reproducibility........................................................................................................................................................ 9
Interferences............................................................................................................................................................ 9
Effect of Dissolved Species..................................................................................................................................... 9
Temperature Influences........................................................................................................................................... 9
Electrode Response ............................................................................................................................................... 10
Limits of Detection................................................................................................................................................ 11
pH Effects.............................................................................................................................................................. 11
Electrode Life........................................................................................................................................................ 11
Electrode Storage .................................................................................................................................................. 11
ELECTRODE THEORY...............................................................................................................................................11
Electrode Operation............................................................................................................................................... 11
Carbon Dioxide Chemistry.................................................................................................................................... 12
ELECTRODE APPLICATION.................................................................................................................................... 13
Carbon Dioxide Content of Wines and Carbonated Beverages ............................................................................ 13
Carbonate Content in Groundwater....................................................................................................................... 14
Carbonate Measurements in Concentrated Ammonium Hydroxide...................................................................... 14
TROUBLESHOOTING GUIDE...................................................................................................................................15
Meter ..................................................................................................................................................................... 15
Glassware.............................................................................................................................................................. 15
Electrodes.............................................................................................................................................................. 15
Standards............................................................................................................................................................... 16
Sample................................................................................................................................................................... 16
Technique.............................................................................................................................................................. 16
TROUBLESHOOTING HINTS.................................................................................................................................... 17
Checking the Electrode Inner Body ...................................................................................................................... 19
SPECIFICATIONS........................................................................................................................................................ 20
ORDERING INFORMATION ..................................................................................................................................... 20

Instruction Manual Carbon Dioxide Electrode
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EUTECH INSTRUMENTS PTE LTD.
CARBON DIOXIDE GAS-SENSING ELECTRODE
INSTRUCTION MANUAL
GENERAL INSTRUCTIONS
Introduction
Eutech Carbon Dioxide Gas-Sensing Electrode is used to measure carbon dioxide, carbonate, and
bicarbonate in aqueous solutions quickly, simply, accurately, and economically. With a flow-
through cap, the electrode can be used in flow-through applications.
Required Equipment
1. A pH/mV meter or an ion meter, either line operated or portable.
2. Semi-logarithmic 4-cycle graph paper for preparing calibration curves when using the
meter in the mV mode.
3. A magnetic stirrer.
4. Eutech Carbon Dioxide Gas-sensing Electrode, Code no. EC-C02-01.
Required Solutions
1. Deionized or distilled water for solution preparation.
2. Eutech Carbon Dioxide Standard, 0.1M NaHCO3, Code no. EC-SCS-CO1-BT. To prepare
this solution from your own laboratory stock, half fill a 1 liter volumetric flask with
distilled water and add 8.40 grams of reagent-grade NaHCO3. Swirl the flask gently to
dissolve the solid. Fill the flask to the mark with distilled water, cap, and upend several
times to mix the solution.
3. Eutech Carbon Dioxide Standard, 1,000 ppm NaHCO3as CO2, Code no. EC-SCS-CO2-
BT. To prepare this solution from your own laboratory stock, half fill a one liter
volumetric flask with distilled water and add 1.91 grams of reagent-grade NaHCO3. Swirl
the flask gently to dissolve the solid. Fill the flask to the mark with distilled water, cap, and
upend several times to mix the solution.
4. Eutech Carbon Dioxide Standard, 100 ppm NaHCO3as CaCO3, Code no. EC-SCS-CO3-
BT. To prepare this solution from your own laboratory stock, half fill a one liter volumetric
flask with distilled water and add 0.084 grams of reagent-grade NaHCO3. Swirl the flask
gently to dissolve the solid. Fill the flask to the mark with distilled water, cap, and upend
several times to mix the solution.
5. Eutech Carbon Dioxide Buffer Solution, Code no. EC-ISA-CO1-BT. To prepare this
solution from your own laboratory stock, half fill a 1 liter volumetric flask with distilled

