阅读材料：卤族元素发现小史

阅读材料：卤族元素发现小史 教学素材/卤族元素 卤族元素发现小史 氟、氯、溴、碘是活泼的非金属元素，它们的发现过程几乎延伸整个十九世纪，凝聚着世纪的沧桑，闪烁着世纪的辉煌。 卤族元素都具有强烈的非金属性，因而它们纯净的单质都是经氧化制得。我们将了解到，浓硫酸、氯气、二氧化锰这些常见的氧化剂，在元素发现的历史中曾经起过不同寻常的作用。这一讲中我们总是碰到氧化还原反应，并将看到拉瓦锡最初纯朴的得氧即氧化反应的概念，是怎样演化、发展的。 无论是纽兰兹的“八音律”中，还是迈耶尔或门捷列夫的元素周期表中，都有氟元素的位置，而且都给出了氟的正确原子量:19 。但是制备出游离态的单质氟，却比元素周期表的发表晚了二十年左右。即氟的发现过程是先确证、后制得，这与氯的发现过程刚好相反。 另外，大部分卤族元素是由法国科学家发现的。这从一个侧面反映了在启蒙运动的影响下，在十八世纪下半叶和十九世纪上半叶，法国科学得到了长足的发展，甚至取代英国成为世界科学的中心。 碘的发现者——是商人还是化学家? 贝尔纳德?库特瓦于1777年2月8日出生于法国的第戎。他的父亲经营着一家硝石工厂，并在著名的第戎学院任教，经常做一些精彩的化学讲演。库特瓦自小耳濡目染，十分喜爱化学。他后来分别在孚克劳、泰纳和塞古恩的指导下学习。塞古恩是法国化学家，曾在拉瓦锡被送上断头台的最后五年里担任拉瓦锡的助手，进行呼吸作用、量热学研究。学成归来，库特瓦帮助父亲经营硝石工厂。 在第戎附近的诺曼底海岸上，许多浅滩生长的海生植物被潮水冲到岸边。退潮后库特瓦常到海边采拾些藻类植物。他把这些藻类植物晒干后烧成灰，再加水浸取，过滤。得到的溶液他称做海藻盐汁。现在我们知道这种溶液里含有钠、钾、镁、钙的卤化物、硫酸盐等。 库特瓦想从“海藻盐汁”中提取氯化钠、氯化钾、硫酸盐等。他首先蒸发溶液。在较高的温度下，氯化钠的溶解度最小，最先结晶析出。其次是氯化钾和硫酸钾。由于在灼烧藻类植物时，硫酸盐被碳还原产生了硫化物， KSO + 2C = KS + 2CO 2422 D. non-destructive inspection report; E. static grounding test records; F. design changes and material substitution file. (2) t清华同方教育技术研究院 he piping system according to the design files have been installed; A. pipe, hangers, material, in the form of the installation location is correct, complete number, strength, welding quality; B. completed welding work, weld quality inspection; C. weld parts should be checked and it should not be hidden. (3) pressure test of temporary reinforcement measures for safe and reliable, such as: temporary support should be strong, can withstand the pressure of water. Temporary blind flange plus reset correctly, and should identify clear, while mark on the single line diagram, records should be complete, high and low discharge point set is complete and correct; (4) cannot participate in the testing of control valves, filters, flow orifice and flow meters should be removed, connected with the temporary spool; (5) approval of pressure test system and construction scheme and the pressure group is disclosure. 1.5.2 pressure test press design offers you the test pressure of the pressure test, pressure test media selected according to design specifications. (1) tests should be used when high point within the exhaust system of air, boosting ratings slowly, reach the test pressure after 10min, then down to pressure regulator 30 min, no pressure drop, no leakage, Visual deformation is qualified. When pressure testing in case of spill shall not be under pressure to repair defect elimination and try again until the qualified. (2) after the piping system passes the test, should slow buck, the test medium emission should be at the right place, try to pressure test water discharged into the nearby sewer pipes or rain. Pressure test after the purge the piping system if not to temporarily blind and short pipe, support should be removed, reset in a timely manner and fill pipe system pressure test records. 1.6 pipe blowing and wash 教学素材/卤族元素 为了氧化而除去这些硫化物，他加入了强氧化剂——浓硫酸。不一会儿，容器里冒出了紫色蒸气，宛如紫色的云彩冉冉上升。这一现象使库特瓦惊喜不已。最后，这种紫色蒸气令人窒息地充满了实验室。当蒸气在冷的物体上凝结时，它并不变成液珠，而是成为一种紫黑色的带有金属光泽的晶体，也即发生了凝华现象。这事发生在1811年。也就是这一年，阿佛加德罗提出了分子假说。 我们现在知道，这是因为浓硫酸氧化出了碘分子。 2KI + 2HSO(浓)= KSO + I + SO + 2HO 2424222 库特瓦用这种新物质做进一步的实验研究。他发现这种新物质不易与氧或碳发生反应，但却能与氢和磷化合，能与几种金属直接化合。尤为奇特的是这种新物质不为高温分解，这一特征使库特瓦猜想可能是发现了一种新元素。 库特瓦的实验室十分简陋，他就请另外两位法国化学家继续这一研究，并允许他们自由地向科学界宣布这种新元素的发现经过。 1813年，这两位化学家写出了报告《库特瓦先生从一种碱金属盐中发现的新物质》，他们描述道:“从海藻灰所得的溶液中含有一种特别奇异的东西，它很容易提取，方法是将硫酸倾入溶液中，放进曲颈甑内加热，并用导管将曲颈甑的口与球形器连接。溶液中析出一种黑色有光泽的粉末，加热后，紫色蒸气冉冉上升，蒸气凝结在导管和球形器内，结成片状晶体。” 这两位化学家之一相信这种结晶是一种新元素，它的性质与氯相似，于是他就向法国化学家、物理学家安培和英国化学家戴维报告。戴维用直流电将碳丝烧成红热，然后与这种结晶接触，并不能使它分解，证明了它是一种新元素。 新的发现使库特瓦很高兴。他制出很纯的碘，分送给化学界的朋友。 后来，库特瓦的硝石工厂停业。他的晚年在贫困中度过。1838年9月27日，库特瓦在巴黎逝世，享年61岁。为电解制氟做出重要探索的弗雷米，他的祖父曾经说过:“把库特瓦仅仅看成是一位制造硝石的平凡的商人是不公道的，他是一位技艺很高的化学家，他应该由于发现碘而受到奖赏，绝不应该听任他因贫困而死去。” 溴的发现与李比希的“错误之柜” 溴首先是由法国化学家巴拉尔发现的。 