结构推理
298 K时,下述电池的电动势E$= 0.268V:Pt,H2(g)|HCl(aq)|Hg2Cl2(s)|Hg(l)
(1) 写出电极反应和电池反应;
(2) 计算Hg2Cl2(s)的DfGm$, 已知DfGm$[Cl – (aq)] = - 131.26 kJ·mol-1;
(3) 计算Hg2Cl2(s)的Ksp,已知DfGm$[Hg22+(aq)] = 152.0 kJ·mol-1。
【正确答案】⑴ (-) H2(g)→2H++2e –
(+) Hg2Cl2(s)+2e -→2Hg(l)+2Cl –(aq)
总反应:H2(g)+Hg2Cl2(s)→2Hg(l)+2H+(aq)+2Cl –(aq)
⑵ DrGm$= - zE$F= - 51.7 kJ·mol-1
DrGm$=2DfGm$(Cl -) –DfGm$(Hg2Cl2)= - 51.7 kJ·mol-1
DrGm$(Hg2Cl2(s))= - 210.82 kJ·mol-1
⑶ Hg2Cl2(s)→Hg22+(aq)+2Cl –(aq)
DrGm$=[152.0+2(– 131.26) – (– 210.82)] kJ·mol-1=100.3 kJ·mol-1
Ksp$=exp(–DrGm$/RT)=2.6×10-18
【答案解析】