Abstract: This paper presents a nonlinear differential model,
for a three-bladed horizontal axis wind turbine (HAWT) suited
for control applications. It is based on a 8-dofs, lumped
parameters structural dynamics coupled with a quasi-steady sectional
aerodynamics. In particular, using the Euler-Lagrange Equation
(Energetic Variation approach), the authors derive, and successively
validate, such model. For the derivation of the aerodynamic model,
the Greenbergs theory, an extension of the theory proposed by
Theodorsen to the case of thin airfoils undergoing pulsating flows,
is used. Specifically, in this work, the authors restricted that theory
under the hypothesis of low perturbation reduced frequency k,
which causes the lift deficiency function C(k) to be real and equal
to 1. Furthermore, the expressions of the aerodynamic loads are
obtained using the quasi-steady strip theory (Hodges and Ormiston),
as a function of the chordwise and normal components of relative
velocity between flow and airfoil Ut, Up, their derivatives, and
section angular velocity ε˙. For the validation of the proposed model,
the authors carried out open and closed-loop simulations of a 5
MW HAWT, characterized by radius R =61.5 m and by mean chord
c = 3 m, with a nominal angular velocity Ωn = 1.266rad/sec.
The first analysis performed is the steady state solution, where
a uniform wind Vw = 11.4 m/s is considered and a collective
pitch angle θ = 0.88◦ is imposed. During this step, the authors
noticed that the proposed model is intrinsically periodic due to
the effect of the wind and of the gravitational force. In order
to reject this periodic trend in the model dynamics, the authors
propose a collective repetitive control algorithm coupled with a PD
controller. In particular, when the reference command to be tracked
and/or the disturbance to be rejected are periodic signals with a
fixed period, the repetitive control strategies can be applied due to
their high precision, simple implementation and little performance
dependency on system parameters. The functional scheme of a
repetitive controller is quite simple and, given a periodic reference
command, is composed of a control block Crc(s) usually added
to an existing feedback control system. The control block contains
and a free time-delay system eτs in a positive feedback loop, and a
low-pass filter q(s). It should be noticed that, while the time delay
term reduces the stability margin, on the other hand the low pass
filter is added to ensure stability. It is worth noting that, in this
work, the authors propose a phase shifting for the controller and
the delay system has been modified as e^(−(T−γk)), where T is the
period of the signal and γk is a phase shifting of k samples of the
same periodic signal. It should be noticed that, the phase shifting
technique is particularly useful in non-minimum phase systems, such
as flexible structures. In fact, using the phase shifting, the iterative
algorithm could reach the convergence also at high frequencies.
Notice that, in our case study, the shifting of k samples depends
both on the rotor angular velocity Ω and on the rotor azimuth
angle Ψ: we refer to this controller as a spatial repetitive controller.
The collective repetitive controller has also been coupled with a C(s) = PD(s), in order to dampen oscillations of the blades.
The performance of the spatial repetitive controller is compared
with an industrial PI controller. In particular, starting from wind
speed velocity Vw = 11.4 m/s the controller is asked to maintain the
nominal angular velocity Ωn = 1.266rad/s after an instantaneous
increase of wind speed (Vw = 15 m/s). Then, a purely periodic
external disturbance is introduced in order to stress the capabilities
of the repetitive controller. The results of the simulations show that,
contrary to a simple PI controller, the spatial repetitive-PD controller
has the capability to reject both external disturbances and periodic
trend in the model dynamics. Finally, the nominal value of the
angular velocity is reached, in accordance with results obtained with
commercial software for a turbine of the same type.
