Annals of Nuclear Energy 106 (2017) 136–142

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Annals of Nuclear Energy

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Effects of temperature and pressure on Henry’s law constant for

hydrogen in the primary water of a simulated pressurized-water reactor
Eun-Hee Lee ⇑, Gyeong-Geun Lee, Kyung-Mo Kim
Korea Atomic Energy Research Institute, 989-111 Daedeok-daero, Yuseong-gu, Daejeon 34057, Republic of Korea

a r t i c l e i n f o a b s t r a c t

Article history: The measurement of dissolved hydrogen in the primary systems of pressurized water reactors (PWRs) is
Received 31 July 2015 difficult; hence, hydrogen concentrations are predicted by model equations. An accurate value for the
Received in revised form 30 March 2017 Henry’s law constant for hydrogen is needed if the use of these equations is to be meaningful. The pur-
Accepted 2 April 2017
pose of this study is to develop an empirical correlation for determining the Henry’s law constant for
Available online 10 April 2017
application to nuclear reactors. The effects of temperature and pressure on the Henry’s law constant
are investigated using simulated PWR primary-water conditions. The Henry’s law constant was calcu-
Keywords:
lated by an in-situ measurement of the partial pressure of hydrogen using a hydrogen sensor based on
Henry’s law constant
Hydrogen
a Pd–Ag alloy tube. At 20 MPa, the Henry’s law constant decreased by
40% as the temperature increased
PWR from 290 to 330 °C. The Henry’s law constant increased by an average of 9% as the pressure increased
PWSCC from 13.8 to 20 MPa at each temperature. Thus, it depends more strongly on the temperature than on
Temperature and pressure the pressure. Based on the experimental data, an empirical correlation for predicting the Henry’s law con-
stant was developed using a linear regression method, which was validated by comparing with results in
the literature. The deviation between the Henry’s law constant obtained using our model and that
reported in the literature was in the range of 0.5%–10%. The hydrogen fugacity estimated using our model
was within 10% of that found in the literature. Thus, the proposed empirical model appears to be more
accurate than previously published models.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction
In pressurized-water reactors (PWRs), hydrogen is added to the
reactor coolant system (RCS) to reduce the oxidation of water by
radiolysis and to maintain reducing conditions. It is important to
maintain the hydrogen concentration within a certain range. This
is because this parameter can lead to primary water stress corro-
sion cracking (PWSCC), general corrosion of the primary structural
materials, higher radiation fields, and deposit build-up on fuel rods
of a PWR (Fruzetti, 2005). Several researchers have demonstrated
that the hydrogen concentration influences the corrosion of struc-
tural materials in PWRs (Cassagne et al., 1997; Lee et al., 2002;
Ahluwalia, 2007). However, the amount of dissolved hydrogen,
which affects the material susceptibility, exhibits a wide scatter.
Computational work has suggested that dissolved hydrogen con-
centrations lower than 15 cc/kg are sufficient to scavenge oxidizing
species under normal PWR operating conditions (Fruzetti, 2005).
During operation, the concentration of dissolved hydrogen is con-
trolled by varying the hydrogen overpressure in a volume control
⇑ Corresponding author.
E-mail address: ehlee@kaeri.re.kr (E.-H. Lee).
tank (VCT). Since the primary water flows from the VCT into the
RCS, the temperature, system pressure, and solution chemistry in
the RCS can affect the hydrogen concentration. In addition, hydro-
gen from the RCS diffuses through the steam generator tubes. To
ensure an optimal operating margin, the Electric Power Research
Institute (EPRI) PWR primary chemistry guide-lines require hydro-
gen levels of 25–50 cc/kg as an optimal margin. To mitigate
PWSCC, the recent EPRI Hydrogen Management Program for fuel
and material reliability focused on plant operations using hydro-
gen levels of up to 60 cc/kg (Hass et al., 2010). The optimization
of the hydrogen concentration in the RCS is regarded as one
approach to the management of material integrity and the reduc-
tion of radiation sources in the primary circuit.
The solubility of gases in water and aqueous solutions is of con-
siderable industrial and theoretical importance. Solubility depends
on many factors, including temperature, pressure, association, dis-
sociation, and the type of solvent (Himmelblau, 1960). However,
inert gases like the hydrogen that is used in the RCS of PWRs do
not react with water or ionize in water, so only the effects of tem-
perature and pressure on the solubility are considered. The amount
of hydrogen dissolved in water is directly proportional to the
hydrogen fugacity (hydrogen partial pressure) in the gaseous

