Open Science Journal of Modern Physics

2015; 2(4): 50-54

Published online July 30, 2015 (http://www.openscienceonline.com/journal/osjmp)

Specific Heat and Thermal Expansion of Refractory

Nonmetal: CaO
Vladimir Yu. Bodryakov*
Institute of Mathematics, Informatics and Information Technologies, Ural State Pedagogical University, Yekaterinburg, Russia

Email address
Bodryakov_VYu@e1.ru

To cite this article

Vladimir Yu. Bodryakov. Specific Heat and Thermal Expansion of Refractory Nonmetal: CaO. Open Science Journal of Modern Physics.
Vol. 2, No. 4, 2015, pp. 50-54.

Abstract
In this paper in the development and dissemination ideas of previously published works on a new class of objects (refractory
nonmetals), a correlation study of molar specific heat C(T), volumetric coefficient of thermal expansion ο(T) and molar volume
V(T) of solid calcium oxide has been made. As for earlier investigated solids, for CaO clear correlation ο(C) takes place not only
at low temperatures, but also to a much wider temperature range. A significant deviation from the linear low-temperature
behaviorο(C) occurs on reaching heat capacity the classical limit 6R by Dulong and Petit law. Temperature dependence is
estimated for calcium oxide of the differential Grüneisen parameter.

Keywords
Calcium Oxide (CaO), Coefficient of Thermal Expansion, Correlation, Differential Grüneisen Parameter, Heat Capacity,
Molar Volume

nonmetals). Namely, the results are presented for solid

1. Introduction calcium oxide (also called lime, quicklime, calcia) of the
correlation study of heat capacity and thermal expansion in the
Alkaline earth metal oxides (AEMO) have numerous whole range of solid state, far beyond the known limits of
technological applications in view of their peculiar physical applicability of low-temperature Grüneisen law. Note an
and chemical properties and high melting points; their essential uncertainty in the melting point Tm of the oxide (K):
behavior at high temperatures and pressures is important from Tm = 3108 [1]; 3200 [2]; 3200 [11]; 2900–50+300 [12]; > 3086
the Geophysics point of view of [1], [2]. Alkaline earth metal [13]; 2903 [14]; 3200 [15]. In this paper accepted value is Tm =
oxides, as well as alkali halides, are also considered as a 3100 K (±100 K). As in [3]–[10], the correlation dependence
convenient model objects, because of their simplest, as is ο(C) is called Grüneisen plot (GP), and according correlation
believed, ionic type of chemical bonding, permitting the analysis – GP-analysis. Cited original sources, without
creating and testing a variety of relatively uncomplicated claiming to be exhaustive list, give quite a clear idea of the
models of their properties. However, a number of important temperature behavior of the properties in question.
physical properties of AEMO insufficiently studied yet; data
of different authors do not agree well with each other. In 2. Results and Discussion
particular, as further seen for CaO, it relates to basic
thermodynamic properties, such as specific heat C(T), Temperature dependence of the molar heat capacity C(T) of
volumetric coefficient of thermal expansion (VCTE) ο(T), solid calcium oxide is shown in Fig. 1. The data [1], [11]–[22]
molar volume V(T), and others. on C(T) (total 13 sets of data, more than 290 points), in general,
Previously published author’s papers [3]–[10] actually reasonably consistent with each other, except for clear
establish a new standard for statistical processing and mutual overestimated data [16]. Data [16] were excluded from the
(correlation) analysis of the fundamental thermodynamic calculation and are just for comparison. It should be
quantities of solids, so here there is no need for a detailed emphasized the urgency for additional modern calorimetric
description of the calculations. The aim of this research is to investigations in the entire temperature range of solid state CaO,
spread the ideas [3]–[10] for a new class of objects (refractory especially at low and high temperatures. These measurements
51 Vladimir Yu. Bodryakov: Specific Heat and Thermal Expansion of Refractory Nonmetal: CaO

should be made on fused and well certified the material. Solid reasonably presents the empirical data on the heat capacity of
(trend) line in Fig. 1 is the result of statistical averaging and calcium oxide. For convenience, the smoothed data C(T), along
smoothing the data C(T) by different authors; the trend with VCTE ο(T) for CaO are given in Table 1.
Table 1. Recommended heat capacity C (JK–1mol–1) and VCTEο (10–6K–1) of solid CaO.

