Investigation into the Thermodynamic Properties of Nano-silver Halides Based on the Principle of Dissolution Thermodynamics†

doi:10.7503/cjcu20180509

Abstract

Abstract:

A series of nano-silver halide(AgX, X=Cl, Br, I) materials was prepared at room temperature. Their composition, morphology and structure were characterized. The surface thermodynamics, partial molar surface thermodynamics and specified thermodynamic functions of nano-silver halide were derived based on the essential difference between bulk-silver halide and nano-silver halide combined with Debye-Hückel formula of dissolution thermodynamics. A new effective and universal method for the determination of surface thermodynamics and thermodynamic function of insoluble salt nanomaterials is provided.

Key words: Nanometer silver halide, Dissolution thermodynamics method, Thermodynamic function, Temperature effect

CLC Number:

O645

TrendMD:

QIN Fanghong,QIU Jiangyuan,XIAO Biyuan,MI Yan,HUANG Zaiyin. Investigation into the Thermodynamic Properties of Nano-silver Halides Based on the Principle of Dissolution Thermodynamics^†[J]. Chem. J. Chinese Universities, 2018, 39(10): 2214.

Figures/Tables 11

Fig.1 SEM images of bulk-AgCl(A), bulk-AgBr(B) and bulk-AgI(C)

Fig.2 SEM images of nano-AgCl(A), nano-AgBr(B) and nano-AgI(C)

Fig.3 Particle size distribution histogram of nano-AgCl(A), nano-AgBr(B) and nano-AgI(C)

Fig.4 XRD patterns of nano-AgCl(A), nano-AgBr(B) and nano-AgI(C)

Table 1 Standard equilibrium constant of AgX

T/K	k_sp/(L·mol^-1)
T/K	Nano-AgCl	Bulk-AgCl	Nano-AgBr	Bulk-AgBr	Nano-AgI	Bulk-AgI
288.15	2.11×10^-9	7.33×10^-11	4.24×10^-11	5.71×10^-13	5.23×10^-15	7.42×10^-16
298.15	2.59×10^-9	7.89×10^-11	5.48×10^-11	8.46×10^-13	2.26×10^-14	2.32×10^-15
308.15	3.26×10^-9	1.49×10^-10	6.53×10^-11	1.81×10^-12	4.24×10^-14	6.10×10^-15
318.15	5.51×10^-9	2.94×10^-10	8.52×10^-11	2.11×10^-12	7.78×10^-14	1.29×10^-14
328.15	1.05×10^-8	4.72×10^-10	1.02×10^-10	4.01×10^-12	1.36×10^-13	2.36×10^-14

Table 2 Standard molar dissolved Gibbs free energy of AgX

T/K	Δ $G m 0 —$ /(kJ·mol^-1)
T/K	Nano-AgCl	Bulk-AgCl	Nano-AgBr	Bulk-AgBr	Nano-AgI	Bulk-AgI
288.15	53.46	56.41	55.21	67.53	72.13	83.45
298.15	54.71	57.17	57.31	68.93	72.37	83.52
308.15	55.96	58.15	59.72	70.36	72.95	83.85
318.15	56.34	58.27	61.33	71.12	73.75	84.65
328.15	56.82	58.59	62.76	71.59	74.58	85.28

Table 2 Standard molar dissolved Gibbs free energy of AgX

T/K	Δ $G m 0 —$ /(kJ·mol^-1)
T/K	Nano-AgCl	Bulk-AgCl	Nano-AgBr	Bulk-AgBr	Nano-AgI	Bulk-AgI
288.15	53.46	56.41	55.21	67.53	72.13	83.45
298.15	54.71	57.17	57.31	68.93	72.37	83.52
308.15	55.96	58.15	59.72	70.36	72.95	83.85
318.15	56.34	58.27	61.33	71.12	73.75	84.65
328.15	56.82	58.59	62.76	71.59	74.58	85.28

Fig.5 Standard molar dissolved Gibbs free energy of AgX vs. T

Table 3 Standard molar dissolved enthalpy and entropy of AgX

System	Δ $H m 0 —$ /(kJ·mol^-1)	Δ $S m 0 —$ /(J·mol^-1·K^-1)
Nano-AgCl	32.11	-75.52
Bulk-AgCl	39.89	-57.61
Nano-AgBr	3.43	-181.12
Bulk-AgBr	38.14	-103.10
Nano-AgI	51.48	-89.14
Bulk-AgI	67.19	-55.30