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water, add 294 grams of Na3C6H5O7.2H2O (sodium citrate dihydrate). Swirl the flask
gently to dissolve the solid. Fill the flask to the mark with distilled water. Stir the solution
and adjust the pH of the solution to 4.5 with concentrated HCl. This buffer is used to adjust
the pH of the solution to the operating range of the electrode. To each 100 ml of sample
and standard solution, add 10 ml of carbon dioxide buffer.
GENERAL PREPARATION
Electrode Preparation
This electrode is shipped dry. Before using, unscrew the large cap (See Figure 5), and remove the
inner glass electrode from the outer body. Fill the outer body with 2 to 3 ml of internal filling
solution. Place inner glass electrode into the outer body, and screw on the large cap until finger
tight. Place the assembled electrode in an electrode holder with a 20oangle from the vertical to
avoid trapping air bubbles at the bottom of the electrode.
Checking Membrane
A small hole of any size on the membrane or breakage of the membrane causes failure of the
electrode. It is recommended to check the membrane on every newly assembled electrode.
1. Connect a newly assembled electrode to a pH/mV meter.
2. Lower the electrode tip in distilled water.
3. Record the reading after stirring the distilled water for about 15 minutes.
4. Add proper buffer solution (see section Required Solutions) to the distilled water. A
drastic change in the reading in a positive direction indicates damage of the membrane.
Changing the Membrane
Unscrew the small cap from the outer body and remove the old membrane cartridge from the small
cap. Insert the new membrane cartridge into place, and re-assemble the electrode. (See Figure 4.)
Connecting the Electrode to the Meter
Connect the electrode to the meter according to the meter manufacturer's instructions. No external
reference electrode is required. To prevent air entrapment, mount the electrode at a 20oangle from
the vertical.
Electrode Slope Check (with pH/mV meter)
(Check electrodes each day)
1. To a clean, dry, 150 ml beaker, add 90 ml of distilled water and 10 ml of carbon dioxide
buffer. Place the beaker on a magnetic stirrer and begin stirring at a constant rate. After
assuring that the meter is in the millivolt mode, lower the electrode tip into the solution.
Remove air bubbles by redipping probe.

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2. Using a pipet, add 1 ml of 0.1M or 1,000 ppm standard into the solution. When the reading
has stabilized, record the mV value.
3. Using a pipet, add 10 ml of the same CO2 standard used above to the beaker. When the
reading has stabilized, record the mV value.
4. Determine the difference between the two readings. The electrode is operating correctly if
a difference of 56 ±3 mV is found, assuming the solution temperature is between 20o and
25oC. See the TROUBLESHOOTING section, if the change in potential is not within this
range.
Slope is defined as the change in potential observed when the concentration changes by a factor of
10.
Electrode Slope Check (with ion meter)
(Check electrodes each day)
1. Prepare standard carbon dioxide solutions whose concentrations vary by tenfold. Use
either the 0.1M or 1,000 ppm carbon dioxide standard. Use the serial dilution method for
this preparation.
2. To a 150 ml beaker, add 100 ml of the lower value standard and 1 ml of ISA. Place the
beaker on the magnetic stirrer and begin stirring at a constant rate. Lower the electrode tips
into the solution. Assure that the meter is in the concentration mode.
3. Adjust the meter to the concentration of the standard and fix the value in the memory
according to the meter manufacturer's instructions. Rinse the electrodes with distilled water
and blot dry.
4. To another 150 ml beaker, add 100 ml of the higher value standard and 2 ml of ISA. Place
the beaker on the magnetic stirrer and begin stirring at a constant rate. Lower the electrode
tips into the solution.
5. Adjust the meter to the concentration of the standard and fix the value in the memory.
Read the electrode slope according to the meter manufacturer's instructions. Correct
electrode operation is indicated by a slope of 90-100%. See the TROUBLESHOOTING
section if the slope is not within this range.
MEASUREMENT
Measuring Hints
Samples should be measured immediately after collection. Samples should be stored according to
the directions given in Sample Storage if immediate measurement is not possible.
The ratio of surface area to volume in the beaker should be minimized. Beakers containing the
samples or the standard should be kept covered between measurements.
Carbon dioxide buffer should be added just before measurement.