http://dx.doi.org/10.1016/j.anucene.2017.04.001
0306-4549/Ó 2017 Elsevier Ltd. All rights reserved.
 E.-H. Lee et al. / Annals of Nuclear Energy 106 (2017) 136–142
phase. Thus, the measured hydrogen fugacity can be used to calcu-
late the Henry’s law constant (Himmelblau, 1960). The Henry’s law
constant is important because it is necessary to predict the dis-
solved hydrogen concentration in a PWR. Using the Henry’s law
constant, the amount of dissolved hydrogen at a given temperature
and pressure can be calculated. Alternatively, when the dissolved
hydrogen concentration is known, the hydrogen fugacity can be
determined using the Henry’s law equation. The values obtained
for the dissolved hydrogen concentration affect the Ni/NiO phase
transition in nickel-based alloys, shifting the Ni/NiO phase bound-
ary up or down. For PWRs, these data can yield erroneous results in
the prediction of PWSCC, and hinder the development of a model
to fit the hydrogen concentrations (Attanasio and Morton, 2003;
Lee et al., 2002; Moss and Was, 2015). Thus, accurate means of
measuring and monitoring the hydrogen fugacity in PWRs are
needed.
In the present study, to measure the hydrogen partial pressure,
we fabricated a sensor based on a Pd–Ag (75/25 wt.%) tube. Using
this sensor, we measured the hydrogen partial pressure in situ as a
function of temperature and pressure in a simulated PWR primary
solution containing lithium hydroxide (LiOH) and boric acid
(H3BO3). Based on the data collected in our experiments, an empir-
ical correlation for predicting the Henry’s law constant was devel-
oped using a linear regression method. It was validated by
comparing the obtained results with the values reported in the
literature.
2. Theoretical background
2.1. Solubility of hydrogen in water
The solubility of hydrogen in water can be determined using the
findings of Henry, given by Eq. (1) and known as Henry’s Law
(Himmelblau, 1960).
f ¼Hx/
where f = fugacity of the solute gas in the vapor phase, H = Henry’s
law constant, x = mole fraction of the solute gas in the liquid phase,
and U = activity coefficient of the solute gas in the liquid phase. For
inert gases such as hydrogen, oxygen, and nitrogen, which obey the
ideal gas law in the vapor phase above the solution, Eq. (1) can be
rewritten to give Eq. (2).
p¼Hx
where p = partial pressure of hydrogen in the vapor phase and U = 1
for ideal solutions. Himmelblau developed theoretical equations to
determine the Henry’s law constant of inert gases at different tem-
peratures using the data reported in the literature. In developing
the modified Henry’s law equations, Himmelblau used high-
pressure data extrapolated to low pressures, and thus considered
only the effect of temperature. He then correlated the solubility
data with various data plots. The plotted data in the graph are cor-
related by Eqs. (3)–(5) (Himmelblau, 1960).

