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Journal of Taibah University for Science 11 (2017) 922–929

Effects of size and shape on the specific heat, melting entropy and
enthalpy of nanomaterials
Madan Singh ∗ , Sekhants’o Lara, Spirit Tlali
Department of Physics and Electronics, National University of Lesotho, P.O. Roma 180, Lesotho
Received 19 July 2016; received in revised form 23 September 2016; accepted 25 September 2016
Available online 11 October 2016

Abstract
A simple theory is proposed to study the size- and shape-dependent specific heat, melting entropy and enthalpy of nanomaterials.
The particle size and shape are demonstrated to affect the specific heat, melting entropy and enthalpy of nanomaterials. The model
is applied to Ag, Cu, In, Se, Au and Al nanomaterials in spherical, nanowire and nanofilms shapes. The specific heat is observed
to increase with the decrease in particle size, whereas the melting entropy and enthalpy decrease as the particle size decreases. Our
theoretical predictions agree well with available experimental and computer simulation results, thereby supporting the validity of
formulation developed.
© 2016 The Authors. Production and hosting by Elsevier B.V. on behalf of Taibah University. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Keywords: Nanomaterials; Specific heat; Melting entropy; Surface properties; Thermodynamic properties

1. Introduction properties of nanomaterials [6,7]. The cohesive energy,

also known as the heat of sublimation, is an important
It has been reported that nanomaterials exhibit physical quantity that accounts for the strength of metal-
interesting physical and chemical properties that are sig- lic bonds, as it is the energy required to divide the metallic
nificantly different from the corresponding properties of crystal into individual atoms. Experimental and theoret-
bulk materials [1–5]. Because of the enormous surface- ical studies of cohesive energy of W, Ag, Co, Al and Cu
area-to-volume ratio of nanomaterials, the energy nanoparticles have been conducted by many researchers
associated with the atoms of these nanomaterials will [8–10]. Modeling the size- and shape-dependent cohe-
be different compared to that of conventional bulk sive energy of nanoparticles and its applications in the
materials, leading to the size-dependent thermodynamic heterogeneous systems has been calculated theoretically
by Li [11], who reported that the cohesive energy of the
free nanoparticles usually decreases as its size decreases.
∗ Considering the effects of particles size, lattice and sur-
Corresponding author.
E-mail address: m.singh@nul.ls (M. Singh). face packing factors and coordination numbers of the
Peer review under responsibility of Taibah University. lattice, Shandiz et al. [12] calculated the melting entropy
and enthalpy of metallic nanoparticles. A theoretical
study involving modeling of the melting enthalpy of
nanomaterials sought to define the conventional shape
factor α [13].
http://dx.doi.org/10.1016/j.jtusci.2016.09.011
1658-3655 © 2016 The Authors. Production and hosting by Elsevier B.V. on behalf of Taibah University. This is an open access article under the
CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
 M. Singh et al. / Journal of Taibah University for Science 11 (2017) 922–929 923

