Surface Thermodynamic Properties of Micro/nano Peanut-shaped CaMoO4†

doi:10.7503/cjcu20140062

Abstract

Abstract:

Mirco/nano peanut-shaped CaMoO₄ with three different sizes were prepared via reverse-microemulsion method at room temperature. Based on the essential difference between thermodynamic properties of nano CaMoO₄ and bulk CaMoO₄, the equations for acquiring molar surface thermodynamic functions of nano CaMoO₄ were derived via combining the basic theory of chemical thermodynamics with thermokinetic principle. According to the derived equations, molar surface thermodynamic functions such as molar surface enthalpy, molar surface Gibbs free energy and molar surface entropy of the synthesized peanut-like mirco/nano CaMoO₄ were successfully gained by in situ microcalorimetry. The results demonstrated that the size has significant influence on surface thermodynamic properties. Along with the size reducing, the molar surface enthalpy, molar surface Gibbs free energy and molar surface entropy increased.

Key words: Micro/nano CaMoO4, Size effect, Microcalorimetry, Surface thermodynamics

CLC Number:

TrendMD:

FAN Gaochao, MA Zhao, HUANG Zaiyin, TAN Xuecai, YAO Xianchao. Surface Thermodynamic Properties of Micro/nano Peanut-shaped CaMo $O 4 †$ [J]. Chem. J. Chinese Universities, 2014, 35(5): 1007.

Figures/Tables 4

Fig.1 XRD pattern of the prepared products 1—3(a—c)(A) and their SEM images(B—D)

Fig.2 SEM image of the purchased bulk CaMoO4

Table 1 Standard molar enthalpy and rate constant of each CaMoO4 reaction system

Reaction system	No.	m/mg	Q/mJ	Δ_r $H m 0 —$ /(kJ?mol^-1)	lnk
Bulk CaMoO₄	1	1.269	-430.154	-67.801	-7.128
	2	1.260	-425.403	-67.531	-7.239
	3	1.265	-427.793	-67.642	-7.099
	4	1.263	-426.681	-67.573	-7.108
	5	1.267	-429.229	-67.762	-7.117
Average value				-67.662±0.117	-7.138±0.057
Product 1	1	1.267	-541.734	-85.523	-6.574
	2	1.259	-537.679	-85.452	-6.669
	3	1.252	-533.230	-85.189	-6.638
	4	1.257	-536.547	-85.378	-6.605
	5	1.254	-534.433	-85.245	-6.556
Average value				-85.357±0.139	-6.608±0.046
Product 2	1	1.270	-621.616	-91.902	-6.474
	2	1.266	-619.367	-91.856	-6.529
	3	1.276	-625.892	-92.112	-6.505
	4	1.272	-623.784	-92.089	-6.462
	5	1.269	-620.403	-91.788	-6.445
Average value				-91.949±0.144	-6.483±0.034
Product 3	1	1.265	-659.847	-103.334	-6.291
	2	1.270	-663.369	-103.478	-6.275
	3	1.264	-652.285	-103.222	-6.316
	4	1.267	-656.031	-103.567	-6.302
	5	1.269	-662.701	-103.455	-6.328
Average value				-103.411±0.135	-6.302±0.021

Table 1 Standard molar enthalpy and rate constant of each CaMoO4 reaction system

Reaction system	No.	m/mg	Q/mJ	Δ_r $H m 0 —$ /(kJ?mol^-1)	lnk
Bulk CaMoO₄	1	1.269	-430.154	-67.801	-7.128
	2	1.260	-425.403	-67.531	-7.239
	3	1.265	-427.793	-67.642	-7.099
	4	1.263	-426.681	-67.573	-7.108
	5	1.267	-429.229	-67.762	-7.117
Average value				-67.662±0.117	-7.138±0.057
Product 1	1	1.267	-541.734	-85.523	-6.574
	2	1.259	-537.679	-85.452	-6.669
	3	1.252	-533.230	-85.189	-6.638
	4	1.257	-536.547	-85.378	-6.605
	5	1.254	-534.433	-85.245	-6.556
Average value				-85.357±0.139	-6.608±0.046
Product 2	1	1.270	-621.616	-91.902	-6.474
	2	1.266	-619.367	-91.856	-6.529
	3	1.276	-625.892	-92.112	-6.505
	4	1.272	-623.784	-92.089	-6.462
	5	1.269	-620.403	-91.788	-6.445
Average value				-91.949±0.144	-6.483±0.034
Product 3	1	1.265	-659.847	-103.334	-6.291
	2	1.270	-663.369	-103.478	-6.275
	3	1.264	-652.285	-103.222	-6.316
	4	1.267	-656.031	-103.567	-6.302
	5	1.269	-662.701	-103.455	-6.328
Average value				-103.411±0.135	-6.302±0.021

Table 2 Surface thermodynamic data of the prepared micro/nano CaMoO4

Product	$H m s$ /(kJ·mol^-1)	$G m s$ /(kJ·mol^-1)	$S m s$ /(J·mol^-1·K^-1)
1	17.695±0.256	1.314±0.255	54.942±1.713
2	24.287±0.261	1.624±0.226	76.012±1.633
3	35.749±0.252	2.072±0.193	112.953±1.493

Table 2 Surface thermodynamic data of the prepared micro/nano CaMoO4

Product	$H m s$ /(kJ·mol^-1)	$G m s$ /(kJ·mol^-1)	$S m s$ /(J·mol^-1·K^-1)
1	17.695±0.256	1.314±0.255	54.942±1.713
2	24.287±0.261	1.624±0.226	76.012±1.633
3	35.749±0.252	2.072±0.193	112.953±1.493

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