22

trends in analytical

Enthalpimetry

chemistry, vol..Ij

no. 1, 1981

- a change of emphasis
J. Keith Grime

Department of Chemistry, University ofDenver,

University Park, Denver, CO 80208, U.S.A.

A change of emphasis
in enthalpimetric instrumental design has widened the scope of this universal analytical tool. These recent developments in enthalpimetric technology have improved the capabilities of the
technique and made possible a wide variety of clinical, biochemical and environmental applications.
Historical development
Enthalpimetric
analysis, in one form or another, has
been in existence since the early 1900s. Although many
variants now exist, all are based on the two classical
procedures of titration and injection (batch mixing)
calorimetry.
These techniques
have been termed
thermometric
enthalpy titrations (TET) and direct injection enthalpimetry
(DIE) respectively. The former
is characterized
by the continuous addition of titrant
to the sample solution under effectively adiabatic
conditions. The cessation of the temperature
change
(whether positive or negative) associated with the titration reaction is used to monitor the end-point. The
elegant simplicity of the TET format is evident; since
most chemical reactions are exo- or endothermic,
the
only prerequisite
imposed on the choice of reagent is
that it reacts stoichiometrically
and instantaneously
with the analyte. A typical TET temperature-time
plot
or enthalpogram
is shown in Fig. 1(a). Cart- has
the
written
a comprehensive
review
covering
quantitative
and qualitative features of TET.
Since its introduction
in 19132 progress in enthalpimetric
analysis has been erratic. Indeed, after

the initial reports, the technique

went almost unnoticed until the landmark paper of Linde, Rogers and
Hume3 in 1953, which introduced the thermistor as the
The
titration
approach
temperature
transducer.
dominated the enthalpimetric
methodology until 1964
when the injection technique, DIE, was introduced4.
DIE utilizes the total temperature
change, engendered
by a chemical or biochemical
reaction reaching its
equilibrium position, as a measure of the number of
moles of sample. Typically, the reaction is initiated by
the injection of a small volume of solution, containing
a stoichiometric
excess of reagent, into the sample
solution. The resultant enthalpogram
is depicted in
Fig. 1(b). Unless a series of analytical standards is
used, implementation
of DIE requires prior knowledge
of AH, the molar enthalpy of reaction and electrical or
chemical calibration of the heat change. The original
motivation for the development
of DIE was that the
large excess of reagent employed ( 1) assisted in driving
the reaction
equilibrium
to completion,
and (2)
ensured that the lifetime of the analytical signal, AT,
was short compared to the rate of heat loss from the reaction cell. The DIE concept was later to be a critical

(a)

(b)

EOUIVALENCE

VOLUME

OR MOL OF TITRANT

Fig. I. Typical enthalpograms:

0 165.9936/RI/WOO-0000/$02.50

POINT

(a) Thermometric enthalpy titration.

______1__

TIME
(6) Direct injection enthal@etry.
0 1981 Elwier

Scientific Publishing Company

trends in an$ytical

factor in the
for biological
There are
which cover

chemistry, vol. 1, no. 1, 1981

23

development
of enthalpimetric
methods
analysis.
several reviews, monographs,
and books
the developments
until 19755-s.

Fundamental

principles

The theoretical basis of enthalpimetric

in classical
thermodynamics.
The
concept is best illustrated by considering
change q(J) associated with a chemical
ceeding to equilibrium.
Thus,

analysis lies
fundamental
the total heat
reaction pro-

q = n,AH

(1)

where np is the number of moles of product and AH is

the molar enthalpy of reaction (J mol-l).
An important feature of enthalpimetric
methods is
that there is no inherent selectivity in the detection
system. The analytical signal is composed of the total
temperature
change engendered by the heat changes
produced from all the chemical reactions occurring in
solution.
Consequently,
if i simultaneous reactions occur with
the introduction of the analytical reagent, equation (1)
becomes
qi = iZni AHi
The corresponding
temperature
therefore be given by

(2)

change

AT

will

AT = k&r;
AHi
(3)
P
where C, is the heat capacity of the cell and its contents
(J C-t).
Equation
(3) illustrates
the essential
characteristics
of TET and DIE determinations.
The
sensitivity, as represented
by the magnitude of the
temperature
change for a given number of moles of
sample, is given by the factor AH/C,,.
Current trends in enthalpimetric analysis
Instrumentation - the changing image of enthalpimetry.

