Accepted Manuscript

Title: Equilibrium and Kinetics of Adsorption of Ruthenium

on Activated Charcoal from Nitric Acid Solutions

Author: S. Ramakrishna Reddy Niranjan K. Pandey C.

Mallika U. Kamachi Mudali

PII: S0263-8762(16)30299-4
DOI: http://dx.doi.org/doi:10.1016/j.cherd.2016.09.014
Reference: CHERD 2400

To appear in:

Received date: 27-5-2016

Revised date: 25-8-2016
Accepted date: 11-9-2016

Please cite this article as: Reddy, S.Ramakrishna, Pandey, Niranjan K., Mallika,
C., Mudali, U.Kamachi, Equilibrium and Kinetics of Adsorption of Ruthenium on
Activated Charcoal from Nitric Acid Solutions.Chemical Engineering Research and
Design http://dx.doi.org/10.1016/j.cherd.2016.09.014

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Equilibrium and Kinetics of Adsorption of Ruthenium on
Activated Charcoal from Nitric Acid Solutions
S. Ramakrishna Reddy, Niranjan K. Pandey*, C. Mallika, U. Kamachi Mudali

Materials, Process and Equipment Development Group, Reprocessing Group

Indira Gandhi Centre for Atomic Research, Kalpakkam, TN 603102, India
Graphical abstract

1
kf = 1.6x10-6 cm/s
0.9

0.8

kf =1.6x10-5 cm/s
C/C0

0.7

0.6
kf = 1.6x10-4 cm/s

0.5

0.4
0 2000 4000 6000 8000 10000 12000
Time [s]

Effect of external mass transfer coefficient on the transport of Ru on to the adsorbent surface
Highlights

Freundlich model is used to describe the equilibrium data of Ru on activate charcoal

Mechanism of adsorption involved an initial rapid rate followed by intra particle diffusion
The diffusion model is numerically assessed
Numerical values of De and kf were estimated from solving model equations
Abstract
Equilibrium and kinetics of adsorption of ruthenium on activated charcoal were investigated
experimentally using batch methods under different conditions. The Freundlich isotherm
model was used to describe the partitioning behaviour of ruthenium between the solution and
adsorbent phase. A pore diffusion model, coupled with Freundlich isotherm equation was
used to interpret the experimentally obtained adsorption kinetic curves at different
concentrations of ruthenium. The model was found to fit with the experimental data fairly
well. The effective diffusivity and external mass transfer coefficient were estimated to be in
the range 10-8 cm2.s-1 and 10-3 cm. s-1 respectively.

Key-words: Adsorption, activated charcoal, ruthenium, PUREX process, Freundlich

isotherm, liquid-solid separation process.

____________________________
*Corresponding Author: N.K. Pandey, Head, PE&MS, RR&DD, MPEDG, RpG, IGCAR, Kalpakkam, Tamilnadu,
India 603102
Email: nkpandey@igcar.gov.in; Ph.: 0091-44-27480126; Fax: 0091-44-27480126
1. Introduction