The melting temperature of nanosolids (such as 2. Methodology

nanoparticles, nanowires and nanofilms) has been pre-
dicted based on size-dependent cohesive energy [14]; it The total cohesive energy is defined as the energy due
is shown that the melting temperature of nanomateri- to the contributions of the interior atoms and the surface
als decreases with decreasing particle size. Researchers atoms of the nanomaterial and is expressed as [14]
have calculated the root mean square amplitude model, 1
the size-dependent Debye temperature model and size- ETotal = E0 (n − N) + E0 N (1)
2
dependent thermal conductivity model [15,16] by
where n is the total number of atoms in the nanosolid,
considering Lindemann’s criterion and Mott’s equa-
and N is the number of surface atoms. Therefore, (n − N)
tion. It is stated that the Debye temperature decreases
is the total number of interiors atoms in the nanomaterial.
for nanomaterials as the size decreases. The effects of
E0 is the cohesive energy of the bulk material per atom.
particle size and thermodynamic energy, based on sur-
To determine the cohesive energy per mole, Eq. (1) may
face thermodynamics and the atomic bond energy, were
be written as
used to calculate the mechanical properties, such as  
surface tension and Young’s modulus of nanocrystals AETotal N 1
= AE0 1 − + AE0 N (2)
[17,18]. The cohesive energy is the basic thermodynamic n n 2n
property used to predict melting temperature, melting where A is Avogadro’s number. Here, AETotal /n is the
enthalpy, melting entropy and specific heat of nanoma- cohesive energy per mole of the nanomaterial En , and
terials. Scholars have proposed different models, namely AE0 is the cohesive energy per mole of the corresponding
the latent heat model, the liquid drop model and the sur- bulk material (Eb ). On substituting the relevant parame-
face area difference model [19–21], to predict cohesive ters in Eq. (2), one can obtain
energy of nanomaterials. Recently, using the concept  
N
of cohesive energy changes with the atomic coordina- E n = Eb 1 −
tion environment, Qi [22] presented a theory based on 2n
the bond energy model to highlights the thermodynam- It is reported [24,25] that the cohesive energy is lin-
ics for the nanoparticles, nanowires, and nanofilms. The early related to the melting temperature; we can therefore
size and coherence dependent cohesive energy, melt- write the relation for melting temperature of nanomate-
ing temperature, melting enthalpy, vacancy formation rials as
energy and vacancy concentration of nanowires and  
N
nanofilms have been reported [23]. The variation direc- Tn = Tb 1 − (3)
2n
tion of the thermodynamic properties is observed to
be determined by the coherent interface and the quan- where Tb is the melting temperature of the bulk material.
tity of variation depends upon the crystal size. Shandiz The Lindemann’s melting criterion, which states that
et al. [12] developed a model for melting entropy and a crystal melts when the root mean square displacement
enthalpy of metallic nanoparticles, which is based on the of atoms exceeds a certain fraction of the interatomic
effect of packing factors, coordination numbers of lattice distance in the crystal, is valid for small particles. Using
and crystalline planes. Thus, it appears that there exist this theory, the relationship between the melting temper-
some attempts to study size-dependent thermodynami- ature and Debye temperature of the bulk material can be
cal properties. Moreover, because the thermodynamical given as [25]
properties also depend on the shape, it may be valu-  1/2
Tb
able to present a model that incorporates the effects of θDb ∝ (4)
MV 2/3
shape.
In this contribution, we present a surface free energy where M is the molecular mass, and V is the volume per
model that does not use adjustable parameters and atom.
depends upon the size and shape with respect to the Similarly, for the nanomaterials, the expression is
cohesive energy of nanomaterials. Using the relation-  1/2
Tn
ship between melting temperature and cohesive energy, θDn ∝ (5)
the expressions for size- and shape-dependent specific MV 2/3
heat, melting entropy and enthalpy are obtained. The Eqs. (3) and (5) give the following correlation:
theoretical predictions of these expressions are applied
θDn
2 Tn
to Ag, Cu, In, Se, Au and Al nanomaterials in spherical, = (6)
nanowire and nanofilms shapes. θDb
2 Tb
924 M. Singh et al. / Journal of Taibah University for Science 11 (2017) 922–929

On the basis of Debye’s theory [26], a relationship is Substituting the values of Eqs. (3) and (12) into Eq.
obtained between specific heat at constant pressure and (14) and rearranging, we obtain
Debye temperature of bulk material [27], that is,     
3RTb N N
Hmn = Hmb + ln 1 − 1−
1 2 2n 2n
Cpb ∝ (7) (15)
θDb
2

Similarly, for the nanomaterials, the expression is

For the values of N/2n, the method has already been
1 reported in the literature [14]. The value of N/2n depends
Cpn ∝ (8)
θDn
2 upon the shape and size of the nanomaterials. The value
of N/2n is 2d/D for spherical nanosolids, where d is the
From Eqs. (6)–(8), we obtain diameter of an atom, and D is the diameter of the spher-
ical nanosolids. For nanowire and nanofilm, the values
Cpn Tb
= (9) of N/2n are 4d/3l and 2d/3h, respectively, where, l is the
Cpb Tn diameter of nanowire, and h is the width of the nanofilm.
On substituting the value of Eq. (3) into Eq. (9), we
obtain 3. Results and discussion
 
N −1 The input parameters [15,29–31] required for the
Cpn = Cpb 1 − (10)
2n present work are given in Table 1. We derived Eqs. (10),
(12) and (15) to calculate the size and shape depen-
This is the relationship of the specific heat for nano- dences of the specific heat, melting entropy and enthalpy
materials and bulk materials at different shapes and sizes. of nanomaterials. The size dependence of specific heat
Next, we derive the equations for melting entropy of Ag nanoparticles is plotted in Fig. 1 along with
and melting enthalpy. The size dependence of the melt- experimental data [32]. Rupp et al. [32] experimentally
ing entropy of nanomaterials can be calculated by the measured the specific heat at constant pressure, consid-
size dependence of their melting points [28]. The melt- ering the particles with surface atoms and inner atoms, as
ing entropy for metallic crystals is largely vibrational in we discussed in our theory. The specific heat is found to
nature, and the electronic entropy is insignificant. The increase with decreasing size of the nanocrystal, indicat-
relationship between melting entropy and melting tem- ing that the specific heat capacity varies inversely with
perature is derived by considering the vibrational entropy the particle size. The cause of the increased specific heat
[28] as given below: at small sizes is the high atomic thermal vibration ener-
3R Tn gies of the surface atoms. Sun [33] also showed that
Smn = Smb + ln (11)
2 Tb
where R is the gas constant; Smn and Smb are the melting
entropy of nanomaterials and bulk materials, respec-
tively.
From Eqs. (3) and (11), we obtain
 
