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Chapter 9 The Rare Gases
Helium (He) å¤ªé³ Neon (Ne) æ°ç Argon (Ar) ææ°ç
Krypton (Kr) 稳å®ç Xenon (Xe) éçç Radon (Rn) åå
ç
Electronic configurationï¼ns2np6 except He 1s2
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ä¸ãGeneral Properties:
1ï¼å®ä»¬é½æ¯ååååå(monatomic molecular)ï¼å¨é常æ¡ä»¶ä¸ï¼å®ä»¬é½æ¯æ°ä½ï¼ä¹ç§°ä¸ºæ°æ§æ°ä½ï¼noble or inert gasesï¼
2ï¼è¸åçãå¨æ°´ä¸ç溶解度以åçã沸ç¹é½å¾å°ï¼å¹¶ä¸éçåååºæ°çå¢å èéæ¸åé«ãæ°¦æ¯æææ°ä½ä¸æé¾æ¶²åçç©è´¨ãHeç沸ç¹ä¸º4.2Kï¼H2ç沸ç¹ä¸º20.4Kãæ°¦å·å´è³2.178Kï¼ååæ第äºç§æ¶²ä½ï¼åçæ ç²åº¦æµå¨ï¼ç§°ä¸ºè¶
æµä½ï¼superfluidityï¼ã
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äºãChemical Properties
å¨ç¨ææ°ä½åç°åä¸æ®µæ¶é´å
ï¼1900-1960å¹´ï¼ï¼æå®ä»¬ä½ä¸ºåå¦æ§è´¨ä¸ç»å¯¹æ°æ§çãç´å°1962å¹´ï¼Bartlettå°PtF6çè¸æ°ä¸çæ©å°çæ°æ··åï¼å¨å®¤æ¸©ä¸å¶å¾äºXePtF6çæ©é»è²åºä½ï¼æ¨ç¿»äºæç»äºè¿70å¹´ä¹ä¹
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1ï¼æ°çæ°åç©ï¼Fluorides of xenonï¼
(1) preparation
ï¼ç±Xeå¨ç¼ºF2æ
åµä¸å åååºï¼
è¾æå¶å¾ï¼å¨å¦ä¸æ¡ä»¶ä¸å å
¥XeåF2 (1:5)æ··åç©ï¼å åå°æ¶å便å¶å¾ã
ï¼Xe : F2 = 1:20ï¼
æ ï¼å¨å¸¸åä¸ï¼
Irradiating a xenon-fluorine mixture with ultra-violet light at ordinary temperature produces XeF2 (together with some XeF4)
为ä»ä¹Xeä¸F2æ··åå¦æ¤å®¹æååä½å
åå¤å¹´é´å´æ²¡æè½åæåºXeçååç©ï¼å½éæ¥æçXeçé太å°ï¼ç»å¯¹å¹²ç¥çç»ç仪å¨ä¸è½è·å¾ï¼å®éªææ¯è½åï¼æ´éè¦çæ¯ææ³ä¸ææ¡æ¡ã
(2) properties
aï¼æ°çæ°åç©é½ä¸æ°´çååºï¼
(i) XeF2å¨æ°´ä¸ç溶解æ¾åºåºæ¿æ§èå³ï¼å¨é
¸æ§æº¶æ¶²ä¸æ°´è§£å¾æ
¢ï¼ä½å¨ç¢±æ§æº¶æ¶²ä¸æ°´è§£å¾å¿«ï¼
2XeF2(s) + 2H2O(l) = 2Xe(g) + 4HF(g) + O2(g)
XeF2å¨ç¢±æ§æº¶æ¶²ä¸åçRedoxååºï¼
(ii) XeF4å¨æ°´ä¸æ¢åçæ§åååºï¼ååçæ°§åè¿åååºï¼
6XeF4 + 12H2O = 2XeO3 + 4Xe + 3O2 + 24HF
å解æï¼3XeF4 + 6H2O = 3Xe + 3O2 + 12HFï¼ä¸æ°´çæ°§åè¿åååºï¼
3XeF4 + 6H2O = 2XeO3 + Xe + 12HFï¼æ§åååºï¼
æ以ä¸è¿°ååºæ¹ç¨å¼åªæ¯XeF4çæ©å°åä¸æ§åååºä»¥åä¸æ°´çæ°§åè¿åçé
å¹³ç»æãå®é
ä¸è¿æ¯ä¸ä¸ªå¤éé
