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Optimization of Dissolved Hydrogen Concentration

for Control of Primary Coolant Radiolysis in
Pressurized Water Reactors

Hideki TAKIGUCHI, Mats ULLBERG & Shunsuke UCHIDA

To cite this article: Hideki TAKIGUCHI, Mats ULLBERG & Shunsuke UCHIDA (2004) Optimization
of Dissolved Hydrogen Concentration for Control of Primary Coolant Radiolysis in
Pressurized Water Reactors, Journal of Nuclear Science and Technology, 41:5, 601-609, DOI:
10.1080/18811248.2004.9715523

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 Journal of NUCLEAR SCIENCE and TECHNOLOGY, Vol. 41, No. 5, p. 601–609 (May 2004)

ORIGINAL PAPER

Optimization of Dissolved Hydrogen Concentration for Control

of Primary Coolant Radiolysis in Pressurized Water Reactors
Hideki TAKIGUCHI1;
, Mats ULLBERG2 and Shunsuke UCHIDA3
1
The Japan Atomic Power Company, 1-1, Kanda-Mitoshiro-cho, Chiyoda-ku, Tokyo 101-0053
2
Studsvik Nuclear AB, SE-611 82, Nyköping, Sweden
3
Tohoku University, 1 Aobayama, Aramaki, Aoba-ku, Sendai 980-8579
(Received October 20, 2003 and accepted in revised form March 2, 2004)

Optimization of the dissolved hydrogen concentration in primary coolant of pressurized water reactors has several
potential advantages in material integrity and dose reduction. To assess the threshold value of dissolved hydrogen for
reducing condition, in-pile loop experiments and radiolysis model calculations were performed. Both experiments and
model calculations indicate that the threshold value of dissolved hydrogen for radiolysis is much less than the present
control level in pressurized water reactors, and the in-core region is more easily affected by reduced dissolved hydro-
gen level than the out-of-core region. The measurement of electrochemical corrosion potential of structural material,
while varying dissolved hydrogen levels, is desirable in the future to compensate for the uncertainty of the model cal-
culation. For this purpose, electrochemical corrosion potential of stainless steel at the top-of-core, in which the refer-
ence electrode could be inserted, was estimated based on the correlation between the experiments and the modeling for
the loop.
KEYWORDS: PWR type reactors, PWR primary system, radiolysis modeling, dissolved hydrogen, water chem-
istry, G-value, in-pile experiment, electrochemical corrosion potential, oxidant, radical, corrosion

I. Introduction Ni þ H2 O ¼ NiO þ H2 : ð1Þ

1. Reconsideration of the Current Dissolved Hydrogen
Specification
To obtain reducing water chemistry in the primary cooling
system of pressurized water reactor (PWR), it is necessary to
inhibit radiolytic decomposition of the coolant. This is
achieved by adding hydrogen to the primary water. The dis-
solved hydrogen (DH) level is specified in PWR primary wa-
ter chemistry guidelines as 25–35 cm3 (STPa) of hydrogen
per kg of water. This corresponds to 783–1,097 mmolm3
at core temperature, 578.15 K (305 C). This specification
is based on experiments carried out at low temperature1,2)
and on calculations based on such experiments. It is recog-
nized today that the controlling radiolytic reactions have ac-
tivation energies that are different in magnitude. As a conse-
quence, the DH level that is required for reducing water
chemistry changes with temperature.3) A considerably lower
DH level, compared to what is normally used, is now be-
lieved to be sufficient to suppress oxidizing species in the
primary water of PWRs.4,5)
2. Advantages of Lower DH Level
A lower concentration of DH in the coolant is believed to
have several advantages on theoretical grounds.3,6)
(1) Corrosion of Structural Material and Radiation Build up
Hydrogen affects the stability of Ni in PWR primary water
via the reaction


Corresponding author, Tel. +81-3-4415-6005, Fax. +81-3-4415-
6191, E-mail: hideki-takiguchi@japc.co.jp.
a
STP: Standard temperature and pressure, at 273.15 K and
0.1013 MPa
A higher concentration of hydrogen (more reducing environ-
ment) enhances the stability of metallic Ni on behalf of NiO
and other nickel-containing oxides. A lower stability of ox-
ides of nickel may lead to increased corrosion rate of nickel
based alloy of steam generator tubing. Hydrogen is also be-
lieved to be one key factor to enhance primary water stress
corrosion cracking (PWSCC).
However, the phenomena of PWSCC itself are not well
understood and it has been suggested that the effect of hy-
drogen is both positive7) and negative8) in this case.
An increased corrosion rate of nickel based alloy will re-
sult in increasing fuel deposits. One of the most important
radioactive corrosion products in PWRs is 58 Co, which is
an activation product of 58 Ni. The corrosion rate of nickel
based alloy, and the solubility of fuel deposits, will conse-
quently also affect dose rates in the plant. An optimized
DH level is therefore an important measure to control dose
rates in PWRs, in addition to other control measures such
as optimized pH level.
There are few data on stress corrosion cracking (SCC) for
stainless steel (SS) under the primary coolant condition of
PWR, because its alkaline and strong reducing chemistry
gives good corrosion performance in many different applica-
tions. However, recently some investigations have been
started to clarify the direct influence of DH on irradiated
and hardened materials. Attention should be paid to these re-
sults to optimize DH level in the coolant.
(2) Fuel Performance
Demands on improving the corrosion properties of fuel
materials will continue to increase in the future as higher
burn-up and longer operational cycles are introduced. The

601
602 H. TAKIGUCHI et al.