Traditionally,
enthalpimetry
has been defined as the
measurement
of temperature
changes associated with
chemical or biochemical
reactions under conditions
where the transfer of heat into and out of the reaction
cell is minimized. Historically,
the boundary between
enthalpimetry
and calorimetry
has been defined by
instrumental
specifications.
In fact, enthalpimetry
evolved from the need to increase sample throughput
and simplify
instrumentation
in order to apply
calorimetric techniques to routine analytical problems.
This philosophy is embodied in the features of DIE. If
one measures temperature
changes associated with
effectively
instantaneous
reactions,
heat transfer
between the cell and its environment
can be virtually
ignored. Moreover, if the analytical signal is based on
a relatively large temperature
change (>O. lC), a
modicum of environmental
temperature
control is required to produce
data with acceptable
precision
(- 1%). The apparatus required for such experiments
is
simple
and
inexpensive;
many
successful

enthalpimetric
determinations,
based on instruments
in which the adiabatic cell consisted of a polythene
bottle enveloped by polystyrene insulation, have been
reported.
The contribution
of this approach
to
thermochemical
determinations,
although
lacking
refinement
instrumentally,
is significant,
since it
popularized the concept of analytical calorimetry. The
simplicity of the apparatus,
its ability to tolerate the
presence of non-reacting,
insoluble or colored matrix
ingredients
and the universal
nature
of a thermochemical
determination
were
the
primary
motivations
for its adoption in the early stages of
development.
As a result, this type of apparatus
dominated
the literature on enthalpimetric
analysis
in the 20 years following the introduction
of the
thermistor.
There is no doubt that the preoccupation
with instrumental simplicity during this period hindered the
widespread
acceptance
of enthalpimetry
as a viable
alternative
method of analysis and precluded its involvement
in many important
areas of analytical
chemistry.
.
In the last live years, however, there has been a
noticeable
change in emphasis
and direction
in
enthalpimetry.
With the trend towards trace analysis
and
particularly
the increased
prominence
of
biological analysis, the arbitrary
boundary between
enthalpimetry
and calorimetry
has become vague. A
new generation of enthalpimetric
instrumentation
has
evolved which represems a compromise between the
rudimentary
enthalpimeter
and the sophisticated
adiabatic calorimeter.
The increased acceptability
of
this form of instrument is perhaps best illustrated by
the fact that a wide variety
of commercial
instrumentation,
non-existent
a few years ago, is now
available,
The most popular type of instrument in use is the
isoperibol calorimeter shown in Fig. 2. Isoperibol is
the term used to describe a quasi-adiabatic
system in
which attention has to be given to the determination
of the contribution to the temperature change from the
small but finite transfer of heat from the reaction cell
to the surroundings.
The specifications of the temperature measurement,
calibration
and reagent addition systems, have not
changed radically in recent years, and the reader is
directed
elsewhere
for informationi+s~lO
on these
components.
Two major instrumental
trends, which are in fact
related, can be identified. These are the diminution in
the size of the reaction cell and the appearance of computerized data treatment
facilities. Cell volumes of
10 cm3 or greater are typical for conventional
enthalpimetric
measurements.
It is apparent
from
Equation (3) however, that all else being equal, a reduction in cell volume increases the sensitivity of the
calorimeter
by decreasing
C,. The observed temperature change is inversely proportional
to the reaction solution volume for a given enthalpy of reaction
and amount of reactant. Unfortunately,
decreasing the

24

trends in analytical

TEMPERATURE
MEASSSR~MENT

chemistry, vol. 1, no. 1, 1981

I

CALIBRATION
[

WHEATSTONE
BRIDGE
CIRCUITRY
.

\
. v%!%!-E
SUPPLY

i AMPLIFI ER i-7

I
THERMOSTAT
I

[P~ZE~~,F-

OUASI- ADhBATlC
REACTION CELL

I
L----*_---_C
------+lNTERFACE+,---a*_

_----

r~iDE0
r----!
LDISPLAY
_,----------+-+.+
___I_
-lb-----_---_
~KEYBOARD
_ 4
1 /HARD@PY:----I PRINTER _,,

----

-+--------1

---3
-__:CO;$J$R+:D~SK
1-----_
(4BK)
~-1Lp_RIv!:

--------

J
L.)--LeTd

---

REPRESENTS

OPTIONAL FACILITIES

DATA COLLECTION
CORRECTION SYSTEM
.

