Brit. J. Anaesth.
(1969), 41, 731
ELECTRODES FOR THE MEASUREMENT OF OXYGEN AND
CARBON DIOXIDE TENSIONS
BY
A. CRAMPTON SMITH AND C. E. W. HAHN
Several comprehensive review articles have
recently been published by anaesthetists on the
measurement of blood-gas tensions and pH (Laver
and Seifea, 1965; Adams, Morgan-Hughes and
Sykes, 1967, 1968; Severinghaus, 1968). These
papers have covered blood sampling and stor-
age, the introduction of samples to electrodes,
the calibration of commercially available systems
and so on. Kelman and Nunn (1966) have empha-
sized the importance of applying correction
factors for elapsed time and electrode drift, and
Linden, Ledsome and Norman (1965) have des-
cribed methods of measuring CO2 and O2 content
using electrodes and have compared these methods
with the manometric method of van Slyke (Peters
and van Slyke, 1958).
In the limited space available to us, we have
attempted a simplified description of the physical
background to O2 and CO2 electrodes, which may
increase the anaesthetist's understanding of in-
struments he uses frequently. This area is not
specifically covered in the articles mentioned
above and is difficult to extract from standard
texts. Discussion of the practicalities of the use of
the O2 and CO2 electrodes is not included except
where the authors' practice differs from that des-
cribed in the reviews—and where the differences
are regarded as important. It must be emphasized
that this paper makes no pretensions to complete-
ness and must be regarded only as an addendum
to the important articles already mentioned.
THE O 2 ELECTRODE
The measurement of the partial pressure of oxy-
gen in gaseous, liquid and semiliquid media is
now everyday practice in most hospitals and
physiology laboratories. The polarographic prin-
ciples developed by Heyrovsky (1922) and his
school had obvious applications in the analysis of
many substances including oxygen, but the
method was not used in biology until it was
adapted for use in biochemistry by Prat (1926).
Davies and Brink (1942) suggested the protection
of the cathode with a membrane for measurements
in blood to eliminate poisoning due to protein
deposition. The results of cathode protection with
a variety of materials remained unsatisfactory
(Shepard, 1956) until the picture was altered when
Clark (1956) introduced the principle of the closed
system. In this system, both the oxygen cathode
and the reference electrode (the anode) are
covered by a single membrane permeable to
oxygen.
Basic system.
The oxygen electrode has been developed from
a simple polarographic cell involving an electro-
chemical reaction and a flow of current. Figure 1
shows a container filled with electrolyte solution,
a cathode and an anode with an external circuit
consisting of a variable voltage source and a
galvanometer to measure any current flowing in
the system. If the cathode is made a few tenths of
a volt negative with reference to the anode, oxygen
molecules at the cathode surface undergo electro-
lytic reduction, resulting in a current which can
be measured by the galvanometer. If the voltage
is increased to more negative values, electrolysis
occurs more rapidly and the current increases in
a manner which can be expressed graphically by a
sigmoid curve (fig. 2). The plateau of the curve
occurs because the electrolytic reduction process
is capable of reducing more molecules of oxygen
than can reach the cathode by diffusion, so that in
spite of an increase in the negativity of the voltage
applied to the cathode, no increase in current
occurs. The shape of this sigmoid curve or polaro-
gram indicates the nature of a substance dissolved
in the electrolyte, and the height of the plateau
A. CRAMPTON SMITH, M.A., M.B., F.F.A.RC.S.; C. E. W.
HAHN, B.SC, M.SC, Nuffield Department of Anaes-
thetics, The University of Oxford.
732
FIG. 1
Basic arrangement of a simple oxygen polarographic
cell.
M Insulating glass
J Rubber " 0 " ring
Quantity
Nature
FIG. 2
Current-voltage curve for the reduction of oxygen at a
constant oxygen concentration.
indicates its concentration. If the voltage applied
is constant and is such that the cell current is in
the plateau region, the heights of a series of
plateaux will be proportional to a series of con-
centrations of the substance dissolved in electro-
lyte, in this case oxygen.
The system in figure 1 would be adequate for
measurements in simple well-stirred solutions, but
is not suitable for measurements in blood because
BRITISH JOURNAL OF ANAESTHESIA
the cathode quickly becomes poisoned by protein
contaminants. The Clark electrode (fig. 3) over-
comes this problem by separating the electrolyte
in which electrolysis takes place from the medium