Ion exchanger
Used water
Decay T C C
chamber
O2 H2

Cooling GC

TOC

IC

O2 H2
Main Pump
Main
loop flow C

T O2 Dissolved O2 meter
T H2 Dissolved H2 meter
P Pressure gauge
Degassed and
Core Core T Thermometer purified water
H2 O2 H2 with B/Li
C Conductivity meter
GC Gas chromatograph Controllable
Electrode and dosage pumps
Main loop test specimen TOC Total organic carbon

IC Ion chromatograph
R2 reactor

Fig. 1 Schematic flow diagram of INCA loop

parameter controlling the lifetime of zirconium alloy fuel
cladding is normally hydriding. An optimized DH level in
the coolant should be investigated as a possible measure to
further reduce hydride formation in zirconium alloy.
The phenomenon of axial offset anomaly (AOA) illus-
trates that fuel deposits can have important effects on fuel
performance in PWRs. The possible role of DH in AOA is
not clear at present. However, phenomena such as AOA
demonstrate the importance of carefully investigating and
optimizing the effects of water chemistry on fuel perform-
ance.
3. Framework of This Study
In this paper, we propose a model for the behavior of ra-
diolytic products in the INCA loop, which was an in-pile
loop installed in Studsvik R2 reactor to simulate a PWR
primary cooling system. We carried out in-pile experiments
using INCA loop. The effects of DH on radiolysis for the
out-of-pile region were monitored by dissolved oxygen
(DO) concentration, while those for the in-pile region were
monitored by electrochemical corrosion potential (ECP) of
SS. Results of both calculations and experiments for the
out-of-pile and the in-pile INCA loop were compared to
check the validity of the radiolysis model.
Based on these results, radiolysis modeling for the pri-
mary system of Tsuruga-2, a four-loop PWR operated by
The Japan Atomic Power Company since 1987, was carried
out to evaluate the threshold of DH level for reducing
condition. The response of ECP of SS at top-of-core, where
the reference electrode for ECP measurement could be
installed in Tsuruga-2, was estimated as a function of DH
level.
II. Experiments
1. Main Characteristics of the In-pile INCA Loop
The INCA loop in the Studsvik R2 reactor is a once
through, in-pile rig with external circuits for water supply
and additives, in the present case hydrogen, boric acid and
lithium hydroxide. The rig is installed in one of the main
loops of the reactor (loop-in-loop), as shown in Fig. 1.9)
The instrumentation includes conductivity, oxygen and
hydrogen (Orbisphere 3623) monitors for inlet and outlet
water. Dissolved gases are also independently monitored
by gas chromatography (GC). Ion chromatography (IC)
and total organic carbon (TOC) analyzer are also provided
to watch the behavior of impurities.
In the present experiments the effect of DH concentration
on radiolysis was monitored in-pile by measuring the ECP of
SS against a Pt electrode and out-of-pile by oxygen monitor.
In the presence of a surplus of hydrogen over oxidants, the Pt
electrode has a well-defined and calculable potential and
may be used as a reference electrode.
The main differences between the INCA loop and the core

JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY

Optimization of Dissolved Hydrogen Concentration for Control of Primary Coolant Radiolysis in Pressurized Water Reactors 603

