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zhulty鐵桿木蟲 (職業(yè)作家)
竹林聽雨
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[求助]
qiuzhu
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| This difference in the melting points may be explained by the molecular structure of the cations and the bulkiness of the anions. Bromide anions exhibit a higher negative charge density than methylsulfonate anions which had a delocalized electron in the conjugated π-electron orbital and a bulkier structure. Therefore, the interaction between cationic ammonium and bromide anions is very strong and the bromide anion would locate near the cation. With unsymmetrical quaternary ammonium bromides, the location of the small bromide anion is fixed, that is, it is at the nearest position. With symmetrical quaternary ammonium bromides, the location of the bromide anion is flexible, and the melting points of symmetrical ammonium bromides become lower than those of unsymmetrical ammonium bromides. |

鐵桿木蟲 (職業(yè)作家)
竹林聽雨

木蟲 (正式寫手)

木蟲 (正式寫手)
| 二者熔點(diǎn)的不同或許可由陽(yáng)離子的分子結(jié)構(gòu)和陰離子的體積龐大來(lái)解釋。由于甲基磺酸根陰離子有一個(gè)非定域電子與π電子成共軛軌道,并且體積較大,故溴陰離子比磺酸根陰離子有更高的負(fù)電荷密度。因此,銨陽(yáng)離子和溴陰離子之間的相互作用更加強(qiáng)烈即溴陰離子將靠近銨陽(yáng)離子。由于銨離子的不對(duì)稱四面體結(jié)構(gòu),體積小的溴離子的結(jié)合位置就被固定,也就是說(shuō)固定在離銨離子最近的位置。由于對(duì)稱的四面體溴化銨結(jié)構(gòu),溴陰離子的結(jié)構(gòu)位置就變得靈活,從而導(dǎo)致結(jié)構(gòu)對(duì)稱的溴化銨的熔點(diǎn)比非對(duì)稱結(jié)構(gòu)的溴化銨的熔點(diǎn)低。 |

| 熔點(diǎn)的不同或許可經(jīng)陽(yáng)離子的分子結(jié)構(gòu)以及陰離子的松厚度來(lái)解釋。溴陰離子的負(fù)電荷密度較甲基磺酸基陰離子為高,因后者基團(tuán)內(nèi)形成的π-電子共軛軌道中只有一個(gè)非定域電子而且集團(tuán)體積較為龐大。因此,胺陽(yáng)離子與溴陰離子之間的相互作用力非常強(qiáng),并且溴陰離子可更為靠近陽(yáng)離子。對(duì)于非對(duì)稱結(jié)構(gòu)的溴化季銨鹽,溴陰離子的位置在結(jié)構(gòu)中是固定的,也就是說(shuō)在最靠近銨陽(yáng)離子的位置。而對(duì)于對(duì)稱結(jié)構(gòu)的溴化季銨鹽,溴陰離子的位置是靈活可變的,因此就熔點(diǎn)而言,結(jié)構(gòu)對(duì)稱的溴化季銨鹽的熔點(diǎn)要低于非對(duì)稱結(jié)構(gòu)的溴化季銨鹽。 |
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