In the aqueous reprocessing of spent nuclear fuels by PUREX process, uranium and
plutonium are separated by solvent extraction using 30% tri-n-butyl phosphate (TBP) in
paraffin hydrocarbon diluent. The high level liquid waste (HLLW) solution generated after
the removal of U and Pu contains the radioactive fission products in nitric acid. The HLLW is
subjected to various waste management processes such as concentration, de-nitration and
vitrification in order to reduce the volume of the waste and to convert it into a solid vitrified
body for safe disposal. Ruthenium is one of the most troublesome fission products because of
103 106
its oxidation to highly volatile and chemically unstable radiotoxic RuO4 and RuO4
(McKibben, 1984). Ruthenium tetroxide decomposes to a non-volatile black deposit of
ruthenium dioxide (RuO2) on contact with the cooler parts of the surface of stainless steel
equipment during waste treatment and thus, the radiation dose of the plant increases.
Deposition of ruthenium was observed to plug the off-gas piping of the equipment owing to
appreciable volatilization of RuO4 during waste treatment. During vitrification of the waste,
platinum group fission product metals (Ru, Rh and Pd) form precipitates as alloy and/or
oxides in molten glass and Ru forms needle like electrically conducting RuO2 crystals
(Krause and Luckscheiter, 1991). It is reported that the vitrification of HLLW was
temporarily stopped in a nuclear reprocessing plant operated by Japan Nuclear Fuel Ltd
(JNPL) due to problems arising from the sedimentation of platinum group metals in the glass
melter, which had led to electric energy loss, local overheating, high viscous glass formation
and unexpected low production rate of vitrified glass (Krause and Luckscheiter, 1991). Thus,
separation of ruthenium species from the HLLW is desirable, prior to nuclear waste treatment
for safe disposal.
Various methods reported in the literature for the removal of ruthenium from HLLW
are volatilization (Holgye and Krivanek, 1978; Holgye, 1987), precipitation (Moore, 1960;
Beamish, 1966; Gandon et al., 1993), solvent extraction (Hyman and Leader, 1959; Kiba et
al., 1963; Fieberg and Edwards, 1978; Fitoussi et al., 1981; Lingen et al., 1989; Dhami et al.,
2012), ion-exchange chromatography (Lee and Chung, 2003; Liu et al., 1993), electro-
oxidation/reduction (Lietzke and Griess, 1953; Kobayashi et al., 1965; Motojima, 1990;
Yoneya et al., 1995; Mousset et al., 2004; Pravati Swain et al., 2014, 2015) and sorption
(Berak et al., 1975; Akatsu et al., 1979; Siddhanta and Das, 1985; Motoki et al., 1986;
Tikhomirova et al., 1992; Pankaj et al., 2007; Qadeer, 2007). Among these methods,
adsorption is preferred over other processes because of its cost effectiveness and the high-
quality treated effluents it produces. Sorption method is suitable for the separation and pre-
concentration of ultra-trace amounts of noble metals from solutions containing large excess
of non-noble metals such as Cu, Fe, Ni, Co, Al, Mg and Ca. Inorganic (activated carbon,
zeolites, silica gel, silica-alumina gel etc.) and organic complex forming sorbents (Amberlite
IRC-50, polystyrene-divinylbenzene (8%) resin with thiosemicarbazide, poly-4-vinyl
pyridine, cross-linked by divinyl benzene etc.) are often considered for the separation of
ruthenium.
Activated carbon is the widely used adsorbent for several applications (Ping and
Lynne, 1997; Ho and McKay, 2000; Sharma et al., 2004; Qadeer and Khalid, 2005) because
of the chemical properties of its surface. It is a non-hazardous, processed carbonaceous
product having an intricate porous structure and a large surface area that is contained
predominantly within the micro-pores. The adsorbent properties of the activated charcoal are
essentially attributed to its large surface area, high degree of surface reactivity, and
favourable pore size distribution.
An understanding of the adsorption kinetics of ruthenium within activated carbon
particles will ensure a better prediction of the transport behavior of ruthenium in fixed bed
columns. As there is lack of information in the literature pertaining to the kinetics of
adsorption of ruthenium within activated carbon particles, it is desirable to carry out a
systematic investigation on the subject. In the present study, fundamental aspects of
adsorption equilibrium and kinetics of ruthenium on activated carbon has been investigated to
establish the mechanistic aspect of the process. Sorption data generated were correlated with
the Langmuir and Freundlich isotherm models. Pore diffusion model was used to interpret the
experimental adsorption kinetic data. Based on the results, pore diffusion coefficient and
intra-particle effective diffusivity of ruthenium in activated charcoal were determined.

2. Experimental

2.1. Materials and Methods

The chemicals used in this study were ruthenium nitrosyl nitrate and activated
charcoal (obtained from pine tree) procured from M/s. Arora Matthey, Kolkata,
hydroxylamine chloride, sodium hydroxide and nitric acid (AR Grade; Merck make),
analytical reagent grade 1,10- phenanthroline monohydrate (chromogenic agent) supplied by
M/s. Loba Chemie and AR grade ethanol. The equipment employed were Thermo shaker
(IKA KS 4000), REMI centrifuge, JULABO circulating water bath (JULABO F-34), Double
walled jacketed vessel Vertex mixer (REMI RQ 20 PLUS), Metrohm 744 pH meter and UV-
Visible spectrophotometer (CHEMITO Spectra scan UV 2600). The characteristics of
activated charcoal used are reported in Table 1.

