Chauhan, R S

Singh, C P

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IiulianJ. PAvJ.78(11). 1215-1219 (2004)< U P \ >Analysis of thermal expansivity of alkali halide crystalsC P Singh a^d R S Chauhan*Department of Physics, R B S f^ oHegc, Agra-282 002, Uttar Pradesh. India E-mail rvscl^ uhan(^ yahoo com Received 10 February 2if04. accepted 16 August 2004Abstract The temperature dependence of thermal expansivity and intcnonic separations have been studied in the present paper for ei^ sht alkali halide crystals viz. NaF, NaCI, KCl, KBr, Kl, RbCI, RbBr and Rbl The expression for inierionic separation obtained earlier by Kumar [Pliysica B205 175 (1995)1 hits been corrected so as to make it compatible with the value of thermal expansivity at initial temperature The values of interionic separation as a function of temperature calculated in the present study using the mcHlified formulation are found to present close agreement with the experimental data for the alkali halides upto their melting temperature^ .Keywords : Thermal expansivity, alkali halides, intcnonic separationPACS No. 65.40.De1. IntroductionThermal expansivity a  is a very imjxirtant physical quantity for understanding the thermoelastic behaviour and equation of state for solids at high temperatures [1-4]. Attempts have been made to develop theoretical models based on first-principle methods for calculating a  at high temperatures [5-8]. The results obtained from these methods at high temperatures deviate substantially from the experimental values. The empirical methods [9,10] are still useful for predicting thermal expansivity of solids at high temperatures upto their melting temperatures. The thermal expansivity data of solids at high temperatures are the basic requirements for computing thermoelastic properties of solids at different temperatures [11].The thermal expansivity a  for many solids has been found [1,12] to increase linearly in an approximate manner with the increase in temperature at T > 0/^, the Debye temperature. For alkali halides to be considered in the present study viz- NaF, NaCI, KCl, KBr, KI, RbCl, RbBr and Rbl. we have the values of which arc close to or less than the room temperature value Tq =r 300 K [13]. Therefore, the variation of a  for these crystals is expected to be approximately linear for the entire range of temperatures from room temperature upto their melting temperatures The melting temperatures of the alkali halidesCorresponding Authorarc about 1000 K, which are 3 to 6 times of their Debye temperatures. We have thus a very wide range of temperatures from T = 6 q Io T - T ^  for studying the thermal expansivity of alkali halides. Kumar [14] has developed a formulation for studying the temperature dependence of a  of alkali halides using the linear relationship between thermal expansivity and temperature. It is shown here that this relationship docs not satisfy the initial boundary condition. The formulation given by Kumar has been revised in the present study. The effect of this modification is then studied by calculating a  and inierionic separation as a function of temperature. Formulation and analysis are presented in Section 2. Results are discussed and compared with the experimental data in Section 3.2. Formulation and analysisThe experimental values of a  for NaCI and KCl at different temperatures have been listed by Anderson [1 ] and Yamamoto et al [15] from the original work due to Enck et at [it] and Enck and Dommel [ 17]. These experimental data are plotted in Figure 1. The variations of a  with T are found to be almost linear for NaCI as well as for KCl. The similar behaviour is expected also for other alkali halides. Kumar [ 14] has developed a formulation using the linear relationship(1)or =  Ofo +  cx%©20041ACS1216 C P Singh and R S Chauhanwhere is the value of a  at 7  = »the room temperaturetaken as the initial temperature* and a '  = d a /d T . Using eq.( 1),400 500 600 700 800Figure 1. Plots of thermal expansivity a  (lO'^K ') versus temperature T (K) for NaCI and KCI using the experimental data (16, 17].Kumar obtained an expression for the interionic separation r as a function of temperature, which is given below :r = Tq exp (2)where r,, is the value of r at r =  T^ y Values of a '  were determined by Kumar using the Anderson-Gruneisen parameter S j  and the pressure derivative of isothermal bulk modulus Kj.It should be pointed out here that eq.(l) is not consistent with the initial boundary condition viz. a  -  T = T .^ In order to satisfy this condition, we have to modify eq.(l) as follows :a  = a o + a '{ T -T o ) . (3)We have revised the formulation gi ven by Kumar (14] using eq.(3) in place of eq.(l).The coefficient of volume thermal expansion or simply the thermal expansivity a  is defined asv [ d r ) . (4)Thus at constant pressure, the following differential equation is obtained, using eqs.(3) and (4):[ao + a 'iT -T o )]d T  = dVOn integrating eq.