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(iii) XeF6 + H2O = XeOF4 + 2HF
XeOF4 + 2H2O = XeO3 + 4HF
bï¼æ°çæ°åç©é½æ¯å¼ºæ°§åå
XeF6 + 8NH3 = Xe + N2 + 6NH4F
å¯ä»¥ä½¿ HCl â Cl2ï¼Ce(III) â Ce(IV)ï¼NH3 â N2
XeF6åå¦æ§è´¨é常活泼ï¼çè³ä¸ç³è±ååºï¼
2XeF6 + SiO3 = 2XeOF4 + SiF4
XeF6å¨ç¢±æ§æ¡ä»¶ä¸ä¹è½åçæ§åååºï¼
4XeF6 + 18Ba(OH)2 = 3Ba2XeO6 + Xe + 12BaF2 + 18H2O
cï¼æ°çæ°åç©é½æ¯è¯å¥½çæ°åå
RbF + XeF6 = RbXeF7
XeF2 + SbF5 = [XeF][SbF6]
2ï¼æ°çæ°§åç©ï¼Oxides of xenonï¼
(1) preparation:
aï¼XeO3ç±XeF4åXeF6水解å¶å¾ã
bï¼XeO4ç±XeF6å¨Ba(OH)2ä¸æ§åå¶å¾çé«æ°é
¸é¡Ba2XeO6åä¸ç¡«é
¸ååºå¶å¾ï¼
Ba2XeO6 + 2H2SO4 = 2BaSO4 + XeO4 + 2H2O
(2) propertiesï¼
aï¼ç¨³å®æ§ï¼stabilizationï¼
æ è²æ å³XeO3(s)ä¸å«æXeO3ååãXeO3å¨æ°´ä¸ç¨³å®ï¼ä½å¨åºææ¶XeO3ä¼å
ççç¸ãå®å¨OHï¼ä»è´¨ä¸å½¢æ 离åï¼æ¤ç¦»ååçç¼æ
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ï¼
å æ¤å¯ä»¥å¾åºè¿æ ·çç»è®ºï¼å¯¹äºæ°çå«æ°§åç©ï¼å¨é
¸æ§åä¸æ§æº¶æ¶²ä¸Xe (VI) 稳å®ï¼å¨ç¢±æ§æº¶æ¶²ä¸Xe (VIII) 稳å®ã
XeO4æ¯ä¸ç§æ°ä½ï¼ç¼æ
¢å解æXeO3åO2ãå½XeO4åºææ¶,å³ä½¿å¨å®¤æ¸©ä¸é½åççç¸ã
bï¼æ°§åæ§ï¼oxidationï¼ï¼
é«æ°é
¸çæ¯æ强çæ°§ååä¹ä¸ãå®è½æMn2+ æ°§åæ ï¼ æ°§åæ
cï¼å¨ç¢±æ§æº¶æ¶²ä¸ï¼é«æ°é
¸çç主è¦å½¢å¼æ¯ ï¼å®è¢«æ°´ç¼æ
¢è¿åï¼ç¶èå¨é
¸
æ§æº¶æ¶²ä¸ï¼Reduction is almost instantaneousï¼
and the hydroxyl radical is involved as an intermediate.
ä¸ãThe Stereo Structures of Xenon Compounds
1ï¼ç¬¦åVSEPRç论(valence shell electron pair repulsion)
XeF2 AB2E3 sp3d ç´çº¿å
XeF4 AB4E2 sp3d2 å¹³é¢åæ¹
XeO3 AB3E sp3 ä¸è§é¥
XeO4 AB4 sp3 æ£åé¢ä½
XeOF4 AB5E sp3d2 åæ¹é¥å
XeO2F2 AB4E sp3d æªåé¢ä½
AB6 sp3d2 æ£å
«é¢ä½
2ï¼ç¹æ®æå
XeF6 The exact structure of the gaseous XeF6 molecular has not been determined, but it is known to be a slightly distored octahedron
(a) lone pair emerging through edge of the octahedron C2v symmetry
(b) lone pair emerging through face of the ctahedron C3v symmetry
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