in which oxygen is to be measured by a mem-
brane permeable to oxygen but impermeable to
ionized contaminants. Suitable materials are
polyethylene, polypropylene, teflon or mylar.
i Anode
To measuring unit
Cathode
Ag-Ag/CI
reference Insulated container
anode
Electrolyte
rod with platinum
wire sealed in
Membrane
Sample
Platinum
tip of
cathode
FIG. 3
Clarke-type oxygen electrode.
These are good electrical insulators and their
ability to diffuse oxygen is practically unchanged
in the presence of water vapour (Myers et al.,
1962). The reference electrode is silver-silver
chloride, silver-silver hydroxide, or calomel half
cell. The electrolyte is chosen to suit the reference
electrode, typical solutions consisting of KC1,
potassium chloride-phosphate buffer or buffered
KOH with pH varying between 6.7 and 10.4
(Heitmann, Buckles and Laver, 1967). The system
is totally enclosed in a thermostated water bath at
37 °C, so that measurements relate to the normal
body temperature (Laver and Seifen, 1965).
ELECTRODES FOR MEASUREMENT OF On AND CO, TENSIONS
Basic theory.
Theoretical models have still to be proposed
which accurately describe the processes occurring
at the indicating electrodes in spite of many recent
attempts (Davies, 1961; Berkenbosch, 1967;
Hudson, 1967). A much simplified model will be
considered which circumvents complex numerical
operations without deviating too far from the real
situation. It is assumed that the current in the
system is the result of chemical processes occur-
ring at the cathode and is proportional to the
number of oxygen molecules diffusing to the
cathode in unit time (Kolthoff and Laitinen,
1940). It is also assumed that the membrane is
directly and tightly stretched over the cathode,
and that there is only a thin layer of electrolyte
between the cathode surface and the membrane.
The primitive linear model to be described is
based on the laws of transport by diffusion (Fick,
1885). Fick's first law states that for a quantity
of substance, Q, being transported in a linear
co-ordinate system, then
d Q / d t = - D A (dC/dx) (1)
Where D i? the diffusion coefficient, A is the
surface area across which Q is transported and
dC/dx is the concentration gradient (fig. 4).
Fick's second law relates the way in which
concentration, C, varies with distance, x, and time,
t, and is expressed by the second order differ-
ential equation
d C / d t = D (d2C/dx2) (2)
Equation (2) is necessary only for a time-
dependent solution for oxygen electrode current
and is included for completeness. It has been
| Thickness X
Concentrations
C,>C;
Volume element of unit surface area for an imaginary
linear diffusion system.
733
solved, however, by many authors (Kolthoff and
Lingane, 1952; Evans and Naylor, 1960; Birken-
bosch, 1967) to give time-dependent solutions for
both spherical and linear co-ordinate systems.
A much simplified steady state result can be
derived by combining the Faraday law of elec-
trolysis (namely, that the amount of a product of
electrolysis at an electrode is proportional to the
current and the time for which it flows) and
equation (1). If it is assumed that every molecule
reaching the cathode surface is reduced, then the
current, i, due to the reduction process is given by
i = n F (dQ/dt) •(3)
where dQ/dt is transport rate of oxygen to the
cathode, F is the Faraday constant, and n is the
net number of electrons involved in the reaction.
Equations (1) and (3) can be combined to give
i = nFDA (dC/dx) (4)
where x is measured from the cathode surface.
For a slab of membrane (similar to fig. 4) with
concentrations Q and C2 on the surfaces, and
thickness x, equation (4) reduces to
i=nFDA [ ( Q - C J / x ] (5)
for d is greater than C2.
The underlying assumption so far has been that
the electrolyte layer is negligibly thin, but Berken-
bosch and Riedstra (1963) considered the effect
of a finite electrolyte layer for the linear diffusion
model and concluded that its effect is very small
(one part in a hundred) compared to the mem-
brane layer. Another important assumption is that
every oxygen molecule is reduced at the cathode
surface, and thus C2 is very much smaller than Q
and can be ignored. Equation (5) can then be
written in its concentration form, as
i = nFDA (Q/x) (6)
To express equation (6) in its final form in
terms of partial pressure of oxygen (Po2), it is
necessary to apply the law of Henry-Dalton
(Henry, 1803), which states that the gas concen-
tration in a solution is proportional to the gas
pressure.
C = a Po2 (7)
The solubility coefficient a is a measure of the
quantity of gas absorbed per unit volume of
solvent (in this case the membrane material) in
the presence of a partial pressure of 760 torr.
734 BRITISH JOURNAL OF ANAESTHESIA