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All samples and standards should be at the same temperature for precise measurement. A difference
of 1oC in temperature will result in approximately a 2% error. All samples must be aqueous.
Always rinse the electrode with distilled water and blot dry between measurements. Use a clean,
dry tissue to prevent cross-contamination.
Constant but not violent, stirring is necessary for accurate measurement. Magnetic stirrers can
generate sufficient heat to change the solution temperature. To counteract this effect, place a piece
of insulating material, such as gauze or styrofoam, between the stirrer and the beaker.
Always check to see that the membrane is free from air bubbles after immersion into standard or
sample.
Sample Storage
Samples should be measured immediately after preparation or collection, if possible. Wait only long
enough for temperature equilibration between the sample and the electrode. At 25oC, in an open
150 ml beaker, carbon dioxide diffuses out of an acidic solution at a rate of about 3% per minute
with stirring and at a rate of about 0.5% per minute without stirring. The loss of CO2increases with
increasing temperature.
If the samples cannot be measured immediately, add 10M NaOH to make them slightly alkaline (pH
8-9) and store them in tightly capped vessels to prevent infusion of CO2from the air. The amount of
10M NaOH needed to adjust the pH to the alkaline range will depend on the sample's buffering
capacity and the initial pH of the sample. If the samples contain less than 100 ppm CO2, collect in a
stoppered glass bottle, filling completely and capping tightly to prevent CO2from escaping. Do not
add NaOH, since carbonate is usually present in the base as a contaminant. If the sample contains
more than 100 ppm CO2, is slightly acidic and un-buffered, adding 1 ml of 10M NaOH per 100 ml
of sample will suffice. Prior to measurement, acidify these stored samples with carbon dioxide
buffer.
Sample Requirements
Carbon dioxide buffer must be added to standards and samples before measurement. When the
buffer solution is added, all standards and samples should be in the range of pH 4.8 to 5.2. In this
range, all bicarbonate and carbonate species are converted to carbon dioxide and all interferences
are minimized. Highly basic, highly acidic, or buffered samples must be adjusted to pH 4.8 to 5.2
before the carbon dioxide buffer is added, since the buffering capacity of the acid buffer is limited.
Adding the buffer solution adjusts the total level of dissolved species in solution to 0.4M. The
sample should be diluted before measurement if the total level of dissolved species is greater than
1M after the addition of the carbon dioxide buffer. For a further explanation, see the section entitled
Effect of Dissolved Species.
Units of Measurement
Measurement of carbon dioxide can be expressed in units of moles/liter, ppm carbon dioxide, ppm
calcium carbonate, or other convenient concentration unit. Table 1 lists conversion units.
TABLE 1: Concentration Unit Conversion Factors
moles/liter ppm CO2ppm CaCO3

Instruction Manual Carbon Dioxide Electrode
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10-2 440.0 1,000.0
10-3 44.0 100.0
10-4 4.4 10.0
MEASUREMENT PROCEDURE
Direct Measurement
Direct measurement is a simple procedure for measuring a large number of samples. A single meter
reading is all that is required for each sample. The ionic strength of samples and standards should
be made the same by adjustment with ISA for all carbon dioxide solutions. The temperature of both
sample solutions and standard solutions should be the same.
Direct Measurement of Carbon Dioxide (using a pH/mV meter)
1. By serial dilution, prepare three standard solutions from the 0.1M or 1,000 ppm stock
standard. The resultant concentrations should be 10-2M, 10-3M, and 10-4M or 1,000 ppm,
100 ppm, and 10 ppm.
2. Place 100 ml of the 10-4M (10 ppm) standard into a 150 ml beaker on the magnetic stirrer,
add 10 ml of carbon dioxide buffer, and begin stirring at a constant rate. After assuring that
the meter is in the mV mode, lower the electrode tip into the solution. After the reading has
stabilized, record the mV reading.
3. Place 100 ml of the 10-3M (100 ppm) standard into a 150 ml beaker on the magnetic
stirrer, add 10 ml of carbon dioxide buffer, and begin stirring at a constant rate. After
rinsing the electrode with distilled water, blot dry, and immerse the tip in the solution.
After the reading has stabilized, record the mV value.
4. Place 100 ml of the 10-2M (1,000 ppm) standard into a 150 ml beaker on the magnetic
stirrer, add 10 ml of carbon dioxide buffer, and begin stirring at a constant rate. After
rinsing the electrode with distilled water, blot dry, and immerse the tip in the solution.
After the reading has stabilized record the mV value.
5. Using the semi-logarithmic graph paper, plot the mV reading (linear axis) against the
concentration (log axis). A typical calibration curve appears in Figure 1.