3R N
Smn = Smb + ln 1 − (12)
2 2n
The melting enthalpy and melting entropy for bulk
materials follow the relationship given below:

Hmb = Tb Smb (13)

Assuming this relationship is still valid in nanomate-

rials, we can write Fig. 1. Variation of the specific heat of Ag nanomaterials of spherical
shape with size. Values calculated in the present study using Eq. (10)
Hmn = Tn Smn (14) are shown as the continuous line, and the experimental data [32] are
shown as the points.
 M. Singh et al. / Journal of Taibah University for Science 11 (2017) 922–929 925

Table 1
Input data used in the calculations [15,29–31].
Nanomaterials d (nm) Smb (J/mol/K) Hmb (kJ/mol) Tb (K) Cpb (J/mol/K)

Cu 0.256 9.76 13.26 1357.6 24.47

Ag 0.319 9.16 11.30 1234 25.35
Au 0.288 9.34 12.5 1337.58 25.41
Al 0.258 11.46 10.7 933.25 24.20
In 0.329 7.65 3.29 429 26.75
Se 0.230 9.76 6.69 494 26.65

the vibrational amplitude of the surface atoms is larger

for nanosolids than that of bulk materials, resulting in
the higher vibrational energy of the surface atoms. The
results obtained from Eq. (10) are found to be in good
agreement with the experimental values [32]. A good
agreement between theory and the experimental results
encouraged the authors to extend the model to study
the specific heat of Cu, In, and Se for different shapes
and sizes for which the experimental values are lack-
ing. Fig. 2 presents the specific heat of Cu nanosolids
in spherical shape calculated by Eq. (10), as shown by
solid lines. For comparison purposes, we also show the
results found theoretically by Zhu et al. [27]. Our results
are very close to the results obtained by Zhu et al. [27] Fig. 3. Variation of specific heat of in nanomaterials of spherical,
as shown in Fig. 2. We extended the model to study dif- nanowire and nanofilm shapes with size. Values calculated in the
ferent shapes, namely spherical, nanowire and nanofilm present study using Eq. (10) are shown with continuous lines.
shapes. Figs. 3 and 4 compare the model prediction of
In and Se nanosolids in different shapes (nanosphere, Cpn is found to increase with the decrease in size, with
nanowire and nanofilm). Our predictions are consistent all three shapes exhibiting a similar trend, as shown in
with the experimentally measured data of Ag nanosolids. Figs. 3 and 4.
Eq. (12) is used to calculate the size-dependent melt-
ing entropy of Ag, Cu and In spherical nanosolids.

Fig. 2. Variation of the specific heat of Cu nanomaterials of spherical

shape with size. The values calculated in the present study using Eq. Fig. 4. Variation of the specific heat of Se nanomaterials of spherical,
(10) are shown as the continuous line, and the values theoretically nanowire and nanofilm shapes with size. The values calculated in the
obtained by Zhu et al. [27] are shown as the dotted line. present study using Eq. (10) are shown with continuous lines.
926 M. Singh et al. / Journal of Taibah University for Science 11 (2017) 922–929

Fig. 7. Variation of the melting entropy of In nanomaterials of spherical

shape with size. The values calculated in the present study using Eq.
Fig. 5. Variation of the melting entropy of Ag nanomaterials of spher- (12) are shown by the continuous line, and the experimental data [30]
ical shape with size. The values calculated in the present study using are shown by the points.
Eq. (12) are shown by the continuous line, and the experimental data
[34] are shown by the points.