6
J
5

4
1 J

2
3

• If y . ~7|
•/! . j . !.
1 .

100 200 300 400 500 600 700 800 900 100 200 300 400 500 600
— mV Po 2 torr
Cathode polarization voltage
with respect to anode
FIG. 5
Folarogram of oxygen at a theoretically perfect membrane-covered electrode. Electrode current,
i, in arbitrary units.

The final expression is thus: commercial electrode systems may not be entirely
linear over a wide range of Po2 (Heitmann, Buckles
i = (nFAaD/x) Po2 •(8) and Laver, 1967), and care should be taken over
It is important to note that both a. and D are calibration. It is usual to calibrate with oxygen-
temperature-dependent. For the exact nature of free N 2 gas, or gas tonometered with sodium
this dependance, the reader is referred to the sulphite solution, for the instrument zero, and
publications of Rogers and others (1962) and of room air (20.93 per cent O2 v/v) for the span.
Barrer (1947). Thus, if the temperature of the For samples of high Po2, the instrument should
polarographic cell is kept constant, the term be calibrated within the range in which it is ex-
nFAaD/x can be considered as constant in equa- pected to work.
tion (8), and the current in this limiting diffusion It is difficult to quote "time-constants" for oxy-
region is directly proportional to the prevailing gen electrode systems, since the numbers obtained
Po2 outside the membrane, will depend upon the nature and thickness of the
membrane material and upon the thickness of the
i.e., electrode current i = constantxPo 2 . electrolyte layer, but it is usually of the order of
This is depicted in figure 5 for a theoretically several seconds for a 90 or 95 per cent response
perfect electrode, which shows the plateaux where to a step change in Po2. The fastest response
equation (8) holds true. Oxygen electrodes are quoted, to our knowledge, is that of Beneken
usually polarized between - 600 mV to - 800 mV Kolmer and Kreuzer (1968) who reported a res-
with respect to the reference electrode, the actual ponse time of 0.2-0.25 sec for 95 per cent deflec-
voltage depending on the particular electrode and tion with a change of O2 concentration between
manufacturer. It is as well to note, however, that 0 and 100 per cent in both directions. The latter
ELECTRODES FOR MEASUREMENT OF O, AND CO, TENSIONS 735