Table 1 Main characteristics of the in-pile INCA loop and the by Studsvik. The chemical basis of the model is the reaction
in-core region of Tsuruga-2 mechanism which has been published previously.10)
However, some of the rate constants are updated as listed
INCA Tsuruga-2
in Table 3. The numerical treatment is based on the
Temperature (K) 563.15 578.15 MAKSIMA-CHEMIST code.11)
( C) (290) (305) Calculations with various DH concentrations have been
Dose rate (W/g) carried out with the aim to determine a DH threshold value,
 4.0 1.5
above which the production of oxidizing species is below a
Fast neutrons 4.3 5
certain value. The PWR primary water guidelines require an
Thermal neutron 1.7E+14 4.2E+13
flux (cm2 s1 ) action to take place if the DO concentration is above
10 mass ppb (219 mmolm3 ). In this study it was decided
to set this ‘‘O2 ’’ limit at only 1 mass ppb (22 mmolm3 ).
However it could only be achieved at the highest tempera-
Table 2 G-values in the INCA loop and Tsuruga-2 ture, 305 C (578.15 K), for the in-core region of operating
PWR. At the lower temperatures, a threshold value for DH
G INCA, Tsuruga-2, concentration was determined: this point is defined as the
(molec./100 eV) 1,600 ppm B 1,200 ppm B DH concentration taken at the oxidant concentration which
eaq  1.43 1.24 is 50% higher than the asymptotic (minimum) value of
H 0.52 0.53 ‘‘O2 ’’. ‘‘O2 ’’ signifies the sum of O2 and decomposed H2 O2 .
H2 1.30 1.19
OH 2.53 2.39
III. Results of Radiolysis Model Calculations for
H2 O2 0.83 0.79
HO2 0.12 0.06 the INCA Loop
1. Out-of-pile Region
Due to the intense radiation field in-pile there are signifi-
region in Tsuruga-2, with respect to radiolysis, are given in cant differences between the water chemistry in-pile and out-
Table 1. The gamma dose rates and the thermal neutron of-pile. The main differences are the following:
fluxes differ somewhat. This affects yields (G-values). – Disappearance of radicals out-of-pile.
Weakly ionizing gamma radiation gives a high proportion – A recombination effect as the radiation intensity decreas-
of radicals. On the other hand, thermal neutrons give a rela- es. This significantly reduces the concentrations of H2 O2
tively higher proportion of molecular radiolysis products due and O2 as the water leaves the in-pile region.
to densely ionizing (higher linear energy transfer) radiation Figure 2 shows radiolytic species in out-of-pile region
from the reaction 10 B(n;
) 7 Li. The higher levels of gamma computed for the experimental conditions of 1,600 mass
radiation and thermal neutron flux in the INCA loop thus parts per million (ppm), i.e., 104 molm3 of B and 2 mass
largely compensate for the lower level of fast neutron flux. ppm (0.202 molm3 ) of Li as functions of the DH level in
As a result, yields in the INCA loop are slightly higher com- the water. Note that the y-axis covers 12 orders of magni-
pared to Tsuruga-2, but qualitatively the difference is small tude.
(Table 2). Radiolysis in a PWR core is thus well simulated It is immediately apparent that the chemistry is totally do-
in the in-pile INCA loop. minated by the added H2 at all but the very lowest levels of
G-values for mixed radiation shown in Table 2 are calcu- DH. The DH threshold for reducing condition is below
lated as follows: 0.5 cm3 (STP)kg1 , i.e., less than 15.7 mmolm3 . This
modeling result appears to be consistent with ECP value of
Gmix ¼ fn  Gn þ f  G þ f
 G
; ð2Þ
SS obtained for the out-of-core region12) and with DO level
where fn : Fraction of dose from fast neutron during low DH chemistry13) in operating PWRs.
f : Fraction of dose from gamma radiation
f
: Fraction of dose from alpha radiation 2. In-pile Region
Gn : G-values for fast neutron The situation in-pile is somewhat more complicated, as
G : G-values for gamma radiation seen in Fig. 3.
G
: G-values for alpha radiation. The in-pile region is characterized by a significantly less
Comparatively large difference in G-value for HO2 be- dominating role for H2 . In-pile, the concentrations of other
tween INCA loop and Tsuruga-2 is due to higher thermal species are only 3 orders of magnitude below that of H2 ,
neutron flux, e.g., higher alpha radiation from 10 B(n;
) as opposed to 7 orders of magnitude out-of-pile. After hydro-
7
Li, in the loop compared to Tsuruga-2. G
(HO2 ) comes gen, there are four very reactive species in-pile, eaq 
to 0.3, while Gn (HO2 ) and G (HO2 ) are 0.05 and 0 respec- (hydrated electron), H2 O2 , OH, and H with concentrations
tively. within an order of magnitude. The concentrations of O2 ,
HO2 and O2  , which is produced from O2 or HO2 , are lower,
2. Radiolysis Model Calculations and these species may be disregarded in comparison to the
Radiolysis calculations for INCA loop and Tsuruga-2 others.
have been performed using the radiolysis model developed Establishing a limit for ‘‘normal’’, reducing PWR condi-