Instruction Manual Carbon Dioxide Electrode
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A calibration curve is constructed on semi-logarithmic paper when using
the pH/mV meter in the millivolt mode. The measured electrode potential
in mV (linear axis) is plotted against the standard concentration (log axis).
In the linear region of the curve, only three standards are necessary to
determine a calibration curve. In the non-linear region, additional points
must be measured. The direct measurement procedures given are for the
linear portion of the curve.
6. To a clean, dry, 150 ml beaker add 100 ml of sample and add 10 ml of carbon dioxide
buffer. Place the beaker on the magnetic stirrer and begin stirring. Rinse the electrode with
distilled water, blot dry, and lower the tip in the solution. When the reading has stabilized
record the mV value. Using the calibration curve, determine the sample concentration.
7. The calibration should be checked every 1-2 hours. Assuming no change in ambient
temperature, place the electrode tips in the mid-range standard. After the reading has
stabilized, compare it to the original reading recorded in Step 3 above. A reading differing
by more than 0.5 mV or a change in the ambient temperature will necessitate the repetition
of Steps 2-5 above. A new calibration curve should be prepared daily.
Direct Measurement of Carbon Dioxide (using an ion meter)
1. By serial dilution of the 0.1M or the 1,000 ppm standards, prepare two standards whose
concentration is near the expected sample concentration. Add 10 ml of carbon dioxide
buffer to each 100 ml of standard. When calibrating, assume that the added buffer has no
effect on the standard concentration.
2. Place the more dilute standard on the magnetic stirrer and begin stirring at a constant rate.
Assure that the meter is in the concentration mode. Lower the electrode tip into the
solution.
3. Adjust the meter to the concentration of the CO2standard and fix the value in the memory
according to the meter manufacturer's instructions after stabilization of the reading.
4. Rinse the electrode with distilled water and blot dry. Place the more concentrated standard
on the magnetic stirrer and begin stirring at a constant rate.
5. Lower the electrode tip into the solution. Adjust the meter to the concentration of the
carbon dioxide standard and fix the value in the memory according to the meter
manufacturer's instructions after stabilization of the reading.
6. After rinsing the electrode and blotting dry, place the electrode tip into 100 ml of the
sample and 10 ml of carbon dioxide buffer. After stabilization, read the concentration
directly from the meter display.
7. The calibration should be checked every 2 hours. Assuming no change in ambient
temperature, place the electrode tip in the first carbon dioxide standard. After the reading
has stabilized, compare it to the original reading in Step 4 above. A reading differing by
more than 0.5 mV or a change in ambient temperature will necessitate the repetition of
Step 2-8 above. The meter should be re-calibrated daily.

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ELECTRODE CHARACTERISTICS
Reproducibility
Electrode measurements reproducible to ±2% can be obtained if the electrode is calibrated every
hour. Factors like temperature fluctuation, drift, and noise limit reproducibility. Reproducibility is
independent of concentration within the electrode's operating range.
Interferences
Certain volatile weak acids are potential electrode interferences. Concentrations of these interfering
species that cause a 10% error at 10-3M CO2 (100 ppm CaCO3or 44 ppm CO2), at pH 4 and 5, are
listed in Table 2.
TABLE 2: Interference Levels - 10% Error at 10-3M CO2
Interferences pH 4 pH 5
HCOOH
(formic acid) 7.5 x 10-3M
(345 ppm) 2.0 x 10-2M (1,840 ppm)
CH3COOH
(acetic acid) 3.6 x 10-3M (216 ppm) 6.2 x 10-3M (372 ppm)
HSO3-(SO2)
(sulfur dioxide) 7.5 x 10-4M (48 ppm) 5.0 x 10-3M (320 ppm)
NO2-(NO2)
(nitrogen dioxide) 5.3 x 10-4M (24 ppm) 3.5 x 10-3M (160 ppm)
Effect of Dissolved Species
One common substance that is a potential electrode interference is water vapor. The concentration
of the internal filling solution under the membrane is changed when water, in the form of water
vapor, moves across the electrode membrane. These changes will be seen as electrode drift. If the
total level of dissolved species in solution - the osmotic strength - is approximately equal to that of
the internal filling solution and the sample and electrode temperatures are the same, water vapor
transport is not a problem.
Samples of low osmotic strength are automatically adjusted to the correct level through addition of
carbon dioxide buffer. If samples have osmotic strengths greater than 1M, they should be diluted
before measurement. However, this dilution should not reduce the carbon dioxide level below 10-
4M. If dilution is not possible, for the reason mentioned, the sample can be measured by adjusting
the osmotic strength of the electrode filling solution. The total level of dissolved species in the
electrode filling solution may be adjusted by adding 0.425 grams of reagent-grade sodium nitrate
(NaNO3) to 10 ml of electrode filling solution.
Temperature Influences
Samples and standards should be within ±1oC of each other, since electrode potentials are
influenced by changes in temperature. Because of solubility equilibrium on which the electrode
depends, the absolute potential of the reference electrode changes slowly with temperature. The
slope of the electrode, as indicated by the factor "S" in the Nernst equation, also varies with