D. non-destructive inspection report; E. static grounding test records; F. design changes and material substitution file. (2) t清华同方教育技术研究院 he piping system according to the design files have been installed; A. pipe, hangers, material, in the form of the installation location is correct, complete number, strength, welding quality; B. completed welding work, weld quality inspection; C. weld parts should be checked and it should not be hidden. (3) pressure test of temporary reinforcement measures for safe and reliable, such as: temporary support should be strong, can withstand the pressure of water. Temporary blind flange plus reset correctly, and should identify clear, while mark on the single line diagram, records should be complete, high and low discharge point set is complete and correct; (4) cannot participate in the testing of control valves, filters, flow orifice and flow meters should be removed, connected with the temporary spool; (5) approval of pressure test system and construction scheme and the pressure group is disclosure. 1.5.2 pressure test press design offers you the test pressure of the pressure test, pressure test media selected according to design specifications. (1) tests should be used when high point within the exhaust system of air, boosting ratings slowly, reach the test pressure after 10min, then down to pressure regulator 30 min, no pressure drop, no leakage, Visual deformation is qualified. When pressure testing in case of spill shall not be under pressure to repair defect elimination and try again until the qualified. (2) after the piping system passes the test, should slow buck, the test medium emission should be at the right place, try to pressure test water discharged into the nearby sewer pipes or rain. Pressure test after the purge the piping system if not to temporarily blind and short pipe, support should be removed, reset in a timely manner and fill pipe system pressure test records. 1.6 pipe blowing and wash 1802年9月30日，巴拉尔出生于法国的蒙彼利埃。他出生于一个普通的家庭，父母整天忙于制酒。巴拉尔的教母发现他很聪明，一心要培养他成才。巴拉尔十七岁时毕业于蒙彼利埃中学，接着升入药物学院学习药物学，二十四岁时获医学博士学位。下图是巴拉尔的画像。 还在他当学生的1824年，二十二岁的巴拉尔在研究盐湖中植物的时候，将从大西洋和地中海沿岸采集到的黑角菜燃烧成灰，然后用浸泡的方法得到一种灰黑色的浸取液。他往浸取液中加入氯水和淀粉，溶液即分为两层:下层显蓝色，这是由于淀粉与溶液中的碘生成了加合物;上层显棕黄色，这是一种以前没有见过的现象。 这棕黄色是什么物质呢,巴拉尔认为可能有两种情况:一是氯与溶液中的碘形成了新的化合物——氯化碘;二是氯把溶液中的新元素置换出来了。于是巴拉尔想了些办法，先试图把新的化合物分开，但都没有成功。巴拉尔分析这可能不是氯化碘，而是一种与氯、碘相似的新元素。 他用乙醚将棕黄色的物质经萃取和分液提出，再加苛性钾，则棕黄色褪掉(我们现在知道， Br + 2KOH = KBr + KBrO + HO 22 溴已经转变为溴化钾和次溴酸钾)。加热蒸干溶液，剩下的物质象氯化钾一样。把剩下的物质与浓硫酸、二氧化锰共热， 2KBr + 2HSO +MnO = KSO + MnSO + Br + 2HO 24224422 D. non-destructive inspection report; E. static grounding test records; F. design changes and material substitution file. (2) t 3 / 12 he piping system according to the design files have been installed; A. pipe, hangers, material, in the form of the installation location is correct, complete number, strength, welding quality; B. completed welding work, weld quality inspection; C. weld parts should be checked and it should not be hidden. (3) pressure test of temporary reinforcement measures for safe and reliable, such as: temporary support should be strong, can withstand the pressure of water. Temporary blind flange plus reset correctly, and should identify clear, while mark on the single line diagram, records should be complete, high and low discharge point set is complete and correct; (4) cannot participate in the testing of control valves, filters, flow orifice and flow meters should be removed, connected with the temporary spool; (5) approval of pressure test system and construction scheme and the pressure group is disclosure. 1.5.2 pressure test press design offers you the test pressure of the pressure test, pressure test media selected according to design specifications. (1) tests should be used when high point within the exhaust system of air, boosting ratings slowly, reach the test pressure after 10min, then down to pressure regulator 30 min, no pressure drop, no leakage, Visual deformation is qualified. When pressure testing in case of spill shall not be under pressure to repair defect elimination and try again until the qualified. (2) after the piping system passes the test, should slow buck, the test medium emission should be at the right place, try to pressure test water discharged into the nearby sewer pipes or rain. Pressure test after the purge the piping system if not to temporarily blind and short pipe, support should be removed, reset in a timely manner and fill pipe system pressure test records. 1.6 pipe blowing and wash 教学素材/卤族元素 SO = KSO + Br + HO KBr + KBrO + H242422 就会产生红棕色有恶臭的气体，冷凝后变为深红棕色液体。巴拉尔判断这是与氯和碘相似的、在室温下呈液态的一种新元素。