Steadystate gas dissolution flow microcalorimeter for determination of heats of

solution of slightly soluble gases in water

Steven F. Dec and Stanley J. Gill

Citation: Review of Scientific Instruments 55, 765 (1984); doi: 10.1063/1.1137814

View online: http://dx.doi.org/10.1063/1.1137814
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 Steady-state gas dissolution flow microcalorimeter for determination of
heats of solution of slightly soluble gases in water
Steven F. Dec and Stanley J. Gill
Department o/Chemistry, University o/Colorado, Boulder, Colorado 80309
(Received 15 September 1983; accepted for pUblication 3 February 1984)

A flow calorimeter of the heat conduction type is described, which is capable of measuring the
heat effect associated with the process of dissolving slightly soluble gases into water. The
calorimeter operates in a steady-state mode. Gas, fed at constant rate, is dissolved in flowing water
within a specially designed microcalorimeter cell and the power is determined for the process.
Computer control of the gas flow is used for convenient establishment of steady states. The
calorimet~r!~ calibrated e~ectrically with a precision of 0.2% for power levels of 150-450 f-lW.
Reproduclblhty of successive measurements of heats of solution of oxygen are within 1%. Results
are presented for the enthalpy change for the dissolution of oxygen gas into pure water at 25 ·C.
PACS numbers: 07.20.Fw, 44.50. + f, 51.30. + i, 82.60.Lf

INTRODUCTION of 0.02%. In these cases, the estimated errors in derived

The properties of apolar substances in water are of special
importance in understanding features of biological macro-
molecules and membranes. The tendency for these com-
pounds, such as hydrocarbons, to interact strongly with each
other as compared with water, has been termed "hydropho-
bic interaction" I or "the hydrophobic effect".2 Low solubil-
ity is a manifestation of this interaction, and has been the
subject of various interpretations. 3- 7 The temperature de-
pendence of the solubility has been practically the only
method for obtaining the key thermodynamic properties, en-
tropy, enthalpy, and the heat capacity change of solution for
such substances. 8 Direct calorimetric measurements were
first attempted on rare gases 9 at rather low precision. Special
calorimetric procedures have been developed for liquid hy-
drocarbons 10 and continued efforts along these lines have
recently produced techniques applicable to gases. II The
steady-state method, which, in principal, promised high-
precision features, was not found in these first developments
to give stable steady-state rates of gas dissolution and was
thus regarded as inferior to batch method process. ll We
wish, in the present paper, to report the results of a complete-
ly new steady-state flow calorimeter, which has been found
to give comparable results as the batch method.
One advantage of having two different calorimetric
procedures for determination of heats of gas dissolution is
that systematic errors can be detected and some measure of
accuracy can be obtained. Direct determination of heats of
solution provide independent data to critically test the gen-
eral accuracy of the indirectly determined values from the
temperature dependence of solubility.
A wide variation of precision of solubility data exists. 8
It may be roughly estimated from typical data sets (25 points
at 2 ·C intervals), giving fits of 1% in relative solubility, that
the standard error at the midpoint of the temperature range
of the derived values of enthalpy change are the order of
± 100 J and at the ends of the temperature range are of the
order of ± 1000 J. 12 Special high-precision solubility meth-
ods have been developed for vapors 13 and for gases 14, which
in the latter give relative solubility errors in the fitting of data
enthalpy changes at midpoint of the temperature range are
reduced proportionally to ± 2 J. Calorimetric measure-
ments provide important confirmation for the presence or
absence of systematic errors in these high precision solubility
studies. Calorimetric data obtained at several temperatures
can also be combined with a single solubility measurement to
characterize the thermodynamics of the dissolution process
for a wide variety of gases.
I. EXPERIMENTAL
The principle of the steady-state method is to feed gas at
a constant rate into a heat conduction calorimeter where
dissolution occurs with a thermally equilibrated liquid (wa-
ter in our case) flowing through the calorimeter at a constant
rate. The power generated by the continuously dissolving
gas is detected by a semiconductor thermopile whose voltage
output is proportional to the power. Calibration of the pro-
portionality constant is achieved by use of precise electrical
resistance heating and measurement of the thermopile vol-
tage output.
The most critical aspect of the development of the in-
strument was the discovery of a suitable flat bubble design,
where water flows radially in a thin layer beneath the bubble
and the rate of dissolution of the gas is roughly proportional
to the thickness of the water layer. A relatively large flat
interface was found to give rates of gas dissolution that were
suitable for accurate calorimetric power measurement.
The attainment of the steady-state condition depends
upon a particular water layer thickness and the adjustment
of this was greatly facilitated by computer controlled feed-
back of the gas flow rate.
Details of the construction and operation of the calori-
meter are given in the following sections.
A. Calorimeter
A schematic diagram of the calorimeter and its immer-
sion submarine is shown in Fig. 1. The immersion submarine