finding is interesting since, in our own experience, dissociation curve of oxyhaemoglobin a consider-
the time response from a high Po2 to a low Po2 able error may occur in derived values of oxygen
is much longer than in the other direction and an saturation if the proper correction is not made.
electrode may well take several minutes to reach This also applies to the use of correction factors
"true zero" after the electrode has been exposed for drift, elapsed time between sampling and
to a sample of blood or gas with a high Po2. This measurement, and for temperature differences
effect may well be due to the overall electrode between the patient and the measuring electrode
reaction taking place at the cathode, (Kelman and Nunn, 1966).
O2 + 2H,O + 2e—>H 2 O 2 + 2OH- (i) The read-out system with most commercial
units consists of a high impedance voltmeter mea-
suring the voltage drop due to a current, i, across
It is generally assumed (Davies, 1961) that re- a larger resistance. This voltage drop is com-
action (ii) proceeds fast enough for all the pensated by means of a feed-back system, and the
hydrogen peroxide to be reduced and that none output read from an analogue moving coil meter
escapes into the bulk of the electrolyte. It has scale, calibrated in torr. Hahn (1969) described a
been suggested, however, by Seaton and Lloyd system of directly measuring the electrode current
(1969, personal communication) that enough and displaying the result on a digital voltmeter.
hydrogen peroxide can escape from the cathode Such a system naturally lends itself to data pro-
area to explain the long time-constants from high cessing, but however accurate the read-out system
to low Po2. The hydrogen peroxide will tend to becomes, it must always be remembered that the
diffuse slowly back to the cathode when the electrode itself has many limitations to its absolute
oxygen supply has been discontinued, and will accuracy.
be reduced according to equation (ii) producing
a current in the absence of any oxygen. THE CO2 ELECTRODE
It has already been stated that it is convenient As the CO3 electrode is in effect a pH electrode,
to calibrate the electrode by using gas mixtures of it may be helpful briefly to consider the principles
known oxygen tension, but it is also well known behind the measurement of pH. This measure-
that the output from an electrode is lower for a ment depends on the fact that if two solutions are
sample of blood than for the gas with which the separated by a membrane of special glass, a
blood has been equilibrated (Bishop, 1960; Polgar potential difference exists across the glass which
and Forster, 1960; Severinghaus, 1962). This bears a relationship to the activity of H+ ions on
difference can be reduced to a large extent by either side of the glass. This relationship is
stirring the blood sample, but is not completely
expressed by an equation, derived from the
eliminated (Heitmann, Buckles and Laver, 1967).
original Nernst equation by substituting "activi-
The blood-gas factor in fact depends on many
ties" for concentrations, hence,
variables, including the rate of stirring, the
influence of pressure and flow changes in the E = ( R T / F In (aH'+/aH"+) (1)
sample, the area of the cathode, and the nature where In is loge, R is the gas constant, T the
and thickness of the membrane. Adams and absolute temperature, F, Faraday's constant
Morgan-Hughes (1967) quote the blood-gas factor (96,494 coulombs), aH+ is H+ ion activity and E
for two commercial unstirred electrode systems as is potential measured in volts. The "activity" of
4 + 2 per cent and describe a thermostatically con- an H+ ion is a term used to indicate the behaviour
trolled bubble tonometer to calibrate oxygen of the ion when in an electrolyte solution. West
electrode systems. The correction factor for the (1963) illustrates the term "activity" by using the
blood-gas difference should be determined for analogy of a footballer who may be relatively
each electrode-membrane system, and for the
immobilized by the presence near him of a large
range of Po2 which is to be measured. A 4 per
number of other footballers, but also may show
cent correction at a Po2 of 500-600 torr may not
more activity with a few other players on the field
be critical to the clinician, but at tensions corres-
than when he alone is present. The term
ponding to the steep section of the sigmoid
"activity" is used, with certain conditions, to
736 BRITISH JOURNAL OF ANAESTHESIA

express the effective concentration of an ion as bicarbonate solution. This changes the pH of the
shown by its properties in solution. bicarbonate solution and causes a change in the
It can be shown (West, 1963) that aH+ is the potential difference across the pH-sensitive glass
hydrogen ion concentration [H+] in mol/litre of what is in effect a pH electrode. The potential
multiplied by an activity coefficient. And so equa- change is measured by reference electrodes as a
tion (1) becomes voltage governed by equation (4).
E = ( R T / F ) In -]) (2) The situation illustrated in the diagram is not
This can be rewritten, practical because of the number of CO2 molecules
necessary to change the pH of a large mass of bi-
E = ( R T / F ) (In [H'+] - In [H"+]) carbonate solution and the time necessary for this
(3) to happen. The CO2 electrode in fact measures
S0rensen (1909) defined pH (the degree of the pH change in a thin film of bicarbonate solu-
acidity or alkalinity of a solution) as equal to tion in close contact with the pH-sensitive glass
- log10[H+]. Thus equation (3) can be rewritten, of the electrode (fig. 7).
converting to log10 and changing sign,
E=2.303(RT/F)(pH" - pHO (4)
This is the potential difference that is registered
on the meter of a pH measuring system and is
equal to 61.5 mV per unit pH change at 37°C.
The CO2 electrode, first described by Stow,
Baer and Randall (1957) and Gertz and Loeschcke
(1958), uses a CO 2 permeable membrane to allow
CO2 to diffuse from an unknown sample of gas
or liquid into a bicarbonate solution until equili-
brium is reached. Figure 6 is a very simplified
diagrammatic representation of the electrical
circuit. CO2 diffuses through a membrane into a CO,

Sample of blood or gas

FIG. 7
Diagram of tip of carbon dioxide electrode.