Instruction Manual Carbon Dioxide Electrode
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temperature. Table 3 gives values for the "S" factor in the Nernst equation for the carbon dioxide
ion. Gases are expelled from a solution at a faster rate as the temperature increases.
TABLE 3: Temperature vs. Values for the Electrode Slope
Temp.(oC) "S"
0 54.20
5 55.20
10 56.18
15 57.17
20 58.16
25 59.16
30 60.15
35 61.14
40 62.13
Electrode Response
Plotting the electrode mV potential against the carbon dioxide concentration on semi-logarithmic
paper results in a straight line with a slope of about 56 mV per decade over the range 1X10-4M to
1X10-2M. (Refer to Figure 1.)
For carbon dioxide concentrations above 1X10-4M, the electrode exhibits good time response (95%
of total mV reading in two minutes or less). Response times are longer below this value and carbon
dioxide loss to air may become a source of error. Samples above 1X10-2M must be diluted before
measurement. Figure 2 indicates the time response of the carbon dioxide electrode to changes in the
carbon dioxide concentration.

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Limits of Detection
The upper limit of detection in pure carbon dioxide solutions is 1X10-2M. Carbon dioxide is rapidly
lost to the air above a concentration of 1X10-2M. Dilution may be used if carbon dioxide
concentrations are above 1M. Also dilute samples between 1M and 10-2M or calibrate the electrode
at 4 or 5 intermediate points.
The lower limit of detection is around 1X10-4M. Refer to Figure 1 for a comparison of the
theoretical response to the actual response at low levels of carbon dioxide. Carbon dioxide
measurements below 10-4M CO2should employ low level procedures.
pH Effects
The carbon dioxide electrode can be used over the pH range 4.8 to 5.2. It is necessary to adjust the
sample pH using the recommended ISA to convert all carbonate and bicarbonate species in solution
to carbon dioxide.
Electrode Life
A carbon dioxide gas-sensing electrode will last six months in normal laboratory use. On-line
measurements might shorten operational lifetime to several months. In time, the response time will
increase and the calibration slope will decrease to the point calibration is difficult and membrane
replacement is required.
Electrode Storage
If storing the carbon dioxide electrode overnight or over the weekend, immerse the tip of the
electrode in the 0.1M NaCl storage solution. For longer periods of time, completely disassemble the
electrode, rinse the inner body, the outer body, and the cap with distilled water. After drying,
reassemble the electrode without filling solution.
ELECTRODE THEORY
Electrode Operation
A gas-permeable membrane is used to separate the sample solution from the electrode's internal
filling solution in the Eutech Carbon Dioxide Gas-Sensing Electrode. Dissolved carbon dioxide in
the sample solution permeates the membrane until an equilibrium is reached between the partial
pressure of the CO2in the internal filling solution and the partial pressure of the CO2in the sample
solution. The partial pressure of carbon dioxide in any given sample will be proportional to the
concentration of carbon dioxide.
Diffusion across the membrane affects the level of hydrogen ions in the internal filling solution:
CO2 + H2O ⇔H++ HCO3-
The relationship between the hydrogen ion, the bicarbonate ion, carbon dioxide, and water is given
by the equation:

Instruction Manual Carbon Dioxide Electrode
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[H+] [HCO3-]
⎯⎯⎯⎯⎯⎯⎯ = constant
[CO2]
The bicarbonate ion level can be considered constant since the internal filling solution contains a
high level of sodium bicarbonate:
[H
+] = [CO2] X constant
The electrode sensing element's potential, with respect to the internal reference element, varies in a
Nernstian manner with changes in the hydrogen level.
The Nernstian equation shows the relationship between the potential of the pH internal element and
the hydrogen ion concentration:
E=E
o+ S log [H+]
where:
E = measured electrode potential
Eo= reference potential (a constant)
[H+] = hydrogen ion concentration
S = electrode slope (~56mV/decade)
Because the hydrogen ion concentration is directly related to the carbon dioxide concentration,
electrode response to carbon dioxide is also Nernstian:
E=E
1+ S log [CO2]
Carbon Dioxide Chemistry
Carbon dioxide exists as bicarbonate and carbonate in basic solutions:
CO2+ OH-⇒HCO3-
CO2+ 2OH-⇔CO3-2 + H2O
The solution's pH governs the amount of carbon dioxide present in the form of carbonate and
bicarbonate ions. At a pH of 5, essentially all the carbon dioxide in solution is in the CO2form.
The pH is held between 4.8 and 5.2 by the carbon dioxide buffer used in carbon dioxide
determinations and converts the carbonate and bicarbonate to the CO2form:
2H++ CO3-2 ⇒H2O + CO2
H+ + HCO3- ⇔H2O + CO2
The total amount of carbon dioxide, carbonate, and bicarbonate is then measurable in the solution.