765 Rev. Sci. Instrum. 55 (5), May 1984 0034-6748/84/050765-08$01.30 © 1984 American Institute of Physics 765

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 GAS temperature controlled environment. Tube (1) is thermally
IN LET
shorted to the calorimetric block by means of a thermal
shorting plug (d), and to the water bath by means of plug (k).
Two 0 rings supported in the Delrin plastic plug (p) serve to
seal the annular region between tubes (1, y). The region
between tubes (y, n) is sealed by the two 0 rings supported in
P plug (r), the upper 0 ring of plug (w), and by wax which is
allowed to flow between plug (w) and tube (n). The region
between tubes (m, n) is sealed by the lower 0 ring of plug (w),

-,f
I
w I-< I em
the upper 0 ring of plug (v), and by wax between tube (n) and
plugs (w, v). The region between tube (n) and the glass cy-
115mm clinder is sealed using the lower 0 ring of plug (v), the 0 ring
of the bell, and the wax seal between tube (n) and plug (v). A
copper disk (f), which is spring loaded (t), serves as a refer-
n
WATER ence cell.
I N LET Pure water, which is pumped into the reaction cell, is
m
brought to thermal equilibrium with the block by pumping
the water through lI8-in. annealed stainless-steel tubing em-
bedded in the thermal shorting plug (e) in the form of a spiral
(i). The water line entrance port is a flange (j). Commercial
thermopiles (h) (Meleor model CP 1.4-71-06L, Meleor,
Trenton, NJ) serve to conduct heat evolved in the calori-
meter (g, q) to the block. Both reaction and reference cells use
four of these units connected in series. The set of thermopiles
of the reference cell is connected in opposition to that of the
reaction cell. The temperature of the block, with respect to
the bath, is monitored by means of a thermopile which is

FIG. I. Calorimeter and immersion submarine. (a) Immersion submarine;

(b) submarine cover; (c) aluminum calorimetric block; (d), (e) thermal short-
ing plugs; (t) reference cell; (g) calorimeter cup; (h) thermopiles; (i) water line
m
spiral; water line entrance port; (k) thermal shorting plug; (I), (m), (n) con-
centric stainless-steel tubes; (p) Delrin plastic plug; (q) calorimeter bell; (r) h-----H--+
steel plug and gas injection port; (s) block support with bath thermopile; (t) t----I I em
spring load to dummy cell; (u) glass cylinder; (v) stainless-steel centering
plug,; (w) stainless-steel plug; (x) hydrophobic glass ring; (y) stainless-steel
tube; (z) spacers. e----+

(a) and its cover (b) are constructed from stainless steel. The
calorimetric block (c) is constructed from aluminum and
serves as the primary heat reservoir of the calorimeter. The
+----H~----g
calorimeter reaction cell consists of a gold-plated copper cup
(g), a gold-plated copper bell (q), a large diameter stainless-
steel tube (1) (diameter 1.625 in., O.020-in. wall), a glass ring r?-r~~4-----H2
(x), a glass cylinder (u), a stainless-steel centering plug (v), a b ---;,-tt.lf-?- d
stainless-steel tube (m) (3/4 in. in diameter, 0.Q10-in. wall), a
stainless-steel plug (w), a stainless-steel tube (y) (1.5 in. in
diameter, O.035-in. wall), and a stainless-steel plug (r). A a
length of lI16-in. stainless-steel tubing (n) is sealed to the top
of the bell with epoxy. Water tight seals between the other
FIG. 2. Calorimeter. (a) copper cup; (b) copper bell; (c) stainless-steel tube; (d)
various parts are made by means of 0 rings. This design hydrophobic glass ring; (e) water inlet line; (f) reaction zone; (g) stainless-
allows the bell portion of the cell to be removed from the m
steel gas inlet line; (h) stainless-steel tube; (i) stainless-steel centering plug;
calorimeter without removing the whole apparatus from its glass cylinder; (HI, H2) position of calibration heaters.