(S) along an isobar, we getttoCT"- 7’o ) + j  a '  = In (V/Vq) ,(5)(6)where is the value of volume at T = TO, the room temperature. In deriving eq.(6), it has been assumed that = da/dT  remains constant. The fact that this assumption holds good for NaCl and KCI is evident from Figure 1. Eq.(6) can be rewritten as followsV = V oexp[ao (7 --r„ ) + l a ' ( r - 7 'o ) ' ] . (7)The volume V is related to the lattice parameter or interionic separation r such that(8)where is the value of interionic separation r at . Eqs. (7) and (8) then yield• = r o e x p |^ i |a o ( r - 7 ’o) + ^ a '( 7 '- 7 'o ) '} (9)Eq.(9) can be used to obtain the values of interionic separation (r) as a function of T provided a '  is known. For determining a ' , Kumar [14] used the following relationship at 7  = 7q based on the thermodynamic approximation considered by Dhoble and Verma [ 18](a ')  = a lM  , (10)where M = [ 2 S r - { d  Kp/d P)] (11)and S-p is the Anderson-Gruneisen parameter defined asSr =-{ l l aKr ) ( dKr / dT) ^ .  (12)Using the values of Sp, dKp/dP and corresponding to temperature 7^ as given in Table 1, we have calculated a '  from eq.(lO) for eight alkali halides under study. These are also given in column (a) of Table 1.Table 1. Values of input data for alkali halides under study [ 14.18]. Values of a ' - d a f i l T  calculated from cq. (10) arc given in column (a) and calculated from eq. (14) are given in column (b).Crystals oto(10‘ K ‘) dK^ /dP S r M a' (10 * aK^ )bNaF 96 5.28 5.84 6.40 5.8 5.3NaCl 118 5.39 5.95 6.51 9.1 8.3KCI 110 5.47 6.29 7.11 S.6 7.6KBr 116 5.47 5.88 6.29 8.4 7 9K1 123 5.55 5.83 6.11 9.2 8.8RbCI 103 5.61 6.73 7.85 8.3 7.1RbBr 108 5.59 6.64 7.69 8.9 7.7Rbl 123 5.60 6.53 7.46 11.0 9 8Analysis of thermal expansivity of alkali halide crystals 1217It has been found by Anderson [11 that the product oK-r docs not change with tem perature for solids at higher temperatures for T > 6 p ,  i.e. txKj- remains constant for the temperature range from = 300 K upto the melting temperatures. Under this condition, one can obtain the relationship5 r = d K r ld P  (13)which holds good for the solids under study and we can make use of this in eq.( 10) to obtain the following simplified expre.ssiol|( a ')  = ao< 5r- (14JValues of a '  obtained from eq.(14) are given in column (b) of Table 1. Values of a '  based on eq.( 10) are about 8 to 14 percent larger than the values estimated from eq.(14). It should be mentioned that eq.(lO) is also an approximation, albeit less so thaneq.(14).3. Results and discussionValues of input data used in calculations are given in Table 1. First, we demonstrate that the Kumar formulation is in error for (X (T). Values of a  (T) calculated from eq. (1) are compared with the experimental values for NaCl and KCl in Table 2. They deviate much from the experimental data. On the other hand, the values of a  calculated from cq. (3) are closer to the experimental data. This justifies the correction made in the present study to the Kumar formulation of a .l^ble 2. Values of thermal expansivity or (lO^ * K *) for NaC'l and KCl (a) calculated from eq. (1) and a '  from cq. (10), (b) calculated from cq (.3) and a ' from eq. (10), (c) calculated from eq (3) and a '  from cq (14) and experimental values [16,17].NaCITemperature a(K) a b C Experimental300 145 118 118 118400 154 127 126 127500 164 136 135 137600 173 145 143 148700 182 155 151 160KClTemperature a(K) a b C Experimental300 136 no 110 110400 144 119 118 117500 153 127 125 126600 162 136 133 137700 170 144 140 147The experimental data on r (T) for the alkali halides under study, have been reported in the literature [2, 19, 20]. We have calculated the values of r (T) using the revised formulation feq.(9)j and compared them with the experimental values (Table 3). The results can easily be obtained with the help of cqs. (2) and(9) using the input data given in Table 1. Here, wc arc giving the comparison ot results only for some representative alkali halides. Similar results are obtained for other alkali halides also. We noteIkbic 3. Values of interiomc separation r m A at different temperatures T in K Value.s given in column A arc calculated using eq (2) and a* from column (a) oflable 1. Values given in column B and C’ aic calculated using eq. (9) and a ' respectively from columns (a) and (b) of Table 1. Values given in column D are based on experimental data 116,17,20]NaF1'cmperaiurc(K)Inicrionic separation i (A)A B C 1)300 2 318 2.318 2 318 2.318400 2 327 2 326 2 326 2.326500 2 336 2 334 2 334 2 334600 2 346 2 342 2 342 2 342700 2 357 2 351 2 351 2 351800 2 368 2 361 2 361 2 361900 2.379 2.371 2.370 2.371CBrTemperature Intcrionic scpuiation i (A)(K) A B r D300 3.289 3.289 3 289 3.289400 3.305 3 302 3.302 3 302500 3 322 3.316 3.316 3 316600 3.340 3 332 3.331 3.331700 3 359 3 348 3 347 3 346800 3.379 3 365 3.364 3.364900 3 400 3.383 3.382 3.382mTemperature Interionic separation r (A)(K) A B C’ D300 3.668 3 668 3 