Basic theory.
When CO2 diffuses through a membrane and
comes into equilibrium with water, the equili-
brium can be expressed by the well-known equa-
tions,
Reference
-electrode K K
CO2 H+ + HCOj

0
(5)
Container
If the liquid behind the membrane is a bicar-
bonate solution, the HCO3 ion at the righthand
Bicarbonate
solution
side of equation (5) is mostly derived from the
salt, but the equation, although written for water,
still holds approximately. The equilibrium of the
CO ;
Membrane righthand side of equation (5) is governed by the
sample first ionization constant of H,CO 3 , K u and so the
FIG. 6 expression can be rewritten,
Simplified diagram of circuit of carbon dioxide
electrode. K 1= ([H+][HCO3]/[H 2 CO 3 ]) (6)
ELECTRODES FOR MEASUREMENT OF O2 AND CO2 TENSIONS
Taking logarithms of both sides of (6) and
defining pK t as - log Kx and pH as - log [H+]
(S0rensen, 1909) yields
P H = p K 1 + log ([HCO3]/[H2CO3])
(7)
This equation expresses the pH of the film of
bicarbonate solution in a CO2 electrode if there
is a change of H 2 C0 3 in the film. The effect of
CO, on H,CO 3 is expressed by the left side of
the equilibrium equation (5). [H2CO3] is, by
Henry's law, linearly proportional to the partial
pressure of CO2 in the sample outside the mem-
brane and therefore can be replaced in equation
(7) by aPco,, where a is the solubility coefficient
of CO2. So equation (7) can be rewritten as
PH=pK1 + log ([HCO3]/«Pco2 (8)
The addition of the HCO3 in equation (8) to
the total of HCO3 ions from NaHCO3 in the
bicarbonate solution of a CO2 electrode (see
above) has a negligible effect and hence [HCOi]
is essentially constant. So equation (8) becomes
pH = pKj + log [HCO3] - log a - log Pco2
= constant - log Pco2 (9)
8.500
8.000
7.500
pH
7.000
6.500
6.000
100
Pco, torr
737
If the CO2 electrode responded perfectly, the
plot of this relationship on semilog paper would
be a straight line with a slope of - 1 (fig. 8).
The relationship between the change of pH
(A pH) in the bicarbonate solution in a CO2 elec-
trode caused by a change, A Pco2, in Pco2 of the
bicarbonate solution has been defined by Sever -
inghaus and Bradley (1958) as the sensitivity
factor " S " for an electrode.
A p H = - S A log Pco,
••• S = - ( A p H / A l o g P c o 2 ) .(10)
This would follow immediately from equation
(9) if it is assumed that S = - 1 and, as has been
said before, this would define the relationship
between pH and log Pco2 in a perfect electrode.
Equation (9) is, however, a gross over-simplifica-
tion of a complex group of chemical reactions and
more exact dissociation equations for a CO 3
electrode (Lunn and Mapleson, 1963; Severing-
haus and Bradley, 1958) must be used to define S.
These take into account the dissociation of
NaHCO 3 and the laws of electroneutrality as well
as those governing the solution of CO2 in the
electrolyte. The value of S changes with different
FIG.8
pH/log Pco2 plot.
1000
738
bicarbonate concentrations in the electrode, but in
certain conditions of concentration of bicarbonate
S can be regarded as constant. So equation (9)
can be rewritten, to acknowledge imperfections in
the electrode, as
pH=constant - S log Pco2 (11)
where S is the sensitivity factor of the electrode
or, in other words, the slope of the plot of pH
against log Pco,.
In summary, the measurement of a change in
Pco2, A Pco2, of a sample introduced into a CO2
electrode, depends on the measurement of the
change in pH of a film of bicarbonate solution
separated from the sample by a CO2 permeable
membrane. The Pco2 of the sample changes the
Pco2 of the bicarbonate solution in the electrode
and hence the H+ activity of the solution. The
potential across the pH-sensitive glass of the
electrode increases or decreases, and this increase
or decrease, measured in mV, is registered by the
meter in the system. The change is governed by
equation (11). Thus if the S of an electrode is - 1,
for each change in Pco2 by a factor of 10, e.g.
from 1 torr to 10 torr, or from 10 torr to 100 torr,
there is a unit change in the pH of the bicarbonate
solution and hence a potential change registered
on the meter of 61.5 mV.
As previously mentioned, however, for many
electrodes S is not equal to - 1 but is almost
always nearly so. The manufacturers of measuring
systems allow for this by providing controls to
match the measuring instrument to the S of any
given electrode between two calibrating gases of
different Pco2's. This assumes that S is constant
between two calibrating gases, but our experience,
and apparently that of Severinghaus and Bradley
(1958), would suggest that this is often not so.
The errors introduced by this assumption are
probably insignificant in clinical practice, but
might be of importance in clinical research, and
their magnitude is at present under study.
The modern CO2 electrode, of which that
manufactured by Radiometer* is a good example,
consists of a silver-silver chloride electrode in a
closed container filled with a phosphate buffer of
pH about 6. One end of this container is made of
special H+ ion sensitive glass (fig. 9) and is
covered by a matrix of nylon mesh, Joseph paper
* Radiometer A.S., Copenhagen, Denmark.
BRITISH JOURNAL OF ANAESTHESIA
To
voltage
amplifier
Reference electrode
Glass rod
pH sensitive glass
Matrix
" O " ring
Membrane Bicarbonate solution
FIG. 9
Diagram of carbon dioxide electrode.
or cellophane, which holds a thin film of solution
containing 0.1 M NaHCO3 with some NaCl and
sometimes silver chloride. Another electrode is
needed to complete the cell circuit for the glass
electrode, and this is again a silver-silver chloride
