In-situ High Temperature Raman Spectroscopic and Decomposition Thermodynamic Study of the Structure of Potassium Hydrogen Sulfate and Its Melt†

doi:10.7503/cjcu20180170

Abstract

Abstract:

In-situ high temperature Raman spectroscopic technology was used to study the phase transitions of KHSO₄ from ambient temperature to 550 ℃. Raman vibrational wavenumber and scattering activity of KHSO₄ crystal and K₂S₂O₇ melt were calculated based on Density functional theory(DFT) and ab initio quantum chemical studies, respectively. The major vibrational modes were assigned, Raman scattering cross sections were also obtained, which led to establish the relationship between the area of the characteristic peak and species concentrations. And thermodynamic enthalpy were also calculated through the Factsage database as a comparison in the process of decomposition to confirm the experimental calculated thermodynamic enthalpy. Results show that the structure of KHSO₄ transforms from chain to dimer at 210 ℃, along with the crystal symmetry changing from monoclinic to orthogonal one. It decomposes during 220—550 ℃, which results in the formation of K₂S₂O₇. The reaction enthalpy(ΔH) of (72.59±2.40) kJ/mol was calculated from the equilibrium constant.

Key words: High temperature Raman spectroscopy, Potassium hydrogen sulfate, Microstructure, Density functional theory(DFT), Thermodynamics

CLC Number:

O641.3

TrendMD:

YANG Yejin,YOU Jinglin,WANG Jian,WANG Min,HE Yingxia,WU Zhidong. In-situ High Temperature Raman Spectroscopic and Decomposition Thermodynamic Study of the Structure of Potassium Hydrogen Sulfate and Its Melt^†[J]. Chem. J. Chinese Universities, 2018, 39(10): 2272.

Figures/Tables 13

Fig.1 One-dimensional chain and zero-dimensional dimer in KHSO4 made up of HSO4- connected by O—H…O hydrogen bonds

Fig.2 Raman spectra of KHSO4 in the frequency range of 300—1400 cm-1 at ambient temperatureD: Dimer; C: chain.

Table 1 Assignment of major vibrational modes of KHSO4 at ambient temperature

Raman shift^a/cm^-1		Structure^b	Vibrational mode	Raman shift^a/cm^-1		Structure^b	Vibrational mode
412	s	D	S—OH bending(β_S—OH)	871	m	C	S—OH symmetric vibration(ν_{s S—OH})
444	s	D	S—OH bending(β_S—OH)	1004	s	C	S—O symmetric vibration(ν_{s S—O})
450	s	C	S—OH bending(β_S—OH)	1028	s	D	S—O symmetric vibration(ν_{s S—O})
570	m	C+D	O—S—O deformation(δ_O—S—O)	1164	w	C	S—O deformation(δ_S—O)
580	s	D	O—S—O deformation(δ_O—S—O)	1224	w	D	S—O deformation(δ_S—O)
588	s	C	O—S—O deformation(δ_O—S—O)	1239	w	D	O—H deformation(δ_OH)
597	s	D	O—S—O deformation(δ_O—S—O)	1250	w	D	O—H bending(γ_OH)
615	m	C+D	O—S—O deformation(δ_O—S—O)	1284	w	D	O—S—O asymmetric vibration(ν_{as O—S—O})
854	s	D	S—OH symmetric vibration(ν_{s S—OH})	1337	w	C	O—S—O asymmetric vibration(ν_{as O—S—O})

Fig.3 Temperature dependent Raman spectra of KHSO4 in the frequency range of 300—1400 cm-1 from ambient temperature to 220 ℃Temperature/℃: a. r. t.; b. 100; c. 110; d. 120; e. 130; f. 140; g. 150; h. 160; i. 170; j. 180; k. 190; l. 200; m. 210; n. 220.

Fig.4 Temperature dependent Raman characteristic bands wavenumber of βS—OH(A), νs S—OH(B) and νs S—O(C) from 100 ℃ to 220 ℃

Fig.5 In-situ Raman spectra of the molten KHSO4 at 190 ℃(a), 200 ℃(b) and 210 ℃(c) along with the deconvolution of the bands of melts(D: dimer, C: chain)(A) βS—OH; (B) νs S—OH; (C) νs S—O. # Represents Raman characteristic band of K2S2O7 decomposed from trace KHSO4.

Fig.6 Temperature dependent Raman spectra of KHSO4-K2S2O7 in the frequency range of 100—1800 cm-1 from 220 ℃ to 550 ℃* and ** represent νs S—O of KHSO4 and νs S—O of K2SO4, respectively.