VOL. 41, NO. 5, MAY 2004

604 H. TAKIGUCHI et al.

Table 3 Reaction mechanism and rate constant k

k22 Activation k290 k305

No. Reactions (295.15 K) energy (563.15 K) (578.15 K)
(dm3 mol1 s1 ) (Jmol1 ) (dm3 mol1 s1 Þ (dm3 mol1 s1 Þ
1 OH+OH=H2 O2 5.500E+09 7.90E+03 2.540E+10 2.662E+10
2 OH+eaq  =OH 3.100E+10 1.47E+04 5.345E+11 5.831E+11
3 OH+H=H2 O 9 300E+09 8.20E+03 4.553E+10 4.779E+10
4 OH+HO2 =H2 O+O2 7.100E+09 1.42E+04 1.111E+11 1.209E+11
5 OH+O2  =O2 +OH 1.000E+10 1.76E+04 3.024E+11 3.356E+11
6 OH+H2 O2 =HO2 +H2 O 2.700E+07 1.42E+04 4.225E+08 4.596E+08
7 OH+H2 =H+H2 O 3.400E+07 1.92E+04 1.401E+09 1.570E+09
8 OH+OH =H2 O+O 1.200E+10 1.42E+04 1.878E+11 2.043E+11
9 OH+HO2  =HO2 +OH 7.500E+09 1.42E+04 1.174E+11 1.277E+11
10 OH+O =HO2  1 800E+10 1.42E+04 2.817E+11 3.064E+11
11 O +H2 O=OH+OH 1.700E+06 na 1.500E+08 1.540E+08
12 eaq  þeaq  =H2 +OH +OH 5.500E+09 na 5.500E+09 5.000E+09
13 eaq  +H=H2 +OH –H2 O 2.400E+10 1.40E+04 3.613E+11 3.926E+11
14 eaq  +O2  =HO2  +OH –H2 O 1 300E+10 1.42E+04 2.034E+11 2.213E+11
15 eaq  +HO2 =HO2  2.000E+10 1.42E+04 3.130E+11 3.405E+11
16 eaq  +H2 O2 =OH+OH 1.200E+10 1.56E+04 2.463E+11 2.701E+11
17 eaq  +O2 =O2  1.900E+10 1.36E+04 2.647E+11 2.869E+11
18 eaq  +Hþ =H 2.300E+10 1.26E+04 2.640E+11 2.845E+11
19 eaq  +H2 O=H+OH 1.900E+01 1.42E+04 2.973E+02 3.234E+02
20 eaq  +HO2  =O +OH 3.500E+09 1.42E+04 5.477E+10 5.958E+10
21 H+H=H2 5.500E+09 1.46E+04 9.301E+10 1.014E+11
22 H+O2  =HO2  2.000E+10 1.42E+04 3.130E+11 3.405E+11
23 H+HO2 =H2 O2 2.000E+10 1.42E+04 3.130E+11 3.405E+11
24 H+H2 O2 =H2 O+OH 5.100E+07 1.07E+04 4.052E+08 4.317E+08
25 H+O2 =HO2 2.100E+10 1.03E+04 1.544E+11 1.641E+11
26 H+OH =eaq  +H2 O 2.200E+07 3.76E+04 3.201E+10 4.000E+10
27 HO2 +HO2 =H2 O2 +O2 8.400E+05 2.06E+04 4.541E+07 5.130E+07
28 HO2 +O2  =O2 +HO2  9 600E+07 7.60E+03 4.184E+08 4.377E+08
29 HO2 =Hþ +O2  8.000E+05 na 3.900E+05 3.900E+05
30 Hþ +O2  =HO2 5.000E+10 1.42E+04 7 825E+11 8.512E+11
31 H2 O2 +OH =HO2  +H2 O 5.000E+08 1.88E+04 1.907E+10 2.132E+10
32 HO2  +H2 O=H2 O2 +OH 5.700E+04 na 1.200E+07 1.230E+07
33 H2 O2 =H2 O+O 4.000E08 6.30E+04 7.973E03 1.158E02
34 O+O=O2 5.000E+09 1.42E+04 7.825E+10 8.512E+10
35 H2 O=Hþ +OH 2.599E05 na 1.400E01 1.640E01
36 Hþ +OH =H2 O 1.430E+11 1.42E+04 2.238E+12 2.434E+12
37 O2  +O2  =HO2  +O2 –Hþ 1.770E+09 8.00E+04 9.497E+15 1.526E+16
na: Not applicable

DH [cm3(STP).kg-1]
DH [cm3(STP).kg-1]
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
1.0E-00 1.0E-00
Concentration [mol.m-3]
Concentration [mol.m-3]

1.0E-02
1.0E-02
1.0E-04

1.0E-06 1.0E-04
1.0E-08
1.0E-06
1.0E-10

1.0E-12
1.0E-08
0 62.7 125 188 251 313 376 439 0 62.7 125 188 251 313 376 439
DH [mmol.m-3] DH [mmol.m-3]
H2O2 O2 H2 H2O2 H2
O2
OH HO2 eaq- OH HO2 eaq-
H H

Fig. 2 Radiolytic species out-of-pile as a function of DH level in Fig. 3 Radiolytic species in-pile as a function of DH level in
INCA loop (1,600 ppm B and 2 ppm Li) INCA loop (1,600 ppm B and 2 ppm Li)

JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY

Optimization of Dissolved Hydrogen Concentration for Control of Primary Coolant Radiolysis in Pressurized Water Reactors 605

tions is not trivial in this case, since there are reactive spe- DH [cm3 (STP).kg -1]
cies of both oxidizing and reducing nature at concentrations 0 2 4 6 8 10 12 14 16 18

that are both similar and significant. For example, the level 300

Concentration [mol.m -3]

1.0E-03

of H2 O2 is around 1 mass parts per billion (ppb), i.e., 200

ECP (mV SHE)

21 mmolm3 , even at a DH concentration of 15 cm3 100
0
(STP)kg1 , i.e. 470 mmolm3 . Under out-of-pile condi- 1.0E-04
tions and at reasonable flow rate of greater than 1 ms1 , -100
-200
such a level of H2 O2 would elevate the potential of well
-300
filmed SS to several hundred millivolts above Pt.14)
1.0E-05 -400
0 62.7 125 188 251 313 376 439 501 564