The computed values of melting entropy of Ag, Cu

and in nanosolids in spherical shape are shown in
Figs. 5–7, along with the available experimental data
[30,33–35]. As revealed from Figs. 5–7, the melting
entropy decreases with the decrease in particle size. The
melting entropy decreases sharply with a small reduc-
tion in particle size. Our results are confirmed to be in
good agreement with the available experimental data.
The size- and shape-dependent melting entropy of Se, Au
and Al nanosolid using Eq. (12) is shown in Figs. 8–10
for different shapes, such as nanospherical, nanowire
and nanofilm shapes. The melting entropy is observed
Fig. 8. Variation of the melting entropy of Se nanomaterials of spher-
ical, nanowire and nanofilm shapes with size. The values calculated in
the present study using Eq. (12) are shown by the continuous lines.

Fig. 6. Variation of melting entropy of Cu nanomaterials of spherical

shape with size. The values calculated in the present study using Eq. Fig. 9. Variation of the melting entropy of Au nanomaterials of spher-
(12) are shown by the continuous line, and the experimental data [35] ical, nanowire and nanofilm shapes with size. The values calculated in
are shown by the points. the present study using Eq. (12) are shown by the continuous lines.
 M. Singh et al. / Journal of Taibah University for Science 11 (2017) 922–929 927

Fig. 11. Variation of the melting enthalpy of Ag nanomaterials of

spherical shape with size. The values calculated in the present study
Fig. 10. Variation of the melting entropy of Al nanomaterials of spher-
using Eq. (15) are shown by the continuous line, and the experimental
ical, nanowire and nanofilm shapes with size. The values calculated
data [30] are shown by the points.
in the present study using Eq. (12) are shown by the continuous lines,
and the experimental data [36] for spherical shapes are shown by the
triangles. in fair agreement with the data of the melting enthalpy
of In nanosolid, thus demonstrating the suitability of
to decrease with the reduction in particle size. More- the model presented here. The decreases of the melting
over, the amount of reduction in the melting entropy is entropy and enthalpy are caused by the surface con-
increasing in the following order: nanofilm, nanowire, tribution associated to the high surface-area-to-volume
and nanosphere. It is evident from Eq. (12) that the melt- ratio and breaking bonds because the atoms at the free
ing entropy is dependent upon N/2n. When we relate surface experience a different background than do the
N/2n [14] for nanofilms to that of nanowires and to that atoms in the bulk of a material. These atoms have excess
of nanospheres, the ratio becomes 1:2:3. Therefore, the energy associated with the surface atoms that is mani-
melting entropy difference for nanofilm to nanowire to fested as surface free energy [38]. In the case of bulk
nanosphere increases for the same particle size. materials, surface free energy is neglected because of
The size-dependent melting entropy for of Al the association of a few layers of the atoms near the
nanoparticle is shown in Fig. 10 along with the avail- surface. Therefore, the ratio of volume occupied by the
able experimental observations reported by Eckert et al. surface atoms and the total volume of the bulk material is
[36] for a spherical shape. Eckert et al. [36] performed the
experiment in an oxygen atmosphere for an Al nanosolid;
in his experiment, the interaction among Al nanosolids
is avoided because of the oxide film on the surface of the
particle. Fig. 10 shows that our results agree well with
the experimental results for a spherical shape.
We used Eq. (15) to calculate the size dependence of
the melting enthalpy of Ag, Cu, In and Se nanosolids.
Figs. 11–14 show comparisons between the model pre-
diction and the experimental records available for these
nanosolids of different shapes. The melting enthalpy is
found to decrease with the decrease of particle size. The
melting enthalpy for a Cu nanosolid of spherical shape
is shown in Fig. 12 along with the molecular simula-
tion results obtained by Delogu [35], which support the
results obtained in our present work. There is a good
harmony between our theory and the findings of Del-
Fig. 12. Variation of the melting enthalpy of Cu nanomaterials of
ogu [35]. Fig. 13 shows the variation of the melting spherical shape with size. The values calculated in the present study
enthalpy of In of spherical shape in terms of their size using Eq. (15) are shown by the continuous line, and the molecular
along with experimental data; Eq. (15) is found to be dynamics simulation results [35] are shown by the points.
928 M. Singh et al. / Journal of Taibah University for Science 11 (2017) 922–929

specific heat, melting entropy and enthalpy was found

to be in good agreement with the molecular dynamics
results and the available experimental data, indicating
that our present model at nanoscale can be applied for
a wide range of surface-related phenomena. The present
model has the potential to be applied for calculation of
the thermodynamical properties of nanomaterials.

Acknowledgements

The authors are thankful to the referee for the valu-

able comments that have been useful in revising the
manuscript.
Fig. 13. Variation of the melting enthalpy of In nanomaterials of spher-
ical shape with size. The values calculated in the present study using
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