logH ¼ 1:142  2:846ð1=TÞ þ 2:486ð1=TÞ2  0:9761ð1=TÞ3
þ 0:2001ð1=TÞ4
H ¼ H=Hmax
ð1=TÞ  ð1=T c Þ
ð1=TÞ ¼
ð1=T max Þ  ð1=T c Þ
where Hmax  104 = 7.54, (1/Tmax)  103 = 3.09, and Tc = critical
temperature of water (647 K).
However, Himmelblau’s study was limited to the effect of tem-
perature on solubility. In addition, the calculated Henry’s constants
137
are for ideal gases and solutions, and are applicable to low pres-
sures only. For hydrogen, the low pressures appear to be
10.3 MPa (1500 psia) at 100 °C and about 13.8 MPa (2000 psia) at
300 °C (Himmelblau, 1960). Many researchers have used the
Henry’s law constants determined by Himmelblau’s equations to
calculate the hydrogen partial pressures or hydrogen concentra-
tions at different temperatures. However, experimentally mea-
sured Henry’s law constants have proven to be quite different
from those calculated from Himmelblau’s equations (Lee et al.,
2002). This difference arises because his equations assume the con-
centration of dissolved hydrogen in water to be independent of
pressure. This assumption gives rise to the difference between
the theoretical and experimental data.
2.2. Sensor for measuring hydrogen partial pressure
The accuracy of the hydrogen-fugacity measurement was also
affected by the hydrogen-sensing materials used. Considerable
research has been directed toward developing high-performance
hydrogen sensors with high permeability, high selectivity, a fast
response time, cost-effective fabrication, and which are easy to
use. Among the various hydrogen-sensing materials tested, metal-
lic palladium (Pd) exhibits high permeability and selectivity with
hydrogen (Ackerman and Koskinas, 1972; Yang et al., 1998). How-
ever, pure Pd undergoes phase transition and hydrogen embrittle-
ment at high temperatures and pressures, leading to fragility after
extended use. To avoid these problems, alloying of Pd with group
IB metals such as Ag was attempted and an optimal value of hydro-
gen permeation was attained at an Ag content of
25 wt.%
(Knapton, 1977; Foletto et al., 2008). The advantage of using a Pd
alloy is that the mechanical strength of the sensor is greater than
that of one made from pure Pd. Several researchers have studied
the effects of various parameters on the permeation of hydrogen
ð1Þ through hydrogen sensors constructed using a Pd–Ag tube, film,
and wire (Economy et al., 1987; Wang and Feng, 2007; Foletto
et al., 2008).
3. Methods
ð2Þ 3.1. Test loop
Fig. 1 shows a schematic of the test loop that we used. The
hydrogen sensor was mounted in an autoclave with a temperature
control precision of ±0.5 °C. Then, 100 l of the test solution was
prepared by adding 2 ppm of nuclear-grade lithium (as LiOH)
and 1200 ppm of boron (as H3BO3) to purified water produced
using an ultrapure water system (18 MOcm). This setup was used
to simulate the representative PWR primary water chemistry. The
amount of dissolved hydrogen was controlled by fixing the hydro-
gen overpressure in the feed tank at a temperature of 21 ± 1 °C. The
amount of dissolved hydrogen was calculated using the Henry’s
ð3Þ law constant for 5.7 kPa (0.826 psia)/(cc/kg) (Himmelblau, 1960).
The solution from the feed tank was fed into the autoclave using
a high-pressure pump and a double-tube heat exchanger. The out-
ð4Þ
let solution from the autoclave was cooled to ambient temperature
by passing it through a heat-exchanger and a cooler, after which it
ð5Þ passed through the sensors for measuring the conductivity and dis-
solved oxygen content. Finally, the solution was returned to the
feed tank. The dissolved oxygen concentration was measured using
a DO-32A (TOADKK Co.) and recorded manually. Throughout the
experiments, the measured oxygen concentration was less than
1 ppb.
138 E.-H. Lee et al. / Annals of Nuclear Energy 106 (2017) 136–142

Fig. 1. Schematic of simulated primary test loop used for measuring hydrogen fugacity in situ.