Abstract: Finite Element Models (FEMs) are widely used in order to study and predict the dynamic properties of structures and usually, the prediction can be obtained with much more accuracy in the case of a single component than in the case of assemblies. Especially for structural dynamics studies, in the low and middle frequency range, most complex FEMs can be seen as assemblies made by linear components joined together at interfaces. From a modelling and computational point of view, these types of joints can be seen as localized sources of stiffness and damping and can be modelled as lumped spring/damper elements, most of time, characterized by nonlinear constitutive laws. On the other side, most of FE programs are able to run nonlinear analysis in time-domain. They treat the whole structure as nonlinear, even if there is one nonlinear degree of freedom (DOF) out of thousands of linear ones, making the analysis unnecessarily expensive from a computational point of view. In this work, a methodology in order to obtain the nonlinear frequency response of structures, whose nonlinearities can be considered as localized sources, is presented. The work extends the well-known Structural Dynamic Modification Method (SDMM) to a nonlinear set of modifications, and allows getting the Nonlinear Frequency Response Functions (NLFRFs), through an ‘updating’ process of the Linear Frequency Response Functions (LFRFs). A brief summary of the analytical concepts is given, starting from the linear formulation and understanding what the implications of the nonlinear one, are. The response of the system is formulated in both: time and frequency domain. First the Modal Database is extracted and the linear response is calculated. Secondly the nonlinear response is obtained thru the NL SDMM, by updating the underlying linear behavior of the system. The methodology, implemented in MATLAB, has been successfully applied to estimate the nonlinear frequency response of two systems. The first one is a two DOFs spring-mass-damper system, and the second example takes into account a full aircraft FE Model. In spite of the different levels of complexity, both examples show the reliability and effectiveness of the method. The results highlight a feasible and robust procedure, which allows a quick estimation of the effect of localized nonlinearities on the dynamic behavior. The method is particularly powerful when most of the FE Model can be considered as acting linearly and the nonlinear behavior is restricted to few degrees of freedom. The procedure is very attractive from a computational point of view because the FEM needs to be run just once, which allows faster nonlinear sensitivity analysis and easier implementation of optimization procedures for the calibration of nonlinear models.
Abstract: The subject of this abstract is related to the notion of 'popular music', a notion that should be treated with extreme care, particularly when applied to Frederic Chopin, one of the greatest composers of Romanticism. By ‘popular music’, we mean a category of everyday music, set against the more intellectual kind, referred to as ‘classical’. We only need to look back to the culture of the nineteenth century to realize that this ‘popular music’ refers to the ‘music of the low’. It can be studied from a sociological viewpoint, or as sociological aesthetics. However, we cannot ignore the fact that, very quickly, this music spread to the wealthiest strata of the European society of the nineteenth century, while likewise the lowest classes often listen to the intellectual classical music, so pleasant to listen to. Further, we can observe that a sort of ‘sacralisation of kitsch’ occurs at the intersection between the classical and popular music. This process is the topic of this contribution. We will start by investigating the notion of kitsch through the study of Chopin’s popular compositions. However, before considering the popularisation of this music in today’s culture, we will have to focus on the use of the word kitsch in Chopin’s times, through his own musical aesthetics. Finally, the objective here will be to negate the theory that art is simply the intellectual definition of aesthetics. A kitsch can, obviously, only work on the emotivity of the masses, as it represents one of the features of culture-language (the words which the masses identify with). All art is transformed, becoming something outdated or even outmoded. Here, we are truly within a process of mythologization of art, through the study of the aesthetic reception of the musical work.
Abstract: Cover or catch crops have beneficial effects for soil, water, erosion, etc. If harvested, they also provide feedstock for biogas without competition for arable land in regions, where only one main crop can be produced per year. On average gross energy yields of approx. 1300 m³ methane (CH4) ha-1 can be expected from 4.5 tonnes (t) of cover crop dry matter (DM) in Austria. Considering the total energy invested from cultivation to compression for biofuel use a net energy yield of about 1000 m³ CH4 ha-1 is remaining. With the straw of grain maize or Corn Cob Mix (CCM) similar energy yields can be achieved. In comparison to catch crops remaining on the field as green manure or to complete fallow between main crops the effects on soil, water and climate can be improved if cover crops are harvested without soil compaction and digestate is returned to the field in an amount equivalent to cover crop removal. In this way, the risk of nitrate leaching can be reduced approx. by 25% in comparison to full fallow. The risk of nitrous oxide emissions may be reduced up to 50% by contrast with cover crops serving as green manure. The effects on humus content and erosion are similar or better than those of cover crops used as green manure when the same amount of biomass was produced. With higher biomass production the positive effects increase even if cover crops are harvested and the only digestate is brought back to the fields. The ecological footprint of arable farming can be reduced by approx. 50% considering the substitution of natural gas with CH4 produced from cover crops.