Table 3 Standard molar dissolved enthalpy and entropy of AgX

System	Δ $H m 0 —$ /(kJ·mol^-1)	Δ $S m 0 —$ /(J·mol^-1·K^-1)
Nano-AgCl	32.11	-75.52
Bulk-AgCl	39.89	-57.61
Nano-AgBr	3.43	-181.12
Bulk-AgBr	38.14	-103.10
Nano-AgI	51.48	-89.14
Bulk-AgI	67.19	-55.30

Table 4 Partial molar surface and molar surface Gibbs free energy of AgX

T/K	$G NP s$ /(kJ·mol^-1)			$G m s$ /(kJ·mol^-1)
T/K	Nano-AgCl	Nano-AgBr	Nano-AgI	Nano-AgCl	Nano-AgBr	Nano-AgI
288.15	2.95	12.32	11.32	4.43	18.48	16.98
298.15	2.46	11.62	11.15	3.69	17.43	16.73
308.15	2.19	10.64	10.90	3.28	15.96	16.35
318.15	1.93	9.79	10.90	2.90	14.69	16.35
328.15	1.77	8.83	10.70	2.66	13.24	16.05

Table 4 Partial molar surface and molar surface Gibbs free energy of AgX

T/K	$G NP s$ /(kJ·mol^-1)			$G m s$ /(kJ·mol^-1)
T/K	Nano-AgCl	Nano-AgBr	Nano-AgI	Nano-AgCl	Nano-AgBr	Nano-AgI
288.15	2.95	12.32	11.32	4.43	18.48	16.98
298.15	2.46	11.62	11.15	3.69	17.43	16.73
308.15	2.19	10.64	10.90	3.28	15.96	16.35
318.15	1.93	9.79	10.90	2.90	14.69	16.35
328.15	1.77	8.83	10.70	2.66	13.24	16.05

Table 5 Partial molar surface as well as molar surface enthalpy and entropy of nano-AgX

System	$H NP s$ /(kJ·mol^-1)	$H m s$ /(kJ·mol^-1)	$S NP s$ /(J·mol^-1·K^-1)	$S m s$ /(J·mol^-1·K^-1)
Nano-AgCl	7.78	11.66	17.09	25.64
Nano-AgBr	34.70	52.05	78.02	117.03
Nano-AgI	15.71	23.56	33.84	50.76

Table 5 Partial molar surface as well as molar surface enthalpy and entropy of nano-AgX

System	$H NP s$ /(kJ·mol^-1)	$H m s$ /(kJ·mol^-1)	$S NP s$ /(J·mol^-1·K^-1)	$S m s$ /(J·mol^-1·K^-1)
Nano-AgCl	7.78	11.66	17.09	25.64
Nano-AgBr	34.70	52.05	78.02	117.03
Nano-AgI	15.71	23.56	33.84	50.76

Table 6 Standard molar formation thermodynamic functions of AgX

System	Δ_f $H m 0 —$ /(kJ·mol^-1)	Δ_f $G m 0 —$ /(kJ·mol^-1)	$S m 0 —$ /(J·mol^-1·K^-1)
Bulk-AgCl	-127.01^[25]	-109.80	96.25
Nano-AgCl	-115.35	-105.38	121.88
Bulk-AgBr	-100.37^[25]	-96.90	107.11
Nano-AgBr	-48.32	-78.42	224.14
Bulk-AgI	-61.48^[25]	-66.19	115.50
Nano-AgI	-37.92	-49.21	64.74

Table 6 Standard molar formation thermodynamic functions of AgX

System	Δ_f $H m 0 —$ /(kJ·mol^-1)	Δ_f $G m 0 —$ /(kJ·mol^-1)	$S m 0 —$ /(J·mol^-1·K^-1)
Bulk-AgCl	-127.01^[25]	-109.80	96.25
Nano-AgCl	-115.35	-105.38	121.88
Bulk-AgBr	-100.37^[25]	-96.90	107.11
Nano-AgBr	-48.32	-78.42	224.14
Bulk-AgI	-61.48^[25]	-66.19	115.50
Nano-AgI	-37.92	-49.21	64.74

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