他将这种新元素定名为muride。 法国科学院于1826年8月14日审查了巴拉尔的新发现。由三位法国化学家孚克劳、泰纳、盖?吕萨克共同审查。他们签署的意见这样写道:“关于溴是否是一种极简单的个体，今日我们更有知道的必要，我们已经做过的不多几次的实验也许还不足以证明它确实是极简单的个体，然而我们认为至少是很有可能的。巴拉尔先生的报告作得很好，即使将来证明溴并不是一种单体，他所罗列的种种结果还是能够引起人们极大的兴趣的。总之，溴的发现在化学上实为一种重要的收获，它给巴拉尔在科学事业上一个光荣的地位。我们认为这位青年化学家完全值得受到科学院的鼓励。”但他们不赞成巴拉尔对溴的命名，把它改称为bromine，含义是恶臭。 另外在1825年，德国海德堡大学学生罗威,往家乡克罗次纳克的一种盐泉水中通入氯气时，发现溶液变为红棕色。他把这种红棕色物质用乙醚萃取提出，再将乙醚小心蒸发，得到了红棕色的液溴。所以说罗威也独立地发现了溴，虽然比巴拉尔晚了一年。 其实早在巴拉尔之前，德国化学大师李比希就得到了一家工厂送来请他分 析的一瓶液体，但他没有经过详细的分析，就认定瓶里的液体是氯化碘，实际上那是一瓶溴。直到他听到巴拉尔发现溴的消息，才认识到自己犯了一个大错误。从此，李比希为了警戒自己，特地把那个瓶子放在一只被他称为“错误之柜”的箱子中，作为永远的教训。 发现氯，未必认识氯 在第一讲我们谈到，瑞典化学家舍勒于1774年用浓盐酸与二氧化锰反应制得了氯气。但它究竟是游离态的单质气体还是化合态的气体，仍然不清楚。后来法国化学权威贝托雷(我们曾在第三讲里提到，他与普罗斯论战，反对定组成定律)继续研究氯气。他首先将氯气通入一个冷的空玻璃瓶里，让氯气里的含酸蒸气受冷凝结，再将除去酸蒸气的氯气依次通入三个盛满水的瓶子使氯气溶于水。他发现溶有氯气的水溶液，在有光照的地方可以分解成盐酸和氧气。(我们现在知道，氯和水反应生成的次氯酸在光照下分解 Cl + HO = HCl + HClO 22 D. non-destructive inspection report; E. static grounding test records; F. design changes and material substitution file. (2) t清华同方教育技术研究院 he piping system according to the design files have been installed; A. pipe, hangers, material, in the form of the installation location is correct, complete number, strength, welding quality; B. completed welding work, weld quality inspection; C. weld parts should be checked and it should not be hidden. (3) pressure test of temporary reinforcement measures for safe and reliable, such as: temporary support should be strong, can withstand the pressure of water. Temporary blind flange plus reset correctly, and should identify clear, while mark on the single line diagram, records should be complete, high and low discharge point set is complete and correct; (4) cannot participate in the testing of control valves, filters, flow orifice and flow meters should be removed, connected with the temporary spool; (5) approval of pressure test system and construction scheme and the pressure group is disclosure. 1.5.2 pressure test press design offers you the test pressure of the pressure test, pressure test media selected according to design specifications. (1) tests should be used when high point within the exhaust system of air, boosting ratings slowly, reach the test pressure after 10min, then down to pressure regulator 30 min, no pressure drop, no leakage, Visual deformation is qualified. When pressure testing in case of spill shall not be under pressure to repair defect elimination and try again until the qualified. (2) after the piping system passes the test, should slow buck, the test medium emission should be at the right place, try to pressure test water discharged into the nearby sewer pipes or rain. Pressure test after the purge the piping system if not to temporarily blind and short pipe, support should be removed, reset in a timely manner and fill pipe system pressure test records. 1.6 pipe blowing and wash )。 2HClO = 2HCl + O2 贝托雷以此判断出氯气是盐酸和氧结合成的: 氯 , 盐酸 ， 氧基 氯气是盐酸和氧结合得很松散的化合物，因此露置在阳光下就分解了。其实在当时人们已经用过许多强烈的药剂或其它手段来处理氯气，都未能使它分解为盐酸和氧。贝托雷的判断显然跟其它一些研究是矛盾的。他得出这个错误判断的表面原因，似乎在于他忽视了水和氯气的反应。但更深层的原因，是他深受拉瓦锡“所有的酸中都含有氧基”结论的影响。 拉瓦锡在提出燃烧的氧化理论的同时，提出了“氧是成酸元素”的论点，认为一切酸中均含有氧。按照这一理论，盐酸应是一种氧化物的水化物，如硫酸、磷酸一般(我们姑且把它写成 HClO )。而氯气是盐酸经二氧化锰氧化得来的，m 应该含有更多的氧(即应该写成 HClO )，当时将氯气称作“氧化盐酸”。结m+n 果氯气不仅不是一种单质，反而比盐酸具有更复杂的结构、更大的分子量。贝托雷的实验很和“逻辑”地证明了拉瓦锡的论点。 1809年法国化学家盖?吕萨克和泰纳，用分解法研究盐酸的组成。当时金属钾已被戴维用电解法制得，并证明钾是一种元素。于是他们就用金属钾和铁等与盐酸气(HCl)反应，看它是不是能够放出氯气。实验得出结果后，他们说:“我们考察金属钾对于盐酸气的反应。在寻常温度时，这个反应很慢;但钾熔融时立刻在盐酸气中发光燃烧，结果得到氯化钾和氢。在这个实验中收集的氢气之量，恰与钾和水接触时发生的相等。我们在暗红热时，用盐酸气通过擦净的铁屑，许多氢气放出，而不觉有盐酸混合在内，同时得到氯化铁;残渣铁屑并没有氧化。当中等温度时，用盐酸气通过既熔而又研成细粉的一氧化铅，又收集到氢，不过已与氧化合变成水的状态了。” 这些实验证明，不是氯气分解成盐酸和氧，而是盐酸分解成氯和氢。 在同一年盖?吕萨克和泰纳用合成法证明了盐酸的组成。他们把同量的氢气和氯气混合在一起，静置数日，或稍微加热，或露置日光中，都能化合成盐酸气。 