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trends in analytical
Enthalpimetry
chemistry, vol..Ij
no. 1, 1981
- a change of emphasis
J. Keith Grime
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
(a)
(b)
EOUIVALENCE
VOLUME
OR MOL OF TITRANT
POINT
______1__
TIME
(6) Direct injection enthal@etry.
0 1981 Elwier
trends in an$ytical
factor in the
for biological
There are
which cover
23
development
of enthalpimetric
methods
analysis.
several reviews, monographs,
and books
the developments
until 19755-s.
Fundamental
principles
analysis lies
fundamental
the total heat
reaction pro-
q = n,AH
(1)
(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
CALIBRATION
[
WHEATSTONE
BRIDGE
CIRCUITRY
.
\
. v%!%!-E
SUPPLY
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I
THERMOSTAT
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[P~ZE~~,F-
OUASI- ADhBATlC
REACTION CELL
I
L----*_---_C
------+lNTERFACE+,---a*_
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r~iDE0
r----!
LDISPLAY
_,----------+-+.+
___I_
-lb-----_---_
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REPRESENTS
OPTIONAL FACILITIES
DATA COLLECTION
CORRECTION SYSTEM
.
ei
Fig. 2. Comprehensive
enthalpimetric
instrumentation.
trends in an&tical
chemistv,
25
VOLUME
OR MOL OF TITRANT
ADDED
(a) Thermometric
enthalpy
titration with
26
trends in anabtical
Reaction
Curves
Calibration
I
QC
I
buffer,
co-substrate
i
I-+tc
I
t
,time
Fig. 4. Direction
Reaction
--
.-
S, by end-point or equilibrium
Curve
__ _. ._
._.. _.
_
--
-_-.-
time
g
trends in nn&tical
4 = ix 9;.
At
AHi
27
(4)
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
of dissolved
sea water
organic
carbon
in
Peter J. Wangersky
Department of Oceanography,
Dalhousie
University, Halifax,
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