醋酸酐与水在化学反应量热方法确认中的应用

doi:10.16085/j.issn.1000-6613.2022-1585

化工进展 ›› 2022, Vol. 41 ›› Issue (S1): 91-96.DOI: 10.16085/j.issn.1000-6613.2022-1585

醋酸酐与水在化学反应量热方法确认中的应用

孙培琴¹(), 陈延青¹, 孔祥北², 金满平³, 刘付芳⁴()

^1.中国合格评定国家认可中心，北京 100062
^2.中国安全生产科学研究院，北京 100012
^3.应急管理部化学品登记中心，山东青岛 266100
^4.通标标准技术服务（上海）有限公司，上海 200233

收稿日期:2022-08-09 修回日期:2022-09-04 出版日期:2022-10-20 发布日期:2022-11-10
通讯作者: 刘付芳
作者简介:孙培琴（1982—），女，硕士，高级工程师，研究方向为化学化工检测实验室认可技术。E-mail：sunpq@cnas.org.cn。
基金资助:
中国合格评定国家认可委员会( CNAS) 项目(2020CNAS06)

Application of acetic anhydride and water in the confirmation of chemical reaction calorimetry

SUN Peiqin¹(), CHEN Yanqing¹, KONG Xiangbei², JIN Manping³, LIU Fufang⁴()

^1.China National Accreditation Center for Conformity Assessment, Beijing 100062, China
^2.China Academy of Safety Science and Technology, Beijing 100012, China
^3.National Registration Center for Chemicals, MEM, Qingdao 266100, Shandong, China
^4.SGS -CSTC Standards Technical Services (Shanghai) Co. , Ltd. , Shanghai 200233, China

Received:2022-08-09 Revised:2022-09-04 Online:2022-10-20 Published:2022-11-10
Contact: LIU Fufang

摘要/Abstract

摘要：

热流法化学反应量热测试获取的目标反应热（ΔH）、反应体系比热容（c_p）和最大热累积度（X_ac）等热安全参数是精细化工反应安全风险评估中不可或缺的关键参数，其测试结果的准确度（即正确度与精密度）直接影响化学反应的工艺危险度分级。目前关于测得的化学反应热安全参数准确度和有效性的研究未见报道。为解决这一问题，提出了以醋酸酐和水作为参考物质，采用“变异系数（CV值）法” 和“道格拉斯（Grubbs）检验法”分别验证热流法反应量热测试醋酸酐水解反应的ΔH、C_p 、X_ac等参数的精密度（即重复性和再现性偏差），采用“t验证法”评估热流法反应量热测试水的比热容的正确度。研究结果表明：热流法反应量热测试醋酸酐水解反应的ΔH、C_p 、X_ac等参数在同一实验室内的重复性标准偏差和与其他4家实验室比对的再现性标准偏差均满足要求；采用热流法量热测试得到25℃水的比热容数据与标准比热容值t验证结果不存在实质性偏倚。因此，测试结果的精密度和正确度均满足要求。

关键词: 安全, 化学反应, 水解, 热流法, 精密度, 正确度

Abstract:

Thermal safety parameters obtained by heat flow chemical reaction calorimetry test such as target reaction heat(ΔH), specific heat capacity of reaction system(c_p ) and maximum heat accumulation(X_ac) etc. are indispensable key parameters in safety risk assessment of fine chemical reactions. The accuracy(precision and trueness) of the test results affects the process risk classification of chemical reactions directly. At present, there is no report on accuracy and effectiveness of thermal safety parameters of chemical reactions. In order to solve this problem, the acetic anhydride and the water were proposed as reference materials. The“coefficient of variation(CV) method”and“Grubbs test method”were used to verify the repeatability and reproducibility deviation of parameters such as ΔH, c_p, and X_ac, which was obtained by the hydrolysis reaction of acetic anhydride measured by the heat flow reaction calorimetry. The“t verification method”was used to evaluate the accuracy of the specific heat capacity of water measured by the heat flow reaction calorimetry. The results showed that the repeatability standard deviation of parameters such as ΔH, c_p, and X_acin the same laboratory and the reproducibility standard deviation compared with the other four laboratories met the requirements, which was obtained from the reaction rate of acetic anhydride hydrolysis measured by heat flow chemical reaction calorimetry test. There was no substantial bias between the specific heat capacity data of 25℃ water obtained by heat flow calorimetry and the standard specific heat capacity value t. Therefore,both the precision and the trueness of heat flow calorimetry were validated satisfied.

Key words: safety, chemical reaction, hydrolysis, heat flow calorimetry, precision, trueness

中图分类号:

TQ03

孙培琴, 陈延青, 孔祥北, 金满平, 刘付芳. 醋酸酐与水在化学反应量热方法确认中的应用[J]. 化工进展, 2022, 41(S1): 91-96.

SUN Peiqin, CHEN Yanqing, KONG Xiangbei, JIN Manping, LIU Fufang. Application of acetic anhydride and water in the confirmation of chemical reaction calorimetry[J]. Chemical Industry and Engineering Progress, 2022, 41(S1): 91-96.

图/表 7

参考文献 17

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参数	试验编号						平均值	标准偏差s
参数	1	2	3	4	5	6	平均值	标准偏差s
ΔH/kJ	13.885	14.029	13.926	13.968	14.046	13.888	13.957	0.057
c_p /J·g^-1·K^-1	4.3704	4.3655	4.2628	4.2693	4.2222	4.3761	4.3111	0.067
X_ac /%	21.84	22.06	21.28	22.19	21.51	22.35	21.87	0.412

参数	试验编号						平均值	标准偏差s
参数	1	2	3	4	5	6	平均值	标准偏差s
ΔH/kJ	13.885	14.029	13.926	13.968	14.046	13.888	13.957	0.057
c_p /J·g^-1·K^-1	4.3704	4.3655	4.2628	4.2693	4.2222	4.3761	4.3111	0.067
X_ac /%	21.84	22.06	21.28	22.19	21.51	22.35	21.87	0.412

热安全参数	实验室内变异系数/%	参考值/%
ΔH/kJ	0.4	2.0
c_p /J·g^-1·K^-1	1.6
X_ac /%	1.8

热安全参数	实验室内变异系数/%	参考值/%
ΔH/kJ	0.4	2.0
c_p /J·g^-1·K^-1	1.6
X_ac /%	1.8

参数	本实验室	实验室1	实验室2	实验室3	实验室4	平均值	标准偏差s
ΔH/kJ	13.957	12.815	11.997	12.279	12.047	12.619	0.815
c_p /J·g^-1·K^-1	4.31	4.23	3.97	4.11	4.18	4.16	0.129
X_ac /%	21.87	20.16	23.19	19.98	21.23	21.29	1.317

醋酸酐与水在化学反应量热方法确认中的应用

Application of acetic anhydride and water in the confirmation of chemical reaction calorimetry

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参数	检出水平α	统计量G_n	临界值G_0.95（5）
ΔH/kJ	0.05	1.642	1.672
c_p /J·g^-1·K^-1	0.05	1.163
X_ac /%	0.05	0.44

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试验编号	水的c_p /J·g^-1·K^-1
1	4.1774
2	4.1656
3	4.1723
4	4.1719
5	4.1801
6	4.1723
平均值	4.1733

试验编号	水的c_p /J·g^-1·K^-1
1	4.1774
2	4.1656
3	4.1723
4	4.1719
5	4.1801
6	4.1723
平均值	4.1733