3.2. Hydrogen sensor

The hydrogen sensor was fabricated using a Pd–25 wt.% Ag tube

with an active length of 200 mm, an outside diameter of 3.2 mm,
and a wall thickness of 0.43 mm (Lee et al., 2002). The inside of
the tube was reinforced with a spring-type Inconel wire to prevent
the collapse of the Pd–Ag tubing when subjected to a system pres-
sure of 21.4 MPa (3100 psia) in the autoclave. Type 316 stainless-
steel tubing was connected to one end of the Pd–Ag tube while
the other end of the tube was connected to the exit of the pressure
boundary. The joint between the 316 stainless-steel tubing and the
Pd–Ag tubing was gold-brazed. The other extremity of the Pd–Ag
tube was sealed with an Inconel plug. The amount of hydrogen per-
meating from the solution through the Pd–Ag tube wall was mea-
sured by an external low-pressure gauge and a vacuum pump.

Fig. 2. Comparison of Henry’s law constants obtained from experimental measure-

3.3. Measurement of hydrogen partial pressure ments and theoretical calculations at different pressures and temperatures.

The Henry’s law constant was determined by measuring the

hydrogen partial pressure in situ at various temperatures (290,
300, 310, 320, and 330 °C) and pressures (13.8/2000, 15.2/2200,
17.9/2600, and 20 /2900 MPa/psia) in an aqueous hydrogenated
solution. The system reached thermodynamic equilibrium in 4 to
12 h, depending on the temperature. After 48 h of equilibrium,
the measurements were performed. All the measurements were
repeated three times to obtain reliable data. The measured hydro-
gen partial pressure was considered to be the hydrogen fugacity in
the autoclave at the given temperature and pressure. The Henry’s
law constant was calculated by dividing the measured fugacity
by the dissolved hydrogen concentration in the feed water.
with the hydrogen concentration and decreased with increasing
temperature. No solution-concentration effect on the hydrogen
partial pressure was observed, indicating that the hydrogen partial
pressure was the same between water and the aqueous solution
within the tested temperature range. These results agree reason-
able well with the literature and our data, and confirm the reliabil-
ity of the Pd–Ag tube for the measurement of the hydrogen partial
pressure (Attanasio and Morton, 2003).
4.2. Effects of temperature and pressure on Henry’s law constant