这个实验证明了盐酸气是氢气和氯气的化合物，而且是这两种气体化合而成的唯一物质，其变化应该表示为: 氯 ， 氢 , 盐酸气(HCl) D. non-destructive inspection report; E. static grounding test records; F. design changes and material substitution file. (2) t 5 / 12 he piping system according to the design files have been installed; A. pipe, hangers, material, in the form of the installation location is correct, complete number, strength, welding quality; B. completed welding work, weld quality inspection; C. weld parts should be checked and it should not be hidden. (3) pressure test of temporary reinforcement measures for safe and reliable, such as: temporary support should be strong, can withstand the pressure of water. Temporary blind flange plus reset correctly, and should identify clear, while mark on the single line diagram, records should be complete, high and low discharge point set is complete and correct; (4) cannot participate in the testing of control valves, filters, flow orifice and flow meters should be removed, connected with the temporary spool; (5) approval of pressure test system and construction scheme and the pressure group is disclosure. 1.5.2 pressure test press design offers you the test pressure of the pressure test, pressure test media selected according to design specifications. (1) tests should be used when high point within the exhaust system of air, boosting ratings slowly, reach the test pressure after 10min, then down to pressure regulator 30 min, no pressure drop, no leakage, Visual deformation is qualified. When pressure testing in case of spill shall not be under pressure to repair defect elimination and try again until the qualified. (2) after the piping system passes the test, should slow buck, the test medium emission should be at the right place, try to pressure test water discharged into the nearby sewer pipes or rain. Pressure test after the purge the piping system if not to temporarily blind and short pipe, support should be removed, reset in a timely manner and fill pipe system pressure test records. 1.6 pipe blowing and wash 教学素材/卤族元素 盖?吕萨克和泰纳的实验，对盐酸的组成作出了正确的结论，但是氯气在他们的眼里仍然是一种化合物。原因如上文所说，拉瓦锡的“氧是成酸元素”的论点已深深地印在广大化学家的脑子里。盖?吕萨克和泰纳是深信这个论点的，因而他们认为氯是某种“基”的氧化物。既然氯气是某种基的氧化物，那么盐酸就应该是某种基跟氧和氢的化合物: 盐酸 , 某种基 ， 氧 ， 氢 如果联系贝托雷的结论，可以看出他们的矛盾之处。而最终解决这个问题的是戴维。这在第二讲中已有所交待。 戴维在研究碲的化学性质时发现碲化氢是一种酸，但是它并不含有氧，使他开始怀疑氧是否存在于所有的酸中。为了寻找更多的证据，戴维开始研究起盐酸。按照拉瓦锡的观点，舍勒用浓盐酸与二氧化锰作用制得的黄绿色气体是氧化盐酸，而盐酸是由氧和另外一种未知的基所组成的，氧化盐酸则是由这种基与更多的氧化合而成的。但是戴维想尽了一切办法也不能从氧化盐酸中把氧夺取出来。他说:“即使木炭被伏打电堆烧成白热状态，也不能使氧化盐酸气发生任何变化，我多次重复这种实验，结果都是一样，因此我怀疑这些物质中是否存在着氧。” 他重做盖?吕萨克和泰纳合成盐酸的实验，并证实氯和氢化合成盐酸的结论是正确的，除了稍有水的痕迹外，没有其它杂质。既然实验中没有发现氯气或盐酸中有氧存在，为什么我们硬要说它们含有氧呢,他感到只有认为氯是一种元素，那么有关氯的所有实验才能得到合理的解释。1810年11月，戴维在英国皇家学会宣读了他的论文，正式提出氯是一种元素。 戴维宣称，只要不存在水，氧化盐酸所发生的一切反应都不会产生氧，他认为最好把氧化盐酸看成是一种不能被分解的物质——元素。他认为事实表明，拉瓦锡和法国化学学派所持的见解，表面看起来很漂亮，也能令人满意，但是从现在已经掌握的知识来考察，它不过是建立在假设基础上的理论。戴维以无可辩驳的事实确认所谓的“氧化盐酸”决不是一种化合物，而是一种化学元素，他将这种元素命名为Chlorine(中译名为氯)，意为黄绿色的。他指出所有的剧烈发光、发热的反应(如铁丝、铜丝、氢气在氯气中的燃烧)都是氧化反应，氯和氧一样都可以助燃，氧化反应不一定非要有氧气参加，经氧化反应生成的酸中也不一定 D. non-destructive inspection report; E. static grounding test records; F. design changes and material substitution file. (2) t清华同方教育技术研究院 he piping system according to the design files have been installed; A. pipe, hangers, material, in the form of the installation location is correct, complete number, strength, welding quality; B. completed welding work, weld quality inspection; C. weld parts should be checked and it should not be hidden. (3) pressure test of temporary reinforcement measures for safe and reliable, such as: temporary support should be strong, can withstand the pressure of water. Temporary blind flange plus reset correctly, and should identify clear, while mark on the single line diagram, records should be complete, high and low discharge point set is complete and correct; (4) cannot participate in the testing of control valves, filters, flow orifice and flow meters should be removed, connected with the temporary spool; (5) approval of pressure test system and construction scheme and the pressure group is disclosure. 1.5.2 pressure test press design offers you the test pressure of the pressure test, pressure test media selected according to design specifications. (1) tests should be used when high point within the exhaust system of air, boosting ratings slowly, reach the test pressure after 10min, then down to pressure regulator 30 min, no pressure drop, no leakage, Visual deformation is qualified. When pressure testing in case of spill shall not be under pressure to repair defect elimination and try again until the qualified. (2) after the piping system passes the test, should slow buck, the test medium emission should be at the right place, try to pressure test water discharged into the nearby sewer pipes or rain. Pressure test after the purge the piping system if not to temporarily blind and short pipe, support should be removed, reset in a timely manner and fill pipe system pressure test records. 