ei
Fig. 2. Comprehensive

cell volume is not without practical problems. The rate

of heat loss increases exponentially
as the vessel size
decreases because there is a limit to the extent that the
measurement
and stirring facilities in the cell can be
miniaturized.
More exact calculations are therefore required
to correct
for heat exchange
during the
experiment l l. In the titration format, the usual requirement that the final titrant volume added is no

enthalpimetric

instrumentation.

more than ca. 10% of the original volume of sample still

holds, if gross changes in heat capacity and resultant
non-linear
titration
data
are
to be avoided.
Accordingly, a more precise titrant delivery system is
required to deliver titrant volumes CO.5 cm3 at a constant rate (20. I %) over periods of up to 20 min.
Finally,
background
stirring
heats become more
significant. Consequently,
if a potentiometric
chart

trends in an&tical

chemistv,

vol. I, no. 1, 1981

25

recorder is the method ofdata collection, a considerable

zero offset capability is necessary. The use of small
volume
(<5 cm3) reaction
cells has taken enthalpimetry
into the sphere of nanomole determinations. Several applications
of microcell instruments
have been reported recently; however, the pioneering
cell designs
and calculations
of heat loss were
published in 1974lz.
The increased significance of background
thermal
sensitivity
limits
are
events
as enthalpimetric
approached
has also resulted in more frequent use of
computerized
data aquisition and treatment facilities
interfaced with contemporary
calorimeters. The components shown in Fig. 2 represent the system used in
the authors laboratory, which is based on an Apple II
Plus microcomputer.
Enthalpograms
can be displayed
on a video screen and corrected for background effects
before printout as hard copy data. This type of data
treatment system will undoubtedly
become more prevalent in the near future.
Sensitivity - electronic and chemical answers

Sensitivity, or rather the lack of it, has always been

a major concern
governing
the, feasibility
of the
enthalpimetric
approach
to a particular
analytical
problem. With a reaction enthalpy of 40 kJmol-1 and
an arbitrarily
assigned precision limit of 2%, the
sensitivity limit of TET is similar to a potentiometric
titration, i.e. about 1 X 10-3 mol dm-3 or 1 X 10-S mol
in a typical 10 cm3 cell. DIE, a less precise procedure,
has a limit of sensitivity of about 2 X 1V mol dm-s at
the 10% precision
level, assuming
a temperature
resolution
capability
of +0.2 C (ref. 1). Enthalpimetric sensitivity has been improved both electronically
and chemically.
The most successful electronic adaptation,
used in
many subsequent
a plications, is based on an a.c.
of a phaseWheatstone
bridge IP. The incorporation
sensitive amplifier to enhance the signal-to-noise ratio
and a linear ramp generator to offset stirring heats and
heat loss has allowed a temperature
resolution of
3-4 X lO-@C. Ultimately,
the precision of this type
of instrument,
-0.2%,
is governed by the titrant delivery system.
A second approach to the sensitivity problem, which
has found considerable success, is catalytic TET. This
technique, first introduced in 1965*, is based on the
premise that the precision of a TET determination
is
related to the difference between the titration slope and
slope in an experimental
enthe post-reaction
thalpogram
(BC and CD respectively
in Fig. l(a)).
The relative magnitudes of these parameters can be regulated by the addition ofa thermochemical
indicator
substance
which reacts with the titrant when the
sample is consumed. The enthalpogram
then takes on
the appearance
of Fig. 3. The fundamental
difference
between this technique and TET is that the precision
of the equivalence point is related to the magnitude of
the temperature
change associated with the indicator
reaction and hence to the amount of indicator present.

VOLUME

OR MOL OF TITRANT

Fig. 3. Typical enthalpogram:

catalysed end-point indication.

ADDED

(a) Thermometric

enthalpy

titration with

The enthalpy of the titration reaction can, and indeed

should, be much smaller than that of the indicator
reaction. Consequently,
much more dilute titrants and
samples can be employed in comparison to TET. It is,
of course, highly desirable that the onset of the indicator reaction occurs as quickly as possible after the
consumption
of the sample and that the temperature
change associated with the reaction be as large as
possible. This is usually achieved by arranging the experimental conditions so that the titrant is the catalyst
for the indicator reaction. A small amount of excess
titrant will therefore initiate the reaction between a
large amount
of indicator
reactants
already
in
solution.
Limits of detection vary according to the indicator
reaction used, but determinations
of 1 X 1O-7 mol of
sample are not unusual. Greenhow has written a detailed review on the analytical
and measurement
aspects of catalytic TET15.
The simplest
and most convenient
method of
improving
sensitivity
is
buffer
so-called
amplification.
Concurrent
buffer reactions serve to
enhance the heat effect associated with the analytical
reaction.
This has proved
particularly
useful in
monitoring biochemical reactions which often involve
the release of protonsi6.
Selectivity - the development of enzymatic enthalpimetry