4. Results and discussion
4.1. Hydrogen-sensor validation
In this study, the hydrogen partial pressure was measured in an
aqueous solution of 2 ppm lithium and 1200 ppm boron using the
Pd–Ag tube at temperatures ranging from 290 to 330 °C and at
20 MPa. These values decreased linearly as the temperature
increased and the determined Henry’s constant was shown in
Fig. 2. Lee et al. (2002) measured the hydrogen partial pressure
using the same Pd–Ag tube that we used in the present study.
The effects of the dissolved hydrogen and lithium/boron-solution
concentration on the hydrogen partial pressure were examined.
They reported that the hydrogen partial pressure increased linearly
Fig. 2 shows the results of the present study and those available
in the literature. In the present study, the Henry’s law constant was
calculated as a function of the temperature at 20 MPa according to
the measured hydrogen fugacity. The Henry’s law constants
reported in the literature (Kishima and Sakai, 1984; Moshier and
Witt, 2002; Moss and Was, 2015) were also plotted for various
pressures, in MPa. These data were determined by the hydrogen
fugacity or dissolved hydrogen content, which were measured
while the temperature and pressure varied. Himmelblau (1960)
and Ziemniak (1992) obtained the Henry’s law constants using the-
oretical equations inferred by thermodynamic data. As shown in
Fig. 2, the Henry’s law constant decreased linearly as the tempera-
ture increased and increased with the pressure at any given tem-
perature. However, none of the plotted data can be compared
quantitatively, because of the different measuring pressures. A
 E.-H. Lee et al. / Annals of Nuclear Energy 106 (2017) 136–142
substantial deviation between the experimental data and the the-
oretical estimation can be seen. This is because the assumption
involved in most of the theoretical equations (that the Henry’s
law constant is independent of the pressure) produced inadequate
results. Himmelblau’s study (1960) examined only the effect of the
temperature on the solubility of the gases: the effect of the pres-
sure was disregarded. Himmelblau used high-pressure data that
were extrapolated to low pressures. Ziemniak (1992) introduced
only the effect of the pressure into the thermodynamic calculations
of the Henry’s law constant at supercritical temperatures.
Fig. 3 shows the results of the present study, in which the
Henry’s law constant, as a function of the temperature and pres-
sure, was determined using the measured hydrogen fugacity. The
Henry’s law constant decreased linearly as the temperature
increased from 290 to 330 °C and increased as the pressure
increased from 13.8 to 20 MPa. These temperature and pressure
dependences of the Henry’s law constant are consistent with the
results of other studies, which are plotted in Fig. 2. When the tem-
perature increased from 290 to 330 °C at 20 MPa, the Henry’s law
constant decreased to
40% of its value at 290 °C. The Henry’s
law constant increased by an average of 9% as the pressure
increased from 13.8 to 20 MPa. It depended more strongly on the
temperature than on the pressure.
4.3. Development of empirical model
Various theoretical models for estimating the Henry’s law con-
stant can be found in the literature. However, some of these mod-
els disregard the effect of the pressure on the Henry’s law constant
(Himmelblau, 1960; Ziemniak, 1992), considering only that of the
temperature. It may be possible to disregard slight changes in
the pressure; however, as shown in Fig. 3, the Henry’s law constant
was found to decrease by a maximum of 9% with the pressure in
