Defect and Diffusion Forum Online: 2008-03-18

ISSN: 1662-9507, Vol. 272, pp 107-116

doi:10.4028/www.scientific.net/DDF.272.107
© 2007 Trans Tech Publications, Switzerland

Theoretical determination of Pressure-Volume-Temperature relationship

of some alkali halides

Quan Liu
Department of Physics, Anhui University, Hefei 230039, China
quanliu@ah172.com.cn

Keywords: Pressure-Volume-Temperature relationship; alkali halide crystal; Anderson-Gruneisen

parameter

Abstract. The Chopelas-Boehler approximation for the volume dependence of the

Anderson-Gruneisen parameter along isotherms and the new approximation for the volume
dependence of the Anderson-Gruneisen parameter along isobars have been used to study the
pressure-volume-temperature relationship for LiF, NaF and CsCl crystals up to a pressure of 90kbar
and in the temperature range 298-1073K. The calculated values of compression data and
experimental values are found to be in good agreement.

1. Introduction
Experimental data on the pressure-volume-temperature (P-V-T) relationship have been reported in
the literature for a number of alkali halide crystals [1-4]. An interpretation of these data has been
provided on the basis of the Birch-Murnaghan equation of state (EOS) using two parameters BT0 and

BT′0 which represent, respectively, the isothermal bulk modulus and its pressure derivative, both at

zero pressure. In order to fit the P-V data at different temperatures, values of BT0 and BT′0 are to be

changed. The values thus determined for these quantities are not unique but depend on the type of
EOS used, such as BE1, BE2, ME1 or ME2 described by Birch [2]. Variations of BT0 and BT′0 with

temperature predicted from one EOS differ appreciably from the other.
An alternative method is based on estimating the effect of pressure and temperature on volume
in an explicit manner [5]. In this method, we calculate V (To, P)/V (To, 0) and V (T, P)/V (To, P)
separately, where T0 is the initial temperature usually taken to be the room temperature. The volume
at simultaneously elevated pressure and temperature is then calculated using the relationship
V (T , P ) = V (T0 , P ) ⋅ V (T , P ) . (1)
V (T0 ,0 ) V (T0 ,0 ) V (T0 , P )
In the present paper we use the method based on Eq. (1) for predicting P-V-T data in the case of
LiF, NaF and CsCl crystals. These materials were chosen partly because they have relatively low bulk
modulus and low Debye temperature so that relatively large effects of pressure upon temperature

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108 Defects and Diffusion in Semiconductors X

derivatives are expected. Furthermore, they are simple and typical ionic crystals, and various
theoretical approaches [6, 7] as well as experimental studies such as X-ray powder diffraction
techniques [1] have been made on their compression data. For estimating V (To, P)/V (To, 0) we use
the formulation based on the Chopelas-Boehler approximation [8] which considers a linear
relationship for the volume dependence of the Anderson-Gruneisen parameter δ T . The value of V (T,

P) IV (To,P) is calculated from the formula derived by considering the isobaric variation of δ T with

volume given by an expression similar to that of the Anderson et al. approximation [9] for isothermal
variation of δ T with volume.

The method of analysis is presented in Section 2. Results are discussed and compared with
available experimental data in Section 3.

2. Method of analysis
Among various approximations used for describing the thermodynamic behavior of solids under the
effect of high pressure and high temperature, the most important approximation is the following [10]:
α BT = K (2)

Where K is a constant for a given solids. α and BT are the coefficient of volume thermal

expansion and isothermal bulk modulus, respectively.

They are defined as
1  ∂V 
α=   (3)
V  ∂T  P
and
1  ∂P 
BT = −   . (4)
V  ∂V T
Eq. (1) represents only approximation, i.e. it does not hold strictly. However, it is useful for
deriving a number of thermodynamic relations of sufficiently wide applicability and simplicity. The
product α BT remains nearly constant under the effect of high pressure and high temperature [11].