1.6 pipe blowing and wash 含有氧。戴维在确认氯是一种单质而非化合物的同时，出色地发展了拉瓦锡的燃烧的氧化理论。 戴维还提出，在酸中氧是非本质性的，无氧酸中不含氧;但是酸中都含有氢，氢在酸中具有重要意义。这个见解未引起人们的注意。直到1837年，德国化学大师李比希对酸类进行了全面的综合分析研究之后，放弃了酸的二元论(酸基 + 水)，振兴了戴维关于酸的氢学说。 氯气自1774年被舍勒发现，到1810年被戴维确认为是一种元素，其间经历了36年。 为制氟气，前仆后继 在化学元素发现史上，持续时间最长、参加人数最多、 危险最大、工作最难的研究课题，莫过于氟单质的制取了。 自1810年安培指出氢氟酸中含有一种新元素——氟，到 1886年法国化学家莫瓦桑制得单质氟，历时76年之久。为 了制取氟气，进而研究氟的性质，许多化学家前仆后继，为 后人留下了一段极其悲壮的历史。他们不惜损害自己的身体健康，甚至被氟气或氟化物夺去了宝贵的生命。 早在十六世纪，人们就开始利用氟化物了。1529年阿格里柯拉就描述过利用萤石(氟化钙)作为熔矿的熔剂，使矿石在熔融时变得更加容易流动。1670年，玻璃加工业开始利用萤石与硫酸反应所产生的氢氟酸腐蚀玻璃，从而不用金刚石就能在玻璃上刻蚀出人物、动物、花卉等图案。1768年马格拉夫发现萤石与石膏和重晶石不同，判断它不是一种硫酸盐。他用浓硫酸处理萤石得到了氟化氢。1771年化学家舍勒用曲颈甑加热萤石和浓硫酸的混合物，曾发现玻璃瓶内壁被腐蚀。后来很多化学家研究氢氟酸，发现它的性质很象盐酸，比盐酸稳定，但它对玻璃和一些硅酸盐矿物的腐蚀性却很强。另外，它有剧毒，挥发出的蒸气更危险。 1810年，戴维确认氯气是一种元素而非化合物的同时，也指出酸中不一定含有氧元素。这一突破性的见解给法国物理学家、化学家安培很大的启发。他根据对氢氟酸性质的研究指出，其中可能含有一种与氯相似的元素。他将这种未知的元素称为“fluorine(氟)”，意思是有强腐蚀性的。氟化氢就是这种元素与氢的 D. non-destructive inspection report; E. static grounding test records; F. design changes and material substitution file. (2) t 7 / 12 he piping system according to the design files have been installed; A. pipe, hangers, material, in the form of the installation location is correct, complete number, strength, welding quality; B. completed welding work, weld quality inspection; C. weld parts should be checked and it should not be hidden. (3) pressure test of temporary reinforcement measures for safe and reliable, such as: temporary support should be strong, can withstand the pressure of water. Temporary blind flange plus reset correctly, and should identify clear, while mark on the single line diagram, records should be complete, high and low discharge point set is complete and correct; (4) cannot participate in the testing of control valves, filters, flow orifice and flow meters should be removed, connected with the temporary spool; (5) approval of pressure test system and construction scheme and the pressure group is disclosure. 1.5.2 pressure test press design offers you the test pressure of the pressure test, pressure test media selected according to design specifications. (1) tests should be used when high point within the exhaust system of air, boosting ratings slowly, reach the test pressure after 10min, then down to pressure regulator 30 min, no pressure drop, no leakage, Visual deformation is qualified. When pressure testing in case of spill shall not be under pressure to repair defect elimination and try again until the qualified. (2) after the piping system passes the test, should slow buck, the test medium emission should be at the right place, try to pressure test water discharged into the nearby sewer pipes or rain. Pressure test after the purge the piping system if not to temporarily blind and short pipe, support should be removed, reset in a timely manner and fill pipe system pressure test records. 1.6 pipe blowing and wash 教学素材/卤族元素 化合物。他将这一观点告诉戴维，反过来启发戴维用他强有力的伏打电堆致力于制备纯净的氟元素。由此我们看到科学家间的相互交流对科学的发展具有多么大的意义～没有交流就没有科学的发展。 安培的雕像 当溴、碘被陆续发现后，人们将各种氟化物与相应的其它卤化物对比，发现它们有极相似的性质，故判断氟、氯、溴、碘属于同类型的元素，并测得了氟的原子量为19。于1864年发表的元素表中就列出了氟的正确的原子量。但这时距离电解分离出氟气还差二十二年。 1813年戴维用电解氟化物的方法制取单质氟，用白金做容器，结果阳极的白金被腐蚀了，还是没有游离出氟。他后来改用萤石做容器，腐蚀问题虽解决了，但也得不到氟。而戴维则因氟化氢的毒害而患病，“出师未捷身先病”，不得不停止了实验。 接着乔治?诺克斯和托马斯?诺克斯弟兄二人把一片金箔放在玻璃接收瓶顶部，再用干燥的氯气处理氟化汞。实验证明金变成了氟化金，可见反应产生了氟。 D. non-destructive inspection report; E. static grounding test records; F. design changes and material substitution file. (2) t清华同方教育技术研究院 he piping system according to the design files have been installed; A. pipe, hangers, material, in the form of the installation location is correct, complete number, strength, welding quality; B. completed welding work, weld quality inspection; C. weld parts should be checked and it should not be hidden. (3) pressure test of temporary reinforcement measures for safe and reliable, such as: temporary support should be strong, can withstand the pressure of water. Temporary blind flange plus reset correctly, and should identify clear, while mark on the single line diagram, records should be complete, high and low discharge point set is complete and correct; (4) cannot participate in the testing of control valves, filters, flow orifice and flow meters should be removed, connected with the temporary spool; (5) approval of pressure test system and construction scheme and the pressure group is disclosure. 