the present study. We developed an empirical model to estimate
the Henry’s law constant, considering the effects of the tempera-
ture and pressure. The model is based on the experimental data
obtained in this study. Because the data shown in Fig. 3 exhibits
a linear correlation between the reciprocal temperatures and pres-
sures and the Henry’s law constant, the following multiple-
regression model can be applied.
Y ¼ A þ Bð1=TÞ þ CðPÞ;
where Y is the predicted Henry’s law constant, which is expressed in
units of atm/(cc(STP)/kg-water); T is the temperature in Kelvin; P is
the system pressure in psia (1 psia = 6.9 kPa); and A is the regres-
Fig. 3. Henry’s law constants calculated using the hydrogen fugacity, measured as a
function of the temperature and pressure in an aqueous solution containing 2 ppm
lithium and 1200 ppm boron.
139
Fig. 4. Comparison of Henry’s law constants obtained using the present model with
experimental data as a function of the reciprocal temperature.
sion constant. The regression coefficients B and C represent the
independent contributions of each independent variable to the pre-
diction of the dependent variable. The regression analysis indicates
that A, B, and C have values of 0.06568, 42.219, and 1.12  106,
respectively. Eq. (6) can be rewritten as follows:
Y ¼ 0:06568 þ 42:219  T 1 þ 1:12  106  P ð7Þ
The coefficient of determination (R2) used to statistically evalu-
ate the model fit is 0.999232. This model equation can be used to
estimate the Henry’s law constant if no data are available for a
temperature range of 290–330 °C and a pressure range of 13.8–
20 MPa. With the calculated Henry’s law constant, the concentra-
tion of the dissolved hydrogen or the hydrogen fugacity in an aque-
ous solution can be obtained using Henry’s law equation
(Himmelblau, 1960).
4.4. Model validation
Fig. 4 compares the Henry’s law constant calculated using the
present model with the experimental data obtained in the present
study. There is excellent agreement between the linear fit and
ð6Þ
experimental data. At 13.8 MPa and at 330 °C, no experimental
data were obtained, because of problems with the apparatus. Thus,
the value for this temperature and pressure was estimated using
Eq. (7) and then extrapolated to fit the experimental results, as
shown in Fig. 4. This estimated value also agrees well with the
trend of the experimental data.
Table 1 shows that both the Henry’s law constants reported in
the literature and those calculated using the present model agree
well with the data in the literature (Himmelblau, 1960; Kishima
and Sakai, 1984; Lee et al., 2002; Moss and Was, 2015; Attanasio
and Morton, 2003; Ziemniak, 1992; Moshier and Witt, 2002). Here,
the large deviations in the Henry’s law constant may arise from
experimental errors or differences in the modeling equation, sen-
sor used to measure the hydrogen fugacity, and the experimental
environment. The Henry’s law constants obtained using Lee et al.
(2002) and Attanasio’s models (2003), as well as those obtained
using the present model were found to agree to within 4% at
20 MPa. As the temperature increased, the deviation also
increased. This indicates that the effect of the pressure increased
with the temperature. Their model disregards the dependence of
the pressure on the Henry’s law constant, even though the exper-
imental data obtained at different temperatures and pressures
were used in the development of the model. This oversight led to
large errors in the estimated results for the Henry’s law constant
when varying the pressure. In the present study, as shown in
140 E.-H. Lee et al. / Annals of Nuclear Energy 106 (2017) 136–142