The isothermal Anderson-Gruneisen parameter δ T can be expressed in the following two

manners [9]:
1  ∂BT  V  ∂BT 
δT = −   =−   (5)
α BT  ∂T  P BT  ∂V  P
and
V  ∂α 
δT =
α  ∂V T
(6)
 Defect and Diffusion Forum Vol. 272 109

Eqs. (5) and (6) are exact thermodynamic relations. However, if we stat from the Eq. (2) by
taking its volume derivative we get
 ∂BT   ∂α 
α  + BT   =0 (7)
 ∂V T  ∂V T
which yields
V  ∂α  V  ∂BT 
δT =   =−   (8)
α  ∂V T BT  ∂V T
Taking the temperature derivative of the Eq. (2) we get

 ∂BT   ∂α 
α  + BT   =0 (9)
 ∂T  P  ∂T  P
which yields

1  ∂BT  V  ∂α 
δT = −  = 
α BT  ∂T  P α  ∂V  P
 (10)

Table 1
Values of BT , δT at zero pressure.
0 0

LiF NaF CsCl

BT0 (kbar ) [1] 662 451 182

δ T [16]
0
6.07 5.84 6.82

2.1. The expression of V (T0 , P ) / V ( T0 , 0 )

It is clear from several experiments that over a wide range of compression, δ T decrease

approximately linearly as η (isothermal compression ratio) decreases [8]. The evidence for linearity

between δ T and η was found in the experimental results of Boehler [12] on alkali metals using a

piston-cylinder pressure device. His adiabatic decompression measurements on Li, Na and K showed
that [∂ ln ( ∂T ∂P ) S ∂V ]T is linear with η down to a compression ofη = 0.6 . Similarly, for NaCl,

Boehler [13] found that [∂ ln ( ∂T ∂P ) S ∂V ]T is linear in V to the limit of measurement, η = 0.86 . It

should be recalled that there are two definition of Gruneisen ratio γ :

110 Defects and Diffusion in Semiconductors X

K S  ∂T  α K SV0η
γ=   = (11)
T  ∂P  S CP
Solving for α from the above equation, we have
CP  ∂T  
α=  ∂P   (12)
TV0η  S 
Combining Eq. (6) and Eq. (12), Chopelas and Boehler [8] showed that
 ∂ ln CP 
δT = η m +   −1 (13)
 ∂ ln V 
Where
  ∂T  
 ∂ ln  ∂P  
 S 
m= (14)
 ∂ η 
 
 T
The dimensionless parameter m is precisely what Boehler measured as a constant in his
decompression experiments. Boehler and his collaborators measured m for many different materials.
They reported that m is independent of materials composition and approximately independent of T .
At high T , ∂CP ∂V → 0 , so that Eq. (13) becomes

δ T = mη − 1 (15)

where m = δ T0 + 1 . By using Eq. (8) and Eq. (15), we get the following form of BT (T0 , P ) after

doing some calculation work

BT ( T0 , P ) V (T0 , P)   V (T0 , P)  
= exp  m 1 −  (16)
BT ( T0 , 0 ) V (T0 , 0)   V (T0 , 0)  

Taking Eq. (4) in Eq. (16) we get, on integration, a simple expression for the P-V relationship:

V (T0 , P )   mP  
= 1 − m −1 ln 1 +
 B (T , 0 )  
(17)
V (T0 , 0 )   T 0  
 Defect and Diffusion Forum Vol. 272 111

2.2. The expression of V (T , P ) / V (T0 , P )

For estimating the isobaric volume change with temperature we use the following relationship
derived by Anderson et al. [14] for the temperature dependence of thermal expansivity:
α (T , P )
= [1 − α (T0 , P )δ T (T − T0 )]−1 (18)
α (T0 , P ) 0

Eq. (18) is based on the assumption that δ T remains constant with temperature. Thus, taking

δT = δ T and Eq. (3) in Eq. (18) we obtain the following expression after integration:
0

V (T , P ) −1/ δ
= [1 − α (T0 , P )δ T0 ( P)(T − T0 )] T 0
(19)
V (T0 , P )

It should be mentioned that δ T can be assumed to remain constant is valid only for small

expansions that are in the low temperature range. In 1995, Anderson and Isaak [15] have listed the
values of δ T as a function of temperature for 14 solids including some alkali halides. The data for

these solids reveal that δ T increases regularly with increase in temperature.

In this paper, we propose the assumption that the function of variation of Anderson-Gruneisen
parameter with relative thermal expansivity along isobars can be expressed as follows:
δT = δ T [V (T , P) V (T0 , P )]k
0
(20)

Table 2
The experimental values of thermal expansivity α (T0 , P )

P(kbar ) α (T0 , P )(10 −4 k −1 ) [1]

LiF NaF CsCl

0 0.996 0.949 1.412
10 0.948 0.888 1.091
20 0.916 0.851 0.853
30 0.894 0.826 0.690
40 0.878 0.806 0.540
50 0.857 0.781 0.440
60 0.839 0.761 0.348
70 0.823 0.746 0.270
80 0.808 0.732 0.204
90 0.794 0.718 0.150