766 Rev. Sci. Instrum., Vol. 55, No.5, May 1984 Flow calorimeter 766

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 situated between the block and the block support (s) in con-
tact with the bath.
Two four-terminal calibration heaters, denoted by HI
and H2, were constructed from Jelliff Alloy 800 (269 fl /m)
(Jelliff Corp., Southport, CT) to give about 320 and 265 fl,
respectively. The location of these heaters is shown in Fig. 2,
which depicts the calorimeter portion of the reaction cell.
The calorimeter is defined by the copper cup (a) and the
copper bell (b). Water is pumped through line (e) and enters
at the center of the reaction zone (t). The bell/cup region is
thermally isolated from the upper portion of the calorimetric
block by a poor heat conductor, a glass cylinder (j), placed
between the bell, and the centering plug (i). A ground glass
ring (d) constructed from the outer cylinder of a lOO-cc sy-
ringe fits snugly onto the bell. A hydrophobic surface is
formed on the surface of the ring by allowing the glass ring
surface to react with a 20% (by volume) solution of dichloro-
dimethyl silane (Alfa Products, Danvers, MA) and toluene
for about 30 min. The hydrophobic surface permits the de-
finition of a highly stable gas-water interface. Twelve equal-
ly spaced flats on the flange of the centering plug (i) allow
water to be pumped out of the reaction zone (t). Gas is intro-
duced into the reaction zone (t) by means of tube (g). The
distance between the hydrophobic ring (d) and the copper
cup is reproducibly determined by means of the stainless-
steel spacers in the Delrin plug at the top of the reaction cell.
(See Fig. 1).
The overall relationship of the other components of the
system is shown schematically in Fig. 3. The submarine (b)
and its contents (c) are placed in a large water bath (a). Tem-
perature control to ± 0.001 K is obtained using a Tronac
PTC-40 (Tronac Inc., Orem, UT) precision temperature
controller (1) and a Lauda-Brinkman K-4/RD (Brinkmann
Instruments, Lauda Division, Westbury, NY) refrigerator
circulator (k), which provides a source of constant cooling
power. Stirring of the bath is obtained with an Eastern Mod-
el10 (Eastern Ind., Hamden, CT) 1/20 hp, 1735 rpm stirrer.
The temperature of the bath is monitored with a Hewlett-
abc
FIG. 3. Block diagram of system components. (a) water bath; (b) submarine;
(c) submarine contents; (d) freshwater supply; (e) peristaltic pump; (f) filter;
(g) water still; (h) peristaltic pump; (i) wastewater container (j) gas-tight sy-
ringes; (k) refrigerator circulator; (I) temperature controller; (m) balast vol-
ume.
767 Rev. ScI. Instrum., Vol. 55, No.5, May 1984
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Packard 2804A quartz thermometer (Hewlett-Packard Co.,
Palo Alto, CAl.
Water flow through the system is provided by two LKB
2132 (LKB Instruments, Rockville, MD) peristaltic pumps
(e, h). One pump (h) pumps deaerated water from a source of
gently boiling water (g) through the cell and to a waste con-
tainer (i). The second pump (e) maintains the level of water in
the still by drawing from a supply of fresh, deionized, dis-
tilled water (16 Mfl cm resistivity) (d). This freshwater is
prefiltered before addition to the still with a Diaflo-type PM-
10 ultrafiltration membrane (t) (Amicon Corp., Lexington,
MA). This double pump mode of operation minimizes the
amount of contamination caused by the decomposition of
the silicone rubber tubing used by the peristaltic pumps. The
tubing and filter are replaced after 1 week of use.
Accurate amounts of gas are added to the calorimeter
by means of two syringes (j). Large volumes are added with a
Hamilton 10 10-LTN (10 cc) gas tight syringe (Hamilton Co.,
Reno, NV) and small amounts with a Hamilton l002-LTN
(2.5 cc) gas tight syringe. Each syringe is thermostated with
water from the bath using a Micropump model 101-60 l-00B
centrifugal pump (Micropump Corp., Concord, CAl. Each
syringe is mounted on a Unislide model A 1506 CM preci-
sion screw (Velmex, Inc., East Bloomfield, NY). The 2.5-cc
syringe slide is driven by a Superior Electric model M061-
FDOR stepping motor (Superior Electric Co., Bristol, CT)
and the 1O-cc syringe slide is driven by a Geartronics model
2201200 gear motor (Geartronics Corp., North Billerica,
MA) geared down to 10 rpm.
Also shown in Fig. 3 is a large ballast volume (m). This
large volume (41) of air minimizes the effect of pressure fluc-
tuations in the system during the course of a gas dissolution
experiment.
B. Electronic components
A block diagram of the electronics used to run and
monitor experiments is shown in Fig. 4. A Hewlett-Packard
HP-85 computer is interfaced to the quartz thermometer
and a Keithley 181 nanovoltmeter via a Hewlett-Packard
HP-IB (IEEE) interface module (Hewlett-Packard 82937
A). The nanovoltmeter measures the differential voltage of
MUL TI- CONSTANT STEPPING
CURFtENT MOTOR
PROGRAMMER
SOURCE TRANSLATOR
GE AR MOTOR
' - - - - - - - - - - - - - - I M U L TI PROGRAMMER f------.J
INTERFACE
FIG. 4. Block diagram of electronic components.
Flow calorimeter 767
 the reaction and reference cell thermopiles. The analog out-
put of the nanovoltmeter is recorded on a Linear chart re-
corder (Linear, Irvine, CAl.
A Hewlett-Packard multiprogrammer (model 6940B)
is interfaced to the computer with Hewlett-Packard GP-IO
general purpose parallel interface module (Hewlett-Packard
82940A). The multi programmer has three accessory cards.
They are a Hewlett-Packard 69335A stepping motor card, a
Hewlett-Packard 69433A relay outputlreadback card, and
a Hewlett-Packard 69506A programmable resistance card.