Table 1
Henry’s law constants from the literature and calculated using the present model.

Ref. Autoclave Henry’s law constant (atm/(cc/kg) Error

conditions (%)
T (°C) P (MPa/psia) Reference Estimated using present
data model
Himmelblau (1960), Ziemniak (1992), Lee et al. (2002), 290 20/2900 0.01244 0.01256 1
and Attanasio and Morton (2003) 300 20/2900 0.0113 0.01125 0.5
310 20/2900 0.01016 0.00999 1.7
320 20/2900 0.00902 0.00876 3
330 20/2900 0.00788 0.00758 4
Kishima and Sakai (1984) 296 9.8/1421 0.0102 0.01011 0.9
326 14.5/2102 0.0072 0.00716 0.6
356 19.8/2871 0.00439 0.00466 5.8
Moshier and Witt (2002) 260 6.9/1000 0.0160 0.01465 9.2
288 10.3/1500 0.0122 0.01126 8.4
316 20.7/3000 0.0101 0.00936 7.9
333 20.7/3000 0.0072 0.00678 6.2
360 22.1/3200 0.0049 0.00460 6.5
Moss and Was (2015) 320 24.83/3600 0.01033 0.00955 8.2
360 24.81/3597 0.00563 0.00505 11.6

Fig. 3, the Henry’s law constant increased by an average of 9% as

the pressure increased from 13.8 to 20 MPa at each temperature.
The Henry’s law constants reported by Kishima and Sakai (1984)
at 9.8 MPa (1421 psia) and 14.5 MPa (2102 psia) are in good agree-
ment with the constants calculated using the present model. How-
ever, the difference between Kishima’s and our data increased
rapidly at 356 °C, even though the pressure was similar in both
studies. The temperature in Kishima’s study (1984) was well in
excess of the present upper temperature of 330 °C, leading to a
large deviation. These results confirm that the Henry’s law con-
stant is more dependent on the temperature than on the pressure.
The deviations between Moshier and Witt (2002) data and the pre-
sent data are greater than those between the present data and the
data reported in the literature. None of the pressure ranges were
consistent with those in the present study, yielding a deviation
of
10%. Moshier and Witt (2002) developed a Henry’s law corre-
lation with the hydrogen fugacity, which was measured according
Fig. 5. Comparison of hydrogen fugacity calculated using the present model with
to the temperature and system pressure. They improved the
experimental data obtained from the literature.
Henry’s law correlation by fitting the hydrogen-fugacity data using
Krichevsky and Kasarnovsky’s equations (1935). However, their
thermodynamic equations were verified at pressures of up to contents of 50 and 17 cc/kg at 20 MPa was in good agreement with
100 MPa (14,500 psia) and at temperatures ranging from 0 to the experimental data obtained by Lee et al. (2002). These results
100 °C. The data obtained using Krichevsky and Kasarnovsky’s confirm the accuracy of the hydrogen-fugacity measuring sensor,
equations were in good agreement with the experimental data the experimental data, and the present empirical model. The errors
obtained at the aforementioned temperature and pressure. How- between the experimental data obtained by Economy et al. and our
ever, it is uncertain whether their equations fit well above estimated data were greater than 17%, and the deviation increased
100 °C. There is a large difference between our data and that slightly with the temperature. Economy and Pement (1989) used a
obtained by Moss and Was (2015). They used Pd–20wt.% Ag tube Pd–25 wt.% Ag tube, but adopted a measurement system that was
with a length of 25.4 mm, an outer diameter of 3.2 mm, and an different from ours. Furthermore, they measured the hydrogen
inner diameter of 1.6 mm. In the literature, the hydrogen perme- partial pressure at a low temperature (100–110 °C). In the present
ability was affected by the Ag content and the thickness of the study, the hydrogen fugacity was measured in situ at given tem-
Pd–Ag tube (Nguyen et al., 2009). The large deviation in the peratures and pressures, and these data were used to develop the
Henry’s law constant may arise from the hydrogen-sensing mate- empirical model. This was because the hydrogen fugacity was
rial and type. affected by both the system temperature and pressure, as shown
Fig. 5 shows the experimental data reported in the literature in Fig. 4. The experimental result obtained by Attanasio and
and the fitting with the data obtained with the present model Morton (2003) at 316 °C agrees reasonable well with the result
(Lee et al., 2002; Attanasio and Morton, 2003; Economy and obtained using the present model.
Pement, 1989). The filled symbols indicate the hydrogen-fugacity
data calculated using the present model, while the open symbols
represent the experimental data obtained from the literature. First, 4.5. Ni/NiO phase transition
the Henry’s law constant was calculated using Eq. (7) at the same
temperature and pressure as were reported in the literature. Sec- Fig. 6 shows the calculated and measured hydrogen-fugacity
ond, the hydrogen fugacity was calculated by multiplying the cal- data corresponding to the Ni/NiO phase transition (Attanasio and
culated Henry’s law constant by the dissolved hydrogen content. Morton, 2003; Moss and Was, 2015) at different pressures and
The estimated hydrogen-fugacity data for dissolved hydrogen hydrogen concentrations. The hydrogen fugacity was calculated
 E.-H. Lee et al. / Annals of Nuclear Energy 106 (2017) 136–142
Fig. 6. Measured and calculated hydrogen-fugacity data corresponding to Ni/NiO
phase transition.
by multiplying the Henry’s law constant by the dissolved hydrogen
concentration. The hydrogen fugacity is a direct measure of the
thermodynamic stability of nickel and exhibits a good correlation