1.5.2 pressure test press design offers you the test pressure of the pressure test, pressure test media selected according to design specifications. (1) tests should be used when high point within the exhaust system of air, boosting ratings slowly, reach the test pressure after 10min, then down to pressure regulator 30 min, no pressure drop, no leakage, Visual deformation is qualified. When pressure testing in case of spill shall not be under pressure to repair defect elimination and try again until the qualified. (2) after the piping system passes the test, should slow buck, the test medium emission should be at the right place, try to pressure test water discharged into the nearby sewer pipes or rain. Pressure test after the purge the piping system if not to temporarily blind and short pipe, support should be removed, reset in a timely manner and fill pipe system pressure test records. 1.6 pipe blowing and wash 但是他们始终收集不到单质的氟气，也就无法确证他们已经制得了氟。在实验中，弟兄二人都严重中毒。 继诺克斯弟兄之后，鲁耶特不避艰辛和危险，对氟作了长期的研究，最后竟因中毒太深而献出了宝贵的生命。不久，法国化学家尼克雷也同样殉难。 照耀我们的真理之光是如此明澈，这时很难联想到盗火者普罗米修斯所经历的苦难。 德国化学家许村贝格曾指出，氢氟酸中所含的这种元素是一切元素中最活泼的，所以要将这种元素从它的化合物中离析出来将是一件非常困难的事情。法国自然博物馆馆长、工艺学院教授弗雷米也认为，电解可能是制取单质氟的唯一有效的方法。弗雷米曾分别高温加热氟化钙、氟化钾和氟化银使之熔融，然后电解。虽然阴极能析出金属，阳极上也产生了少量的气体，但是他即使想尽了一切办法，也始终未能收集到氟气。他想，一定是温度太高了，产生的氟气立即与容器和电极发生反应而消失了。什么氟化物不需加热就呈液态呢,他又电解无水氟化氢，但是它虽呈液态却不导电。只有电解含水的氟化氢液体，才有电流通过，但却只能收集到氢气、氧气和臭氧。看来是电解产生的氟与水反应生成了氧气和臭氧。 与此同时，英国化学家哥尔也用电解法分解氟化氢，但是在实验时发生了爆炸，显然是产生的少量氟气与氢气发生了剧烈的反应。他还试验过各种电极材料，如碳、金、钯、铂，但是在电解时碳电极被粉碎，金、钯、铂也不同程度地被腐蚀。 这么多化学家的努力，虽然都没有制得单质氟，但是他们的心血没有白费。他们从失败中获得了许多宝贵的经验和教训，为后来莫瓦桑制得氟气摸索了道路。 莫瓦桑百折不挠制得氟气 1852年9月28日，亨利?莫瓦桑出生于巴黎的一个铁路职员家庭。因家境贫困，莫瓦桑中学未毕业就到巴黎的一家药房当学徒，在实际中获得了一些化学知识和技艺。他怀着强烈的求知欲，常去旁听一些著名科学家的讲演。1872年他在法国自然博物馆馆长、工艺学院教授弗雷米的实验室学习化学。1874年到巴黎药学院的实验室工作，1877年25岁时才获得理学士学位。 D. non-destructive inspection report; E. static grounding test records; F. design changes and material substitution file. (2) t 9 / 12 he piping system according to the design files have been installed; A. pipe, hangers, material, in the form of the installation location is correct, complete number, strength, welding quality; B. completed welding work, weld quality inspection; C. weld parts should be checked and it should not be hidden. (3) pressure test of temporary reinforcement measures for safe and reliable, such as: temporary support should be strong, can withstand the pressure of water. Temporary blind flange plus reset correctly, and should identify clear, while mark on the single line diagram, records should be complete, high and low discharge point set is complete and correct; (4) cannot participate in the testing of control valves, filters, flow orifice and flow meters should be removed, connected with the temporary spool; (5) approval of pressure test system and construction scheme and the pressure group is disclosure. 1.5.2 pressure test press design offers you the test pressure of the pressure test, pressure test media selected according to design specifications. (1) tests should be used when high point within the exhaust system of air, boosting ratings slowly, reach the test pressure after 10min, then down to pressure regulator 30 min, no pressure drop, no leakage, Visual deformation is qualified. When pressure testing in case of spill shall not be under pressure to repair defect elimination and try again until the qualified. (2) after the piping system passes the test, should slow buck, the test medium emission should be at the right place, try to pressure test water discharged into the nearby sewer pipes or rain. Pressure test after the purge the piping system if not to temporarily blind and short pipe, support should be removed, reset in a timely manner and fill pipe system pressure test records. 1.6 pipe blowing and wash 教学素材/卤族元素 1872年莫瓦桑成为弗雷米教授的学生，开始了真正的化学实验研究工作。但他一开始是研究生理化学的。当时几乎所有的化学家都在研究有机化学。法国化学家杜马在1876年发表感想说:“我国的化学研究领域大部分为有机化学所占领，太缺少无机化学的研究了。”