One of the most often cited advantages

of
enthalpimetry,
its universal detection system, also represents a major limitation, a complete lack of inherent
selectivity.
The practicability
of titrating mixtures
depends on the magnitude of AC (and hence K,,) and
AH for the pertinent reactions.
The incorporation
of the intrinsic selectivity
of

26

trends in anabtical

Reaction

Curves

chemistry, voli i, no. I, 1981

Calibration

I
QC
I

- < 30 min ,-I

Substrate,

buffer,

co-substrate

i
I-+tc

I
t

,time
Fig. 4. Direction

injection enthalfio~cram .fir the determination of (a) substrate concentration,

constant, K,,,. Curv& I, 2,3;

enzymatic reactions into the enthalpimetric

methodology during the past five years has produced
an
analytical
method with considerable
potential,
one
which embodies selectivity and wide applicability. The
theoretical
principles,
experimental
procedures
and
successful
applications
of
of this combination
technologies, termed enzymatic enthalpimetry,
have
been the subject of a recent review16.
Experimentally,
the technique is based on DIE. The
fundamental
difference
between
enzymatic
enthalpimetry
and conventional
DIE is that enzyme-

Reaction

--

.-

S, by end-point or equilibrium

method or (b) the Michaelis

SI > ST >- S, (constant E),

catalysed reactions have a finite reaction rate. The

sequence of addition of reagents and their relative
amounts is manipulated
to an extent commensurate
with the ultimate goal of the investigation.
For substrate determinations,
the pertinent signal is qi, the
total heat change associated with the reaction going
to completion,
calculations
are therefore based on
Equation
(2). Amounts
of kinetic determinants,
enzymes and inhibitors, can be calculated directly or
indirectly
from the time-dependent
versions
of
Equation (2) namely,

Curve

__ _. ._
._.. _.

_
--

-_-.-

time
g

Fig. 5. Kinetic enthalpogram for the determination of (a) enpe

activity, EA, (b) inhibitor concentrate, I, or (c) substrate concentration, S, by the initial
slope method. Curves I, 2, 3 (a) EA, > EA2 > EA3 (constant S). (6) 11 < 12 C I 3 ( constant S, E). (c) S, > S, > S, (constant E).

trends in nn&tical

chemistry, vol. I, no. I, 1981

4 = ix 9;.
At

AHi

27

(4)

By use of appropriate dimensions and with the correct

kinetic conditions prevailing, AnilAt can be presented
in terms of enzyme activity. The experimental
procedures and typical enthalpograms
associated with enzymatic enthalpimetry
are summarized schematically
in Figs 4 and 5.
Clinical enthalpimetry
Enzymatic
enthalpimetry
can
be successfully
applied to almost every facet of clinical analysis, e.g.
the determination
of enzyme activity, substrate and
inhibitor
concentration
and
the
magnitude
of
biochemical
constantsi6. The enthalpimetric
detection
system is ideal for the determination
of analytes in
complex biological fluids. A minimal amount of sample
pretreatment
(often none) is required if selective reagents are utilized. Claims that enthalpimetry
is a
panacea for all clinical analysis problems are of course
exaggerated.
The technique is a classic example of the
perennial compromise that must be made in analytical
chemistry between sensitivity and analysis time. The
reality of any enthalpimetric
method is that one cannot
maximize both. If sample throughput is of paramount
importance,
then flow enthalpimetry
is the answer.
The applications
and characteristics
of enthalpimetric
devices based on flow technology have recently been
summarized16,17.
Microenthalpimetric
methods,
on
the other hand, will provide high sensitivity at the
expense of sample throughput because of the increased
thermal equilibration
periods necessary as the signalto-noise ratio is lowered.
A notable development
in the area in recent years
has been
the emergence
of the term
enzyme
thermistor.
The rationale
behind these devices is
that the time constants
normally
associated
with
microcalorimetric
measurements
can be considerably
reduced and heat losses minimized, if the thermistor
is placed
in close proximity
to the site of an
immobilized
enzyme reaction. This also results in a
considerable simplification
and reduction in cost of the
apparatus
compared
with that required
for conventional microenthalpimetry.
Since the design of the
enzyme
thermistor
has evolved
as far as the
implantation
of a thermistor in the center of a packedbed microcolumn
of immobilized
enzyme, it is simply
an enthalpimetric
flow reactor and is subject to the
same considerations6.
The thermal equivalent of an enzyme electrode is
in fact embodied
in the thermal
enzyme probe
concept I9 . This is effectively a non-destructive
probe
based on the immobilization
of an enzyme in the
microenvironment
around or on the sensing bead of
the- thermistor
itself. The very small temperature
changes generated
under these conditions
and the
ensuing background noise problems have restricted the
development of this novel idea.

