光气

  • 基本信息
  • 制备方法及用途
  • 物化性质
  • 安全信息
  • 毒理性
  • MSDS
  • 结构与计算化学
  • 上游产品
  • 下游产品

光气 基本信息

中文名称:
光气 
中文别名:
光气;
氯代甲酰氯 
英文名称:
phosgene
英文别名:
phosgene;
thionyl chloride;
Fosgene;
carbonic dichloride;
Phosgenegas;
Fosgeen;
PHOSGENE;
dichloro-ketone;
Phosgen;
combatgas;
carbonyl chloride;
Fosgen;
Phlsgene 
CAS No.:
75-44-5
分 子 式:
CCl2O
分 子 量:
98.91610
精确分子量:
97.93260
PSA:
17.07000
MDL:
MFCD00036119
EINECS:
200-870-3
BRN:
1098367
InChI:
The Key: YGYAWVDWMABLBF-UHFFFAOYSA-N
风险术语:
26-34
分子结构式:
SDS:
查看

光气 制备方法及用途

制备方法

1.当需要少量光气时,可将四氯化碳与硫酸反应。将四氯化碳加热至55-60℃,滴加入发烟硫酸,即发生逸出光气,如需使用液态光气,则将发生的光气加以冷凝工业上通常采用一氧化碳与氯气的反应得到光气。2.工业制法以二氧化碳和氯气作原料,以活性炭催化反应,温度控制在60~150℃之间生成的气体冷却到-25℃至-30℃,液化装入钢瓶中。实验室制法以CCl4和发烟硫酸为原料,在烧瓶中加入四氯化碳,加热至沸腾后,滴加入30%的发烟硫酸,此时生成光气COCl2,将之冷凝,即可得到液体COCl2。市售品中含有很多杂质,如CO2、CO、空气等,含量均在1%左右,可以采用如下方法提纯:(1)将气体导入烧瓶中,用冰盐水冷却液化,然后在烧瓶上装上球形回流冷凝管通水冷凝,冷凝管和装满7~8℃的水的亨普尔气体量管连接,量管与用冰盐水冷却的冷凝器相连接,冷凝管和接收器相连接,除去烧瓶外的冷冻剂(冰盐水)后,液体即会蒸发,冷却接收器便可得到冷凝下来的COCl2。(2)将气体导入烧瓶中,用冰盐水使之冷凝后,再撤去冰盐水,待冷凝物的约1/5蒸发后,在高真空下分馏残留物至所有的馏分都保持相同的蒸气压,纯COCl2的蒸气压为556.5mmHg。

合成制备方法

1.当需要少量光气时,可将四氯化碳与硫酸反应。将四氯化碳加热至55-60℃,滴加入发烟硫酸,即发生逸出光气,如需使用液态光气,则将发生的光气加以冷凝

工业上通常采用一氧化碳与氯气的反应得到光气。

2.工业制法以二氧化碳和氯气作原料,以活性炭催化反应,温度控制在60~150℃之间生成的气体冷却到-25℃至-30℃,液化装入钢瓶中。

实验室制法以CCl4和发烟硫酸为原料,在烧瓶中加入四氯化碳,加热至沸腾后,滴加入30%的发烟硫酸,此时生成光气COCl2,将之冷凝,即可得到液体COCl2。

市售品中含有很多杂质,如CO2、CO、空气等,含量均在1%左右,可以采用如下方法提纯[11]:

(1)将气体导入烧瓶中,用冰盐水冷却液化,然后在烧瓶上装上球形回流冷凝管通水冷凝,冷凝管和装满7~8℃的水的亨普尔气体量管连接,量管与用冰盐水冷却的冷凝器相连接,冷凝管和接收器相连接,除去烧瓶外的冷冻剂(冰盐水)后,液体即会蒸发,冷却接收器便可得到冷凝下来的COCl2。

(2)将气体导入烧瓶中,用冰盐水使之冷凝后,再撤去冰盐水,待冷凝物的约1/5蒸发后,在高真空下分馏残留物至所有的馏分都保持相同的蒸气压,纯COCl2的蒸气压为556.5mmHg。

用途简介

用于合成氨基甲酸酯类杀虫剂,聚氨酯硬泡、软泡、弹性体、人造革的重要原料,也有的特殊品种用于粘结剂制碳酸酯、氯甲酸酯、异氰酸酯、异腈、醛、氯代烷、酸酐,与腈生成杂环。用于有机合成,特别是制造异氰酸酯和聚氨酯等,还用于制造染料、橡胶、农药和塑料等。