Table 1 Characteristics of activated charcoal

Adsorbent Activated charcoal from Arora Matthey, Kolkata
Surface area (BET) ~ 854 m2.g-1
Mean particle size ~ 22.73m
Porosity ~ 0.54
Particle density ~ 0.54 g.cm-3
Moisture content ~ 27.6 %
Pore volume ~ 0.6084 cm3.gm-1

2.2. Measurement of Adsorption Isotherm

For the measurement of adsorption isotherm, a weighed quantity of activated charcoal

was added to a known volume V of the aqueous solution of ruthenium concentration C
taken in a stoppered 50 mL flask, which was kept under isothermal condition using a thermo
shaker. The content of the flask was mixed for 3 h (maintaining the shaker speed at 100 rpm)
to ascertain that the solution concentration reached equilibrium value within this time. The
solution was then sampled and analysed for ruthenium concentration by spectrophotometric
method (Banks and OLaughlin, 1957). The experiment was repeated with different
concentrations of ruthenium in the aqueous solution (6002850 mg L-1).

2.3. Measurement of Adsorption Rate

The influence of contact time on the transport of ruthenium onto the surface of
adsorbent was studied in a separate batch experiment by measuring the change in
concentration of ruthenium in solution with time. In this experiment, a known mass of
activated charcoal and 1000 mL ruthenium solution of known concentration were taken in a
double jacketed vessel, which was maintained at constant temperature (300K) using a
circulating water bath (JULABO-SW23). The content of the vessel was mixed at 200 rpm
using a vertex mixer (REMI RQ 20 PLUS). The liquid samples were withdrawn at regular
intervals and analysed for ruthenium concentration until it attained the equilibrium value.
Samples were analysed more frequently in the initial phase of the experiment than towards
the end, to achieve a suitable distribution of measured concentration.
2.4. Check for the Reproducibility of Experimental Data

All the experiments were repeated twice. The average value for each set of experiments
is presented in this study. One such data set is shown in Fig. 1. To verify the precision of
experimental results, paired t-test was carried out using two experimental data from the same
set. The calculated t value was 1.62. The t value from the 95% confidence table (Vogel 1989)
was 2.23. As tcal < ttab, it is confirmed with 95% confidence that there is no significant difference
between the two experiments of the same set. Hence, the average values have been selected for
the results of subsequent experiments.

-3
x 10
5

4.8
[Ru]soln. [mol.cm-3]

4.6

4.4

4.2

3.8
0 0.5 1 1.5 2
Time [s] 4
x 10
Fig. 1 Check for reproducibility of experimental data

3. Results and Discussion

3.1. Adsorption Isotherm

The equilibrium amount of ruthenium adsorbed on activated charcoal was determined
from the difference between the initial concentration (C0) and equilibrium concentration (Ce)
of ruthenium in the aqueous solution and is given by

qe
Ce C0 V
(1)
m

Values of qe calculated for the adsorption of ruthenium on charcoal were plotted

against the final concentration of the respective solutions in Fig. 2, to give adsorption
isotherm (i.e. the amount of ruthenium adsorbed per unit weight of charcoal at equilibrium).
Two commonly used mathematical expressions to describe the adsorption equilibria (the
Langmuir and the Freundlich isotherm models) were tested with experimental data. The
Langmuir isotherm model is derived mechanistically while the Freundlich model is an
empirical formulation. Owing to its flexibility, the Freundlich isotherm usually fits the
experimental data over a reasonable range of concentrations. In view of its empirical nature,
it is frequently employed in connection with adsorption from solutions. The Freundlich
model is expressed as,

q e K F C1 / n (2)

The Freundlich model of isotherm was found to fit the experimental data better than
Langmuir model, as could be observed from the comparison between the two models, in Fig.
2. Logarithmic linearization of Eq. (2) facilitated the determination of model constants KF
and n and the numerical values of these constants for the present case were 0.005 and 8.15
respectively. The model fits the experimental data reasonably well giving a standard
deviation of about 7.19%.