就在这时，莫瓦桑转而研究无机化学。 年轻的莫瓦桑知道制取单质氟这个课题难倒了许多化学家，可是莫瓦桑对氟的研究却非常感兴趣，不但没有气馁，反而下定决心要攻克这个难关。由于工作的变化，这项研究没有及时进行，直到十年后才得以集中精力开展研究。 莫瓦桑先花了好几个星期的时间查阅科学文献，研究了几乎全部有关氟的著作。他认为已知的方法都不能把氟单独分离出来，只有戴维设想的方法还没有试验过。戴维曾预言:磷和氧的亲合力极强，如果能制得氟化磷，再使氟化磷和氧作用，则可能生成氧化磷和氟。由于当时戴维还没有办法制得氟化磷，因而设想的实验没有实现。 于是莫瓦桑用氟化铅与磷化铜反应，得到了气体的三氟化磷。他把三氟化磷和氧的混合物通过电火花，虽然也发生了爆炸反应，但得到的并非单质的氟， )。 而是氟氧化磷(POF3 莫瓦桑又进行了一连串的实验，都没有达到目的。经过长时间的探索，他终于得出了这样的结论:他的实验都是在高温下进行的，这正是实验失败的症结所在。因为氟是非常活泼的，随着温度的升高，它的活泼性也就大大地增加了。即使在反应过程中它能够以游离的状态分离出来，它也会立刻和任何一种物质相化合。显然，反应应该在室温下进行，当然，能在冷却的条件下进行那就更好一些。他还想起他的老师弗雷米说过的话:电解可能是唯一可行的方法。他想如果用某种液体的氟化物，例如用氟化砷来进行电解，那么怎样呢,这种想法显然是大有希望的。莫瓦桑制备了剧毒的氟化砷，但随即遇到了新的困难——氟化砷不导电。在这种情况下，他只好往氟化砷里加入少量的氟化钾。这种混合物的导电性很好，可是在电解几分钟后，电流又停止了。原来阴极表面覆盖了一层电解出的砷。 莫瓦桑疲倦极了，十分艰难地支撑着。他关掉了联通电解装置的电源，随即倒在沙发椅上，心脏病剧烈发作，呼吸感到困难，面色发黄，眼睛周围出现了黑圈。莫瓦桑想到，这是砷在起作用，恐怕只好放弃这个方案了。出现这样的现 D. non-destructive inspection report; E. static grounding test records; F. design changes and material substitution file. (2) t清华同方教育技术研究院 he piping system according to the design files have been installed; A. pipe, hangers, material, in the form of the installation location is correct, complete number, strength, welding quality; B. completed welding work, weld quality inspection; C. weld parts should be checked and it should not be hidden. (3) pressure test of temporary reinforcement measures for safe and reliable, such as: temporary support should be strong, can withstand the pressure of water. Temporary blind flange plus reset correctly, and should identify clear, while mark on the single line diagram, records should be complete, high and low discharge point set is complete and correct; (4) cannot participate in the testing of control valves, filters, flow orifice and flow meters should be removed, connected with the temporary spool; (5) approval of pressure test system and construction scheme and the pressure group is disclosure. 1.5.2 pressure test press design offers you the test pressure of the pressure test, pressure test media selected according to design specifications. (1) tests should be used when high point within the exhaust system of air, boosting ratings slowly, reach the test pressure after 10min, then down to pressure regulator 30 min, no pressure drop, no leakage, Visual deformation is qualified. When pressure testing in case of spill shall not be under pressure to repair defect elimination and try again until the qualified. (2) after the piping system passes the test, should slow buck, the test medium emission should be at the right place, try to pressure test water discharged into the nearby sewer pipes or rain. Pressure test after the purge the piping system if not to temporarily blind and short pipe, support should be removed, reset in a timely manner and fill pipe system pressure test records. 1.6 pipe blowing and wash 象不是一次，他曾因中毒而中断了四次实验。莫瓦桑的爱妻莱昂妮看到他漫无节制地给自己增加工作，而且又经常冒着中毒的危险，对他的健康状况极为担心。 休息了一段时间后，莫瓦桑的健康状况有了好转，他继续进行实验。剩下唯一的方案是电解氟化氢。他按照弗雷米的办法，在铂制的容器中蒸馏氟氢酸钾 )，得到了无水氟化氢液体。他用铂制的U型管作容器，用强耐腐蚀的(KHF2 铂铱合金作电极，并用氯仿作冷却剂将无水氟化氢冷却到-23?C进行电解。在阴极上很快就出现了氢气泡，但阳极上却没有分解出气体。电解持续近一小时，分解出来的都是氢气，连一点氟的影子也没有。莫瓦桑一边拆卸仪器，一边苦恼地思索着，也许氟根本就不能以游离状态存在,当他拨掉U型管阳极一端的塞子时，惊奇地发现塞子上覆盖着一层白色粉末状的物质。可不是么，原来塞子被腐蚀了～氟到底还是分解出来了，不过和玻璃发生了反应。这一发现使莫瓦桑受到了极大的鼓舞。他想，如果把装置上的玻璃零件都换成不能与氟发生反应的材料，那就可以制得单体的氟了。荧石不与氟起作用，用它来试试吧，于是他用荧石制成试验用的器皿。莫瓦桑把盛有液体氟化氢的U型铂管浸入制冷剂中，用荧石制的螺旋帽盖紧管口，再进行电解。 多少年来化学家梦寐以求的理想终于实现了～1886年6月26日，莫瓦桑第一次制得了单质的氟气～这种气体遇到硅立即着火，遇到水即生成氧气和臭氧，与氯化钾反应置换出氯气。通过几次化学反应，莫瓦桑发现氟气确实具有惊人的活泼性。 由于莫瓦桑不是法国科学院院士，他的论文只能请人代为递交。法国科学院为了确认这一发现，指定了一个由三人组成的审查委员会，其中包括莫瓦桑的老师弗雷米和有机化学家贝特罗。莫瓦桑以最细心的准备工作来迎接审查。当他的老师等三位化学界的前辈到来时，他的电解装置竟然出现了前所未有的故障——没有一点电流通过，当然也不会有一点氟的踪影。 三位科学家离开后，莫瓦桑经过几天的努力，终于找到了这次实验失败的原因，是因为将氟化氢精制得太纯净。以往实验电解的氟化氢中都含有氟化钾，残留的氟化钾使液体可以导电。而这次莫瓦桑仔细将氟化氢蒸馏了又蒸馏，其中不再含氟化钾，所以不能导电。