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ELECTRODE APPLICATION
Carbon Dioxide Content of Wines and Carbonated Beverages
Wines and carbonated beverages have a high (greater than 2X10-2M or 880 ppm) carbon dioxide
concentration. As a result, samples are measured after dilution. When samples are collected, they
must be made basic immediately or CO2will escape into the atmosphere (see Sample Storage
section). After diluting the sample, it must be acidified with carbon dioxide buffer. The carbon
dioxide concentration is determined by direct measurement (see MEASUREMENT section). Finally,
the original carbon dioxide concentration is calculated, taking the dilution factor into account.
The required equipment and solutions are found in Required Equipment and Required Solutions.
In addition, pH Adjustment Solution, 10M NaOH, is required.
To measure a sample:
1. Calibrate the meter according to the directions in the MEASUREMENT section.
2. Add enough 10M NaOH solution to adjust the pH of the sample above 10
immediately when the sample container is opened.
3. To a 100 ml volumetric flask, quantitatively transfer 10 ml of the alkaline sample to
the flask and fill to the mark with distilled water. After agitating the flask to mix the
contents, transfer the solution to a 150 ml beaker.
4. Place the beaker on the magnetic stirrer and begin stirring at a constant rate. Add 10
ml of carbon dioxide buffer. Lower the tip of the electrode in the solution. Record
the mV reading when stable. Determine the measured concentration from the
calibration curve.
5. Using the following formula, determine the carbon dioxide sample concentration:
Vs+ VNaOH
C
s= 10 X ——————— X Cm
Vs
where: Cs= sample concentration
Vs= sample volume before adding NaOH
VNaOH = volume of NaOH added to sample
Cm= measured concentration
Example: Assume 12 ml of 10M NaOH was added to 360 ml of sample. The total volume would
then be 372 ml. Add 10 ml of this mixture to a 100 ml volumetric flask. Dilute to the mark with
distilled water. By taking into account the addition of base to the sample and the sample dilution,
the measured concentration is related to the actual sample concentration:
Cs= 10 X 360+12 Cm
360
Cs= 10.33 Cm

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Carbonate Content in Groundwater
Free CO2, bicarbonate, and carbonate - the total amount of carbonate - in ground water or seawater,
will depend on location, temperature, depth, and pH. Using the measurement procedure in the
MEASUREMENT section, the carbonate level in groundwater or seawater can be measured. Grab
samples taken in the field or ocean can be preserved for laboratory testing by following the
procedures given in the Sample Storage section.
Carbonate Measurements in Concentrated Ammonium Hydroxide
Since carbon dioxide is easily absorbed by highly basic solutions, concentrated ammonium
hydroxide often contains carbonate as an impurity. By a variation of the direct measurement
procedure, the amount of carbonate in concentrated ammonium hydroxide can be measured. By
adding increments of a 10,000 ppm standard to an acid reagent, a calibration curve is constructed,
the sample concentration is determined from the calibration curve, taking the dilution factor into
account.
The required equipment is found in the Required Equipment section. You will also need a 1 ml
graduated pipet and a 10 ml pipet.
In addition to the solutions found in the Required Solutions section prepare the following:
1. A standard solution of 10,000 ppm carbonate, CO3-2. To prepare this solution from your
own laboratory stock, half fill a one liter volumetric flask with distilled water, add 14.0
grams of reagent-grade sodium bicarbonate (NaHCO3). Swirl the flask to dissolve the
solid. Fill to the mark with distilled water, cap, and upend several times to mix the
solution.
2. 3M sulfuric acid reagent. To prepare this solution from your own laboratory stock, add
approximately 500 ml of distilled water to a one liter volumetric flask. Using a hood and
protective safety equipment and extreme caution, add 167 ml of concentrated sulfuric acid
(18M H2SO4) to the flask. Swirl the flask slowly after small additions to mix the acid and
dissipate the heat. Finally, add remaining distilled water to the mark. Allow the solution to
cool to room temperature. Upend the stoppered flask several times to mix the solution.
To measure a sample:
1. To a clean, dry 150 ml beaker, add 100 ml of 3 M sulfuric acid to a 150 ml beaker. Place
the beaker on the magnetic stirrer and begin stirring at a constant rate. Lower the electrode
tip in the solution. Add the standard solution (10,000 ppm), using the steps given in Table
4 below. Record the mV reading after each addition. Plot the concentration (log axis)
against the mV potential (linear axis) on semi-logarithmic paper. The plotted concentration
is eleven times the actual concentration due to sample dilution.
2. To another 150 ml beaker, add 100 ml of the acid reagent. Place the beaker on the
magnetic stirrer and begin stirring at a constant rate. Lower the tip of the electrode in the
solution. Add 10 ml of the sample to the beaker and record the mV reading. Determine the
concentration from the calibration curve.