-3
x 10
1.8

1.6

1.4

1.2

1
qe [mol.g-1]

0.8

0.6
Exp.
0.4 Freeundlich model
Langmuir model
0.2

0
0 0.5 1 1.5 2
Ce [mol.cm-3] -5
x 10

Fig. 2 Equilibrium data of Ru on activated charcoal

3.2. Rate of Adsorption

Time dependence of the rate of adsorption of Ru on charcoal at different initial

solution concentrations were obtained from batch contact-time experiments. Figure 3 shows
the results of contact time experiments. It was observed that with change in concentration of
adsorbate in the solution from 185 ppm (1.83 x 10-6 mol.cm-3) to 465 ppm (4.61 x 10-3
mol.cm-3), the amount adsorbed at equilibrium increased from 93.1 mg/g to 115.7 mg/g
respectively. It is also observed from the Fig. 3 that ruthenium uptake is very rapid in the
beginning of the experiment (~0 - 30 min.) and later transport of ruthenium from solution to
adsorbent phase becomes slow. This phenomenon is possibly due to rapid saturation of fast
diffusing pores which would result in a net decrease in effective diffusion rate as adsorption
proceeds. The equilibrium time was found to be independent of concentration and was
established in about 90 min.

1.5

1
[Ru]ad. (mol.g-1)

0.5
[Ru]aq,t=0 = 185ppm
[Ru]aq,t=0 = 270ppm
[Ru]aq,t=0 = 465ppm

0
0 2000 4000 6000 8000 10000 12000
Time (s)

Fig. 3 Amount of Ru adsorbed on activated charcoal from aqueous solution of different initial
concentrations against time

3.3. Transport Mechanism of Solute in Sorbent

Adsorption is a surface phenomenon; however, it involves the transfer of solute from

one phase to the other. Various adsorption kinetic models have been adopted to describe the
behaviour of batch sorption process under different experimental conditions (Ruthven 1984,
Mckay et al 1987, El-Geundi 1993, Meshko et al 2001). Sorption kinetics is controlled by the
following steps: (i) external mass transfer of solute from bulk solution to the outer surface of
particles (film diffusion), (ii) diffusion of solute from the sorbent surface to the pores of the
particles and (iii) the adsorption of solute on the active sites of the pore surface. Figure 4
shows the schematic representation of solute transfer into the adsorbent phase.

Co
C s (R p , t)

liquid filled
film pores in the solid

Fig. 4 Schematic representation of solute transfer into the adsorbent phase

3.4. Mathematical Model for the Transport of Solute from the Solution into the Adsorbent
Phase
Development of model equations is based on the following assumptions: (a)
diffusivity is constant at constant temperature and pressure, (b) activated charcoal particles
are considered as spherical and porous, (c) the adsorption sites are uniformly distributed
throughout the grains and (d) the external mass transfer coefficient and diffusivity are
constant for the range of solute concentrations under consideration.

The rate of change of Ru concentration in the bulk solution is proportional to the

concentration difference between the bulk phase and the outer surface of the particle. The
mass balance in the bulk liquid phase describes the relation between the decreasing solute
concentration in solution phase and mass transfer into the solid phase and can be written as

C 3M p k f
(C Cs ) (3)
t VR p

where C is the bulk concentration of solute in the solution phase, and Cs is the concentration
of solute at the outer surface of the spherical particle. R represents the radius of the particle,
p is the density of adsorbent powder, Mp is the total mass of the particle, V is the volume of
solution used in the batch reactor and kf is the external mass-transfer coefficient. Here, mass
flow rate of solute through external film is proportional to the concentration difference
between bulk phase Ru concentration (C) and concentration of Ru at the particle surface, Cs
(Rp, t)

The mass balance of Ru within a spherical particle at a distance r from the centre of
particle is given as (from Ficks 2nd law of diffusion in spherical co-ordinate)

C r q 1 C r
p p r De 2 r 2 (4)
t t r r r

where De is the effective diffusivity of solute within the particle (could be treated as a
combination of pore diffusion and surface diffusion), p is the porosity, Cr is the solution

concentration of Ru within the pores of charcoal particle and qr is the solid phase
concentration of Ru. The first and second terms on the left hand side of Eq. (4) give the
accumulation of Ru in the void space of the adsorbent particles and solid phase respectively.
The Freundlich isotherm can be used for the correlation of Cr and qr. Then Eq. (4)
becomes

C r De 1 2 C r
1n / n 2 r (5)
t p ( p K F / n )C r r r

The initial and boundary conditions can be written as

t = 0: C = C0, Cr = 0 (6)