IV. Experimental Results in the INCA Loop DH [mmol.m-3]

The INCA loop was operated at 563.15 K (290 C) and a
flow rate of 0.0139 kgs1 (50 kgh1 ) with 1,600 mass ppm
(104 molm3 ) of B and 2 mass ppm (0.202 molm3 ) of Li
in the water, corresponding to a pH of 6.75 at 573.15 K
(300 C). The DH level was varied in the interval 0–
16.8 cm3 (STP)kg1 (0–527 mmolm3 ). The upper limit
corresponded to the solubility of H2 in water at atmospheric
pressure and room temperature. Compared to PWR condi-
tions the boron concentration was somewhat high, and tem-
perature and pH somewhat low. The test conditions were
conservative in the sense that radiolytic decomposition of
water increased with boron level and decreased with temper-
ature and pH.
1. Out-of-pile Results
The computed and measured oxygen levels out-of-pile in
the INCA loop (downstream from in-pile region) are shown
in Fig. 4. In both cases it has been assumed that hydrogen
peroxide decomposed completely according to the reaction
1
H2 O2 ¼ O2 þ H2 O:
2 (STP)kg1 (12.5 mmolm3 ), the ECP also rose slightly.
The sum of O2 and decomposed H2 O2 is denoted ‘‘O2 ’’. At
all but the two lowest DH levels, ‘‘O2 ’’ was below the limit
of detection, which was estimated to be 0.1 mass ppb
(2 mmolm3 ). This was in agreement with experimental data
from the INCA loop, although more measurements are desir-
able.
DH [cm3(STP).kg-1]
0 1 2 3
219000
Concentration [µmol.m-3]
Ox = [OH] + 2 [H2O2]
Red = [H] + [eaq-]
Measured ECP
Fig. 5 In-pile stainless steel ECP (SHE) and reactive oxidizing
and reactive reducing species in INCA loop as a function of
DH level (1,600 ppm B and 2 ppm Li)
2. In-pile Results
To investigate the in-pile red-ox environment as a func-
tion of DH concentration, the ECP of SS was measured
against a Pt electrode. Extensive experience from BWRs
has demonstrated that the Pt electrode may be used as a
pseudo-reference electrode when the level of oxidizing spe-
cies in the water is significantly less than the H2 -level. The
ECP of SS, as measured as measured against Pt electrode,
was converted to the standard hydrogen electrode (SHE)
scale, taking into account pH, temperature, and H2 concen-
tration at the Pt electrode. After conversion to the SHE scale,
the SS ECP curve in Fig. 5 was obtained.
ð3Þ As the DH concentration rose from zero to 0.4 cm3
This could be an artifact due to an influence of O2 and H2 O2
on the Pt reference electrode at the lowest DH concentration.
At DH concentration zero, the levels of both O2 and H2 O2
were high as shown in Fig. 3.
V. Discussion
1. Evaluation of In-pile ECP Behavior
To establish a connection between SS ECP and the radio-
lytic species concentrations that are computed in the calcula-
tions, we propose the following argument: SS is known to be
4 5 a relatively poor electrode for H2 . We therefore disregard
10000 hydrogen and consider only the four species H2 O2 , OH,

Computed “O2”out-of-pile eaq  , and H. The three radical species OH, eaq  , and H
[mass ppb]

2190 Measured “O2”out-of-pile 100 are all very reactive. Hydrogen peroxide is known to react
rapidly on metal oxide surfaces at high temperature. At the
21.9 1
reduced DH levels considered here, the concentration of
0.219 Less Than Detectable 0.01
OH is significantly higher than that of HO2 (including
O2  ). Also, the standard Electrode Potential for oxidation
0.00219 0.0001 in basic solution is 1.8 V for OH and 0.4 V for HO2 .15) We
0 31.3 62.7 94.0 125 157
DH [mmol.m-3]
have therefore, also in this case, disregarded HO2 in compar-
ison to OH.
Fig. 4 Computed and measured levels of oxygen plus decom- The resulting ECP is assumed to depend on whether there
posed hydrogen peroxide in INCA loop (1,600 ppm B and is a stoichiometric excess of reactive oxidizing species or of
2 ppm Li) reactive reducing species. The sum of reactive oxidizing spe-