Abstract: The objective of this work was to develop a theoretical model to study the dynamic thermal behavior of a flat plate solar collector integrated with a phase change material (PCM). The PCM acted as a heat source for the solar system during low intensity solar radiation and night. The energy balance equations for the various components of the collector as well as for the PCM were formulated and numerically solved using MATLAB computational program. The effect of natural convection on heat during the melting process was taken into account by using an effective thermal conductivity. The model was used to investigate the effect of inlet water temperature, water mass flow rate, and PCM thickness on the outlet water temperature and the melt fraction during charging and discharging modes. A comparison with a collector without PCM was made. Results showed that charging and discharging processes of PCM have six stages. The adding of PCM caused a decrease in temperature during charge and an increase during discharge. The rise was most enhanced for higher inlet water temperature, PCM thickness and for lower mass flow rate. Analysis indicated that the complete melting time was shorter than the solidification time due to the high heat transfer coefficient during melting. The increases in PCM height and mass flow rate were not linear with the melting and solidification times.
Abstract: Propagation of fire through a non-air conditioned
railway compartment is studied by virtue of numerical simulations.
Simultaneous computational fire dynamics equations, such as
Navier-Stokes, lumped species continuity, overall mass and energy
conservation, and heat transfer are solved using finite volume based
(for radiation) and finite difference based (for all other equations)
solver, Fire Dynamics Simulator (FDS). A single coupe with an eight
berth occupancy is used to establish the numerical model, followed
by the selection of a three coupe system as the fundamental unit
of the locomotive compartment. Heat Release Rate Per Unit Area
(HRRPUA) of the initial fire is varied to consider a wide range of
compartmental fires. Parameters, such as air inlet velocity relative
to the locomotive at the windows, the level of interaction with the
ambiance and closure of middle berth are studied through a wide
range of numerical simulations. Almost all the loss of lives and
properties due to fire breakout can be attributed to the direct or
indirect exposure to flames or to the inhalation of toxic gases and
resultant suffocation due to smoke and soot. Therefore, the temporal
stature of fire and smoke are reported for each of the considered
cases which can be used in the present or extended form to develop
guidelines to be followed in case of a fire breakout.
Abstract: The purpose of this study is to present a mathematical phrase for calculating the dispersion rate of spilled oil in water column under non-breaking waves. In this regard, a multiphase numerical model is applied for which waves and oil phase were computed concurrently, and accuracy of its hydraulic calculations have been proven. More than 200 various scenarios of oil spilling in wave waters were simulated using the multiphase numerical model and its outcome were collected in a database. The recorded results were investigated to identify the major parameters affected vertical oil dispersion and finally 6 parameters were identified as main independent factors. Furthermore, some statistical tests were conducted to identify any relationship between the dependent variable (dispersed oil mass in the water column) and independent variables (water wave specifications containing height, length and wave period and spilled oil characteristics including density, viscosity and spilled oil mass). Finally, a mathematical-statistical relationship is proposed to predict dispersed oil in marine waters. To verify the proposed relationship, a laboratory example available in the literature was selected. Oil mass rate penetrated in water body computed by statistical regression was in accordance with experimental data was predicted. On this occasion, it was necessary to verify the proposed mathematical phrase. In a selected laboratory case available in the literature, mass oil rate penetrated in water body computed by suggested regression. Results showed good agreement with experimental data. The validated mathematical-statistical phrase is a useful tool for oil dispersion prediction in oil spill events in marine areas.
Abstract: Visual simulation has emerged as a key planning tool in built environment because it enables architects, engineers and project managers to visualize construction process evolution before the project actual commences. This provides an efficient technology for reducing time and cost through planning and controlling resources, machines and materials. With the development of infrastructure projects and the massive civil constructions such as bridges, urban tunnels and highways as well as sensitivity of their construction operations, it is very necessary to apply proper planning methods. Implementation of visual techniques into management of construction projects can provide a fundamental foundation for projects with massive activities and duplicate items. So, the purpose of this paper is to develop visual simulation management techniques for infrastructure projects such as highways bridges by the use of Four-Dimensional Computer-Aided design Models. This project simulates operational assembly-line for Box-Girder Concrete Bridges which it would be able to optimize the sequence and interaction of project activities and on the other hand, it would minimize any unintended conflicts prior to project start. In this paper, after introducing the various planning methods by building information model and concrete bridges in highways, an executive case study is demonstrated and then a visual technique (4D CAD) will be applied for the case. In the final step, the user feedback for interacting by this system evaluated according to six criteria.