electrode in physical contact with the bicarbonate
solution. These two reference electrodes produce
a constant potential with regard to the chlorine
solution in which they find themselves (Eisenman
et ah, 1966) and therefore a constant potential
difference reading with respect to each other.
The special glass of the CO2 electrode is
separated from a test solution by a teflon mem-
brane permeable to CO2 molecules. When the
electrode is in use, the Pco2 of an unknown solu-
tion comes into equilibrium with the Pco2 of the
bicarbonate solution in the matrix immediately
adjacent to the special H+ ion sensitive glass (fig.
9). This changes the pH or the H+ ion concentra-
tion in the bicarbonate solution in the immediate
neighbourhood of the special glass and therefore
changes the electrical potential existing across the
glass between the two solutions. This change is
ELECTRODES FOR MEASUREMENT OF O, AND CO, TENSIONS
amplified and read on a sensitive voltmeter. Both
electrodes and the special glass membrane must
be kept at the same constant temperature. It has
been agreed (New York Academy of Sciences,
1966) that the temperature used should be 37 "C
to be comparable with the normal physiological
temperature in man.
Calibration of a CO* electrode.
Calibration of CO, electrodes is simplified by
the fact that there is no blood-gas difference for
CO, (Adams and Morgan-Hughes, 1967). The
electrode can therefore be calibrated with gas and
used to measure the Pco, of blood. Manufacturers
of electrode systems find it convenient to calibrate
electrodes with two gases of fairly widely differing
CO, contents, e.g. 3 and 7 per cent v/v. One gas
is given its correct value on the scale of the instru-
ment and the other calibrating gas is matched to
the scale of the measuring instrument by means
of a control. This allows for the fact that the S
of an electrode may be less than 1 but assumes
that the pH/log Pco2 response of the electrode is
linear.
We see advantages of constructing a semilog
plot of pH or mV/per cent CO2 (v/v) for the
electrode in use. It would be logical to construct
a plot using 100 and 0 per cent CO, v/v but this
is not practicable. CO, electrodes do not respond
to 0 per cent CO, v/v, and because of the log-
arithmic relationship between mV or pH and
Pco,, at 100 per cent CO2 v/v it becomes very
difficult to inscribe a point with any accuracy. We
investigate the characteristics of any new
electrode with a Wosthoff pump* giving 1 per
cent step changes of CO2 content from 1 to 10
per cent v/v, and with a cylinder of nominal 5 per
cent CO2 (v/v) which has been carefully analyzed
with a Haldane apparatus. The 5 per cent gas is
called the "hinge" gas and the electrode is exposed
to it after each exposure to another gas. In this
way, an accurate calibration line is drawn for each
electrode using a relatively large number of points.
In normal use, the electrode is exposed to the
"hinge" gas, a low gas and a high gas twice a day.
If the pH values observed agree with the values
on which the calibration line is based to within
2 or 3 thousandths of a pH unit, the original line
is used to give the value of an unknown concen-
* H. Wosthoff. O. H. G., 463. Bochum, Hagenstrasse,
30, Germany.
739
tration in per cent CO, v/v. This is multiplied by
the barometric pressure of the day to give Pco2.
The hinge gas reading is, of course, checked
before and after each sample measurement.
This method has two advantages. The semilog
graph paper chosen gives considerably better dis-
crimination than the best of several commercial
meters available (Trubuhovich, 1968). A range of
10-100 torr is expressed on 250 mm of log scale
on the paper used, whereas 10-100 torr is ex-
pressed on 176 mm on the longest and 114.3 mm
on the shortest commercial scales, and the twice-
daily check with three gases is virtually certain to
disclose a faulty electrode.
The use of linearizing circuits enable Pco2 to
be read directly and digitally from a change in
electrical output from the electrode and should
result in increased accuracy. Any linearizing
circuit must, however, by definition assume a
linear relationship between electrical output or pH
and log Pco,, at least for the range of Pco2 under
study. The extent to which circuits can be modi-
fied to reduce inaccuracies from this assumption
is under study.
Trubuhovich (1968), in a study of the perform-
ance of CO, electrodes, made observations which
will be more fully described elsewhere, and in
respect of calibration again drew attention to two
potential sources of error. He showed first of all
that if humidified gas is passed into an electrode
at a rate just fast enough to compensate for leaks
and diffusion (Lunn and Mapleson, 1963), a very
stable and reproducible equilibration pattern can
be achieved. In the example shown, the output of
the electrode changes by less than 0.001 of a pH
unit over periods of 10-20 minutes. If the elec-
trode "dries out", however, the pH reading
changes some 10 minutes later and may subse-
quently be constant at its new value or irregular
(fig. 10). This source of error may be diminished
or avoided, either by using warmed and humidi-
fied calibrating gases or by introducing very small
quantities of water into the equilibration chamber
from time to time. The ideal situation is when
the calibrating gas bubbles through a small
amount of water remaining in the equilibration
chamber.
Trubuhovich also showed that if gases are in-
troduced into the equilibration chamber at fast
flow rates, the output from the CO, electrode
740 BRITISH JOURNAL OF ANAESTHESIA