(我们现在知道，氟化氢属于共价化合物，它和 D. non-destructive inspection report; E. static grounding test records; F. design changes and material substitution file. (2) t 11 / 12 he piping system according to the design files have been installed; A. pipe, hangers, material, in the form of the installation location is correct, complete number, strength, welding quality; B. completed welding work, weld quality inspection; C. weld parts should be checked and it should not be hidden. (3) pressure test of temporary reinforcement measures for safe and reliable, such as: temporary support should be strong, can withstand the pressure of water. Temporary blind flange plus reset correctly, and should identify clear, while mark on the single line diagram, records should be complete, high and low discharge point set is complete and correct; (4) cannot participate in the testing of control valves, filters, flow orifice and flow meters should be removed, connected with the temporary spool; (5) approval of pressure test system and construction scheme and the pressure group is disclosure. 1.5.2 pressure test press design offers you the test pressure of the pressure test, pressure test media selected according to design specifications. (1) tests should be used when high point within the exhaust system of air, boosting ratings slowly, reach the test pressure after 10min, then down to pressure regulator 30 min, no pressure drop, no leakage, Visual deformation is qualified. When pressure testing in case of spill shall not be under pressure to repair defect elimination and try again until the qualified. (2) after the piping system passes the test, should slow buck, the test medium emission should be at the right place, try to pressure test water discharged into the nearby sewer pipes or rain. Pressure test after the purge the piping system if not to temporarily blind and short pipe, support should be removed, reset in a timely manner and fill pipe system pressure test records. 1.6 pipe blowing and wash 教学素材/卤族元素 离子化合物氟化钾不同，即使液态也不电离、不导电。)查明原因之后，莫瓦桑再次实验获得成功，审查委员会终于确认了他的发现。 为了表彰莫瓦桑(右图)在制备氟方面所做出的突出贡献，法国科学院发给他一万法郎的拉?卡泽奖金。莫瓦桑用这笔钱偿 还了实验的费用。四个月后，他被任命为巴黎药学院的毒物学 教授，同时还建造了一座不大的私人实验室供他进行科学研究。在这里，他继续改进氟的制法，用铜制的电解容器代替价格昂 贵的铂制容器，进行了规模较大的实验，每小时能电解出五升氟气。他进一步制备出许多新的氟化物，如氟代甲烷、氟代乙烷、异丁基氟等。其中四氟化碳的沸点是-15?C，很适合做制冷剂。这是最早的氟里昂。 他将研究成果写成了《氟及其化合物》一书，这是一本研究氟的制备及其氟化物性质的开山之作。1906年莫瓦桑获得了诺贝尔化学奖。关于获奖成就是这样写的:通过电解氟化钾的无水氟化氢溶液首次离析出单质氟，并对这一元素的性质及与其它元素的反应作了充分的研究。此外还发明了“莫瓦桑电炉”，并用它制备了很多新化合物。 “莫瓦桑电炉”使化学实验能达到2000?C，从而开辟了高温化学这一新的领域。不止这些，莫瓦桑在化学实验的很多领域都有独到的突破。 下面是莫瓦桑获得的诺贝尔奖章和有关成就证书。 诺贝尔奖令世人仰慕，却不能给莫瓦桑的生命以 更多的时间。1907年2月6日，莫瓦桑得了阑尾炎。 手术很成功，但他的心脏病却加剧了。他终于认识到 多年以来一直没有关心自己的身体健康。莫瓦桑不得 不承认:“氟夺走了我十年的生命”。2月30日，这位 在化学实验科学上闪烁着光芒的化学家永远地陨落 了。 这时，莫瓦桑还不到55岁。 D. non-destructive inspection report; E. static grounding test records; F. design changes and material substitution file. (2) t清华同方教育技术研究院 he piping system according to the design files have been installed; A. pipe, hangers, material, in the form of the installation location is correct, complete number, strength, welding quality; B. completed welding work, weld quality inspection; C. weld parts should be checked and it should not be hidden. (3) pressure test of temporary reinforcement measures for safe and reliable, such as: temporary support should be strong, can withstand the pressure of water. Temporary blind flange plus reset correctly, and should identify clear, while mark on the single line diagram, records should be complete, high and low discharge point set is complete and correct; (4) cannot participate in the testing of control valves, filters, flow orifice and flow meters should be removed, connected with the temporary spool; (5) approval of pressure test system and construction scheme and the pressure group is disclosure. 1.5.2 pressure test press design offers you the test pressure of the pressure test, pressure test media selected according to design specifications. (1) tests should be used when high point within the exhaust system of air, boosting ratings slowly, reach the test pressure after 10min, then down to pressure regulator 30 min, no pressure drop, no leakage, Visual deformation is qualified. When pressure testing in case of spill shall not be under pressure to repair defect elimination and try again until the qualified. (2) after the piping system passes the test, should slow buck, the test medium emission should be at the right place, try to pressure test water discharged into the nearby sewer pipes or rain. Pressure test after the purge the piping system if not to temporarily blind and short pipe, support should be removed, reset in a timely manner and fill pipe system pressure test records. 1.6 pipe blowing and wash