VOL. 41, NO. 5, MAY 2004

606
cies ‘‘Ox’’ is calculated as Ox=[OH]+2[H2 O2 ], taking into
account that reduction of hydrogen peroxide is a two-elec-
tron process. The sum of reactive reducing species ‘‘Red’’
is calculated as Red=[H]+[eaq  ]. This is analogous to the
well-known situation of a Pt electrode in the presence of
both hydrogen and oxygen. Both hydrogen and oxygen have
high exchange current densities on Pt. Limiting diffusion
current density is therefore easily reached. The ECP of Pt
will accordingly be high or low, depending on whether there
is a stoichiometric excess of O2 or H2 at the surface of the Pt
electrode.
In addition to measured ECP of SS, Fig. 5 shows the in-
pile Ox and Red concentrations. We call the water chemistry
with a stoichiometric excess of Red over Ox ‘‘kinetically re-
ducing’’. When the DH concentration increases further from
0.4 to 2 cm3 (STP)kg1 (from 12.5 to 62.7 mmolm3 ), the
ECP rapidly drops by 400 mV, from 250 mV SHE to
150 mV SHE. This rapid shift to more reducing potential
correlates well with the onset of ‘‘kinetically reducing’’ con-
dition. The surprisingly high SS ECP is considered to be a
consequence of the fact that the ratio of Red to Ox is not
more than a factor of 4, even at high DH concentrations.
This means that the fully reducing condition can be not
reached in-pile, differing completely from that out-of-pile.
If we consider the ratio of Red to Ox, we can transform
Fig. 5 into Fig. 6. Below 100 mV SHE there is a good cor-
relation between the ECP value and the logarithm of the ra-
tio of Ox to Red. The correlation means that below
100 mV SHE the ECP is a linear function of the logarithm
of the ratio of Ox to Red. More precisely, the correlation of
Fig. 6 translates into the following relation
ECP ¼ 350  logðOx/RedÞ  100;
where the ECP is expressed in mV SHE.
A natural question is whether the good correlation below
100 mV SHE is simply a coincidence, or if it has a mech-
anistic background. Actually, the functional relationship of
Eq. (4) can be shown to be a consequence of two factors:
(1) The fact that Ox and Red change by approximately
DH [cm3 (STP).kg -1]
0 5 10 15 20
10
Calc. by Eq.(4)
Measured ECP
Ratio
1 then change more rapidly with log (Ox/Red). This is a pos-
0.1 -450
0 157 313 470 627
DH [mmol.m-3]
Fig. 6 In-pile stainless steel ECP (SHE) and ratio of reactive ox-
idizing species to reactive reducing species in INCA loop as
function of DH level (1,600 ppm B and 2 ppm Li)
H. TAKIGUCHI et al.
initial DH level
increased DH level
reduction reaction of “Ox”
ECP of SS
ECP changes
proportional to
∆(log Ox)
oxidation reaction of “Red”
current density [ log (i) ]
Fig. 7 Schematic Evans Diagram indicating the effect on corro-
sion potential of increased DH level
inverse factors when the DH concentration changes
(Fig. 5)
(2) The assumption of linear Tafel slopes.
The first point implies that the product OxRed is approx-
imately constant. Eq. (4) can then be transformed to give the
ECP value as a function of log (Ox) or, alternatively, of log
(Red), only.
We can consider an Evans’ diagram i.e., ECP vs. log (cur-
rent density ‘‘i’’) diagram, for the oxidation and reduction re-
actions on the surface of SS in-core. A schematic example is
shown in Fig. 7. We draw the Tafel slopes of the sum of the
reduction reactions almost vertically to indicate that the cur-
rent density may be close to being diffusion limited as a con-
sequence of low concentrations and rapid kinetics. When the
ð4Þ
DH concentration increases, the current densities change
with the concentrations of oxidizing and reducing species,
respectively. The Tafel slope for the reduction reaction
moves to the left as log (Ox). The Tafel slope for the oxida-
tion reaction moves to the right by the same distance, since
Ox and Red change by inverse factors. Because of the as-
sumed linear Tafel slopes, the ECP changes proportional
to
(log Ox). Alternatively, the ECP may be expressed as
a function of
(log Red), or of
(log (Ox/Red)). This,
again, follows from the fact that the Ox and Red change
by inverse factors when the DH concentration is altered.
The variation of the ECP value as log (Ox/Red) breaks
250 down at both high and low ratios of Ox/Red, since the Tafel
150 slopes are then no longer linear. We indicate in Fig. 7 that
ECP (mV SHE)
50
diffusion limited current density will be reached for the ox-
idation reaction at high polarization (low DH). The ECP will
-50
-150 sible cause for the deviation of the two curves seen at low
-250 DH levels in Fig. 6.
-350 A change in dose rate will cause all concentrations (except
for hydrogen) to change more or less in concert. The curves
representing the oxidation and the reduction reactions, re-
spectively, will then both move either to the left or to the
right in Fig. 7. In principle, this has no effect on the ECP;
in practice, the shapes of the curves will also change. The
diffusion limit will be reached more easily at low dose rate,
which gives low concentrations. The tendency of the ECP to
JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY
Optimization of Dissolved Hydrogen Concentration for Control of Primary Coolant Radiolysis in Pressurized Water Reactors 607

flip between extreme values should then become more pro- DH [cm3 (STP).kg -1]
nounced. Also, the relative influence of hydrogen will in- 0 5 10 15 20 25 30
crease as the dose rate is lowered. Under reducing condition, 1.0E-01

