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Kinetics study on the dissolution of UO2 particles by

microwave and conventional heating in 4 mol/L nitric
acid
ZHAO YunFeng & CHEN Jing†
Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 102201, China

The dissolution of UO2 particles in 4 mol·L−1 nitric acid medium at temperatures of 90－110℃ by mi-
crowave heating and conventional heating has been investigated, respectively. It is found that the
dissolution ratios of UO2 particles by microwave heating were 10%－40% higher than that by conven-
tional heating. Kinetics research shows that the dissolution of UO2 particles in 4 mol·L−1 nitric acid is
controlled by the diffusion control model for microwave heating and by the surface reaction control
model for conventional heating. The diffusion control model for the dissolution of UO2 particles by mi-
crowave heating could be explained by the diffuseness on the surface of UO2 particles.

uranium dioxide, nitric acid, dissolution, microwave heating

1 Introduction of extracted metal and to reduce processing time[6]. Mi-

The data of dissolution of UO2 particles or powders are
essential for the reprocessing of spent fuels in the head-
end process. Some studies on dissolution of UO2 parti-
－
cles or powders have been reported[1 5]. Taylor et al.[1]
have studied the dissolution of sintered UO2 particles in
HNO3 by conventional heating and reported that the
dissolution rate was controlled by chemical reaction at
temperatures below 95℃ and by diffusion at tempera-
tures near boiling point. Ikeda et al.[2] have studied the
kinetics of the UO2 powders by conventional heating
and have found that the dissolution of UO2 powders was
affected by temperatures, [NO3−]T and nitrous acid.
However, some problems may exist during the dissolu-
tion of the UO2 process. These include the following:
Incomplete recovery of uranium for the neediness of
reprocess, dissolution difficulties for some metals, and
the effect of NOX gases generated from the dissolution
process.
Microwave energy in mineral processing has been
widely used in an attempt to improve the leaching ratios
crowave energy has remarkable characteristics, such as
short processing time, and selective and rapid volumet-
ric heating. Thus, it could be a potential alternative for
the treatment of the dissolution of UO2 particles in nitric
acid solution by microwave heating. The microwave
system could provide airproof reactor so that the NOX
gases would not escape from the reaction system. Many
metals which were insoluble under conventional heating
condition could be easily dissolved by microwave en-
ergy.
In order to explore a new concept of head-end process
for the treatment of spent fuel from high temperature
gas-cooling reactor (HTGR), the dissolution of UO2 par-
ticles in the nitric acid solution by microwave heating is
considered. In this paper, the dissolution of UO2 parti-
cles in nitric acid medium by microwave heating and
conventional heating has been studied respectively in
order to compare the difference of the two methods.
Received May 5, 2007; accepted August 6, 2007
doi: 10.1007/s11426-007-0128-3
†
Corresponding author (email: jingxia@tsinghua.edu.cn)