with the free energy of nickel oxidation (Moss and Was, 2015).
As the temperature increased, the calculated hydrogen fugacity
exhibited a trend similar to that reported by Attanasio and
Morton (2003) and Moss and Was (2015) The filled square symbols
indicate the hydrogen fugacity of the Ni/NiO phase transition
reported by Attanasio and Morton (2003) at various pressures
(6.9, 10.3, 20.7, 20.7, and 22.1 MPa) and concentrations (2, 4, 7.5,
13.8, and 25 cc/kg), respectively. The open-triangle symbols repre-
sent the hydrogen fugacity calculated using the present model
under the same conditions as those used by Attanasio and
Morton (2003). The calculated data were found to be within 8%
of the experimental data obtained by Attanasio et al. over a tem-
perature range of 260 to 360 °C. The discrepancies between the
two sets of data are explained as follows. Attanasio and Morton
(2003) determined the hydrogen fugacity using the hydrogen con-
centration that was experimentally obtained from exposure tests
and using the Henry’s law correlation reported by Moshier and
Witt (2002). Moshier and Witt (2002) used the thermodynamic
equations of Krichevsky and Kasarnovsky (1935) to improve the
Henry’s law correlation. These results indicate that the hydrogen-
fugacity data reported by Attanasio and Morton (2003) accurately
reflected the thermodynamic properties. However, the present
model was developed using only experimental data. Therefore,
the present data are more reasonable than those reported by
Attanasio and Morton (2003). Fig. 6 shows that the present model
can be extrapolated to temperatures and pressures ranging from
260 to 360 °C and 7 to 22 MPa, respectively. The filled circles rep-
resent the data obtained by Moss and Was (2015), which were gen-
erated at 320 °C (6 cc/kg H2) and 330 °C (8 cc/kg H2) at 25 MPa;
these circles are located in the NiO regime. Using the present
model, their data were recalculated under the same conditions;
the recalculated values are indicated by the open circles. These
data points are also located in the NiO regime, according to the lit-
erature (Attanasio and Morton, 2003; Moss and Was, 2015). In the
study by Moss et al., when the dissolved hydrogen content
increased from 6 to 8.5 cc/kg at 320 °C and at 25 MPa, this data
point moved into the Ni regime. In this case, a change in the pres-
sure from 25 to 20 MPa shifted the hydrogen fugacity calculated
using the present model downward; this value is denoted by an
open diamond. As the pressure decreased, the hydrogen fugacity
also decreased, which may have caused a crossing of the Ni/NiO
phase boundary. In PWRs, the maximum PWSCC susceptibility of
141
alloys occurred in the proximity of the Ni/NiO phase boundary.
Therefore, both the temperature and pressure are important for
determining the location of the Ni/NiO phase boundary. Many
researchers have determined the hydrogen fugacity by using
Henry’s law constants obtained from their thermodynamic models,
experimental data, or the literature. The present model was
obtained by a linear regression analysis of the experimental data,
as discussed in this study. Thus, more accurate data can be
obtained using the present model, relative to other models.
5. Conclusion
A hydrogen sensor made using a Pd–25 wt.% Ag tube was used
to indirectly determine the Henry’s law constant for hydrogen in
an aqueous solution containing lithium and boron. Using this sen-
sor, in-situ measurements of the hydrogen fugacity were per-
formed for temperature and pressure ranges of 290–330 °C and
13.8–20 MPa, respectively. The Henry’s law constant was calcu-
lated by dividing the measured hydrogen fugacity by the dissolved
hydrogen concentration. The Henry’s law constant decreased lin-
early as the temperature increased and the pressure decreased.
The Henry’s law constant was found to be more strongly depen-
dent on the temperature than on the pressure. When the temper-
ature increased from 290 to 330 °C at 20 MPa, the Henry’s law
constant decreased to
40% of its initial value at 290 °C. However,
the Henry’s law constant increased by a maximum of 9% as the
pressure increased at each given temperature. An empirical model
that uses the experimental data was developed to estimate the
simultaneous effects of the temperature and pressure on the
Henry’s law constant. The deviations in the Henry’s law constants
obtained using the present model and those indicated in the liter-
ature were in a range of approximately 0.5%–10%. The hydrogen
fugacity calculated using the Henry’s law constant estimated using
the present model was found to agree reasonably well with that
reported in the literature. The deviations in the hydrogen fugacity
data corresponding to the Ni/NiO phase transition were within 10%
of the values in the literature, indicating that the Ni/NiO phase
transition can be traversed by decreasing the pressure. Using the
hydrogen sensor and the present model, the dissolved hydrogen
concentration and hydrogen fugacity can be determined. The abil-
ity to calculate these values will be useful for applications in
nuclear reactors and other fields.
Acknowledgements
This work was financially supported by the Korean Nuclear R&D
Program organized by the National Research Foundation of Korea
grant funded by the Ministry of Science, ICT & Future Planning
(2017M2A8A4015155) and was carried out as a part of the R&D
Program supported by Korea Atomic Energy Research Institute.
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