用途

1.用于合成氨基甲酸酯类杀虫剂,聚氨酯硬泡、软泡、弹性体、人造革的重要原料,也有的特殊品种用于粘结剂

2.制碳酸酯、氯甲酸酯、异氰酸酯、异腈、醛、氯代烷、酸酐,与腈生成杂环。

3.用于有机合成,特别是制造异氰酸酯和聚氨酯等,还用于制造染料、橡胶、农药和塑料等。[23]

光气 物化性质

外观与性状:
无色气体
密度:
0.94 g/mL at 20 °C
熔点:
-118ºC
沸点:
8.2ºC at 760 mmHg
闪点:
4 °C
折射率:
1.419
存储条件/存储方法:
库房通风低温干燥,轻装轻卸
稳定性相关:

1.稳定性[18]    稳定

2.禁配物[19]   水、醇类、碱类

3.避免接触的条件[20]   潮湿空气、受热

4.聚合危害[21]   不聚合

其它信息:

1.性状:纯品为无色有特殊气味的气体,低温时为黄绿色液体。[1]

2.熔点(ºC):-127.9~-118[2]

3.沸点(ºC):8.2[3]

4.相对密度(水=1):1.4[4]

5.相对蒸气密度(空气=1):3.4[5]

6.饱和蒸气压(kPa):161.6(20ºC)[6]

7.临界温度(ºC):182[7]

8.临界压力(MPa):5.67[8]

9.辛醇/水分配系数:-0.710[9]

10.溶解性:微溶于水,溶于芳烃、苯、四氯化碳、氯仿、乙酸等多数有机溶剂。[10]

11.液相标准热熔(J·mol-1·K-1):112.0

12.气相标准声称热(焓)( kJ·mol-1) :-219.1

13.气相标准熵(J·mol-1·K-1) :283.87 

14.气相标准生成自由能( kJ·mol-1):-208.4

15.气相标准热熔(J·mol-1·K-1):57.70

光气 安全信息

风险类别:
2.3
海关代码:
2812103000
WGK_Germany:
2
德国有关水污染物质的分类清单
危险类别码:
26-34-67-65-63-48/20-11
安全说明:
S9-S26-S36/37/39-S45-S62-S28
RTECS号:
SY5600000
安全标志:
S9:保持容器在一个有良好通风放的场所。
S26:万一接触眼睛,立即使用大量清水冲洗并送医诊治。
S45:出现意外或者感到不适,立刻到医生那里寻求帮助(最好带去产品容器标签)。
:
危险标志:
T+,F

光气 毒理性

CHEMICAL IDENTIFICATION

RTECS NUMBER :
SY5600000
CHEMICAL NAME :
Phosgene
CAS REGISTRY NUMBER :
75-44-5
BEILSTEIN REFERENCE NO. :
1098367
LAST UPDATED :
199801
DATA ITEMS CITED :
39
MOLECULAR FORMULA :
C-Cl2-O
MOLECULAR WEIGHT :
98.91
WISWESSER LINE NOTATION :
GVG