Instruction Manual Carbon Dioxide Electrode
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TABLE 4: Step-wise Calibration for Measurement
Step Pipet Added Volume Concentration
1 A 0.1 ml 109.9 ppm
2 A 0.9 ml 1,089 ppm
3 B 10.0 ml 10,900 ppm
A = 1 ml graduated pipet; B = 10 ml volumetric pipet
TROUBLESHOOTING GUIDE
The goal of troubleshooting is the isolation of a problem through checking each of the system
components in turn: the meter, the glassware, the electrodes, the standards, the sample, and the
technique.
Meter
The meter is the easiest component to eliminate as a possible cause of error. Most meters are
provided with an instrument check-out procedure in the instruction manual and a shorting strap for
convenience in troubleshooting. Consult the manual for complete instructions and verify that the
instrument operates as indicated and is stable in all steps.
Glassware
Clean glassware is essential for good measurement. Be sure to wash the glassware well with a mild
detergent and rinse very well with distilled or deionized water. Clean glassware will drain without
leaving water droplets behind.
Electrodes
The electrodes may be checked by using the procedure found in the sections entitled Electrode
Slope Check.
1. Be sure to use distilled or deionized water when following the procedures given in
Electrode Slope Check.
2. If the electrode fails to response as expected, see the sections Measuring Hints and
Electrode Response. Repeat the slope check.
3. If the electrode still does not perform as described, determine whether the carbon dioxide
inner body is working properly as directed in Checking the Electrode Inner Body.
4. If the stability and the slope check out properly, but measurement problems persist, the
standards may be of poor quality, the sample may contain interferences or the technique
may be in error. (See Standard, Sample and Technique sections below.)
5. Before replacing a "faulty" electrode, review the instruction manual and be sure to:
- Clean and rinse the electrode thoroughly.
- Prepare the electrode properly.
- Use proper filling solution, buffer, and standards.
- Measure correctly and accurately.
- Review TROUBLESHOOTING HINTS.

Instruction Manual Carbon Dioxide Electrode
16
Standards
The quality of results depends greatly upon the quality of the standards. ALWAYS prepare fresh
standards when problems arise. It could save hours of frustrating troubleshooting! Error may result
from contamination of prepared standards, accuracy of dilution, quality of distilled water, or a
mathematical error in calculating the concentrations.
The best method for preparation of standards is by serial dilution. This means that an initial
standard is diluted, using volumetric glassware, to prepare a second standard solution. The second
is similarly diluted to prepare a third standard, and so on, until the desired range of standards has
been prepared.
Sample
If the electrode works properly in standards but not in sample, look for possible interferences,
complexing agents, or substances which could affect response or physically damage the sensing
electrode or the reference electrode. If possible, determine the composition of the samples and
check for problems. See Sample Requirements and Interferences.
Technique
Be sure that the electrode's limit of detection has not been exceeded. Be sure that the analysis
method is clearly understood and is compatible with the sample.
Refer to the instruction manual again. Reread sections on GENERAL PREPARATION and
ELECTRODE CHARACTERISTICS.
If trouble still persists, call Eutech Instruments Pte Ltd. at (65) 6778-6876 and ask for the Customer
Services Department.

Instruction Manual Carbon Dioxide Electrode
17
TROUBLESHOOTING HINTS
Symptom Possible Causes Next Step
Out of Range defective meter perform meter checkout
Reading procedure (see meter
instructionmanual)
defective inner body refer to Checking the
Electrode Inner Body
electrode not unplug electrode and reset
plugged in properly
internal filling fill outer body of electrode
solution not added with proper amount of
internal filling solution
air bubble on membrane remove bubble by
re-dipping electrode
electrode not in solution put electrode in solution
Noisy or Unstable insufficient internal fill outer body of electrode
Reading (readings filling solution with proper amount of
continuously or internal filling solution
random changing.)
defective meter perform meter checkout
procedure (see meter
instruction manual)
bottom cap loose ensure that bottom cap is
screwed on tight enough
to close gap between
bottom cap and body
defective inner body refer to Checking the
Electrode Inner Body
air bubbles on membrane remove bubbles by
redipping electrode
meter or stirrer check meter and stirrer
improperly grounded for grounding
Drift (reading slowly internal filling solution ensure that membrane is
changing in one leakage installed properly
direction)

