EUTECH INSTRUMENTS CARBON DIOXIDE GAS Instruction manual

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Instruction Manual Carbon Dioxide Electrode

EUTECH INSTRUMENTS PTE LTD.

INSTRUCTION MANUAL

CARBON DIOXIDE ION ELECTRODE

1

Instruction Manual Carbon Dioxide Electrode

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

2

Instruction Manual Carbon Dioxide Electrode

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 flowthrough 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 NaHCO

3

, 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 NaHCO

3

. 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

as 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 NaHCO

3

. 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 NaHCO3 as CaCO

3

, 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

3

Instruction Manual Carbon Dioxide Electrode water, add 294 grams of Na

3

C

6

H

5

O7.2H

2

O (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 20 o

angle 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 20 o

angle 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.

4

Instruction Manual Carbon Dioxide Electrode

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 CO

2 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 20 o and

25 o

C. 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.

5

Instruction Manual Carbon Dioxide Electrode

All samples and standards should be at the same temperature for precise measurement. A difference of 1 o

C 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 25 o

C, 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 CO

2

increases 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 CO

2

from 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 CO

2

, collect in a stoppered glass bottle, filling completely and capping tightly to prevent CO

2

from escaping. Do not add NaOH, since carbonate is usually present in the base as a contaminant. If the sample contains more than 100 ppm CO

2

, 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 CO

2

ppm CaCO

3

6

Instruction Manual Carbon Dioxide Electrode

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

-2

M, 10

-3

M, and 10

-4

M or 1,000 ppm,

100 ppm, and 10 ppm.

2. Place 100 ml of the 10

-4

M (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

-2

M (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.

7

Instruction Manual Carbon Dioxide Electrode

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 CO

2

standard 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.

8

Instruction Manual Carbon Dioxide Electrode

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

-3

M CO

2

(100 ppm CaCO

3

or 44 ppm CO

2

), at pH 4 and 5, are listed in Table 2.

TABLE 2: Interference Levels - 10% Error at 10

-3

M CO

2

HCOOH

(formic acid)

CH

3

COOH

(acetic acid)

HSO

3-

(SO

2

)

(sulfur dioxide)

7.5 x 10

-3

M

(345 ppm)

3.6 x 10

-3

M

(216 ppm)

7.5 x 10

-4

M

(48 ppm)

5.3 x 10

-4

M

(24 ppm)

2.0 x 10

-2

M

(1,840 ppm)

6.2 x 10

-3

M

(372 ppm)

5.0 x 10

-3

M

(320 ppm)

3.5 x 10

-3

M

(160 ppm)

NO

2-

(NO

2

)

(nitrogen dioxide)

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

-

4

M. 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

(NaNO

3

) to 10 ml of electrode filling solution.

Temperature Influences

Samples and standards should be within

±1 o

C 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

9

Instruction Manual Carbon Dioxide Electrode 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.

Temp.( o

C) "S"

0

5

54.20

55.20

10

15

20

25

56.18

57.17

58.16

59.16

30

35

40

Electrode Response

60.15

61.14

62.13

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

-4

M to

1X10

-2

M. (Refer to Figure 1.)

For carbon dioxide concentrations above 1X10

-4

M, 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

-2

M must be diluted before measurement. Figure 2 indicates the time response of the carbon dioxide electrode to changes in the carbon dioxide concentration.

10

Instruction Manual Carbon Dioxide Electrode

Limits of Detection

The upper limit of detection in pure carbon dioxide solutions is 1X10

-2

M. Carbon dioxide is rapidly lost to the air above a concentration of 1X10

-2

M. Dilution may be used if carbon dioxide concentrations are above 1M. Also dilute samples between 1M and 10

-2

M or calibrate the electrode at 4 or 5 intermediate points.

The lower limit of detection is around 1X10

-4

M. 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

-4

M CO

2

should 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 CO

2

in the internal filling solution and the partial pressure of the CO

2

in 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:

CO

2

+ H

2

O

⇔ H +

+ HCO

3-

The relationship between the hydrogen ion, the bicarbonate ion, carbon dioxide, and water is given by the equation:

11

Instruction Manual Carbon Dioxide Electrode

[H

+

] [HCO

3-

]

⎯⎯⎯⎯⎯⎯⎯ = constant

[CO

2

]

The bicarbonate ion level can be considered constant since the internal filling solution contains a high level of sodium bicarbonate:

[H

+

] = [CO

2

] 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:

where:

E = Eo + S log [H

+

]

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 [CO

2

]

Carbon Dioxide Chemistry

Carbon dioxide exists as bicarbonate and carbonate in basic solutions:

CO

2

+ OH-

⇒ HCO

3-

CO

2

+ 2OH-

⇔ CO

3

-2

+ H

2

O

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 CO

2

form.