Table 2 Raman vibrational mode assignments of K2S2O7-K2SO4 melt at 550 ℃

Raman shift/cm^-1	Vibrational mode	Raman shift/cm^-1	Vibrational mode
186w	S—O swing vibration(ρ_S—O)	739m	S—O—S symmetric vibration(ν_{s S—O—S})
318s	S—O—S deformation(δ_S—O—S)	971w^**	S—O symmetric vibration(ν_{s S—O})
506w	S—O—S bending(β_S—O—S)	1060w^*	S—O symmetric vibration(ν_{s S—O})
556w	S—O deformation(δ_O—S)	1090s	S—O symmetric vibration(ν_{s S—O})
590w	S—O deformation(δ_S—O)

Fig.7 Experimental and calculated Raman spectra at 220 and 550 ℃The scaling factor is 0.92 and the Lorentzian smearing is 15 cm-1. a. Calculated Raman spectrum of KHSO4 cluster; b. KHSO4(l) experimental Raman spectrum at 220 ℃; c. calculated Raman spectrum of K2S2O7 cluster; d. K2S2O7(l) experimental Raman spectrum at 550 ℃.

Table 3 Raman characteristic band area at 1060, 1090 cm-1 (AHSO4-, AS2O72-), molar fraction of HSO4-, S2O72-(xHSO4-, xS2O72-) and lnK from 230 ℃ to 550 ℃

Temperature/℃	$A HS O 4 -$ (1060 cm^-1)	$A S 2 O 7 2 -$ (1090 cm^-1)	$x HS O 4 -$	$x S 2 O 7 2 -$	lnK
230	13196	623	0.9762	0.0238	-3.6884
250	23750	2448	0.9494	0.0506	-2.8792
300	13689	5287	0.8335	0.1665	-1.4282
350	11894	11403	0.6684	0.3316	-0.2983
400	9676	15741	0.5430	0.4570	0.4383
450	5423	17596	0.3733	0.6267	1.5036
500	1180	6022	0.2748	0.7252	2.2624
550	834	8331	0.16208	0.8380	3.4632

Table 3 Raman characteristic band area at 1060, 1090 cm-1 (AHSO4-, AS2O72-), molar fraction of HSO4-, S2O72-(xHSO4-, xS2O72-) and lnK from 230 ℃ to 550 ℃

Temperature/℃	$A HS O 4 -$ (1060 cm^-1)	$A S 2 O 7 2 -$ (1090 cm^-1)	$x HS O 4 -$	$x S 2 O 7 2 -$	lnK
230	13196	623	0.9762	0.0238	-3.6884
250	23750	2448	0.9494	0.0506	-2.8792
300	13689	5287	0.8335	0.1665	-1.4282
350	11894	11403	0.6684	0.3316	-0.2983
400	9676	15741	0.5430	0.4570	0.4383
450	5423	17596	0.3733	0.6267	1.5036
500	1180	6022	0.2748	0.7252	2.2624
550	834	8331	0.16208	0.8380	3.4632

Fig.8 Curves of molar fraction of K2S2O7 and the reaction equilibrium constant K associated with temperature of molten KHSO4 from 230 ℃ to 550 ℃

Fig.9 Arrhenious-like plot of lnK vs. T-1 for the dissociation equilibrium of molten KHSO4 from 230 ℃ to 550 ℃

Table 4 Thermodynamic properties of KHSO4, K2S2O7 and H2O*

System	Δ $H m 0 —$ / (kJ·mol^-1)	T_fus/K	Δ_fusH/ (kJ·mol^-1)	T_trans/K	Δ_transH/ (kJ·mol^-1)	C_p/ (J·mol^-1·K^-1)	T/K	C_p/ (J·mol^-1·K^-1)	T/K
KHSO₄	-1163.00	495	18.00	442	2.10(α→β)	-62.50+0.56T	298—488	287.00	488—545
				453	4.00(β→γ)
K₂S₂O₇	-1997.96	419	21.20	591	21.80(s₁→s₂)	134.7+0.177T	298—590	260.40	590—692
H₂O	285.83	500	40.86	—	—	2.47×10^-6T³-	298—500	-5.52×10^-7T² +	500—1000
						3.19×10^-3T²+		0.016T+
						1.52T+		1107.27T^-1-
						3848757.66T^-2-		27999.32T^-2+
						203.12		25.78

Table 4 Thermodynamic properties of KHSO4, K2S2O7 and H2O*

System	Δ $H m 0 —$ / (kJ·mol^-1)	T_fus/K	Δ_fusH/ (kJ·mol^-1)	T_trans/K	Δ_transH/ (kJ·mol^-1)	C_p/ (J·mol^-1·K^-1)	T/K	C_p/ (J·mol^-1·K^-1)	T/K
KHSO₄	-1163.00	495	18.00	442	2.10(α→β)	-62.50+0.56T	298—488	287.00	488—545
				453	4.00(β→γ)
K₂S₂O₇	-1997.96	419	21.20	591	21.80(s₁→s₂)	134.7+0.177T	298—590	260.40	590—692
H₂O	285.83	500	40.86	—	—	2.47×10^-6T³-	298—500	-5.52×10^-7T² +	500—1000
						3.19×10^-3T²+		0.016T+
						1.52T+		1107.27T^-1-
						3848757.66T^-2-		27999.32T^-2+
						203.12		25.78

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