Abstract: In this study, water monitoring was performed from Nov. 2012 to Oct. 2013 to assess water quality and evaluate the spatial and temporal distribution of physicochemical and biological variables in water. Water samples were collected from 10 coastal water stations of West Port. In the case of water-quality assessment, multi-metric indices and operational indicators have been proposed to classify the trophic status at different stations. The trophic level of West Port coastal water ranges from eutrophic to hypertrophic. Chl-a concentration was used to estimate the biological response of phytoplankton biomass and indicated eutrophic conditions in West Port and mesotrophic conditions at the control site. During the study period, no eutrophication events or secondary symptoms occurred, which may be related to hydrodynamic turbulence and water exchange, which prevent the development of eutrophic conditions in the West Port.
Abstract: The triple diffusive boundary layer flow of nanofluid under the action of constant magnetic field over a non-linear stretching sheet has been investigated numerically. The model includes the effect of Brownian motion, thermophoresis, and cross-diffusion; slip mechanisms which are primarily responsible for the enhancement of the convective features of nanofluid. The governing partial differential equations are transformed into a system of ordinary differential equations (by using group theory transformations) and solved numerically by using variational finite element method. The effects of various controlling parameters, such as the magnetic influence number, thermophoresis parameter, Brownian motion parameter, modified Dufour parameter, and Dufour solutal Lewis number, on the fluid flow as well as on heat and mass transfer coefficients (both of solute and nanofluid) are presented graphically and discussed quantitatively. The present study has industrial applications in aerodynamic extrusion of plastic sheets, coating and suspensions, melt spinning, hot rolling, wire drawing, glass-fibre production, and manufacture of polymer and rubber sheets, where the quality of the desired product depends on the stretching rate as well as external field including magnetic effects.
Abstract: The main objective of this paper is to give a comprehensive review of non-renewable energy and renewable energy utilization in Malaysia, including hydropower, solar photovoltaic, biomass and biogas technologies. Malaysia mainly depends on non-renewable energy (natural gas, coal and crude oil) for electricity generation. Therefore, this paper provides a comprehensive review of the energy sector and discusses diversification of electricity generation as a strategy for providing sustainable energy in Malaysia. Energy policies and strategies to protect the non-renewable energy utilization also are highlighted, focusing in the different sources of energy available for high and sustained economic growth. Emphasis is also placed on a discussion of the role of renewable energy as an alternative source for the increase of electricity supply security. It is now evident that to achieve sustainable development through renewable energy, energy policies and strategies have to be well designed and supported by the government, industries (firms), and individual or community participation. The hope is to create a positive impact on sustainable development through renewable sources for current and future generations.
Abstract: Impact behavior of striker on graphene sheet and carbon nanotube is investigated based on molecular dynamics (MD) simulations. A MD simulation is conducted to obtain the maximum dynamic deflections of a square and rectangular single-layered graphene sheets (SLGSs) with various values of side-length and striker parameter. Effect of (i) chirality, (ii) graphene side-length and nanotube length, (iii) striker mass on the maximum dynamic deflections of graphene and nanotube are investigated. The effect of different types of boundary condition on the maximum dynamic deflections is studied for zigzag and armchair SWCNTs with various aspect ratios (Length/Diameter).
Abstract: The continued growth of tourism in the future relies on maintaining a clean environment by achieving sustainable development. The erosion and degradation of beaches, the deterioration of coastal water quality, visual pollution of coastlines by massive developments, all this has contributed heavily to the loss of the natural attractiveness for tourism. In light of this, promoting the concept of sustainable coastal development is becoming a central goal for governments and private sector. An ecolodge is a small hotel or guesthouse that incorporates local architectural, cultural and natural characteristics, promotes environmental conservation through minimizing the use of waste and energy and produces social and economic benefits for local communities. Egypt has some scattered attempts in some areas like Sinai in the field of ecolodging. This research tends to investigate the potentials of the North West Coast (NWC) in Alexandria as a new candidate for ecolodging investments. The area is full of primitive natural and man-made resources. These, if used in an environmental-friendly way could achieve cost reductions as a result of successful resource management for investors on the one hand, and coastal preservation on the other hand. In-depth interviews will be conducted with stakeholders in the tourism sector to examine their opinion about the potentials of the research area for ecolodging developments. The candidates will be also asked to rate the importance of the availability of certain environmental aspects in such establishments such as the uses of resources that originate from local communities, uses of natural power sources, uses of an environmental-friendly sewage disposal, forbidding the use of materials of endangered species and enhancing cultural heritage conservation. The results show that the area is full of potentials that could be effectively used for ecolodging investments. This if efficiently used could attract ecotourism as a supplementary type of tourism that could be promoted in Alexandria aside cultural, recreational and religious tourism.