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 CO

2

form:

2H

+

+ CO

3

-2 ⇒ H

2

O + CO

2

H

+

+ HCO

3-

⇔ H

2

O + CO

2

The total amount of carbon dioxide, carbonate, and bicarbonate is then measurable in the solution.

12

Instruction Manual Carbon Dioxide Electrode

ELECTRODE APPLICATION

Carbon Dioxide Content of Wines and Carbonated Beverages

Wines and carbonated beverages have a high (greater than 2X10

-2

M 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 CO

2

will 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

Cs = 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

13

Instruction Manual Carbon Dioxide Electrode

Carbonate Content in Groundwater

Free CO

2

, 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, CO

3

-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 (NaHCO

3

). 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 H

2

SO

4

) 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.

14

Instruction Manual Carbon Dioxide Electrode

Step Pipet Added Volume Concentration

1 A

2 A

0.1 ml

0.9 ml

109.9 ppm

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

.

15

Instruction Manual Carbon Dioxide Electrode

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.

16

Instruction Manual Carbon Dioxide Electrode

TROUBLESHOOTING HINTS

Symptom

Out of Range

Possible Causes defective meter

Next Step perform meter checkout

Reading procedure instruction manual)

defective inner refer to

Electrode Inner Body electrode not plugged in properly unplug electrode and reset fill outer body of electrode with proper amount of internal filling solution internal filling solution not added air bubble on membrane electrode not in solution

Noisy or Unstable

Reading (readings continuously or insufficient internal filling solution random changing.) defective meter remove bubble by re-dipping electrode put electrode in solution fill outer body of electrode with proper amount of internal filling solution perform meter checkout procedure (see meter instruction manual) bottom cap loose defective inner body air bubbles on membrane meter or stirrer improperly grounded

Drift (reading slowly changing in one internal filling solution leakage direction) ensure that bottom cap is screwed on tight enough to close gap between bottom cap and body refer to

Checking the

Electrode Inner Body remove bubbles by redipping electrode check meter and stirrer for grounding ensure that membrane is installed properly

17

Instruction Manual Carbon Dioxide Electrode incorrect internal filling solution total sample level electrode in sample too long; CO

2

loss membrane failure

(wet, perforation, discoloration) refill outer body of electrode using filling solution shipped with electrode dilute sample of dissolved species above 1M reduce surface area-to- volume ratio, slow down rate of stirring, avoid high temperatures replace membrane samples and standards not at constant temperature heat generated by magnetic stirrer defective inner body electrode exposed to air for extended period

Low Slope or No Slope standards contaminated or incorrectly made allow samples and standards to come to room temperature

before use place insulating material between stirrer and beaker refer to

Checking the

Electrode Inner Body hold electrode by outer body and pull on electrode cable.

Internal filling solution will flow under membrane and restore electrode response prepare fresh standards standard used as buffer electrode exposed to air for extended period membrane failure

(wet, perforation, discoloration) defective inner body use buffer hold electrode by outer body and pull on electrode cable.

Internal filling solution will flow under membrane and restore electrode response replace membrane refer to

Checking the

Electrode Inner Body

18

Instruction Manual Carbon Dioxide Electrode

"Incorrect Answer" incorrect scaling

(but calibration of semi-log paper curve is good) incorrect sign plot millivolts on the linear axis. On the log axis, be sure concentration numbers within each decade are increasing with increasing concentration be sure to note sign of millivolt value correctly incorrect standards wrong units used buffer added to prepare fresh standards apply correct conversion factor:

10

-3

CO

2

M = 44 ppm as

= 100 ppm as CaCO add same standards

3 samples sample carryover buffer to standards and samples 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.

19

Instruction Manual Carbon Dioxide Electrode

SPECIFICATIONS

Concentration Range: pH Range:

Temperature Range:

1 x 10

-2

M to 1 x 10

4.8 to 5.2

0 o

to 50 o

C

-4

M CO

(440 ppm to 4.4 ppm CO

2

)

2

Inner Body Resistance:

Reproducibility:

~1,000 Mohm

± 2%

Size:

Storage:

110 mm length; 12 mm diameter; 1 m cable length

Store electrodes in 0.1M NaCl

ORDERING INFORMATION

CODE NO. DESCRIPTION

EC-CO2-01

EC-MIS-CD

Carbon Dioxide Gas Sensing Electrode

Carbon Dioxide Membrane Cartridge Kit, box of 3 membrane cartridges and spare o-rings

EC-SCS-CO1-BT Carbon Dioxide Standard, 0.1M NaHCO

3

EC-SCS-CO2-BT Carbon Dioxide Standard, 1,000 ppm as CO

2

EC-SCS-CO3-BT Carbon Dioxide Standard, 100 ppm as CaCO

3

EC-ISA-CO1-BT Carbon Dioxide Buffer Solution, 1M Citrate Buffer

20

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