The square-wave output of the stepping motor card is
fed into the superior electric model ST-101 stepping motor
translator which in turn drives the stepping motor. The pro-
grammable resistance card is connected to a Hewlett-Pack-
ard 6177 C dc constant current source and controls the mag-
nitude of the current output to the calibration heaters of the
calorimeter. The relay outputlreadback card has three func-
tions. Two of the relays are used as switches to select which
of the two calibration heaters of the calorimeter is to be part
of the calibration circuit. Another relay is used to vary the
output frequency of the stepping motor card from 667 to 120
pulses s - I. Two other relays each drive a Crydom model
5442 solid-state relay (International Rectifier, El Segundo,
CAl, located in the gear motor-multi programmer interface.
This allows clockwise and counterclockwise motion of the
gear motor to be computer controlled.
II. OPERATIONAL PROCEDURES
A. Instrument calibration
The thermopile of the instrument is calibrated by using
either of the two four-terminal calibration heaters HI or H2,
connected in series with a four-terminal precision resistor
(463.91 n). The electrical power generated in HI or H2 is
given by
p = VVs =~ V;
e Rs Vs Rs'
where Pe is the electrical power, V is the potential drop
across HI or H2, Vs is the potential drop across the standard
resistor, and R s is the resistance of the standard resistor. The
quantities Vand Vs are measured with the Keithley nano-
voltmeter (typical setting: 2 V range, high resolution on, fil-
ter on) for set values of the output current of the dc current
source. Values of Vs range from about 260 to 650 m V with a
resolution on the order of 5 /-lV. The standard error in Vs is
less than 0.004 mY. The ratio V IVs is then calculated for
each allowed current value and the resulting mean of V I Vs
for HI and H2 is, subsequently, used in calibration experi-
ments. For HI and H2, it was determined that V IVs are
0.686777 ± 0.000 010 and 0.567001 ± 0.000 040, respec-
tively.
A computer program is used to run and monitor the
calibration experiments and is designed to perform up to ten
independent experiments in series. In order to run a series of
calibration experiments, the calibration program param-
eters are preset by the operator. The parameters of the nano-
voltmeter are programmed for the whole series of experi-
768 Rev. Scl.lnstrum., Vol. 55, No.5, May 1984
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ments. Typical settings for the nanovoltmeter are the 20-m V
range with the high resolution and filter on. The heater and
current output are then preprogrammed for each experi-
ment in the series. When the calorimeter has reached a stable
base line, as determined by the trace on the chart recorder,
the program is allowed to begin execution. Usually, the com-
puter reads the voltage displayed by the nanovoltmeter every
5 s. These numbers are stored in computer memory for later
manipulation and storage on magnetic tape.
The calorimetric response of the system during a cali-
bration experiment is best described in terms of five time
periods. The data collected in the initial time period corre-
spond to the initial base line potential of the experiment.
Typically, initial and final base line data is accumulated for
10 min. When the initial base line has been collected the dc
current is turned on. The second time period is an exponen-
tial increase of the calorimetric response to a new steady
state. The length of this time period depends on the response
of the calorimeter. The third time period corresponds to the
accumulation of the observed steady-state potential data.
This time period is usually 10 min and as soon as the ob-
served steady-state data has been collected the dc current is
turned off. The fourth time period is an exponential decay of
the calorimetric response and the fifth time period is the time
during which the final base line potential data is collected.
The experiment is complete as soon as the final base line
potential has been collected. The computer then calculates
the power output of the calibration heater, the actual steady-
state potential, the mean temperature of the experiment, the
signal-to-noise ratio, the time response of the system (half-
life), and the calibration constant (power output of the cali-
bration heater divided by the actual steady state voltage).
The next calibration experiment in the programmed series is
then run and monitored. The above procedure is continued
until all of the series of calibration experiments are run and
analyzed. Calibration experiments are usually run once a
week. The time response of the system is such that a series of
(1 )
ten calibration experiments may be run in 24 h (five for each
heater).
B. Gas dissolution experiments
Our experience over the past 3 years has led to a system
which involves a mixture of computer control and data aqui-
sition with minimal operator assistance. The attainment of
the steady state is facilitated by computer control of the gas
flow rate and once reached the steady-state power output is
measured over a period of time, typically 1 h. The results of
these procedures is shown in Fig. 5 for the response of the
calorimeter when gas in introduced, steady state is achieved,
and finally when gas flow is stopped. The detailed manipula-
tions that are required to give this situation are outlined in
the following discussion.
The capacity of the dual-syringe system is large enough
to run two independent experiments. To run an experiment,
the system is closed to the atmosphere and when a stable base
line has been obtained the computer is instructed to begin