The above approximation is similar to that proposed by Anderson et al. [9] for isothermal
compression. Where k is a dimensionless thermoelastic parameter, whose value is about 1.4-1.5 for
some alkali halides. Because the variation of the parameter k with temperature is very small, here we
take its average value 1.45.
The Eqs. (10) and (20) yield
112 Defects and Diffusion in Semiconductors X

α (T , P )  δ   V (T , P )  k  
= exp  − 1 −   
T 0
(21)
α (T0 , P )  k   V (T0 , P )   
  
Now taking Eq. (3) in Eq. (21) we get the following expression:

V  δ    V ( T , P )  k  
1  T0   1 −  
T
 dV = α (T0 , P )dT .
∫ V  k    V (T0 , P )   
exp  ∫T0 (22)
V0
    

Though the left-hand side of Eq. (22) cannot be integrated exactly, we can use an approximate
method for evaluating this integral. In the range of the temperature and pressure considered in this
paper, we can integrate Eq. (22) by using the approximate expansion formula e z ≈ 1 + z + z 2 2 , and
obtained the following equation:
 δT0 δT20  δT0  δT0  δT20
1 + + 2  ln x + 2  +1 (1 − x ) − 3 (1 − x ) = α (T0 , P)(T − T0 ) .
k 2k
(23)
 k 2k  k  k  4k

where x = V (T , P ) V (T0 , P ) . Eq. (23) represents the relation between the temperature and the

compression V (T , P ) V (T0 , P ) at a fixed pressure.

Table 3
Values of V (T , P ) V (T0 ,0) for LiF crystal

P 298 k 573 k 873 k 1073 k

(kbar ) This Exp. This Exp. This Exp. This Exp.
work [1] work [1] work [1] work [1]
0 1.0000 1.0000 1.0306 1.0330 1.0737 1.0814 1.1106 1.1240
10 0.9854 0.9854 1.0137 1.0165 1.0527 1.0609 1.0854 1.0992
20 0.9717 0.9717 0.9986 1.0011 1.0350 1.0422 1.0651 1.0767
30 0.9588 0.9589 0.9846 0.9865 1.0192 1.0248 1.0475 1.0560
40 0.9467 0.9467 0.9716 0.9728 1.0048 1.0087 1.0317 1.0368
50 0.9352 0.9352 0.9591 0.9597 0.9907 0.9936 1.0161 1.0190
60 0.9242 0.9243 0.9473 0.9473 0.9775 0.9795 1.0017 1.0024
70 0.9138 0.9140 0.9361 0.9355 0.9652 0.9663 0.9882 0.9869
80 0.9039 0.9041 0.9255 0.9243 0.9535 0.9538 0.9755 0.9722
90 0.8944 0.8946 0.9154 0.9135 0.9423 0.9419 0.9634 0.9584

3. Results and Discussion

Using Eq. (17) and Eq. (23), we can calculated the values of V (T0 , P ) V (T0 ,0 ) and V (T , P ) V (T0 , P )

respectively. The input data, i.e. BT0 , δ T0 and α ( T0 , P ) for LiF, NaF and CsCl are given in tables 1 and

2. With the help of Eq. (1), the calculating results of V (T , P ) V (T0 ,0 ) reported in Table 3-5. For
 Defect and Diffusion Forum Vol. 272 113

convenience of comparison, the experimental values [1] are also listed together with our calculated
results.

Table 4
Values of V (T , P ) V (T0 ,0) for NaF crystal

P 298 k 473 k 673 k 873 k 1073 k

(kbar ) This Exp. This Exp. This Exp. This Exp. This Exp.
work [1] work [1] work [1] work [1] work [1]
0 1.0000 1.0000 1.0176 1.0185 1.0408 1.0419 1.0681 1.0685 1.1011 1.1007
10 0.9791 0.9791 0.9952 0.9966 1.0159 1.0176 1.0400 1.0409 1.0683 1.0697
20 0.9605 0.9605 0.9755 0.9768 0.9949 0.9960 1.0170 1.0170 1.0429 1.0426
30 0.9437 0.9436 0.9580 0.9588 0.9763 0.9766 0.9970 0.9958 1.0210 1.0187
40 0.9284 0.9283 0.9421 0.9423 0.9595 0.9591 0.9792 0.9768 1.0017 0.9972
50 0.9144 0.9142 0.9275 0.9270 0.9439 0.9430 0.9624 0.9596 0.9834 0.9778
60 0.9014 0.9012 0.9139 0.9129 0.9296 0.9282 0.9472 0.9439 0.9670 0.9601
70 0.8893 0.8890 0.9014 0.8997 0.9165 0.9144 0.9333 0.9295 0.9522 0.9438
80 0.8780 0.8777 0.8897 0.8873 0.9043 0.9017 0.9204 0.9162 0.9384 0.9287
90 0.8674 0.8673 0.8787 0.8757 0.8928 0.8897 0.9083 0.9038 0.9255 0.9147

