PH Measurement, pCO2, Po2

NON-ELECTRIC PARAMETER MEASUREMENTS
Blood pH measurement
The acidity or alkalinity of a solution depends on its concentration of hydrogen ions. Increasing the
concentration of hydrogen ions makes a solution more acidic, decreasing the concentration of
hydrogen ions makes it more alkaline. The amount of hydrogen ions generally encountered in
solutions of interest is extremely small and, therefore, the figure is usually represented in the more
convenient system of pH notation. pH is thus a measure of hydrogen ion concentration, expressed
logarithmically. Specifically, it is the negative exponent (log) of the hydrogen ion concentration.
pH = –log (H+)
If the number 10–7 represents the concentration of hydrogen ions in a certain solution, then its pH
would be 7. As hydrogen ion concentration rises, pH falls because the logarithm gets smaller, and as
hydrogen ion concentration falls, pH rises because the logarithm gets larger. As we deal in
logarithms to base 10, a pH of 7 represents 10 times the number of hydrogen ions as does a pH of 8.
Electrochemical pH determination utilizes the difference in potential occurring between solutions of

different pH separated by a special glass membrane. If the pH of one of the solutions is kept
constant, so that the potential varies in accordance with the pH of the other solution, then the
system can be used to determine pH. The device used to affect this measurement is the glass
electrode.
pH Measurement
For making pH measurements, the solution is taken in a beaker. A pair of electrodes: one glass or
indicating electrode and the other reference or calomel electrode, are immersed in the solution. The
voltage developed across the electrodes is applied to an electronic amplifier, which transmits the
amplified signal to the display. The pH meter is usually equipped with controls for calibration and
temperature compensation.
The error caused in pH measurements due to temperature effect can be compensated either
manually or automatically. In manual adjustment the instrument is calibrated at 25°C.
Electrodes for Blood pH Measurement:

Several types of electrodes have been developed for the measurement of blood pH. They are all of
the glass electrode type but made in different shapes so that they may accept small quantities of
blood and yield accurate results. The most common type is the syringe electrode, which is preferred
for the convenience of taking small samples of blood anaerobically. The small ‘dead space’ between
the electrode bulb and the inner surface of the syringe barrel is usually filled with dilute heparin
solution to prevent blood coagulation. Before making measurements, the syringe should be rolled
between the hands to ensure thorough mixing.
Microcapillary glass electrodes are preferred when it is required to monitor pH continuously: for
example during surgery. These types of electrodes are especially useful when a very small volume of
the sample is to be analyzed.
The blood pCO2 measurement
The blood pCO2 is the partial pressure of carbon dioxide of blood taken anaerobically. It is expressed
in mmHg and is related to the percentage CO2 as follows:
% CO 2
p CO2=Barometric pressure−water vapour pressure X
100
At 37°C, the water vapour pressure is 47 mmHg, so at 750 mm barometric pressure, 5.7% CO2
corresponds to a pCO2 of 40 mm. A pCO2 electrode basically consists of a pH sensitive glass
electrode having a rubber membrane stretched over it, with a thin layer of water separating the
membrane from the electrode surface. The technique is based on the fact that the dissolved CO2
changes the pH of an aqueous solution. The CO2 from the blood sample defuses through the
membrane to form H2CO3, which dissociates into (H+) and (HCO–3) ions. The resultant change in pH
is thus a function of the C02 concentration in the sample. The emf generated was found to give a
linear relationship between the pH and the negative logarithm of pCO2. Although the electrode
could not provide sensitivity and stability required for clinical applications, it made way for realizing
a direct method for the measurement of pCO2.
Performance requirements of pH meters in measurement of pCO2
 Since 0.01unit pH change corresponds to a 2.5% change in pCO2 or 1 mmHg in 40 mmHg, for
achieving an accuracy of 0.1 mmHg, it is desirable to read 0.001 pH unit, i.e. a resolution of
60 mv. This order of accuracy can be read only on a digital readout type pH meter or on an
analog meter with expanded scale. The instrument should have a very high degree of
stability and a very low drift amplifier.
 It is essential to maintain the temperature of the electrode assembly constant within close
limits. It is experimentally shown that variation in the temperature of ± 1°C produces an
error of ± 1.5 mmHg or about }3% at 5 mm pCO2. The combined effects of temperature
change upon the sensitivity of the pH electrode and upon the pCO2 of the blood sample
amount to a total variation in sensitivity of 8% per degree centigrade.
Measurement of blood pO2
The partial pressure of oxygen in the blood or plasma indicates the extent of oxygen exchange
between the lungs and the blood, and normally, the ability of the blood to adequately perfuse the
body tissues with oxygen. The partial pressure of oxygen is usually measured with a polarographic
electrode. There is a characteristic polarizing voltage at which any element in solution is
predominantly reduced and in the case of oxygen, it is 0.6 to 0.9 V. In this voltage range, it is
observed that the current flowing in the electrochemical cell is proportional to the oxygen
concentration in the solution.
Most of the modern blood gas analyzers utilize an oxygen electrode for measuring oxygen partial
pressure. This type of electrode consists of a platinum cathode, a silver/silver chloride anode in an
electrolyte filling solution and a polypropylene membrane. The electrode is of a single unit
construction and contains the reference electrode also in its assembly.
Oxygen from the blood diffuses across the membrane into the electrolyte filling solution and is
reduced at the cathode. The circuit is completed at the anode, where silver is oxidized, and the
magnitude of the resulting current indicates the partial pressure of oxygen. The reactions occurring
at the anode and cathode are:
Cathode reaction:
O2 + 2H2O + 4e-  4 OH–
Anode reaction:
4Ag  4Ag+ + 4e–
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NON-ELECTRIC PARAMETER MEASUREMENTS

Electrochemical pH determination utilizes the difference in potential occurring between solutions of

Electrodes for Blood pH Measurement:

The blood pCO2 measurement

Performance requirements of pH meters in measurement of pCO2

Measurement of blood pO2

O2 + 2H2O + 4e-  4 OH–

4Ag  4Ag+ + 4e–

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