execution. The computer reads and stores the display of the
nanovoltmeter and thermometer every 5 and 60 s, respec-
Flow calorimeter 768
 (d) (e) (f)
(c)
--L
34fLWATTS OR 2.5fLV
(h) T The dual-gas syringe system is connected to the calori-
-l I HOUR r- (i)
FIG. 5. Recorder trace of voltage vs time for a typical gas dissolution experi-
ment. (Trial 10 Table I.) Steady-state gas flow of about 1.8 mllh into water
at 96 ml/h. (a) base line; (b) gas bubble formation; (c) effect of continued gas
addition; (d) period of computer adjusted flow rate; (e) final period of fixed
gas flow rate; (f) steady-state period; (g) decay period-zero gas input; (h)
effect of gas withdrawal (i) base line.
tively. Initial base line data is collected for 10 min [see (a) of
Fig. 5]. At this point, 8.8 to 9.4 X 10- 6 m 3 of gas is delivered
to the calorimeter with the lO-cc syringe at a rate of
1. 8 X 10 - 8 m 3 s - 1 to form the gas bubble. The calorimetric
response is (b) of Fig. 5. When the initial volume of gas has
been added the lO-cc syringe motion is halted and the 2.5-cc
syringe begins to add gas at some preprogrammed rate (typi-
cally 4.0 to 6.7X 10- 10 m 3 S-I) for the next 1400 s. The ca-
lorimetric response is region (c) of Fig. 5. At this point the
computer begins a steady-state gas input rate search and set
routine. The computer adjusts the gas input rate to reHect
the output of the thermopiles relative to a preprogrammed
calibration gas How rate and the estimated output voltage.
The calibration How rate and voltage are estimated the first
time a gas is studied. Thereafter, results from previous gas
dissolution experiments may be used. The search and set
routine is an iterative procedure. The computer adjusts the
gas How rate every 100 s for the next 500 s and then continues
to add gas at a final How rate as determined by the fifth
iteration. The response of the calorimeter during the search
and set routine is (d) of Fig. 5. The calorimetric response is
usually within 1% of the steady-state value, which is reached
by natural adjustment of the thickness of the water layer
beneath the gas bubble in order to accommodate the fixed
gas How rate (e). The smaller the thickness of the layer, the
larger the rate of dissolution. The iterative gas input rate
adjustment procedure is essential to obtaining acceptable
steady states in a reasonable time period.
The response of the calorimeter during the steady-state
addition of gas is (t) of Fig. 5. After a sufficient data collec-
tion interval (generally 1200 s) the gas input is terminated.
Note that the reaction zone is still occupied by gas. The ca-
lorimetric response is observed to decay as depicted by (g) of
Fig. 5. At the end of this steady-state decay period, the gas is
withdrawn from the bell/cup region and the calorimetric
response is observed to decrease to a final base line, parts (h)
and (i) of Fig. 5, respectively. The computer stores the vol-
tage data on magnetic tape, calculates the mean temperature
of the experiment, the actual steady-state voltage, and the
steady-state gas rate stepping motor frequency (total number
769 Rev. Sci. lnstrum., Vol. 55, No.5, May 1984
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132.204.37.217 On: Mon, 01 Dec 2014 20:32:48
of steps divided by total time). A second experiment may
now be run. Four experiments may be run in a 24-h period.
C. Miscellaneous procedures
meter, a vacuum pump, and the source of gas by a set of
Whitey model SS-OVM2 valves (Whitey Co., Highland
Heights, OH). Gas enters the syringes after passing through
a bubbler filled with water. This saturates the gas phase with
water vapor.
The amount of gas displaced per step of the stepping
motor is determined by weighing the amount of water dis-
placed by a known number of steps. The accuracy of this
measurement is better than 0.07%.
The value of the calorimeter calibration constant de-
pends on the rate at which water is pumped through the cell.
For this reason, the water How rate is measured daily by
weighing the amount of water pumped by the peristaltic
pumps per unit time.
The pressure of the system is the sum of the atmospher-
ic pressure and that due to the water head on the bubble. The
atmospheric pressure is measured with a mercury barom-
eter. The pressure due to the water head is measured with a
water manometer placed between the peristaltic pump (h) of
Fig. 3 and the reaction cell.
III. PRINCIPLES OF THE STEADY·STATE METHOD
A major effort of our work has been to develop a system
where the basic properties of rate of gas dissolution into a
Howing water layer could be investigated and understood in
simple terms. The system may be considered to consist of a
syringe with volume Vs connected to a gas of volume Vg in
contact with the water layer of volume Vw ' The total volume
is the sum of three. The pressure within the system is essen-
tially constant from the nature of the experimental appara-
. tus so one may consider the effects of gas dissolution in terms
of these volumes. As the syringe moves to decrease Vs the
water layer volume Vw decreases unless gas is dissolving to
decrease Vg • A steady state is achieved when Vw is constant
and the rate of syringe volume change is equally opposite to
the rate of gas volume change, i.e.,
dVs dVg dVw
--+--=0 when --=0. (2)
dt dt dt
Unfortunately, we do not have a direct way to tell what the
actual water layer thickness or Vw is at this condition. How-
ever, the measured calorimeter voltage output E is directly
proportional to (dVg/dt) under steady-state conditions. By
recognizing the calorimeter time response one can obtain the
