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Materials Today: Proceedings 12 (2018) 671–675 www.materialstoday.com/proceedings

NCMD-2018

Thermodynamical Properties of K1-XRbX Alloys in Liquid State

a, b, c
Salman Rajesh C. Malan *, Aditya M. Vora
a
Applied Science and Humanities Department, Government Engineering College, G. T. U., Valsad -396001, Gujarat, India bDepartment of
Physics, University School of Sciences, Gujarat University, Ahmedabad-380009, Gujarat, India

Abstract

One of the K- based binary alloys – K 1-XRbX has been studied in the present work. Various thermodynamical properties are
computed with the help of pseudopotential theory. The combination of successive elements of the alkali group has been selected
for the formation of binary alloys. The well-behaved pseudopotential proposed by Fiolhais et al. is used for the whole calculation.
Eight various local field correction functions (namely Hartree (H), Hubbard-Shame (HS), Nagy (N), Vashishtha-Singwi (VS),
Taylor (T), Sarkar et al. (S) Ichimaru-Utsumi (IU) and Farid et al .(F) are employed to determine the effect of exchange and
correlation on bare ion potential. The present thermodynamical study is based on the successful approach suggested by Gibbs-
Bogoliubov (GB). The article includes the calculation of different parts of energy (E), entropy(S) and Helmholtz free energy
(EH). The good agreement of the present data with the other theoretical data as well as experimental data is found.
© 2019 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the National Conference on Materials and Devices, NCMD-2018.

Keywords: Thermodynamical properties; liquid alkali alloys; pseudopotential theory.

1. Introduction

The thermodynamics incorporated with any of the chemical reaction can play an important role in the final
outcome of the reaction. It has also a definite role in deciding the properties gained by the final product. The
thermodynamics of an alloy mainly depends upon the electronic configuration of the constituent particle. In the case
of alloys, one more variable is added i.e. the proportion of the participating elements which has an impact on the
total energy. The present study focused on the computation of the Helmholtz free energy  F , internal energy
F  S
h

int and entropy ( ). Various contributions for each of the above quantities are calculated separately and merged to
find the final values of the respective quantity. The pseudopotential theory along with the Gibbs–Bogoliubov

* Corresponding author. Tel.: +91-97251-50991.

E-mail address: rcmgecv@gmail.com

2214-7853 © 2018 Elsevier Ltd. All rights reserved.

Selection and peer-review under responsibility of the scientific committee of the National Conference on Materials and Devices, NCMD-2018.
672 Malan and Vorab / Materials Today: Proceedings 12 (2018) 671–675

(GB) inequality is applied for the thermodynamical investigation of the metals [1-2]. The tendency of a metal to
theoxidize is the same as other spontaneous reactions, characterized by changes in free energy that accompany oxide
formation [3-5]. The ΔG0 value for oxide formation is negative. Each release of 1 mole of free energy is an oxidizing
agent with a metal adalag ΔG0 and is usually called gibs free energy.

2. Theory

An alloy has the electronic free energy [20-21],

Fe  Fg  Fa  Fb (1)

The above equation contains is the free energy of the electron gas Fg that can be given by [20-21],

 3 3 3 1 2 
Fg  kF  k f  Ec  gT Z ,
(2)
10 4 2 
plus two more perturbation contributions denoted by Fa and Fb [20-21],

Now, the effective potential averaged over some reference system can be given by,
F F F F F
PS g . M a b
(3)
The Helmholtz free energy is Fh calculated as

Fh  Fps  Fhs
(4)
The free energy per particle Fhs of the hard sphere mixture can be expressed as [20-21],

F  3 k T  TS
hs 2 B hs .
(5)
Where, Shs is an entropy contribution and can be given as [20-21],

S S
hs g S S S .
c   (6)

3. Results and Discussion

The potential parameters and other constants used for the present calculation are shown in Table 1.
The potential independent parts of the total free energy are presented in Table 2. It includes Fg , Fa , FM and Fhs
. Table 3 shows the potential dependent part Fb measured with eight different local field correction functions. The
correction functions are required to minimize the error in the quantity due to screening as well as exchange and
correlation effect. The correction due to Hartree static function only gives the minimum values of all contributions
at all the concentration level (X), while the correction function due to N gives the maximum values of them at all
the stages of the concentration (X). At equi-atomic concentration (X=0.5), the band structure energy is found
maximum.
 Malan and Vorab / Materials Today: Proceedings 12 (2019) 671–675 673

Table 1. Input parameters and constants

Constants Potential parameters
Metal
Ω (au) kF (au)  (au) R (au)
K 528.67 0.3826 2.807 0.745
Rb 626.13 0.3616 2.748 0.824
F
It is to be noted that except the a , remaining all the components have negative values. As the computation is
related to the liquid environment, the entropy of the system has also its own significance.
3
Table 2. Contributions to F (in 10 au )
int
F
X Fg Fa FM hs

0.00 -79.90 63.38 -209.48 -8.52

0.10 -79.77 64.27 -205.78 -8.69
0.20 -79.63 67.22 -209.80 -8.85
0.30 -79.49 70.05 -214.99 -9.02
0.40 -79.36 72.77 -218.63 -9.18
0.50 -79.22 75.39 -219.50 -9.34
0.60 -79.08 77.91 -217.21 -9.50
0.70 -78.94 80.34 -212.17 -9.66
0.80 -78.80 82.68 -205.57 -9.82
0.90 -78.66 84.94 -199.76 -9.98
1.00 -78.52 87.12 -200.21 -10.14

The total entropy (S) is assumed to be a sum of four different entropies. It includes the entropy of the free
electron gas S g , the ideal entropy of mixing (Shs ) , entropy related to packing density S  and entropy due to
the difference between the diameters of the atoms of the alloy S . All the entropy contributions are depicted in
figure 1.