Environmental and energy related applications

Enthalpimetry
has recently found application in the
analysis of airborne particulates and the determination
of sulfur s ecies associated .with the combustion
of
fossil fuels2 g. In one project, a combination ofTET and
DIE was used to determine
nanomole
amounts of
S(IV)
and S(V1)
extracted
from filters containing
airborne
particulates.
S(IV)
was first oxidized to
S(V1) in a TET microtitration
with K2Cr207.
BaS04
solution was then injected into the titrate and the
original S(V1) content determined
by subtraction
of
the two results. In a more qualitative study, pK, and
AH data
extracted
from simultaneous
pH and
enthalpimetric
titrations, allowed the identification
of
strong and weak acid species in aerosols collected in
New York City 2o. In a similar vein, the identification
and quantitative determination
of sulfur species in coal
process streams, notably S2-, HS03-,
HS-, SOP(g),
SOs*- and HSO,-,
are the objectives of a combined
enthalpimetric
and voltammetric
study21. To the
authors knowledge, this particular project marks the
first practical application
of gas enthalpimetry
since
its introduction
several years ago.
The future of enthalpimetric methods
The
emergence
of isoperibol
instrumentation,
microcell technology,
selective enzyme reagents and
computerized
data collection and treatment facilities
has allowed enthalpimetry
to enter the mainstream of
analytical
methods. Judging from the literature,
the
current trend is to utilize both the thermodynamics
and
analytical
information
available from enthalpimetric
data. In this context, simultaneous potentiometric
and
enthalpimetric
measurements
provide a wealth of
qualitative,
quantitative,
analytical and fundamental
information in a single experiment. As microelectrode
technology
advances,
this will undoubtedly
be a
growth area.
In conclusion,
with the change of emphasis in instrumental specifications,
enthalpimetry
can no longer
be described as a solution in search of a problem.
References
Carr, P. W. (1972) Crit. Rev. Anal. Chem. 3, 491
Bell, J. M. and Cowell, C. F. ( 1913) J. Am. Chem. Sot. 35, 49
Linde, H. W., Rogers,
L. B. and Hume, D. N. (1953) Anal.
Chem. 25, 404
Wasilewski,
J. C., Pei, P. T. S. and Jordan, J. (1964) Anal. Chem.
36, 2131
Tyrell,
H. J. V. and Beezer,
A. F. (1968) in Thermomkic
Titrimetry, Chapman
and Hall, London
Bark, L. S. and Bark, S. M. (1969) in Thermometric Titrimetry,
Pergamon
Press, Oxford
Bark, L. S., Bate, P. and Grime, J. K. (1972) in Selected Annual
Rcuiems of the Analytical Sciences, Vol. 2
Vaughan,
G. A. (1973)
in Thermometric and Enthalpimetric
Titrimetry, Van Nostrand
Reinhold,
London
Barthel, J. (1975) in Thermometric Titrations, Wiley-Interscience,
London
10 Jordan, J., Grime, J. K., Waugh, D. H., Miller, C. D., Cullis,
H. M. and Lohr, D. (1976) Anal. Chem. 48,427A
11 Hansen, L. D., Jensen, T. E., Mayne, S., Eatough, D. J., Izatt,
R. M. and Christensen,
J. J. (1975) J. Chem. Tfwmodynam.
7,
919

