庚醛与亚硫酸氢钠加成反应动力学研究

doi:10.11949/0438-1157.20201920

摘要/Abstract

摘要：

醛能与亚硫酸氢钠发生快速的可逆亲核加成反应，该反应可用于去除混合物中的醛。目前醛类加成的动力学研究多集中于低碳醛或芳香醛，缺少高碳脂肪醛的相关数据，且常用的分析方法如碘量法和紫外分光光度法应用局限性大。以庚醛为研究对象，利用在线红外光谱仪，实时监测了283.15~298.15 K温度下庚醛与亚硫酸氢钠的加成反应过程，通过对实验数据的计算与拟合，求得不同温度的反应速率常数和平衡常数，确定了反应的动力学方程，为庚醛的分离应用提供理论基础。结果表明，随着反应温度升高，庚醛反应速率增大，而平衡转化率减小。庚醛与亚硫酸氢钠的加成反应为放热过程，反应热为-60.01 kJ?mol^-1。正反应的活化能为34.68 kJ?mol^-1，指前因子为1.369×10⁷ L?mol^-1?min^-1，逆反应的活化能为94.69 kJ?mol^-1，指前因子为2.500×10¹⁵ min^-1。

关键词: 庚醛, 亚硫酸氢钠, 亲核加成反应, 动力学, 平衡

Abstract:

Aldehydes can undergo a rapid reversible nucleophilic addition reaction with sodium bisulfite, which can be used to remove aldehydes from the mixture. The kinetics of these reactions mostly focused on low carbon aliphatic aldehydes and aromatic aldehydes, lacking of kinetic studies on high carbon aliphatic aldehydes, besides, the commonly analytical methods such as iodine titration and ultraviolet spectrophotometry had many limitations in application. In this paper, heptaldehyde was taken as the research object, and the reaction processes between heptaldehyde and sodium bisulfite were monitored by means of ReactIR at 283.15—298.15 K. Through the calculation and fitting of the experimental data, the rate constants and equilibrium constants of the reaction at different temperatures were obtained, and the kinetic equation of the reaction was determined, which provided a theoretical basis for the separation of heptaldehyde. The results show that as the reaction temperature increases, the reaction rate of heptaldehyde increases, while the equilibrium conversion rate decreases. The addition reaction of heptaldehyde and sodium bisulfite is an exothermic process, and the reaction heat is -60.01 kJ?mol^-1. The activation energy of the forward reaction is 34.68 kJ?mol^-1, and the pre-exponential factor of the forward reaction is 1.369×10⁷ L?mol^-1?min^-1. The activation energy of the reverse reaction is 94.69 kJ?mol^-1, and the pre-exponential factor of the reverse reaction is 2.500×10¹⁵ min^-1.

Key words: heptaldehyde, sodium bisulfite, nucleophilic addition reaction, kinetics, equilibrium

中图分类号:

TQ 203.7

袁慎峰, 万周娜, 陈志荣, 尹红. 庚醛与亚硫酸氢钠加成反应动力学研究[J]. 化工学报, 2021, 72(8): 4177-4183.

Shenfeng YUAN, Zhouna WAN, Zhirong CHEN, Hong YIN. Study on addition reaction kinetics of heptaldehyde and sodium bisulfite[J]. CIESC Journal, 2021, 72(8): 4177-4183.

图/表 7

图1 实验装置示意图1—反应器;2—恒速搅拌电机;3—光纤探头;4—温度计;5—恒温浴锅;6—在线红外主机;7—计算机

Fig.1 Schematic diagram of the experimental apparatus

图2 反应过程红外光谱叠加图

Fig.2 Overlay of IR spectra of the reaction process

图3 浓度与峰高线性定量关系

Fig.3 The relationship between concentration and peak height

图4 不同温度下计算值与实验值的比较

Fig.4 Comparison of calculated values with experimental data at different temperatures

表1 速率常数和平衡常数

Table 1 Rate constants and equilibrium constants

T/K	$k 1'$ / (L·mol^-1·min^-1)	k_-1 / min^-1	K_h	k₁/ (L·mol^-1·min^-1)	K₁/ (L·mol^-1)
283.15	4.100	8.926×10^-3	0.3564	5.561	623.1
288.15	5.089	1.631×10^-2	0.3031	6.631	406.5
293.15	7.693	3.142×10^-2	0.2748	9.807	312.1
298.15	9.051	6.812×10^-2	0.2283	11.12	163.2

表1 速率常数和平衡常数

Table 1 Rate constants and equilibrium constants

T/K	$k 1'$ / (L·mol^-1·min^-1)	k_-1 / min^-1	K_h	k₁/ (L·mol^-1·min^-1)	K₁/ (L·mol^-1)
283.15	4.100	8.926×10^-3	0.3564	5.561	623.1
288.15	5.089	1.631×10^-2	0.3031	6.631	406.5
293.15	7.693	3.142×10^-2	0.2748	9.807	312.1
298.15	9.051	6.812×10^-2	0.2283	11.12	163.2

图5 lnk1、lnk-1、lnKh、lnK1与T-1的关系

Fig.5 lnk1,lnk-1,lnKh,lnK1versusT-1

表2 羰基化合物与亚硫酸氢钠加成反应的反应热与活化能

Table 2 The reaction heat and activation energy of the reaction between carbonyl compound and NaHSO3

羰基化合物	?H /(kJ?mol^-1)	E_a1 /(kJ?mol^-1)	文献
甲醛	-81.4	24.9	[32-33]
乙醛	-63.3	27.1	[17,34]
庚醛	-60.01	34.68	本研究
苯甲醛	-51.3	38.7	[16,32]
丙酮	-41.3	—	[34]

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