as in a PWR, we may therefore expect the SS ECP to de-
crease when the dose rate is reduced. However, no data
are available to evaluate quantitatively how the ECP changes
with the dose rate.
2. Radiolysis Calculations for In-core Region of
Tsuruga-2
A decrease of the hydrogen concentration in the PWR pri-
mary environment is considered for future applications. To
control the necessary amount of hydrogen, ECP measure-
ments will be required. A few monitoring points are availa-
ble to follow any response due to the decreased hydrogen
concentration. We calculated radiolysis products and esti-
mate ECPs based on the calculated concentrations of radiol-
ysis products for two locations in the core of Tsuruga-2.
(1) Results at the Top-of-core
Figure 8 shows the results at the top of the core,
corresponding to a time of 0.9 s spent in the core. The DH
concentration was varied from 0.112 to 28 cm3 (STP)kg1
(3.51–878 mmolm3 ). With 0.112 cm3 (STP)kg1 (3.51
mmolm3 ) hydrogen in the coolant strongly oxidizing con-
ditions prevailed (about 250 mass ppb (5.16 mmolm3 ) of
H2 O2 ). Already at a small increase to 0.224 cm3 (STP)kg1
(7.02 mmolm3 ) hydrogen the H2 O2 concentration decreas-
ed almost two orders of magnitude. With 0.56 cm3
(STP)kg1 (17.6 mmolm3 ) hydrogen the H2 O2 concentra-
tion decreased further (about 2.5 times). The H2 O2 concen-
tration decreased gradually to about 0.5 mass ppb (0.01
mmolm3 ) when the initial hydrogen concentration was fur-
ther increased to 28 cm3 (STP)kg1 (878 mmolm3 ). It
should be noted that the concentration of OH radicals was
rather high, almost the same as the concentration of H2 O2
with hydrogen concentrations between 0.224 and 3.36 cm3
(STP)kg1 (7.02 and 105 mmolm3 ). The OH radical is
known to be a strongly oxidizing species and may play a role
in determination of the ECP. The concentration of the O2 
DH [cm3 (STP).kg -1]
0 5 10 15 20 25
1.0E-01
Concentration [mol.m-3]
Concentration [mol.m-3]
1.0E-02
1.0E-03
1.0E-04
1.0E-05
1.0E-06
1.0E-07
1.0E-08
1.0E-09
0 157 313 470 627 783 940
DH [mmol.m-3]
OH
H2O2 O2
HO2+O2 eaq- H
Fig. 9 Radiolytic species at max dose rate as a function of DH
level in Tsuruga-2 (1,200 ppm B and 2 ppm Li)
radical was lower than that of the OH radical, thus the
sum of HO2 and O2  is given in Fig. 8. Due to the alkaline
pH of the PWR the concentration of O2  was 2–3 times
higher than that of HO2 (acid-base equilibrium).
(2) Results at the Maximum Dose Rate In-core
The results are shown in Fig. 9. The maximum dose rate
corresponded to a position in the middle of the fuel channel
at a time of 0.45 s from the entrance of the coolant into the
core. The maximum dose rate was two times higher than the
dose rate at the top-of-core. Compared with the position in
the top-of-core the increased dose rate in the middle of the
core resulted in most cases in a 40 to about 100% increase
in oxidant concentrations.
3. Estimation of SS ECPs In-core in Tsuruga-2
A reasonable way to circumvent the radiolytic species
measurement problem in-core of an operating PWR is to
measure instead the ECP of the structural material, e.g.,
SS. Therefore the behavior of SS ECP at the top-of-core,
in which the reference electrode for in situ measurements
could be installed, was estimated based on data from the
INCA loop, as a function of DH concentration. The dose
rate, including alpha rays from 10 B(n;
) 7 Li, in the INCA
30
loop and at the two in-core locations in Tsuruga-2 consid-
ered are shown in Table 4. The dose rate in the INCA loop

1.0E-02 was in reasonable agreement with the maximum dose rate in

1.0E-03
1.0E-04
1.0E-05
1.0E-06
Table 4 Dose rate at two in-core locations in Tsuruga-2 and in
1.0E-07
the INCA loop
1.0E-08
1.0E-09 Dose rate
0 157 313 470 627 783 940 Location
(W/g)
DH [mmol.m-3]
H2O2 O2 OH Top-of-core electrode
6.7
HO2+O2- eaq- H position
Max. core dose rate 13.5
Fig. 8 Radiolytic species at top of core as a function of DH level INCA loop 12.6
in Tsuruga-2 (1,200 ppm B and 2 ppm Li)