corrected Ec values that give values of (dVg/dt) under gen-
eral time-dependent conditions.
If we consider what happens following an initial steady-
state condition [It) of Fig. 5] by holding the syringe volume
constant, then we see an immediate decrease in calorimetric
power as the rate of gas uptake decreases due to an increase
in the water layer volume [(g) of Fig. 5]. This situation is
given by
Flow calorimeter 769
 dVg dVw dVs
- - + - - = 0 when --=0. (3)
dt dt dt
The increase in water layer volume following stoppage of the
syringe motion is given by the integral of the rate of gas
volume uptake (or the time response corrected voltage of the
calorimeter) :
.1 Vw = f( d;g )dt = k fEc dt, (4)
where k is the conversion factor relating calorimeter
voltage to gas uptake. A specific application of this equation
to the dissolution of oxygen following an initial steady-state
condition gives the dependence of the rate of dissolution
(dVg/dt) upon the increase in layervolume.1 Vw (Fig. 6). The
important feature of these measurements is the apparent lin-
ear decrease in dissolution rate with layer thickness. The
maximum rate of gas dissolution apparently occurs when the
layer has zero thickness. Extrapolation of this linear relation
to the value of maximum rate of dissolution as determined by
the solubility of oxygen and the rate of water flow, i.e., (dVg /
dt )max = 7.4 X 1O~ 10 m 3 s ~ I gives a new origin for Fig. 6 at
5400 X 1O~ 10 m 3 for this particular experiment. These fea-
tures of the dissolution process allow the system with water
and gas flowing to automatically reach a steady-state condi-
tion. The time to reach this condition depends on the starting
water layer thickness, the solubility of the gas, and the water
and gas flow rates.
IV. CALCULATION PROCEDURES
The formulation of the principles used in the steady-
state method has been given. II The power (P) generated with
the introduction of the gas bubble into the calorimeter is the
sum of three effects: (1) the gas dissolution Pg , (2) the water-
vapor condensation P w , and (3) the change in water flow-
viscous heating due to the presence of the bubble Pb. In the
present design, no pressure drop effect could be observed
upon introduction of the gas bubble and thus the third power
contribution was negligible. The heat of solution .1Hsol may
5,--------------------------------,
...-
CIl
>< 2 the heat flow pattern of the process of interest. One goal of
-$"1-
"0 "0
I
o 5000
FIG. 6. Plot of the gas dissolution rate vs change in volume of the water layer
under steady-state decay conditions.
770 Rev. Sci. Instrum_, Vol. 55, No.5, May 1984
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then be expressed II as follows:
(5)
wherepw andpg are the water vapor and gas pressures, (dV /
dt ) is the steady-state gas flow rate, .1Hcond is the enthalpy of
water-:vapor condensation, Bw and Bg are the second vi rial
coeffiCients for water and gas, and R is the gas constant.
Values of .1 Hcond , p w , B H 0' and B 0 were taken from the
literature. 15-17 The determination of P'is made by multiplica-
tion of the steady-state calorimeter output voltage E by the
calorimeter calibration constant c. Thus, all the necessary
quantities for evaluation of llHsol are available.
V. RESULTS AND DISCUSSION
The overall stability of the system may be judged from
the long-term drift of the base line output of the thermopiles.
Over a time span of 3 h the base line is rarely observed to
change more than 50 n V or 0.7 J.l W. In fact, for a gas dissolu-
tion experiment, which requires on the order of 3 h for com-
pletion, the difference between the initial and final base line
potentials is generally about 20 n V.
Typical signal-to-noise ratios for power levels the order
of 200 J.l Ware about 2000 and 1000 for electrical calibration
experiments and gas dissolution experiments, respectively.
The fluctuations in the calorimetric response are larger
when a gas bubble is present due to pressure fluctuations in
the system.
Elimination of systematic errors in the calibration of a
calorimeter is a nontrivial task. The solution to the problem
is potentially more difficult to find in the case of a flow calor-
imeter where heat is constantly removed from the detection
region by the transport of fluid out of this region. The two
classical methods of calibration are to add energy to the sys-
tem electrically or via some physical or chemical process and
to measure the response of the system per unit energy or
power input. The latter method has the advantage that it
may be possible to produce a heat flow pattern out of the
reaction region, which corresponds exactly to that of the
process of interest. The difficulty with this method is that the
heat effect per unit physical or chemical process must be
obtainable from some other method. This information is not
always available. On the other hand, electrical energy or
power can be easily and accurately measured. The difficulty
with this method is that it is not always possible to duplicate
our work was to develop a fundamental method to directly
measure the enthalpy of dissolution of slightly soluble gases
into water. Thus, it is desirable to electrically calibrate the
instrument in order to obtain an absolute calibration.
In order to investigate the calibration problem, two
calibration heaters in radically different positions were built
into the system. Heater HI is embedded in the reaction cell
cup in a position such that it is roughly in the same plane
where the gas is dissolving into the flowing water. Heater H2
Flow calorimeter 770
 500,-----------------------------~r__, 14.0 ,----------------------------------,