C
r 0: r 0 (7)
r r 0

C
r R : k f ( C CS ) D e r (8)
r r R

Equations (1) and (3) can be written into dimensionless form as

X 3M p
Bi (X X S ) (9)
V P

X r 1 2 Xr 2Xr
(10)
p ( p K f / n )C 1n / n x x x
2

 1 2 Xr
ar x
x 2 x x

and the initial and boundary conditions in dimensionless form can be written as,

0 : X 1, X r 0 (11)

X
x 0 : r 0 (12)
x x 0
X
x 1 : r Bi(X X S ) (13)
x x 1

The dimensionless parameters are defined as

C Cr r tDe kf R
X , Xr , x , , and Bi
C0 C0 R R2 De

For solving the set of partial differential Eqs. (9) and (10), they are changed to
coupled ordinary differential equations by finite difference methods as follows:

dX i X 2X i X i 1 X i 1 X i 1
a (i) i 1 (14)
d (x ) 2 x i x

Applying the boundary conditions (12) and (13) then, Eq. (10) becomes

At the centre of the particle, i = 1,

dX1 2(X 2 X1 )
a (1) [since, at X = 0, X2 = X0] (15)
d (x )
2

At the surface of the particle, i = 1,

dX N 2X 2xBi (X X N ) 2X N
a ( N) N1 Bi(X X N ) (16)
d (x ) 2

The total N+1 coupled ordinary differential equations for X, X1, X2, ---- XN are solved
numerically by the fourth order Runge-Kutta method using ODE-45 solver of MATLAB
software, in order to obtain concentration profiles. The external mass transfer (kf) and the
effective diffusivity (De) are the two unknown parameters, which are estimated by
superimposing the experimental data on to the diagrams of numerical solution of model
equations using a nonlinear regression technique. The best values were obtained by
minimizing the following objective function:

f [Ru ]aq ,exp [Ru ]aq ,calc

p
2
(17)
1

where, p is the number of observations. Computations were performed using MATLAB

software, which has built-in algorithm to perform a nonlinear least-squares data fit by Nelder-
Mead Search method. The agreement between the experimental results and the model
predicted values, as illustrated in Fig. 5 is found to be good. The values of effective
diffusivity (De) and external mass transfer coefficient (kf) were found to be 1.3 x 10-8 cm2/s
and 2.6 x 10-4 cm/s respectively. The values of De and kf reported here is the average of
calculated values at three different concentrations (as mentioned in Fig. 5), as only slight
variations were observed in the calculated values of De and kf while fitting the model
equations to the experimental data.

1
Exp. (C 0 ~ 185ppm)
Calc. (C 0 ~ 185ppm)

0.9 Exp. (C 0 ~ 271ppm)

Calc. (C 0 ~ 271ppm)
Exp. (C ~ 464ppm)
0
0.8 Calc. (C 0 ~ 464ppm)
C/C0

0.7

0.6

0.5

0.4
0 2000 4000 6000 8000 10000 12000
Time [s]

Fig. 5 Comparison between experimental and model predicted concentrations against time

3.5. Sensitivity Analysis

Sensitivity analysis was performed for the changes in kf and De. Figure 6 represents
the effect of kf on model predicted results. If kf is 10-100 times lower than the estimated
value of 2.6 x 10-4 cm/s, then the removal rate of ruthenium is slow. Nevertheless, when kf
value exceeds the estimated value, the removal rate remained nearly unchanged, because the
external mass transfer coefficient is a function of intensity of mixing. In a stirred vessel, the
thickness of the stagnant interfacial film surrounding the particle is thicker at low impeller
speed and diffusion limits the rate. With increase in impeller speed, stationary diffusion film
becomes thinner and the external diffusional resistance becomes smaller. At some value of
stirring speed, the external mass transfer coefficient has no influence on the entire removal
process.

Figure 7 shows the effect of diffusivity on model predicted results. If the effective
diffusivity (De) value is 10 to 100 times higher than the specified value of 2.3 x 10-7 cm2/s,
then the removal rate becomes faster. However, when De is lower than the estimated value,
the removal rate is almost similar to that of estimated value. Thus, from simulation studies it
is predicted that the effect of De on the removal rate of Ru is less sensitive in comparison to
the effect of external mass transfer coefficient.