trends in analytical chemistry, vob. 1, no. I, 1981

I

28
12 Hansen, L. D., Izatt, R. M., Eatough, D. J., Jensen, T. E. and
Christensen, J. J. (1974) Anal. Calorim. 3, 7
13 Smith, E. B., Barnes, C. S. and Cat-r, P. W. (1972) Anal. Chem.
44, 1663
14 Vaughan, G. A. and Swithenbank, J. J. (1965) Analyst 90,
594
15 Greenlow, E. J. (1977) Chem. Rev. 77, 835
16 Grime, J. K. (1980) Anal. Chim. Acta 118, 191
17 Schifreen, R. S., Hanna, D. A., Bowers, L. D. and Carr, P,, W.
(1977) Anal. Chem. 49, 1929
ia Danielsson, B., Matiasson, B. and Mosbach, K. (1979) Pure
A#. Chem. 51, 1443
19 Weaver, J. C., Cooney, C. L., Tannenbaum, S. R. and Fulton,
S. P. (1977) in Biomedical Applications of Immobilized Enwes and
Proteins (Chang, T. M. H. ed.), Plenum Press, New York,
Vol. 2
20 Eatough, D. J. (1978) J. Therm. Anal. 14, 45
2 1 Jordan, J. ( 1978) Instrumental Analysis of Sulfur Compounds in Coal
Process Streams, FE 2710-l et seq. U.S. Dept. of Energy

The determination

Dr Grime is an Assistant Professor

of chemistry at the University of
Denver, Colorado, U.S.A. A
native of England, he obtained his
undergraduate andgraduate
degrees at the University of
Salford, U.K. Following
postdoctoral appointments at
Florida State and Pennsylvania
State Universities, Dr Grime was
on thefaculty of the Universityof
Otago in Dunedin, New Zealand
for threeyears before taking up his
._
.
present posrtron tn December,
1978.

of dissolved
sea water

organic

carbon

in

Peter J. Wangersky
Department of Oceanography,

Dalhousie

University, Halifax,

N.S., B3H 4J1, Canada

For most oceanographic applications, methods based on wet oxidation of the organic fraction, followed by
stripping of the resulting CO* and measurement in the gas phase by non-dispersing infrared detectors give
acceptable results. Oxidation by high-intensity ultraviolet light has advantages, particularly in ease of
automation, over persulfate oxidation.
The role of dissolved organic carbon (DOC) in the
control of elemental distributions
in sea water has
become the subject of intensive investigation
in the
past few years, as we have become less concerned with
elemental abundances
and more interested in speciation in sea water. We are no longer content to assign
all peculiarities of distribution
to the black boxes of
chelation and complexation,
and are beginning to
inquire into the nature of the organic compounds
present. A limiting factor on many of our studies has
been the actual determination
of DOC, both in sea
water and in the various fractions we have separated
and concentrated
from sea water. Until fairly recently,
the techniques available have not been equal to the
tasks we have set them.
For the purposes of oceanographic
research, certain
constraints can be placed on these techniques. First,
they should be rapid, so that answers can be obtained
while it is still possible to make use of the information.
Second, the methods should be amenable to automated
analysis. Along with the ability to deal with large
automated
methods
usually
numbers
of samples,
produce
increased
precision,
as operator
error is
reduced. Third, the method should cover a range of
0.1-3.0 mg C/l for sea water samples, with the
possibility of extention to 10-20 mg C/l, to deal with
fractions of concentrates.
It is possible to cope with the
more concentrated
samples by dilution, but the production of organic-free
distilled water is difficult
enough to make us prefer some other method of range
0165.9936/8l/oooO-oOW/SO2.50

extension.
Fourth, a precision of +0.05 mg C/l is needed, as
a minimum. Since most of our samples from deeper
waters range from 0.3 to 0.7 mg C/l, this level of precision is needed to find differences between samples.
Fifth, the method should be seaworthy.
Ideally, we
might consider that each laboratory should have two
instruments,
one of high sensitivity and precision, to
be used for experimental
work at the shore
laboratory,
and one of lesser precision but greater
ruggedness
and stability,
to be taken
to sea.
However,
few laboratories
can afford two DOC
analysers,
and so some compromise
instrument
is
usually sought. Until fairly recently,
laboratories
wishing to automate the measurement
of DOC had
to develop their own instruments,
since the commercially available units, while satisfactory
for use
in eutrophic
fresh waters, were usually unable to
cope with the high salt and low organic content of sea
water.
Wet oxidation methods of analysis
All of the methods in common use involve sparging
of the acidified samples to remove carbonates, followed
by oxidation of the organic compounds to CO*, then
separation and measurement
of this COP. While some
laboratories have developed other methods for making
this final measurement,
most laboratories and all of the
commercially
available
instruments
use the nondispersive
infrared
gas analyser
(NDIR).
These
0 1981 Elsevier Scientific Publishing Company