~400
I--
I-- I--
<l ...J 13.5
3: 300
o
::1.. >
.....
I--
a:: I--
<l
~ 200 ~
o - 13.0
CL

CL 100

I 2.5 '---------------'------------'------------'
o 10 20 30 40 o 10 20 30
E POTENTIAL (!LVOLT)
dV w x I09(m3 xs- l )
dt
FIG. 7. Plot of Heater HI output power vs calorimetric response.
FIG. 8. Plot of calibration constant vs water flow rate. D. heater HI; 6.
heater H2.
is embedded in the upper portion of the calorimeter bell.
Figure 7 shows a plot of the power output of heater HI of the fit is well within the experimental error. The fact that
versus the calorimetric response. The response is linear in the calorimetric response varies linearly with the output
both cases (HI and H2) over a wide range of output power. power has an important consequence, i.e., the calorimetric
The fit to a straight line of power versus voltage yields stan- response at any steady state is easily converted to the power
dard errors of a point of 0.6 and 0.3 flW for HI and H2, being produced using a simple multiplicative factor.
respectively, for powerlevels greater than 150fl W. The error A plot of the calibration constant (€) versus the water

TABLE I. Results of steady-state solution measurements with O 2 at 298.15 K:pg is pressure of gas; (dV /dt) is the gas flow rate; Eis the electrical calibration
factor; E is the calorimeter voltage output under steady-state conditions. Water flow rate is 2.7 X 10- 8 m 3 s - '. Uncertainty given at twice the uncertainty of
the means.

Trial pg/(kPa) (dV Idt)X 101O/(m3 s-') d(JY-' s-') E /(jlY) - 4H,0' /(kJ mol-')

1 86.80 5.132 13.682 17.833( ± 0.013) 11.961

2 86.32 5.113 13.684 17.746( ± 0.009) 12.016
3 86.40 3.769 13.684 12.991( ± 0.019) 11.912
4 86.40 4.997 13.684 17.399( ± 0.014) 12.049
5 86.20 5.094 13.684 17.724( ± 0.027) 12.067
6 86.17 4.821 13.671 16.978( ± 0.019) 12.224
7 86.54 4.763 13.671 16.743( ± 0.022) 12.114
8 86.54 4.780 13.671 16.704( ± 0.015) 12.065
9 86.60 4.886 13.671 17.096( ± 0.015) 12.075
10 86.60 5.015 13.671 17.532( ± 0.011) 12.061
11 86.87 5.054 13.671 17.678( ± 0.020) 12.033
12 86.87 5.053 13.671 17.685( ± 0.022) 12.004
13 86.79 4.062 13.671 13.963( ± 0.053) 11.808
14 86.79 4.904 13.671 17.096( ± 0.018) 11.999
15 86.00 4.729 13.685 16.450( ± 0.017) 12.093
16 86.00 4.597 13.685 16.049( ± 0.017) 12.142
17 86.92 4.797 13.685 16.702( ± 0.019) 11.976
18 86.88 4.573 13.610 16.198( ± 0.014) 12.142
19 86.88 4.703 13.610 16.616( ± 0.016) 12.107
20 87.40 4.823 13.654 17.034( ± 0.017) 12.075
21 87.40 4.805 13.654 16.856( ± 0.015) 11.982
22 87.41 4.754 13.654 16.715( ± 0.012) 12.010
23 86.76 4.913 13.654 17.181( ± 0.019) 12.027
24 85.81 4.117 13.654 14.607( ± 0.019) 12.360
25 85.81 4.510 13.654 15.750( ± 0.013) 12.141
26 86.40 3.296 13.629 11.424( ± 0.019) 11.931
27 87.28 4.017 13.642 14.239( ± 0.012) 12.127
28 87.28 4.277 13.642 14.940( ± 0.012) 11.926
29 87.40 4.196 13.642 14.871( ± 0.011) 12.109
30 87.40 4.435 13.642 15.589( ± 0.017) 11.996
31 87.27 4.406 13.642 15.448( ± 0.010) 11. 981
32 87.65 4.263 13.642 14.916( ± 0.012) 11.898
33 87.65 4.390 13.642 15.503( ± 0.011) 12.022
34 87.70 4.236 13.642 14.799( ± 0.017) 11.873
35 87.70 4.391 13.642 15.380( ± 0.013) 11.908
36 87.55 4.391 13.642 15.311( ± 0.014) 11.868
Mean 12.031 ± 0.036