Abstract: This paper presents a numerical analysis for the dynamic performance of a finite journal bearing lubricated with couple stress fluid taking into account the effect of the deformation of the bearing liner. The modified Reynolds equation has been solved by using finite difference technique. The dynamic characteristics in terms of stiffness coefficients, damping coefficients, critical mass and whirl ratio are evaluated for different values of eccentricity ratio and elastic coefficient for a journal bearing lubricated with a couple stress fluids and a Newtonian fluid. The results show that the dynamic characteristics of journal bearings lubricated with couple stress fluids are improved compared to journal bearings lubricated with Newtonian fluids.
Abstract: Chromite ores are primarily used for extraction of chromium, which is an expensive metal. For low grade chromite ores (containing less than 40% Cr2O3), the chromium extraction is not usually economically viable. India possesses huge quantities of low grade chromite reserves. This deposit can be utilized after proper physical beneficiation. Magnetic separation techniques may be useful after reduction for the beneficiation of low grade chromite ore. The sample collected from the sukinda mines is characterized by XRD which shows predominant phases like maghemite, chromite, silica, magnesia and alumina. The raw ore is crushed and ground to below 75 micrometer size. The microstructure of the ore shows that the chromite grains surrounded by a silicate matrix and porosity observed the exposed side of the chromite ore. However, this ore may be utilized in refractory applications. Chromite ores contain Cr2O3, FeO, Al2O3 and other oxides like Fe-Cr, Mg-Cr have a high tendency to form spinel compounds, which usually show high refractoriness. Initially, the low grade chromite ore (containing 34.8% Cr2O3) was reduced at 1200 0C for 80 minutes with 30% coke fines by weight, before being subjected to magnetic separation. The reduction by coke leads to conversion of higher state of iron oxides converted to lower state of iron oxides. The pre-reduced samples are then characterized by XRD. The magnetically inert mass was then reacted with 20% MgO by weight at 1450 0C for 2 hours. The resultant product was then tested for various refractoriness parameters like apparent porosity, slag resistance etc. The results were satisfactory, indicating that the resultant spinel compounds are suitable for refractory applications for elevated temperature processes.
Abstract: The total mass attenuation coefficients m/r, of some halides such as, NaCl, KCl, CuCl, NaBr, KBr, RbCl, AgCl, NaI, KI, AgBr, CsI, HgCl2, CdI2 and HgI2 were determined at photon energies 279.2, 320.07, 514.0, 661.6, 1115.5, 1173.2 and 1332.5 keV in a well-collimated narrow beam good geometry set-up using a high resolution, hyper pure germanium detector. The mass attenuation coefficients and the effective atomic cross sections are found to be in good agreement with the XCOM values. From these mass attenuation coefficients, the effective atomic cross sections sa, of the compounds were determined. These effective atomic cross section sa data so obtained are then used to compute the effective atomic numbers Zeff. For this, the interpolation of total attenuation cross-sections of photons of energy E in elements of atomic number Z was performed by using the logarithmic regression analysis of the data measured by the authors and reported earlier for the above said energies along with XCOM data for standard energies. The best-fit coefficients in the photon energy range of 250 to 350 keV, 350 to 500 keV, 500 to 700 keV, 700 to 1000 keV and 1000 to 1500 keV by a piecewise interpolation method were then used to find the Zeff of the compounds with respect to the effective atomic cross section sa from the relation obtained by piece wise interpolation method. Using these Zeff values, the electron densities Nel of halides were also determined. The present Zeff and Nel values of halides are found to be in good agreement with the values calculated from XCOM data and other available published values.
