P329 1
实验测得Fe-C熔体中碳的活度aC(以纯石墨为标准态)与温度T及浓度xC的关系如下
x11803400xClgaC?lg(C)??0.87?(0.72?)()
1?2xCTT1?xC(1)求lg?C与温度T及浓度xC的关系式;
??(2)求lg?C与温度T的关系式及1600℃时的?C;
(3)求反应C(石墨)=[C]1%的
T
?solG?与温度的二项式关系表达式;
(4)当1600℃铁液含碳量为w[C]=0.24%时,碳的活度(以w[C]=1%溶液为标准态)是多少? 解:
(1)以纯石墨为标准态aC??C?xC,则
x11803400xClg?C?lgaC?lgxC?lg(C)?lgxC??0.87?(0.72?)()1?2xCTT1?xC111803400xC?lg()??0.87?(0.72?)()1?2xCTT1?xC (2)由
aR,CaH,C??C?xifH,C?xi????C,得出?C??C?fH,C,0?xC?1,该式在全浓度范围内成立,没有限制条件。
?在极稀溶液xC?0且满足Henry定律,fH,C?1,则?C??C,
111803400xC?lg?C?lg?C?lg()xC?0??0.87?(0.72?)()xC?01?2xCTT1?xC1180??0.87T当T=1600℃=1873K时,lg?C?
?
1180??0.87??0.24,?C?0.575 1873
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C(石墨)??C?1% ?%,c(3)?R,c ???solG???%,??cR,c??
C在铁液中的化学势一定,即?R,C??%,C???%,C??%,C?RTlna%,c;?R,C??R,C?RTlnaR,c,
?????G?????RTln?R?RTlna???RTlnasol%,CR,C,CR,C%,C%,CaR,Ca%,C?2.303RTlgaR,Ca%,C
在0?xC?1时,
aR,Ca%,C???xC??C
?当[%C]?1时,xC?xC?[%C]?MFe?0.045[%C](MFe?MC)?100MC?solG??2.303RTlgaR,Ca%,C??2.303RTlg(0.045?C)1180?2.303?8.314?T?lg0.045?2.303?8.314?T?(?0.87)
T?T?2.303?8.314?(lg0.045?0.87)?2.303?8.314?1180?22593.628?42.445T
(4)xC?[%C]MFe???0.011;aR,C题目以给出,xC与?C已求出。
[%C](MFe?MC)?100MClga%,C?lgaR,C?lga%,CaR,C?lgaR,C?lg(1)??xC??C
x11803400xC1?lg(C)??0.87?(0.72?)()?lg(??)1?2xCTT1?xCxC??C0.011118034000.0111?lg()??0.87?(0.72?)()?lg()1?2?0.011187318731?0.0110.0448?0.575??0.5739a%,C?0.267
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?9Fe-Si溶液与纯固态SiO2平衡,平衡氧分压P。试求1600℃时[Si]在以下不同标准态O2?8.26?10Pa时的活度:
(1)纯固态硅;(2)纯液态硅;(3)亨利标准态;(4)w[Si]=1% 溶液标准态。 已知 Si(s)+O2(g)=SiO2(s) ?fG???902070?173.64T, J/mol,Tf*,Si?1410℃,
???fusHSi?50626 /Jmol,?Si?0.00116,MFe=55.85kg/mol, MSi=28.09kg/mol。
解:(1)以纯固态硅为标准态
Si(s)+O2(g)=SiO2(s),?rG???fG?
aSiO2101325?rG??RTln()??8.314?1873?In(),J/molpO2aSi?8.26?10?9aSi??
p??fG???902070?173.64?1873??576842.28,J/molaSi?0.001
(2)以纯液态硅标准态 由
?*??fusG???fusHSi?Tf,Si??fusSSi?0得到:
??fusSSi?30.08J/mol?K
???Si(s)?Si(l)(1)?rG1??fusHSi??fusSSi?T?50626?30.08T,J/mol
?Si(s)?O2(g)?SiO2(s)(2)?rG2??902070?173.64T,J/mol
?Si(l)?O(g)?SiO(s)?G??952696?203.72T,J/mol 22r(2)-(1)得:
T=1873K时,
p??rG??RTln()aSi,lpO2???8.314?1873?In(101325)aSi?8.26?10?9
??952696?203.72?1873??571126.9265,J/mol得出:aSi,l?0.00145
(3)亨利标准态1600℃时,Si以液态存在
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