RADIOLYSIS OF AQUEOUS SOLUTION OF CYANIDE ION Investigating the Mechanism of the formation of the Radiolytic Products by Using Formate as Radical Scavenger

Qi Shengchu; Shen Qinzhang; He Yongke; Wu Jilan

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RADIOLYSIS OF AQUEOUS SOLUTION OF CYANIDE ION Investigating the Mechanism of the formation of the Radiolytic Products by Using Formate as Radical Scavenger

更新时间：2023-04-18

- RADIOLYSIS OF AQUEOUS SOLUTION OF CYANIDE ION Investigating the Mechanism of the formation of the Radiolytic Products by Using Formate as Radical Scavenger
- Journal of Radiation Research and Radiation Processing Vol. 1, Issue 1, Pages: 17-25(1983)
- 作者机构：
  
  1.北京大学
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Qi Shengchu, Shen Qinzhang, He Yongke, et al. RADIOLYSIS OF AQUEOUS SOLUTION OF CYANIDE ION Investigating the Mechanism of the formation of the Radiolytic Products by Using Formate as Radical Scavenger. [J]. Journal of Radiation Research and Radiation Processing 1(1):17-25(1983)
DOI：

Qi Shengchu, Shen Qinzhang, He Yongke, et al. RADIOLYSIS OF AQUEOUS SOLUTION OF CYANIDE ION Investigating the Mechanism of the formation of the Radiolytic Products by Using Formate as Radical Scavenger. [J]. Journal of Radiation Research and Radiation Processing 1(1):17-25(1983) DOI：

摘要

本文研究了充N,2, KCN水溶液体系的γ辐解，测得主要辐解产物产额为：,G,（甘氨酸）,= 0.37，,G,（Rf=0.14产物）,=0.15，,G,（Rf=0.21产物）,=0.62，,G,（Rf=0.25产物）,=0.34,G,（尿素）,=0.11，,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489715&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489727&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489733&type=,，,G,(HCONH2),=1.0,G,（甲醛）,=0.08，,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489728&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489730&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489729&type=,。尿素由下列反应生成：,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489731&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489736&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489732&type=,因此,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489752&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489742&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489740&type=,，测定了甲酸钠对主要辐解产物产额的影响，并与缺氧条件下的结果进行了比较。实验和动力学处理结果表明，CNO,-,和HCONH,2,的生成除与OH自由基有关外，还分别与H（以H,2,CN形式）和水化电子（以HCN,-,形式）有关。求得由•CONH,2,自由基岐化反应生成的,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489744&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489758&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489757&type=,和,G,（HCONH2）,值分别为0.36，H,2,CN与·CONH,2,自由基反应生成的,G,（CNO,-,）为0.14，HCN,-,与•CONH,2,自由基反应生成的G,（HOONHO）,为0.64。以,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489759&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489761&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489760&type=,为自由基清除剂求得,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489762&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489764&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489763&type=,为3.0±2×10,9,M,-1, S,-1,，以C,2,H,5,OH为自由基清除剂求得,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489765&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489767&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489766&type=,。,实验表明甘氨酸的生成与水化电子有关，甲醛可能为刺点反应产物，R,f,=0.21未知物似乎与水化电子和HCN形成的产物有关。在较高pH值时，使用自由基清扫法，判明了由水化电子和HCN形成的HCN,-,在化学行为上与由H原子形成的H,2,CN不同。从物料平衡估算得体系每吸收100eV能量分解的CN,-,离子数,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489768&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489782&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489770&type=,，与实验值4.3±0.3一致。

Abstract

The radiolysis of the dilute aqueous solution of cyanide ion in N,2,-containing system has been investigated. The yields of the main radiolytic products are as follows:,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489774&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489788&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489787&type=,It may be considered that urea can be formed by the following reaction,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489776&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489794&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489793&type=,in this case,G,(CNO,-,) equals 0.50.,The Main radiolytic products under O,2,-lacking conditions also has been investigated. The experimental results and kinetic calculations show that cyanate and formamide can be formed not only by the disproportionative reaction (3).,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489792&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489798&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489796&type=,but also by the reactions (9) and (11),http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489799&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489809&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489801&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489811&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489823&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489806&type=,where H,2,CN and HCN,-, radicals were formed by the reactions of H atom and hydrated electron with HCN.,The contributed ,G,(CNO-) values are 0.36 and 0.14 for the reactions (3) and (9)respectively. The presented ,G,(HCONH,2,) values from the reactions (3) and (11) are 0.36 and 0.64, separately. The rate constants have been determined: ,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489824&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489826&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489825&type=,M,-1,sec,-1, from the variations of ,G, values of cyanate versus formate concentrations and 2.8×10,9,M,-1,sec,-1, from that of formamide. By using ethanol as scavenger,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489827&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489829&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489828&type=, value has been determined, which is equal to 1.7×10,9,M,-1,sec,-1,. All the values agree well with the published data. The exprimental result also show that the formation of glycine is related to hydrated electron and the formaldehyde is formed by spur reaction.,The unknown (R,f,=0.21) seems to be related to the intermediate product formed by the reaction of hydrated electron with HCN. From the material balance, estimated,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489830&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489832&type=,http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=42489831&type=, value is equal to 4.5, which is consistent with the experimental value 4.3±0.3.

关键词

KCN水溶液的辐解甲酸钠自由基清除剂甘氨酸的生成甲酰胺的生成氰酸盐的生成

Keywords

Radiolysis of aqueous KCN solutionFormate radical scavengerFormation of glycineFormation of formamideFormation of cyanate

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