Abstract: The paper describes conceptual design, control strategies, and partial simulation for a new fully autonomous lower limb wearable exoskeleton system for human motion enhancement that can support its weight and increase strength and endurance. Various problems still remain to be solved where the most important is the creation of a power and cost efficient system that will allow an exoskeleton to operate for extended period without batteries being frequently recharged. The designed exoskeleton is enabling to decouple the weight/mass carrying function of the system from the forward motion function which reduces the power and size of propulsion motors and thus the overall weight, cost of the system. The decoupling takes place by blocking the motion at knee joint by placing passive air cylinder across the joint. The cylinder is actuated when the knee angle has reached the minimum allowed value to bend. The value of the minimum bending angle depends on usual walk style of the subject. The mechanism of the exoskeleton features a seat to rest the subject’s body weight at the moment of blocking the knee joint motion. The mechanical structure of each leg has six degrees of freedom: four at the hip, one at the knee, and one at the ankle. Exoskeleton legs are attached to subject legs by using flexible cuffs. The operation of all actuators depends on the amount of pressure felt by the feet pressure sensors and knee angle sensor. The sensor readings depend on actual posture of the subject and can be classified in three distinct cases: subject stands on one leg, subject stands still on both legs and subject stands on both legs but transit its weight from one leg to other. This exoskeleton is power efficient because electrical motors are smaller in size and did not participate in supporting the weight like in all other existing exoskeleton designs.
Abstract: It is known that stationary human occupants act as dynamic mass-spring-damper systems and can change the modal properties of civil engineering structures. This paper describes the full scale measurement to explain the tuned mass damper effects of stationary people on structural damping of footbridge with center span length of 33 m. A human body can be represented by a lumped system consisting of masses, springs, and dashpots. Complex eigenvalue calculation is also conducted by using ISO5982:1981 human model (two degree of freedom system). Based on experimental and analytical results for the footbridge with the stationary people in the standing position, it is demonstrated that stationary people behave as a tuned mass damper and that ISO5982:1981 human model can explain the structural damping characteristics measured in the field.
Abstract: Natural circulation loops (NCLs) are buoyancy driven flow systems without any moving components. NCLs have vast applications in geothermal, solar and nuclear power industry where reliability and safety are of foremost concern. Due to certain favorable thermophysical properties, especially near supercritical regions, carbon dioxide can be considered as an ideal loop fluid in many applications. In the present work, a high temperature NCL that uses supercritical carbon dioxide as loop fluid is analysed. The effects of relevant design and operating variables on loop performance are studied. The system operating under steady state is modelled taking into account the axial conduction through loop fluid and loop wall, and heat transfer with surroundings. The heat source is considered to be a heater with controlled heat flux and heat sink is modelled as an end heat exchanger with water as the external cold fluid. The governing equations for mass, momentum and energy conservation are normalized and are solved numerically using finite volume method. Results are obtained for a loop pressure of 90 bar with the power input varying from 0.5 kW to 6.0 kW. The numerical results are validated against the experimental results reported in the literature in terms of the modified Grashof number (Grm) and Reynolds number (Re). Based on the results, buoyancy and friction dominated regions are identified for a given loop. Parametric analysis has been done to show the effect of loop diameter, loop height, ambient temperature and insulation. The results show that for the high temperature loop, heat loss to surroundings affects the loop performance significantly. Hence this conjugate heat transfer between the loop and surroundings has to be considered in the analysis of high temperature NCLs.
Abstract: In this study, pomegranate skin, a material suitable for the conditions in Algeria, was chosen as adsorbent material for removal of lead in an aqueous solution. Biosorption studies were carried out under various parameters such as mass adsorbent particle, pH, contact time, the initial concentration of metal, and temperature. The experimental results show that the percentage of biosorption increases with an increase in the biosorbent mass (0.25 g, 0.035 mg/g; 1.25 g, 0.096 mg/g). The maximum biosorption occurred at pH value of 8 for the lead. The equilibrium uptake was increased with an increase in the initial concentration of metal in solution (Co = 4 mg/L, qt = 1.2 mg/g). Biosorption kinetic data were properly fitted with the pseudo-second-order kinetic model. The best fit was obtained by the Langmuir model with high correlation coefficients (R2 > 0.995) and a maximum monolayer adsorption capacity of 0.85 mg/g for lead. The adsorption of the lead was exothermic in nature (ΔH° = -17.833 kJ/mol for Pb (II). The reaction was accompanied by a decrease in entropy (ΔS° = -0.056 kJ/K. mol). The Gibbs energy (ΔG°) increased from -1.458 to -0.305 kJ/mol, respectively for Pb (II) when the temperature was increased from 293 to 313 K.