HEALTH HAZARD DATA

ACUTE TOXICITY DATA

TYPE OF TEST :
LCLo - Lowest published lethal concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Human
DOSE/DURATION :
50 ppm/5M
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
REFERENCE :
TABIA2 Tabulae Biologicae. (The Hague, Netherlands) V.1-22, 1925-63. Discontinued. Volume(issue)/page/year: 3,231,1933
TYPE OF TEST :
LCLo - Lowest published lethal concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Human - man
DOSE/DURATION :
360 mg/m3/30M
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
REFERENCE :
85GMAT "Toxicometric Parameters of Industrial Toxic Chemicals Under Single Exposure," Izmerov, N.F., et al., Moscow, Centre of International Projects, GKNT, 1982 Volume(issue)/page/year: -,99,1982
TYPE OF TEST :
TCLo - Lowest published toxic concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Human
DOSE/DURATION :
25 ppm/30M
TOXIC EFFECTS :
Lungs, Thorax, or Respiration - other changes
REFERENCE :
29ZWAE "Practical Toxicology of Plastics," Lefaux, R., Cleveland, OH, Chemical Rubber Co., 1968 Volume(issue)/page/year: -,207,1968
TYPE OF TEST :
LCLo - Lowest published lethal concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Mammal - cat
DOSE/DURATION :
190 mg/m3/15M
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
REFERENCE :
85GMAT "Toxicometric Parameters of Industrial Toxic Chemicals Under Single Exposure," Izmerov, N.F., et al., Moscow, Centre of International Projects, GKNT, 1982 Volume(issue)/page/year: -,99,1982
TYPE OF TEST :
LCLo - Lowest published lethal concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Mammal - species unspecified
DOSE/DURATION :
50 ppm/5M
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
REFERENCE :
AEPPAE Naunyn-Schmiedeberg's Archiv fuer Experimentelle Pathologie und Pharmakologie. (Berlin, Ger.) V.110-253, 1925-66. For publisher information, see NSAPCC. Volume(issue)/page/year: 138,65,1928
TYPE OF TEST :
LCLo - Lowest published lethal concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Mammal - species unspecified
DOSE/DURATION :
11 mg/m3/30M
TOXIC EFFECTS :
Details of toxic effects not reported other than lethal dose value
REFERENCE :
TABIA2 Tabulae Biologicae. (The Hague, Netherlands) V.1-22, 1925-63. Discontinued. Volume(issue)/page/year: 3,231,1933 ** OTHER MULTIPLE DOSE TOXICITY DATA **
TYPE OF TEST :
TCLo - Lowest published toxic concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Rodent - rat
DOSE/DURATION :
200 ppb/6H/4W-I
TOXIC EFFECTS :
Lungs, Thorax, or Respiration - structural or functional change in trachea or bronchi Lungs, Thorax, or Respiration - changes in lung weight
REFERENCE :
FAATDF Fundamental and Applied Toxicology. (Academic Press, Inc., 1 E. First St., Duluth, MN 55802) V.1- 1981- Volume(issue)/page/year: 37,54,1997
TYPE OF TEST :
TCLo - Lowest published toxic concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Rodent - rat
DOSE/DURATION :
250 ppb/4H/17D-I
TOXIC EFFECTS :
Lungs, Thorax, or Respiration - other changes Lungs, Thorax, or Respiration - changes in lung weight Biochemical - Enzyme inhibition, induction, or change in blood or tissue levels - dehydrogenases
REFERENCE :
JTEHD6 Journal of Toxicology and Environmental Health. (Hemisphere Pub., 1025 Vermont Ave., NW, Washington, DC 20005) V.1- 1975/76- Volume(issue)/page/year: 19,413,1986
TYPE OF TEST :
TCLo - Lowest published toxic concentration
ROUTE OF EXPOSURE :
Inhalation
SPECIES OBSERVED :
Rodent - rat
DOSE/DURATION :
500 ppb/6H/12W-I
REFERENCE :
FAATDF Fundamental and Applied Toxicology. (Academic Press, Inc., 1 E. First St., Duluth, MN 55802) V.1- 1981- Volume(issue)/page/year: 37,54,1997 *** REVIEWS *** ACGIH TLV-TWA 0.40 mg/m3 (0.1 ppm) DTLVS* The Threshold Limit Values (TLVs) and Biological Exposure Indices (BEIs) booklet issues by American Conference of Governmental Industrial Hygienists (ACGIH), Cincinnati, OH, 1996 Volume(issue)/page/year: TLV/BEI,1997 TOXICOLOGY REVIEW ANAEA3 Annals of Allergy. (American College of Allergists, POB 20671, Bloomington, MN 55420) V.1- 1943- Volume(issue)/page/year: 35,165,1975 TOXICOLOGY REVIEW AEHLAU Archives of Environmental Health. (Heldref Pub., 4000 Albemarle St., NW, Washington, DC 20016) V.1- 1960- Volume(issue)/page/year: 28,272,1974 TOXICOLOGY REVIEW CMTVAS Cahiers de Medecine du Travail. (Association Professionnelle Belge des Medecine du Travail, rue du Bultia, 6280 Gerpinnes, Belgium) V.1- 1963- Volume(issue)/page/year: 10(3),49,1973 *** U.S. STANDARDS AND REGULATIONS *** MSHA STANDARD-air:TWA 0.1 ppm (0.4 mg/m3) DTLVS* The Threshold Limit Values (TLVs) and Biological Exposure Indices (BEIs) booklet issues by American Conference of Governmental Industrial Hygienists (ACGIH), Cincinnati, OH, 1996 Volume(issue)/page/year: 3,208,1971 OSHA PEL (Gen Indu):8H TWA 0.1 ppm (0.4 mg/m3) CFRGBR Code of Federal Regulations. (U.S. Government Printing Office, Supt. of Documents, Washington, DC 20402) Volume(issue)/page/year: 29,1910.1000,1994 OSHA PEL (Construc):8H TWA 0.1 ppm (0.4 mg/m3) CFRGBR Code of Federal Regulations. (U.S. Government Printing Office, Supt. of Documents, Washington, DC 20402) Volume(issue)/page/year: 29,1926.55,1994 OSHA PEL (Shipyard):8H TWA 0.1 ppm (0.4 mg/m3) CFRGBR Code of Federal Regulations. (U.S. Government Printing Office, Supt. of Documents, Washington, DC 20402) Volume(issue)/page/year: 29,1915.1000,1993 OSHA PEL (Fed Cont):8H TWA 0.1 ppm (0.4 mg/m3) CFRGBR Code of Federal Regulations. (U.S. Government Printing Office, Supt. of Documents, Washington, DC 20402) Volume(issue)/page/year: 41,50-204.50,1994 *** OCCUPATIONAL EXPOSURE LIMITS *** OEL-ARAB Republic of Egypt:TWA 0.1 ppm (0.4 mg/m3) JAN 1993 OEL-AUSTRIA:TWA 0.1 ppm (0.5 mg/m3) JAN 1993 OEL-DENMARK:TWA 0.05 ppm (0.2 mg/m3) JAN 1993 OEL-FINLAND:STEL 0.05 ppm (0.2 mg/m3);Skin JAN 1993 OEL-GERMANY:TWA 0.1 ppm (0.4 mg/m3) JAN 1993 OEL-THE NETHERLANDS:TWA 0.1 ppm (0.4 mg/m3) JAN 1993 OEL-THE PHILIPPINES:TWA 0.1 ppm (0.1 mg/m3) JAN 1993 OEL-SWEDEN:TWA 0.05 ppm (0.2 mg/m3) JAN 1993 OEL-THAILAND:TWA 0.1 ppm (0.4 mg/m3) JAN 1993 OEL-TURKEY:TWA 0.1 ppm (0.4 mg/m3) JAN 1993 OEL-UNITED KINGDOM:TWA 0.1 ppm (0.4 mg/m3) JAN 1993 OEL IN BULGARIA, COLOMBIA, JORDAN, KOREA check ACGIH TLV OEL IN NEW ZEALAND, SINGAPORE, VIETNAM check ACGIH TLV *** NIOSH STANDARDS DEVELOPMENT AND SURVEILLANCE DATA *** NIOSH RECOMMENDED EXPOSURE LEVEL (REL) : NIOSH REL TO PHOSGENE-air:10H TWA 0.1 ppm;CL 0.2 ppm/15M REFERENCE : NIOSH* National Institute for Occupational Safety and Health, U.S. Dept. of Health, Education, and Welfare, Reports and Memoranda. Volume(issue)/page/year: DHHS #92-100,1992 NIOSH OCCUPATIONAL EXPOSURE SURVEY DATA : NOHS - National Occupational Hazard Survey (1974) NOHS Hazard Code - 57710 No. of Facilities: 408 (estimated) No. of Industries: 10 No. of Occupations: 11 No. of Employees: 5729 (estimated) NOES - National Occupational Exposure Survey (1983) NOES Hazard Code - 57710 No. of Facilities: 57 (estimated) No. of Industries: 5 No. of Occupations: 10 No. of Employees: 2358 (estimated) No. of Female Employees: 282 (estimated)
毒理学数据:

1.急性毒性[11]  LC50:1400mg/m3(大鼠吸入,1/2h)

2.刺激性   暂无资料

3.亚急性与慢性毒性[12]   动物吸入0.0008mg/L,每天5h,共5d,40%出现肺水肿。

4.其他[13]

LCLo:50ppm(人吸入,5min),360mg/m3(人吸入30min)

TCLo:25ppm(人吸入,30min)

生态数据:

1.生态毒性[14]  LD50:60mg/L(24h)(鱼)

2.生物降解性[15]

好氧生物降解(h):168~672

厌氧生物降解(h):678~2688

3.非生物降解性[16]

光解最大光吸收波长范围(nm):234.2~274.5

一级水解半衰期(h):1.9

4.其他有害作用[17]   该物质对环境有危害,应特别注意对空气、水环境及水源的污染。

光气 MSDS

第一部分:化学品名称

光气 分子结构与计算化学数据

分子结构数据

1、摩尔折射率:16.4

2、摩尔体积(cm3/mol):64.9

3、等张比容(90.2K):153.8

4、表面张力(dyne/cm):31.5

5、介电常数:无可用

6、偶极距(10-24cm3):无可用

7、极化率:6.5

计算化学数据

1.疏水参数计算参考值(XlogP):1.8

2.氢键供体数量:0

3.氢键受体数量:1

4.可旋转化学键数量:0

5.互变异构体数量:无

6.拓扑分子极性表面积17.1

7.重原子数量:4

8.表面电荷:0

9.复杂度:29

10.同位素原子数量:0

11.确定原子立构中心数量:0

12.不确定原子立构中心数量:0

13.确定化学键立构中心数量:0

14.不确定化学键立构中心数量:0

15.共价键单元数量:1

光气 上游产品

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