T, K C ο T, K C ο T, K C ο T, K C ο
5 0.0025 0.002 150 26.26 20.17 750 51.47 40.79 1950 56.58 48.47
10 0.020 0.015 160 28.13 21.60 800 51.81 41.24 2000 56.77 48.76
15 0.068 0.051 170 29.83 22.91 850 52.10 41.68 2050 56.96 49.05
20 0.162 0.125 180 31.37 24.09 900 52.37 42.06 2100 57.15 49.34
25 0.316 0.243 190 32.76 25.16 950 52.63 42.49 2150 57.34 49.62
30 0.547 0.42 200 34.03 26.13 1000 52.89 42.87 2200 57.53 49.91
35 0.868 0.67 210 35.17 27.01 1050 53.12 43.22 2250 57.73 50.21
40 1.29 0.99 220 36.20 27.81 1100 53.33 43.54 2300 57.94 50.53
45 1.84 1.42 230 37.14 28.53 1150 53.53 43.86 2350 58.16 50.87
50 2.51 1.92 240 38.03 29.21 1200 53.73 44.15 2400 58.39 51.22
55 3.30 2.53 250 38.84 29.83 1250 53.92 44.44 2450 58.63 51.59
60 4.22 3.24 260 39.58 30.39 1300 54.11 44.73 2500 58.89 51.98
65 5.26 4.03 270 40.27 30.92 1350 54.30 45.01 2550 59.17 52.41
70 6.39 4.91 280 40.92 31.42 1400 54.49 45.30 2600 59.47 52.86
75 7.61 5.84 290 41.52 31.89 1450 54.68 45.59 2650 59.79 53.35
80 8.89 6.83 300 42.15 32.37 1500 54.87 45.88 2700 60.13 53.86
85 10.21 7.84 350 44.87 34.48 1550 55.06 46.16 2750 60.49 54.41
90 11.58 8.89 400 46.72 35.93 1600 55.25 46.45 2800 60.87 54.98
95 12.94 9.94 450 47.97 36.98 1650 55.44 46.74 2850 61.28 55.61
100 14.30 10.99 500 48.94 37.84 1700 55.63 47.03 2900 61.73 56.29
110 16.99 13.05 550 49.63 38.49 1750 55.82 47.32 2950 62.23 57.05
120 19.56 15.02 600 50.22 39.10 1800 56.01 47.61 3000 62.79 57.90
130 21.98 16.88 650 50.71 39.74 1850 56.20 47.89 3050 63.42 58.86
140 24.21 18.59 700 51.12 40.29 1900 56.39 48.19 Tm 64.15 59.97

handbook [24]). There aren’t clear reasons for preferring one set
of data to another, so all of them, including theoretical
estimations, were involved in the computation. Much greater
inconsistency in VCTE compared with heat capacity is
probably due to methodological difficulties in carrying
high-temperature measurements of thermal expansion, and
essentially higher quality requirements to the dilatometric, than
calorimetric, specimens. It is necessary to carry out additional
modern dilatometric studies of well certified fused solid
calcium oxide over the entire temperature range.

Fig. 1. Temperature dependence of molar heat capacity C(T) for solid CaO.
Symbols – tabular data: 1 – [16], 2 – [17], 3 – [18], 4 – [19], 5 – [11], 6 – [12],
7 – [20], 8 – [13], 9 – [14], 10 – [21], 11 – [1], 12 – [15], 13 – [22], 14 (solid
line) – trend.

Temperature dependence of the volumetric coefficient of

thermal expansion of calcium oxide ο(T) is shown in Fig. 2.
Data from [1], [14], [21]–[30] for thermal expansion (a total of
12 sets of data, more than 230 points) are only in
semi-quantitative agreement; dispersion increases coming to
the melting temperature of CaO. Original data of direct Fig. 2. Temperature dependence of volumetric coefficient of thermal expansion
ο(T) for solid CaO. Symbols – tabular data: 1 – [23], 2 – [24], 3 – [25], 4 – [14],
measurements of thermal expansivity of the oxide are very 5 – [21], 6 – [26], 7 – [1], 8 – [27], 9 – [28], 10 – [22], 11 – [29], 12 – [30], 13
scarce and contradictory (see e.g. survey in well-known (solid line) – trend.
 Open Science Journal of Modern Physics 2015; 2(4): 50-54 52

change in the character of ο(C) dependence. Above 600 K,

where C> 6R, the slope ο(C) increases and remains
approximately constant up to the melting point Tm= 3100 K.
The temperature of the kink in the dependence ο(C)
approximately accords to Debye temperature of calcium oxide
at this condition: θ(600 K) ∼ 650 K [1], [21]. Estimates [1],
[21] of Debye temperature θ(T) from the elastic constants
show a monotonic decrease θ(T) from ∼ 670 K at T = 300 K
down to ∼ 620 K at T = 1200 K. Calorimetric estimates [18]
indicate more complex temperature behavior and somewhat
smaller values θ(T):θ(300 K) ∼ 570 K.

Fig. 3. GP-diagram – correlation dependence ο(C) for CaO. Symbols –

averaged and smoothed data of VCTE and molar heat capacity; straight line
– linear regression οlin(C) for low-temperature values ο(C). Arrow indicates
classical limit 6R by Dulong and Petit for heat capacity.