Instruction Manual Carbon Dioxide Electrode
18
incorrect internal filling refill outer body of electrode
solution using filling solution shipped
with electrode
total sample level dilute sample of dissolved
species above 1M
electrode in sample reduce surface area-to-
too long; CO2loss volume ratio, slow down rate
of stirring, avoid high
temperatures
membrane failure replace membrane
(wet, perforation, discoloration)
samples and standards allow samples and standards
not at constant to come to room temperature
temperature before use
heat generated by place insulating material
magnetic stirrer between stirrer and beaker
defective inner body refer to Checking the
Electrode Inner Body
electrode exposed to hold electrode by outer body
air for extended period and pull on electrode cable.
Internal filling solution will
flow under membrane and
restore electrode response
Low Slope or No Slope standards contaminated prepare fresh standards
or incorrectly made
buffer not used use recommended buffer
standard used as use buffer
buffer
electrode exposed hold electrode by outer body
to air for extended and pull on electrode cable.
period Internal filling solution will
flow under membrane and
restore electrode response
membrane failure replace membrane
(wet, perforation, discoloration)
defective inner body refer to Checking the
Electrode Inner Body

Instruction Manual Carbon Dioxide Electrode
19
"Incorrect Answer" incorrect scaling plot millivolts on the linear
(but calibration of semi-log paper axis. On the log axis, be sure
curve is good) concentration numbers within
each decade are increasing
with increasing concentration
incorrect sign be sure to note sign of millivolt
value correctly
incorrect standards prepare fresh standards
wrong units used apply correct conversion factor:
10-3M = 44 ppm as
CO2= 100 ppm as CaCO3
buffer added to add same standards
standards and not proportions of
samples buffer to standards and samples
sample carryover rinse electrodes thoroughly
between samples
Checking the Electrode Inner Body
If the electrode slope is found to be low during operation, the following solutions will be necessary
to check the inner body:
- pH 4 Buffer (0.1M NaCl added)
Add 2.9 grams of reagent-grade NaCl to 500 ml of pH 4 buffer. Dissolve the solid. The solution
may be stored for repeated use.
- pH 7 Buffer (0.1M NaCl added)
Add 2.9 grams of reagent-grade NaCl to 500 ml of pH 7 buffer. Dissolve the solid. The solution
may be stored for repeated use.
Disassemble the carbon dioxide electrode. If the electrode is dry, soak the glass tip of the inner
body in Eutech Carbon Dioxide Electrode Filling Solution, Code No. EC-ISA-CO1 for two hours.
Rinse the electrode thoroughly with distilled water. Put 100 ml of pH 7 buffer (0.1M NaCl added)
in a 150 ml beaker. Place the beaker on the magnetic stirrer, and begin stirring. Immerse the tip of
the inner body in the solution so that the reference element is covered. Make sure that the meter is
in the mV mode. Record the meter reading when stable.
Rinse the inner body thoroughly in distilled water. Put 100 ml of pH 4 buffer (0.1M NaCl added) in
a 150 ml beaker, place the beaker on the magnetic stirrer, and begin stirring. Immerse the tip of the
inner body in the solution so that the reference element is covered. Observe the change in the meter
reading carefully. In less than 30 seconds after immersion, the reading should change 100 mV. The
meter reading should stabilize in 3-4 minutes, with a difference greater than 150 mV if the inner
body sensing elements are operating properly.

Instruction Manual Carbon Dioxide Electrode
20
SPECIFICATIONS
Concentration Range: 1 x 10-2M to 1 x 10-4M CO2
(440 ppm to 4.4 ppm CO2)
pH Range: 4.8 to 5.2
Temperature Range: 0oto 50oC
Inner Body Resistance: ~1,000 Mohm
Reproducibility: ± 2%
Size: 110 mm length; 12 mm diameter; 1 m cable length
Storage: Store electrodes in 0.1M NaCl
ORDERING INFORMATION
CODE NO. DESCRIPTION
EC-CO2-01 Carbon Dioxide Gas Sensing Electrode
EC-MIS-CD Carbon Dioxide Membrane Cartridge Kit,
box of 3 membrane cartridges and spare o-rings
EC-SCS-CO1-BT Carbon Dioxide Standard, 0.1M NaHCO3
EC-SCS-CO2-BT Carbon Dioxide Standard, 1,000 ppm as CO2
EC-SCS-CO3-BT Carbon Dioxide Standard, 100 ppm as CaCO3
EC-ISA-CO1-BT Carbon Dioxide Buffer Solution, 1M Citrate Buffer