Sci China Ser B-Chem | Jul. 2008 | vol. 51 | no. 7 | 700-704

2 Experimental
2.1 Materials
The ceramic UO2 particles (450－550 μm) were made
as the simulation kernel of the TRISO coated fuel parti-
cles for fuel elements of the 10 MW high temperature
gas-cooled reactor (HTR-10) in China. These UO2 parti-
cles were made from the UO2 (NO3)2 solutions by the
method called total-gelation process (TGU)[7], which
includes the following steps: Preparation, gelation, dry-
ing, deoxidizing, and sintered with hydrogen at 1500℃.
The products are called “ceramic” UO2 particles com-
pared with the conventional UO2 particles.
2.2 Apparatus
A MARS 5 microwave oven[8] with the Teflon vessels
was used to study the dissolution of UO2 particles. The
Teflon vessel is airproof and transparent to microwaves
so that the solution and samples can absorb the maxi-
mum amount of microwave energy. The MARS system
is able to automatically accelerate and control the proc-
ess of chemical reaction according to the thermody-
namic condition based on automatically power emission
adjustable according to the real time thermodynamic
response.
For the conventional heating system, the dissolution
vessel is a 500 mL 3-neck-boiling flask equipped with a
condenser and a stirrer. Gas phase in the vessel was
purged with air gas in order to remove NOX gases gen-
erated during the dissolving procedure.
The concentrations of UO22+ in the dissolution solu-
tion[9] were determined by the absorbance at 652 nm
using spectrophotometer with arsenazo Ⅲ as chro-
mogenic reagent[10].
2.3 Dissolution experiments
The dissolution of UO2 particles by microwave heating
was carried out under controlled pressure and tempera-
ture in 600W, 2.45 GHz microwave power field. 4
mol·L−1 nitric acid (20 mL) solution and UO2 particles
(0.0500 g) were put into the Teflon vessel. The mixture
was stirred at high speed to eliminate the effect of liquid
film. The UO2 particles were dissolved in microwave
field for regulating time, and then the particles and the
solution were separated by filtration and cooled down to
be analyzed.
The dissolution of UO2 particles heated by conven-
ZHAO YunFeng et al. Sci China Ser B-Chem | Jul. 2008 | vol. 51 | no. 7 | 700-704
tional energy was carried out in a reactor of 500 mL
3-neck-boiling flask heating by oil bath and the tem-
perature was controlled within ±1℃. The mixture of 4
mol·L−1 nitric acid solution (200 mL) and samples
(0.500 g) was stirred at 500 r·min−1, because the disso-
lution rate was independent of the stirring speed at
above 300 r·min−1.
3 Experimental results
The experimental program was devised to investigate
the difference of dissolution kinetics of UO2 particles in
4 mol·L−1 nitric acids at different temperatures between
microwave heating and conventional heating.
3.1 Dissolution ratios data
The experiments were carried out at different tempera-
tures of 90－110℃ in 4.0 mol·L−1 nitric acid. Figures 1
and 2 show the dissolution ratios of the UO2 particles by
microwave heating and conventional heating, respec-
tively. It was found from the results that the dissolution
ratios increased slowly by conventional heating, while
they increased quickly by microwave heating. The dis-
solution ratios of UO2 particles by microwave heating
were 10%－40% higher than those by conventional
heating. For example, there were only 40.6% of the UO2
particles dissolved at 110℃ for 40 min by conventional
heating; however, the dissolution ratio was 79.1% for 40
min by microwave heating, about two times of that by
conventional heating.
3.2 Kinetics study
The dissolution procedure can be modeled by the well-
known shrinking core models. In the case of spherical
Figure 1 Dissolution ratios of UO2 particles by microwave heating.
701
 Figure 3 Plot of 1 + 2(1 − x) − 3 (1 − x)2/3 by microwave heating.
Figure 2 Dissolution ratios of UO2 particles by conventional heating.

particles, these models can be expressed as follows[11]:

For surface reaction control:
1 − (1− x)1/3 = kst. (1)
For diffusion control:
1 + 2(1 − x) − 3(1 − x)2/3 = kDt, (2)
where x is the reacted fraction at time t, and kS, kD are
apparent rate constants.
These constants are given in the following equations:
kS = bkM(CHNO3)n/ρro, (3)
kD = 2bDeMCHNO3/ρro2, (4)
where b stoichiometric coefficient; M the molecular Figure 4 Plot of 1 − (1 − x)1/3 by conventional heating.
weight of reacted substance; ρ the density of reacted
particle; ro initial particle radius; k intrinsic rate constant;
De effective diffusivity; CHNO3 the bulk concentration of
HNO3; n reaction order in the term of HNO3 concentra-
tion.
The data shown in Figure 1 were analyzed by using
eqs. (1) and (2). Figure 3 gives the results of the plots of
1 + 2(1 − x) − 3(1 − x)2/3 against time at different tem-
peratures. The straight line relationship obtained in Fig-
ure 3 suggests that the dissolution of UO2 particles is
well-fitted with the product layer diffusion control
model other than the surface reaction control model.
In the same way, the data shown in Figure 2 were Figure 5 Plots of lnk against 1/T for microwave heating.
analyzed by using eqs. (1) and (2). Figure 4 shows the
straight line relationship of the plots of 1 − (1 − x)1/3 activation energy was 77.4 kJ/mol for microwave heat-
against time at different temperatures. It can be seen ing and 31.1 kJ/mol for conventional heating.
from the result that when the system was heated by
conventional energy, the dissolution of UO2 particles 4 Discussions
was controlled by the surface reaction model.
The activation energy can be obtained from the Ar- Microwave heating is different from conventional heat-
rhenius plots. Figures 5 and 6 show the plot of lnk ing. Microwaves can penetrate the Teflon vessel and
against 1/T. From the Arrhenius plots, the value of the lead to efficient volumetric heating for the materials of