VOL. 41, NO. 5, MAY 2004

608
DH [cm3 (STP).kg -1]
0.1 1 10 100
150
50 Eq. (4)
ECP(mV SHE)
-50 Upper Limit
Lower Limit
-150
-250
-350
-450
-550
3.13 31.3 313 3130
DH [mmol.m-3]
Fig. 10 Estimated stainless steel ECP (SHE) at top-of-core (elec-
trode position) in Tsuruga-2 (1,200 ppm B and 2 ppm Li)
Tsuruga-2. ECP estimates for the center of the core in Tsur-
uga-2, based on data from the INCA loop, should
therefore be realistic. ECP values at the electrode position
(top-of-core) would be expected to be lower.
We used the correlation of Fig. 6 to estimate the SS ECP
value in the center of the core of Tsuruga-2. The procedure
involved the following steps.
(1) The Ox and Red were calculated based on the concen-
trations of radiolytic products.
(2) The quotient Ox/Red was formed.
(3) Equation (4) was applied.
The results are shown in Fig. 10. Since the SS ECP value
at the top-of-core, which is the electrode position, should not
exceed the values at the maximum dose rate position, the SS
ECP curve for the center of core is plotted in Fig. 10 as the
upper limit for the top-of-core. If, for example, the DH level
is reduced from 30 to 15 cm3 (STP)kg1 (940 to 470
mmolm3 ), the ECP is expected to rise by approx. 30 mV,
from 380 mV SHE to 350 mV SHE. The ECP value is
expected to reach 100 mV SHE at 35.1 mmolm3 H2 , cor-
responding to 1.1 cm3 (STP)kg1 .
The SS ECP value in the top-of-core (the electrode posi-
tion) is calculated by Eq. (4) and indicated in Fig. 10. At
the electrode position, the ECP value is expected to be lower
than in the center of the core because of the 50% lower dose
rate (Table 3). In this calculation, only the change in the ra-
tio of Ox to Red is taken into account, while the diffusion
limit of the reactive species is reached more easily and the
relative influence of hydrogen increases also under lower
dose rate. The calculated SS ECP value at this position, thus,
might be overestimated.
A limit to the effect of lower dose rate is desirable and can
be given as follows. At the highest DH level of 28 cm3
(STP)kg1 (878 mmolm3 ), Ox and Red are both about
30% lower at the top-of-core, compared to the core center.
Lower limit for the SS ECP at the top-of-core in Fig. 10 cor-
responds to a higher DH level in the core center, giving the
same level of Ox and a two-fold increase in Red assumed by
a 2 times higher dose rate at the core center as compared to
the top-of-core. Clearly, the ECP value at the top-of-core
must be higher than the curve of the lower limit.
H. TAKIGUCHI et al.
VI. Conclusions
Lowering dissolved hydrogen (DH) concentration in pri-
mary coolant of PWR is considered to be associated with po-
tential advantages. To quantify the optimum concentration
of DH for reducing condition from the viewpoint of radiol-
ysis, we determined the threshold DH value in the in-pile
INCA loop and compared it with computer modeling results
for this loop.
(1) Both experimental data and modeling results for the
INCA loop highlighted the fact that the red-ox condi-
tions are different in-pile and out-of-pile.
(2) The DH threshold out-of-pile was below 0.5 cm3
(STP)kg1 (15.7 mmolm3 ). Fully reducing condition
was obtained above the threshold
(3) The approximate DH threshold in-pile was higher by
more than a factor of two. The threshold was less sharp
and condition gradually became more reducing as the
DH concentration was further increased
(4) Fully reducing condition was possibly not reached
in-pile, even at high DH concentrations.
Using the same parameters in the modeling for INCA
loop, we carried out radiolysis calculations simulating 12
conditions in a fuel channel of the Tsuruga-2 PWR. Conse-
quently, we found that the threshold DH concentration for
the suppression of radiolysis was much less than the current
control range of DH concentration specified in the primary
water chemistry guidelines, and the in-core region was also
critical for radiolysis in operating PWRs, the same as found
in the INCA loop. The electrochemical corrosion potential
(ECP) measurements of structural material, under varying
DH levels, for the in-core region of operating PWRs is desir-
able in the future to compensate for uncertainty of the mod-
eling results. For this purpose, ECP of stainless steel at the
top-of-core, in which the reference electrode could be insert-
ed, was estimated for Tsuruga-2 based on both results from
experiments and modeling for the INCA loop.
Abbreviations
AOA: Axial offset anomaly
DH: Dissolved hydrogen
DO: Dissolved oxygen
ECP: Electrochemical corrosion potential
Ox: The sum of reactive oxidizing species (Ox=[OH]+2[H2 O2 ])
ppb: Parts per billion
ppm: Parts per million
PWSCC: Primary water stress corrosion cracking
PWR: Pressurized water reactor
Red: The sum of reactive reducing species (Red=[H]+[eaq  ])
SHE: Standard hydrogen electrode
SS: Stainless steel
STP: Standard temperature and pressure (at 273.15 K and 0.1013
MPa)
Acknowledgments
We are grateful to Dr. H. Christensen and Mr. A.
Molander of Studsvik Nuclear AB for their cooperation with
the calculations and fruitful discussions of radiolysis model-
ing and the in-pile loop experiments.
JOURNAL OF NUCLEAR SCIENCE AND TECHNOLOGY
Optimization of Dissolved Hydrogen Concentration for Control of Primary Coolant Radiolysis in Pressurized Water Reactors
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