1
kf = 1.6x10-6 cm/s
0.9

0.8

kf =1.6x10-5 cm/s
C/C0

0.7

0.6
kf = 1.6x10-4 cm/s

0.5

0.4
0 2000 4000 6000 8000 10000 12000
Time [s]
Fig. 6 Effect of external mass transfer coefficient on the transport of Ru from solution to the
adsorbent surface
 1

0.9

0.8

D =2.3x10-9 cm2/s
C/C0

e
0.7

D = 2.3x10-8 cm2/s
0.6 e

-7 2
D =2.3x10 cm /s
e
0.5

0.4
0 2000 4000 6000 8000 10000 12000
Time [s]
Fig. 7 Effect of diffusivity on the transport of Ru from solution to the adsorbent surface

3.6. Effect of pH on the Adsorption Process

The pH of the solution is an important parameter in the adsorption of ruthenium on

activated charcoal because it alters the surface properties of the adsorbent by invoking
complex mechanisms (Siczek and Steindler, 1978). The influence of hydrogen ion
concentration on the adsorption of ruthenium was monitored in the pH range 0.511 and the
initial concentration of ruthenium in the solution was fixed at 1g/L. Figure 8 represents the
effect of initial pH on the removal of ruthenium by activated carbon. Ruthenium uptake by
activated carbon was observed to increase initially with increasing pH, reached a maximum
(144 mg/g at about 3 pH) and then showed a rapid decline. The low metal sorption from the
acidic solution (i.e. at pH lower than three) could be explained on the basis of active sites
being protonated, resulting in a competition between H+ and nitrosyl ruthenium
[Ru(NO)(H2O)5]+3 ions for the occupancy of the binding sites (Qadeer, 2013). The lower
adsorption capacity of ruthenium for the pH values ranging from 4 to 10 is due to its
hydrolysis and formation of Ru(NO)(OH)3 (colloidal solution).
 -4
x 10
16

14

12
qe [mol.g-1]

10

2
0 2 4 6 8 10 12
pH of the solution

Fig. 8 Effect of pH on the transport of Ru from solution to the adsorbent surface (initial
concentration of Ru in the solution: 1g/L
4. Conclusions

Studies on equilibrium and kinetics of sorption of ruthenium on activated charcoal were

carried out for the removal of ruthenium from aqueous solutions. Theoretical model was
evolved to validate the experimental data. The following conclusions could be drawn from
the results of the present investigation:

a. The adsorption isotherm could be correlated using Freundlich model of adsorption. The
Freundlich isotherm fitted well with experimental data.

b. The mechanism of adsorption involved an initial rapid rate for the removal of ruthenium
due to surface diffusion followed by intrapaticle diffusion. At later stages, rate of
adsorption of ruthenium decreased with time, possibly due to the decreased concentration
gradient.

c. The diffusion model was numerically assessed and there was conformity between
theoretical prediction and batch experimental data. Theoretical values of De and kf were
estimated from diffusion model.

d. Kinetic modelling revealed that pore diffusion model to be appropriate for the description
of transport of ruthenium within activated charcoal particles.
Nomenclature

C Bulk solution concentration of Ru at any time t, (mol/cm3)

Ce Equilibrium concentration of Ru (mol/cm3)

Ci Interfacial concentration of Ru (mol/cm3)

C0 Initial concentration of Ru in solution (mol/cm3)

Cr Pore liquid concentration of Ru at any time t (mol/cm3)

Cs Concentration of Ru at the particle surface (mol/cm3)

De Effective diffusivity (cm2/s)

kf External mass transfer coefficient (cm/s)

KF Freundlich constant (mol(n-1)/n.cm(3/n)/g)

Mp Mass of the particle (g)

n Freundlich constant

q Amount adsorbed at time t (mol/g)

qe Amount adsorbed at equilibrium (mol/g)

qm Maximum adsorption capacity on solid phase for monolayer formation (mol/g)

qr Solid phase concentration of Ru at any time t (mol/cm3)

r Radial distance from the centre of the particle (cm)

R Radius of the particle (cm)

V Volume of the solution (ml)

t Time (s)

p Density of the particle (g/cm3)

p Porosity of the particle

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