702 ZHAO YunFeng et al. Sci China Ser B-Chem | Jul. 2008 | vol. 51 | no. 7 | 700-704
 also showed that there was significant difference be-
tween the two heating methods. The activation energy
value for the conventional heating was consistent with
what had been reported that the activation energy value
for the dissolution of UO2 particles changed from 62
kJ/mol to 8.4－20 kJ/mol with increasing temperature[1].
However, the activation energy for microwave heating
was much higher than that. This may indicate a different
mechanism of the dissolution to be investigated.
The diffusion control model for the dissolution of
UO2 particles by microwave heating could be explained
by the diffuseness on the surface of UO2 particles. Fig-
Figure 6 Plots of lnk against 1/T for conventional heating.
ure 7 shows the profile of UO2 particles dissolved within
20 min by microwave heating and conventional heating,
high dielectric loss factor. The nitric acid and UO2 parti-
respectively. It is apparent that the surface of the UO2
cles are both materials of high dielectric loss factor so
dissolved by microwave heating is much like crossed
that they can extremely absorb microwaves[12]. Thus, it
ravine. However, it is more flat for the UO2 dissolved by
is possible that the solvents and uranium dioxide can be
conventional heating. This phenomenon indicates that
directly heated by microwave energy, compared with the
the dissolution is so deep on the surface by microwave
conductive heating by conventional energy. The energy
heating that the products may not diffuse in good time.
must be conducted through the walls of the vessel con-
Therefore, the dissolution reaction was controlled by the
taining the solution for conventional heating. The mi-
product layer diffusion control model.
crowave heating is different with the conventional heat-
ing. It can directly heat the uranium dioxide and the ni-
tric acid solution. In addition, the Teflon vessel is air-
proof so the pressure of the vessel is higher for micro-
wave heating. The pressure will definitely affect the
dissolution rate. However, there is not any data shown in
the paper because the microwave oven was not equipped
with the pressure detector. Also, because of the airproof,
the NOX gas generated with the dissolution of UO2 par-
ticles cannot be removed from the solution. The NOX
gas can be dissolved in the nitric solution which makes
the color of the solution brown. The dissolved NOX gas
then transformed into nitrous acid which can accelerate
the dissolution reaction process[2]. However, the NOX
gas was removed from the vessel when the experiments
carried out in the boiling flask by conventional heating.
The dissolution ratios of UO2 particles were higher
when the system was heated by microwave energy. Thus,
it could be a potential alternative for the treatment of the
dissolution of UO2 particles in nitric acid solution by
microwave heating.
According to the kinetics study, it could be seen that
the dissolution of UO2 particles fits very well with the
diffusion control model by microwave heating, and it
was consistent with the surface reaction control model Figure 7 The profile of the dissolved UO2 particles. (a) Conventional
by conventional heating. The activation energy study heating; (b) microwave heating.

ZHAO YunFeng et al. Sci China Ser B-Chem | Jul. 2008 | vol. 51 | no. 7 | 700-704 703
5 Conclusions
(1) Microwave heating could promote the dissolution
of UO2 particles in nitric acid compared with conven-
tional heating. The dissolution ratios could be 10%－
40% higher by microwave heating.
(2) Kinetics research showed that the dissolution of
UO2 particles in 4 mol·L−1 nitric acid by microwave
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