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五,實(shí)驗(yàn)數(shù)據(jù)處理,,,,,,

(1)晶體碘的特征溫度θ,,,,,,

碘升華氣固平衡時(shí)飽和蒸汽壓與溫度的數(shù)據(jù)表,,,,,,

,,,,,,,

T/K,298.25,303.35,308.35,313.25,318.65,323.25

透光率I/I0,0.965,0.951,0.925,0.898,0.870,0.831

蒸汽壓P/Pa,52.5573,75.3834,118.9038,166.6921,219.4918,295.9894

ln(PT5/2(1-e-θv/T))與T-1的數(shù)據(jù)表,,,,,,

,,,,,,,

T/K,298.25,303.35,308.35,313.25,318.65,323.25

T-1,0.00335,0.00330,0.00324,0.00319,0.00314,0.00309

蒸汽壓P/Pa,52.5573,75.3834,118.9038,166.6921,219.4918,295.9894

PT5/2(1-e-θv/T),51876270,76874889,125120927,180780814,245934600,340818091

ln(PT5/2(1-e-θv/T)),17.7644,18.1577,18.6448,19.0128,19.3206,19.6469

,,,,,,,

,,,,,,,

"由公式ln(PT5/2(1-e-θv/T))=ln((2mπk/h2)3/2kθ6/σθr)-(D0-We)/kT得ln(PT5/2(1-e-θv/T))與1/T為線性相關(guān),其圖像斜率為-(D0-We)/k,截距為ln((2mπk/h2)3/2k/σθr)+6lnθ,而又由實(shí)驗(yàn)數(shù)據(jù)的,線性方程截距為42.220,即ln((2mπk/h2)3/2k/σθr)+6lnθ=18.395+6lnθ=42.220,解得碘的特征溫度θ=58.98K",,,,,,

,,,,,,,

,,,,,,,

,,,,,,,

,,,,,,,

(2)晶體碘的標(biāo)準(zhǔn)熵SΘ(T)與升華焓ΔH,,,,,,

"a.由公式S(T)=6Nsk(1+ln(T/θ))得,各溫度下晶體碘的標(biāo)準(zhǔn)熵,而氣體碘的的摩爾標(biāo)準(zhǔn)熵隨溫度變化不大,實(shí)驗(yàn)過(guò)程中可看作常數(shù),其值為Sm,g(298K)=260.69J·K-1·mol-1,故碘在升華過(guò)程中ΔST=Sg(T)-Ss(T)",,,,,,

,,,,,,,

"b.在298.15K時(shí),碘升華的ΔH(298.15K)=62.438kJ·mol-1,而碘升華過(guò)程中ΔCp,m=Cp,m(s)-Cp,m(g)=-17.54J·K-1·mol-1,而根據(jù)基?;舴蚬溅(T)=ΔH(298.15K)+ΔCp,m(T-298.15)/1000,據(jù)此可計(jì)算出實(shí)驗(yàn)的相對(duì)誤差。",,,,,,

,,,,,,,

T/K,298.25,303.35,308.35,313.25,318.65,323.25

Ss/J·K-1,130.7323,131.578,132.3936,133.18,134.0326,134.7476

ΔST,129.9577,129.112,128.2964,127.51,126.6574,125.9424

Kp,52.55730,75.38340,118.90380,166.69210,219.49180,295.98940

ΔHT=TΔST-RTlnKp(實(shí)驗(yàn)值),57.48,57.30,56.83,56.60,56.58,56.36

ΔH(T)(理論值),62.44,62.35,62.26,62.17,62.08,62.00

相對(duì)誤差,7.93%,8.09%,8.73%,8.96%,8.86%,9.09%

"另:利用克-克方程求解ΔH(lnp=-ΔH/RT+C,直線斜率為-ΔH/R,)",,,,,,

T/K,298.25,303.35,308.35,313.25,318.65,323.25

1/T,0.00335,0.00330,0.00324,0.00319,0.00314,0.00309

蒸汽壓P/Pa,52.5573,75.3834,118.9038,166.6921,219.4918,295.9894

lnp,3.9619,4.3226,4.7783,5.1161,5.3913,5.6903

,,,,,,,

,,,,,,,

,,,,,,,

,,,,,,,

,,,,,,,

"由圖像得,直線斜率為-ΔH/R=-6693.6,代入解得ΔH=55.651kJ·mol-1.與298.15時(shí)的

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