771 Rev. Scl.lnstrum., Vol. 55. No.5, May 1984 Flow calorimeter 771

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 flow rate through the reaction cell is shown in Fig. 8. The
calibration constant varies linearly with flow rate for both
heaters. The fit to a straight line of the calibration constant
versus the water flow rate gives standard errors of a point of
0.028 and 0.033 WIV for HI and H2, respectively. Note that
heater HI has a slightly larger calorimetric response than
H2, the difference between the calibration constants for HI
and H2 being essentially independent of the water flow rate.
The calorimetric response of both heaters is observed to de-
crease as the water flow rate increases. This is due to the fact
that the residence time of the relatively hotter water which is
pumped out of the bellicup region decreases as the flow rate
increases.
As shown in Fig. 8, the agreement between the calibra-
tion constants of the two heaters is very good (about 1.0%
difference over the entire water flow rate range). We feel the
agreement is as good as it is because the bell and cup of the
reaction cell, both constructed from copper, are effectively
thermally shorted to each other. The heat flow pattern due to
the dissolution of gas is between that produced solely by HI
and H2. Thus, an average value of the two calibration con-
stants is used. The time response of the calorimeter was
found to be characterized by a half-life of 160 s with water
flowing at 2.8 X 10- 8 m 3 S-I.
In order to further test the accuracy of this system we
have chosen to use oxygen as a standard, since the solubility
of this gas has been determined to the highest precision of
any gas yet studied. 14
Results for the enthalpy of dissolution of oxygen gas
into water at 298.15 K are given in Table I. The oxygen used
in the experiments was research grade oxygen (minimum
purity 99.999%) obtainable from Scientific Gas Products
(Scientific Gas Products, Inc., South Plainsfield, NJ). The
mean value of J1Hsol for 36 measurements taken over a peri-
od of 6 months is - 12.031 kJ/mol with twice the standard
deviation of the mean of 0.036 kJ/mol. These results are to
be compared with those derived from the temperature-de-
pendent solubility measurements of Benson and Krause l4
who obtained J1Hsol = - 12.02 kJ/mol and the results of
Wilhelm et a/. 8 who give J1 Hsol = - 12.06 kJ/mol as de-
rived from earlier solubility measurements. No indication of
the error is given in these values which are derived from the
temperature dependence of solubility. The statistical analy-
sis of Clarke and Glew l2 gives a means for estimation of the
precision ofthe enthalpy change in terms: (1) of the tempera-
tures over which solubility data is given and (2) the precision
772 Rev. ScLlnstrum., Vol. 55, No.5, May 1984
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of the fit of the solubility data to a Taylor series equation.
The estimated standard error of the fit to the superb data of
Benson and Krause l4 is 0.02% which gives an estimated
standard error of 2 J mol- I for J1Hsol at 25°C. The estimat-
ed standard error of 0.5% for the fits obtained by Wilhelm et
al. 8 1eads to an estimated standard error of J1Hsol at 25°C of
20 J mol-I. Based on the 36 results listed in Table I, the
precision (one standard deviation) of our method is about 18
J. Our enthalpy of solution is 0.1 % higher and 0.3% lower
than the enthalpies of solution of Benson and Krause l4 and
Wilhelm et al. 8 , respectively. The agreement is perhaps bet-
ter than one could expect from the 1.0% difference given
between our two calibration heaters. In fact, it lends support
to the use of the average calibration constant. The compari-
son with the value of 12.056 ± 0.019 kJ mol- I obtained in
the batch calorimeter procedure I I is also indicative that the
methods developed in this work are capable of high-preci-
sion determination. The general agreement of these various
determinations by different experimental methods provides
strong support for the absence of systematic error.
ACKNOWLEDGMENTS
This work was supported by NSF Grant PCM8019930.
We want to express our thanks to Professor Ingemar Wad so
for his counsel and helpful discussions on many aspects of
this work.
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Flow calorimeter 772