668 3.668400 3.688 3.684 3.684 3.683500 3.709 3.701 3.701 3.699600 3.732 3 720 3.719 3.716700 3.756 3.740 3.738 3 734800 3.782 3 761 3.759 3.753900 3.809 3.784 3.782 3 7741218 C P Singh and R S Chauhanfrom Table 3 for NaP\ KBr and RbF that the values of r (T) calculated from eq. (9) arc in closer agreement with the experimental values than those calculated from eq. (2). We have obtained two sets of results with the help of eq. (9) corresponding to two different values of a '  given in Table 1. The different values of a '  used as input in calculations, do not affect the final results appreciably. The difference in the values of a '  obtained from cqs. (10) and (14) is of the order of 10 % only. However, more important is the correction made in the Kumar formulation which replaces the factor ~ Tq ) appearing in the last term of eq. (2) by the factor (T-TJ,)^ appearing in the last term of eq. (9). The effect of this modification increases with the increase in temperature. At the highest temperature T = 900 K and Tq = 300 K considered in the present study, the value of the factor (r-Tjj)^ is exactly fifty percent as compared to the value o f appearing in the Kumar formulation. Thiscorrection o f 50 percent is considerably higher than the difference of 10 percent in the values of Of' obtained from eqs.(10) and (14). In order to demonstrate this with more clarity, we have plotted the values of A r  = r{T) -  r(7Jj) where Tq = 300 K versus temperature in Figures 2-4 for NaCl, KI, and RbCl. Values of A r represent the changes in interionic separations with the increase in temperature. The agreement for the values of Ar obtained from eq. (9) with the experimental data, as is evident from the figures, is much better than that for the values of Ar calculated from eq. (2),4. ConclusionWe have shown that the equation for thermal expansivity as taken by Kumar [14] is not consistent with the initial boundary condition viz. a  = at 7 =  7q . This yields the values of a  (7) and r  (7), which are not consistent with the experimental data. The Kumar formulation has subsequently been used by Pandey[21] for studying the thermal expansivity of NaCl at higher temperatures. Therefore, the study performed by Pandey is also subject to the same criticism. The formulation given by Kumar has been modified in the present study so as to make it consistent with the initial boundary condition. The modified formulation has been found to yield much improved agreement with the experimental data for a  (7 ) and r (T) of alkali halides at higher temperatures.AcknowledgmentsAuthors are thankful to the referee for his helpful comments which have been useful in revising the manuscript. Thanks are also due to Prof. Jai Shanker, Institute of Basic Sciences, Khandari, Agra for his valuable guidance. The financial support received from the University Grants Commission, New Delhi in the form of a research project is gratefully acknowledged.200 300 400 500 600 700 800 900 1000 IIQO0.12200 300 400 500 600 700 800 900 1000 1100200 300 400 500 600 700 600 900 1000 1100Temperature (K) -------------- -(4)Figure 24 , Plots of d r  = r(7)-r(7J)) in A versus temperature 7 in K for NaF. NaCl, KCI. KBr. Kl, RbCI. RbBr and Rbl ciystols. A, B. C. and D have the same meaning as described in Tiible 3.Experimental data [ 1 6 .17,201  are shown by continuous curve.Analysis o f  thermal expansivity o f  alkali halide crystals 121 9References[1] 0  L Anderson Equation of State of Solids for Geoplmir\ and Ceramics (Oxford : Oxford University Press) (1995)[2] K Wang and R R Reeber J PIm. Chem Solids 56 895 (1995)[3] K Wang and R R Reeber J. Mater. Res 11 1800 (19%)[4] S S Kushwah and J Shanker J. Phys. Chem Solids 59 197 (1998)[5] D O  Isaak, R E Cohen and M J Mchl J. Geophys. Res 95 7055 (1990)[6J I Inbar and R E Cohen Geophys. Re.\. Lett. 22 1533 (1995)17] B B Karki, R M Wentzcovitch, S de Gironcoli and S Baroni Phys Rev. B61 8793 (2000)18] M P Madan Phy.sica 124 B 35 (1984)(9) X Xia and J K Xiao J Phy.\. Chem Solids 54 629 (1993)(lOJ S S Kushwah and J Shanker P/ivwVa B225 283 (199()) j111 ] 0  L Anderson and K Masuda Phy.\. Earth Planet Inter. 85 227(1994)112] K S Singh and R S Chauhan Plmtca B315 74 (2002)[13] R S Chauhan and ( ' P Singh Physica B324 151 (2002)114) M Kumar Physira B205 175 (1995)115] S Yamamoio, I Ohno and 0  L Anderson J. Phvs Chem Solids 48 175 (1987)[16] F D Enck, 1) G Engle and K 1 Marks J AppI Phys 33 2070 (1962)[17] F i) Enck and J G Dommel J Appl Phys 36 839 (1%5)118] A Dhohle and M P Verma Phys Slat Sol (/>) 136 497 (1986)[19] J Corish, C R A Callow and P W M Jacob J Physique Utl 42 369 (1981)[20] Q He and Z T Yan Phys Stat Sol (b) 223 767 (2001)[21] R K Pandey J Plivs Chem Solids 59 989 (1998)

Analysis of Thermal Expansivity of Alkali Halide Crystals

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Analysis of Thermal Expansivity of Alkali Halide Crystals

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