I I!
I -I I! i

ilLiiJ: .j.
1 . 4 - .1

FIG. 10
Carbon dioxide 5 per cent v/v dry gas at 5 ml/min through water in equilibration chamber.
Upper record pressure in equilibration chamber, lower record pH 0.1 pH unit full scale. Time
scale in minutes. Pressure drops when water dries out and bubbling spikes almost cease. pH
reading becomes acid (Trubuhovich, 1968).

FIG. 11
Upper record pressure, lower record pH. 5 ml/min humidified gas. Time scale minutes. At A,
gas flow turned off. Alkaline "decay" drift starts 20 sec later. At B, gas flow increased to 25 ml/
min. giving more acid reading by 0.010 pH units. At C, gas flow turned off. Recovery from
pressure change overtaken by "decay" drift, showing no recognizable end point (Trubuhovich,
1968).
ELECTRODES FOR MEASUREMENT OF O2 AND CO, TENSIONS
changes, no doubt because the Pco2 is increased
in the chamber by increased ambient pressure.
When the gas has been flowing at a fast rate and
is stopped, the electrode reading falls, first of all
due to pressure changes, but this fall is later over-
taken by the fall due to leaks and diffusion. There
is no recognizable end point such as can be
achieved with a slow—5 ml per minute—flow of
humidified gas into a wet chamber (fig. 11).
Trubuhovich's (1968) re-examination of the
performance of CO2 electrodes has suggested to
us that their reproducibility is high, and if allow-
ance can be made for the fact that the S of an
electrode is a perfectly straight line over only a
limited range, the potential accuracy of CO2
electrodes is quite considerable. This potential
accuracy is still under study.
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