Reference Hydrogen Partial Pressure on Accurancy of Hydrogen Determination Utilizing Concentration Cell Type Sensor Based on Solid State Electrolyte

doi:10.15541/jim20170027

Abstract

Abstract:

High temperature proton conductor CaZr_0.9In_0.1O_3-_α powders were prepared. By using the prepared powders, solid state electrolyte tubes were prepared. After assembling two types of concentration cell type hydrogen sensors, the effects of reference hydrogen partial pressures on electromotive force errors and hydrogen partial pressure calculation errors were investigated. At temperatures ranging from 873-1073 K and in the hydrogen partial pressure range of 0.005-0.1 atm (1 atm=1.013×10⁵Pa), the relative errors of electromotive forces increase when the hydrogen partial pressure difference between reference and measurement sides enlarged. This phenomenon is more obvious at low temperature of 873 K. The calculation error of the hydrogen partial-pressure according to the Nernst law is greatly dependent on hydrogen pressure ratio of the two sides of the cell. This error can be eliminated through reference hydrogen partial pressure at electromotive force of zero instead of hydrogen partial pressure. Hydrogen pressures platforms of β-ZrH_x and δ-ZrH_x coexistence zone were calculated by this method, as well as the formation enthalpy and formation entropy in the phases conversion process.

Key words: solid state electrolyte, high temperature proton conductor, Nernst law, hydrogen partial pressure, CaZr_0.9In_0.1O_3-_α;

CLC Number:

TB321

CHEN Jian-Xun, WU Shu-Sen, ZHANG Ya-Nan, MAO You-Wu, LÜ Shu-Lin. Reference Hydrogen Partial Pressure on Accurancy of Hydrogen Determination Utilizing Concentration Cell Type Sensor Based on Solid State Electrolyte[J]. Journal of Inorganic Materials, 2017, 32(11): 1195-1201.

Figures/Tables 12

Fig. 1 Schematic drawing of hydrogen concentration cell

Fig. 2 Schematic (a) and corresponding photo (b) of type A sensor, schematic (c) of type B sensor and assembly photo (d)

Fig. 3 Schematic layout of experimental apparatus for hydrogen determination

Fig. 4 XRD phases analysis (a) and rietveld fitted (b) patterns of solid state electrolyte powders

Fig. 5 Fracture surface image of a CaZr0.9In0.1O3-α electrolyte tube showing an average grain size of no more than 3 μm

Fig. 6 Sensing results of type A sensor: (a) response curves, (b, c) stable electromotive forces vs reference hydrogen partial pressure of 104 Pa and 5×104 Pa, respectively (The solid straight lines represent the electromotive forces calculated according to function (6))

Fig. 7 Electromotive force ratios of measurement values to theory Nernst values for type A sensor with variable reference hydrogen partial pressure at temperatures of 873 K (a), 973 K (b) and 1073 K (c)

Fig. 8 Electromotive force response curves (a) and stable electromotive forces (b) of type B sensor towards variable reference hydrogen partial pressures

Fig. 9 Hydrogen pressures of (β+δ) ZrHx at temperatures ranging from 873 K to 1073 K calculated according to Equation (8) utilizing electromotive forces values in Fig. 8(b)

Fig. 10 Hydrogen calculation errors obtained from different hydrogen pressures ratios and electromotive force errors

Table 1 Comparisons of (β+δ) ZrHx hydrogen partial pressures, formation enthalpy and formation entropy obtained from different research methods

In(P_eq/ Pa)	ΔH^f/(kJ·mol^-1)	ΔS^f/(kJ·K^-1·mol^-1)	Temperature/K	Method	Reference
-26119/T+34.1	-217.2	-0.284	823-1123	Exp.	Ref. [20]
-28160/T+37	-234.1	-0.305	823-873	Calc.	Ref. [21]
-25078/T+32.9	-208.5	-0.274	873-1073	Exp.	This work

Fig. 11 Hydrogen pressures of (β+δ)ZrHx calculated from null points after data fitting of data in Fig. 8(b) at different tempeartures

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