Table 3. The band structure energy F2 .

X H HS VS T S IU F N
0.0 -17.31 -16.44 -15.45 -14.89 -15.87 -14.50 -14.42 -12.98
0.1 -32.56 -31.49 -30.35 -29.79 -30.86 -29.34 -29.27 -26.67
0.2 -29.26 -28.30 -27.28 -26.78 -27.74 -26.37 -26.31 -23.94
0.3 -20.88 -20.12 -19.30 -18.88 -19.66 -18.55 -18.49 -16.76
0.4 -13.24 -12.68 -12.03 -11.68 -12.31 -11.43 -11.38 -10.24
0.5 -9.05 -8.60 -8.07 -7.77 -8.30 -7.57 -7.53 -6.73
0.6 -9.42 -8.99 -8.48 -8.20 -8.70 -8.00 -7.97 -7.15
0.7 -13.82 -13.30 -12.72 -12.43 -12.98 -12.20 -12.16 -10.98
0.8 -20.22 -19.56 -18.84 -18.49 -19.16 -18.20 -18.16 -16.42
0.9 -24.43 -23.63 -22.75 -22.33 -23.15 -21.98 -21.93 -19.79
1.0 -16.22 -15.49 -14.64 -14.19 -15.01 -13.85 -13.79 -12.26

The internal energy  Fint is shown in Table 4. The last two columns of Table 4 show the comparison with the
theoretical results of others and experimentally available data for two extreme concentration values respectively. It
674 Malan and Vorab / Materials Today: Proceedings 12 (2019) 671–675

can be observed from Table 4 that present results show more deviation from the results of the experiment
(maximum 38.4% due to static function H and minimum 36.22% due to N) at lowest concentration value (X=0). At
the highest concentration (X=1.0), the deviation is minimum from the experimental data (maximum 11.8 % due to
N and minimum due 9.6% due to H). Unfortunately, the trend of the deviation from experimental data with respect
to the concentration values (X) cannot be obtained due to the lake of experimental data. But it is clear that for the
highest concentration value (X), the deviation found minimum.
F
int
Table 4. The internal energy
(F 103 au )
int
X
H HS VS T S IU F N Others [22] Exp [23]
0.0 268.61 267.75 266.75 266.20 267.18 265.80 265.73 264.28 261.46, 260.46 194
0.1 218.86 217.79 216.65 216.10 217.16 215.64 215.57 212.98 - -
0.2 210.23 209.27 208.25 207.75 208.71 207.35 207.28 204.92 - -
0.3 196.69 195.93 195.11 194.69 195.47 194.36 194.30 192.56 - -

0.4 184.09 183.52 182.87 182.53 183.15 182.27 182.23 181.09 - -

0.5 175.16 174.71 174.18 173.88 174.40 173.67 173.63 172.83 - -

0.6 171.03 170.60 170.09 169.82 170.31 169.62 169.58 168.76 - -
0.7 171.20 170.69 170.11 169.82 170.37 169.59 169.55 168.37 - -
0.8 173.67 173.01 172.28 171.93 172.61 171.65 171.60 169.87 - -
0.9 174.22 173.42 172.55 172.13 172.94 171.78 171.73 169.59 - -
1.0 162.67 161.95 161.09 160.64 161.46 160.31 160.25 158.71 251.68, 249.94 180

Fig. 1. Entropy of the alloy

The  Fh  of the alloy is presented in Table 5. The deviation from the experimental data is continuously
deceasing while going from lower X to higher X. It compensates overall deviation from the experimental value
which was observed in the internal energy  Fint . Figure 1 shows the five different contributions of the
entropy.
 Malan and Vorab / Materials Today: Proceedings 12 (2019) 671–675 675

Table 5. The Helmholtz free energy Fh

( F  103 au )
X h

H HS VS T S IU F N Others [22] Exp [23]

0.0 313.56 312.70 311.71 311.15 312.13 310.75 310.68 309.23 270.70, 269.70 199.10
0.1 262.53 261.46 260.32 259.76 260.83 259.31 259.24 256.64 - 198.47
0.2 260.32 259.37 258.35 257.85 258.80 257.44 257.38 255.01 - 197.68
0.3 254.33 253.57 252.75 252.33 253.11 252.00 251.94 250.21 - 196.78
0.4 247.64 247.07 246.42 246.08 246.70 245.82 245.78 244.64 - 195.41
0.5 241.72 241.27 240.74 240.44 240.96 240.24 240.19 239.40 - 193.33
0.6 237.29 236.86 236.36 236.08 236.57 235.88 235.84 235.02 - 192.19
0.7 234.24 233.73 233.15 232.85 233.40 232.62 232.58 231.41 - 192.11
0.8 231.73 231.07 230.35 230.00 230.67 229.71 229.66 227.93 - 192.61
0.9 227.88 227.08 226.20 225.78 226.60 225.43 225.38 223.24 - 191.59
1.0 217.96 217.23 216.38 215.93 216.75 215.59 215.53 214.00 262.08, 260.34 189.98

4. Conclusions

Brief discussion about the thermodynamical properties has been delivered through the present article. Internal
 
energy  Fint  and entropy S are calculated to get the total free energy Fh  of the liquid alloys K1-XRbX. The
present potential with eight different local field correction functions has been successfully provided for the
calculation of the properties of the K 1-XRbX. For many of the properties, the results are in well agreement with the
experimental and others results.

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