Fig. 5. Temperature dependence of molar volume V(T) for solid CaO: 1 –

[31], 2 – [23], 3 – [32], 4 – [33], 5 – [34], 6 – [35], 7 – [36], 8 – [24], 9 – [21],
10 – [1], 11 – [29], 12 – [37], 13 – [30], 14 (solid line) – trend.

Fig. 4. The same as Fig. 3 for difference ∆ο(C)for CaO.

Accuracy of smoothed values C(T) and ο(T) in Fig. 1, 2 can

be estimated visually – by an extent to which the trend lines
accord to empirical data [1, 2, 11-30], and quantitatively – by
standard deviation (SD) of empirical points from the trends
C(T), ο(T) at each temperature point.
GP – correlation dependence ο(C), where averaged and
smoothed values of molar heat capacity and volumetric Fig. 6. Temperature dependence of differential Grüneisen parameter γ′(T) for
thermal expansivity of CaO are taken in the according solid CaO. Dashed line – a piecewise linear approximation.
temperature points, – is shown in Fig. 3. In the temperature
range 0 <T≤ 500 K, for which the specific heat 0 <C≤ 48.94 J As clearly seen from the difference GP-diagram (Fig. 4)
K-1 mol-1, and VCTE 0 <ο≤ 37.84×10-6 K-1, the dependence
ο(C) is linear with the high level of correlation (R2 = 0.999997, ∆ο(C) = ο(C) – οlin(C), (2)
n = 47 points): points ο(C) well above CDP fit well with smooth growing
οlin(C)=(0.7684±0.0002)×С, (1) dependence close to the straight line. Shown in Fig. 3, 4, the
results can be interpreted as almost strict constancy below ∼
where in VCTE is in units 10-6 K-1, and the heat capacity is in 600 K of differential Grüneisen parameter:
the J K-1 mol-1. SD of ο(C) points out of the regression straight
line (1) is of small value σ≈0.040×10-6 K-1. In achieving heat γ′ = V0K0(∂ο/∂C), (3)
capacity the classical limit by Dulong and Petit CDP = 6R≈ where’s accepted: V0 = 16.71 ± 0.02 cm3 mol-1 and K0 = 112 ±
49.88 J K-1 mol-1 for CaO, there is a drastic, close to the kink, 2 GPa – low-temperature limits of the molar volume and bulk
53 Vladimir Yu. Bodryakov: Specific Heat and Thermal Expansion of Refractory Nonmetal: CaO

modulus for CaO. The value K0 is estimated based on the V(T) = V0exp ο . (4)
values of the elastic constants [21]. The value V0 is obtained
from dilatometric data [1], [21], [23], [24], [29]–[37] (13 sets The comparison of molar volume V(T) computed using Eq.
of data, about 230 points). Additional checking molar volume (4) with the dilatometric data [1], [21], [23], [24], [29]–[37]
of CaO was necessary because of the valuable dispersion of (Fig. 5) confirms its quantitative adequacy and therefore
thermal expansion data by various authors. For this, the trend established trend ο(T). For convenience, the smoothed
dependence ο(T) was numerically integrated and temperature temperature dependences of molar volume V(T) and density ρ
dependence of molar volume was get: = µ/V, where µis the molar mass of CaO, are given in Table 2.
Table 2. Recommended molar volume V (cm3mol–1) and densityρ (kgm–3) of solid CaO.

T, K V ρ T, K V ρ T, K V ρ T, K V ρ
5 16.71 ± 0.02 3356 ± 4 500 16.92 3315 1400 17.57 3191 2300 18.35 3057
50 16.71 3356 600 16.98 3302 1500 17.65 3177 2400 18.44 3041
100 16.72 3355 700 17.05 3289 1600 17.74 3162 2500 18.54 3025
150 16.73 3352 800 17.12 3275 1700 17.82 3147 2600 18.63 3010
200 16.75 3348 900 17.19 3262 1800 17.90 3132 2700 18.73 2994
250 16.77 3344 1000 17.27 3248 1900 17.99 3117 2800 18.84 2977
300 16.80 3338 1100 17.34 3234 2000 18.08 3102 2900 18.94 2961
350 16.83 3333 1200 17.42 3220 2100 18.16 3087 3000 19.05 2944
400 16.86 3327 1300 17.49 3206 2200 18.26 3072 Tm 19.16 2927

Above ∼ 800 K (beyond the transition area) differential

Grüneisen parameter γ′ is close to a greater also constant value Acknowledgements
(Fig. 6). To find the parameter γ′ with use of Eq. (3) digital
differentiation of correlation GP-dependence ο(C) was The author is grateful to Mrs. Irina V. Ivanova (USPU,
applied (without further smoothing). Piecewise-linear Yekaterinburg) for assistance in providing sources of original
approximation is shown in Fig. 6 by dashed line. Increased thermodynamic data.
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