From tables 3—5 it is clear that there is a good agreement between the experimental data and the
calculated values of V (T , P ) V (T0 ,0 ) . The maximum deviation is only about 1% for LiF, NaF and

CsCl crystals. One may conclude that the approximations used to develop the P-V-T relationship are
good ones. It also confirms the internal consistency of thermodynamic approximation and relations. It
should be mentioned here that the approximation presented in this paper and P-V-T relation derived
here are of general nature and independent of the structure of solids. Therefore, alkali halides are not
special cases, the applicable of the P-V-T relation, based the phenomenological and semi-empirical
approximation, may be extended to different classes of solids, minerals etc, provided that the
corresponding experimental data are available.
But in the process of developing P-V-T relation, we suppose the parameter k a constant and take
its average value 1.45. Furthermore, we have used the approximation α BT = K in deriving isobaric

P-V-T relation. In fact, with the variation of temperature the parameter k and the product α BT are

also variable [11], only their variations are very small, especially when temperature above or close to
the Debye temperature of solid. With the decrease of temperature, that is, in the field of
low-temperature physics of solids, the parameters in the approximations under study need to consider
their temperature dependence.
114 Defects and Diffusion in Semiconductors X

Table 5
Values of V (T , P ) V (T0 ,0) for CsCl crystal

P 298 k 473 k 673 k 873 k

(kbar ) This Exp. This Exp. This Exp. This Exp.
work [1] work [1] work [1] work [1]
0 1.0000 1.0000 1.0275 1.0272 1.0680 1.0647 1.1230 1.1090
10 0.9527 0.9526 0.9723 0.9713 0.9990 0.9972 1.0323 1.0248
20 0.9162 0.9159 0.9306 0.9295 0.9494 0.9487 0.9712 0.9678
30 0.8864 0.8860 0.8976 0.8961 0.9116 0.9109 0.9273 0.9248
40 0.8613 0.8609 0.8697 0.8684 0.8800 0.8801 0.8912 0.8903
50 0.8396 0.8391 0.8462 0.8448 0.8542 0.8541 0.8627 0.8617
60 0.8205 0.8201 0.8256 0.8242 0.8317 0.8317 0.8380 0.8372
70 0.8034 0.8031 0.8073 0.8060 0.8118 0.8120 0.8165 0.8159
80 0.7879 0.7878 0.7907 0.7897 0.7941 0.7945 0.7975 0.7971
90 0.7738 0.7739 0.7758 0.7748 0.7782 0.7780 0.7806 0.7802

Summarily, the approximation presented here and other approximations under study are very
applicable and valid in the field of high-temperature and high-pressure physics of solids. We can use
them to study other classes of crystals and geophysical materials.

Acknowledgements
This work has been financially supported by Key Laboratory of Opto-electronic Information
Acquisition and Manipulation of Ministry of Education of China (No. 9603)

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[13] R.Boehler, Journal of Geophysical Research, 86 (1981) 7159

[14] O.L.Anderson, D.Isaak, H.Oda, Reviews of Geophysics, 30 (1992) 57
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Defects and Diffusion in Semiconductors X
10.4028/www.scientific.net/DDF.272

Theoretical Determination of Pressure-Volume-Temperature Relationship of Some Alkali Halides

10.4028/www.scientific.net/DDF.272.107

DOI References
[9] T.Yagi, Journal of Physics and Chemistry of Solids, 39 (1978) 563 F.Birch, Journal of Geophysical
Research, 91 (1986) 4949 J.M.Brown, Journal of Applied Physics, 86 (1999) 5801 S.Ono, T.Kikegawa,
Y.Ohishi, Solid State Communications, 137 (2006) 517 K.Sushil, Physica B: Physics of Condensed Matter,
367 (2005) 114 Z.H.Fang, physica status solidi (b), 241 (2004) 2886 Q.Liu, L.R.Chen, Chinese Journal of
High Pressure Physics, 19 (2005) 159 A.Chopelas, R.Boehler, Geophysical Research Letters, 19 (1992) 1983
O.L.Anderson, D.G.Isaak, Journal of Physics and Chemistry of Solids, 54 (1993) 221
10.1016/j.physb.2005.06.004