第一章热力学第一定律补充.pptxVIP

总结与习题热力学基础：概念以及基本定律体系与环境（封闭，敞开，孤立）过程与途径（恒压，恒温，恒容，绝热，循环）状态与状态函数（关系）热和功（含义与计算）热力学第一定律（表述，数学式，计算，应用） 例题 1系 统QW△U电热丝（T 恒定）水电热丝 + 水电热丝 + 水+电源等－+0R+0+0++000-10 kJ例题 2某循环过程 Q = 5 kJ, 则 ?U + 2W + 3 ?(pV) = __________. ∵这是个循环过程 ∴ △U = 0 ?(pV) =0又∵△U = W + Q = 0 ∴ W =－ Q =－ 5 kJ定压下再由 U = f ( T、V ) 0= R对理想气体Cp－CV = nR对凝聚态物质证明：压缩速度快Q = 0T1 = 298.15Kp1 =101.3kPaV1T2 = 352.15Kp2 = 192.5 kPaV2 V3 W = ?U例 某压缩机气缸吸入101.325 kPa, 25℃的空气, 快速压缩后压力提高至192.5 kPa, 相应使温度上升到79℃. 已知该温度范围内空气的CV,m近似为25.29J?mol－1 ? K－1, 试求1mol 空气在该压缩过程的W、 Q 及系统的 ?U.设快速压缩为一绝热过程。?U = nCV,m(T2－T1) = 1 ? 25.29(352.15－298.15)J = 1366J(空气视为理想气体)W = ?U = 1366J因是非恒容过程, Q不是恒容热, 故Q ? ?U, 也不能用CV,m直接求非恒容过程的热. Q= nCV,m(T2－T1) = 1366 J 例题：求下列过程的Q、 W、 ?U 、和?H真 空1molH2O (g)101.325kPa101.325kPa1mol H2O(l)100℃100℃?vapHm = 40.67 kJ mol－11、恒压蒸发2、向真空蒸发因是理想气体的恒温过程， ?U = 0、?H = 0。2、向真空蒸发?H = 40.67 kJ?U = 37.61 kJW = 0Qp = ?H = 40.67 kJ 1、恒压蒸发H = n ?vapHm = 40.67 kJ Qp = ?H = 40.67 kJW = －p (V2 － V1)≈－pV2 ≈nRT = － 8.314×373.2J = － 3.06kJ?U = Qp + W = 37.61 kJ或 ?U = ?H － ? ( pV ) =37.61 kJQ = ?U =37.61 kJ 例题 在一绝热刚性容器中发生下列反应V = 1dm3H2 (g)+ Cl2 (g) = 2 HCl (g)?fHm?(HCl, g ) = - 92.0 kJ mol-1 T1=298Kp1= 2 atm = 202.65 kPa T2=1193Kp2= 8 atm = 1617.30 kPa求：　Q、W、ΔU、ΔH解： Q = 0 W = 0 ΔU = 0 ΔH = Q = 0n = pV/RT = 0.0817 molΔH = n ?fHm? = - 7.52 kJ mol-1ΔH = ΔU+Δ( pV ) = VΔ p=· ······ = 607J？＞0H2 + Cl2 = 2 HCl理想气体n = 1 molCV, m =2.5R　γ = 1.4T0 = 298.15K p0 = 101325PaT2 = ？ p2= 303975Pa2、绝热可逆p0V0γ = p2V2 γ V2 = ( p0 / p2 ) 1/γV0 V0 = 24.46dm31、恒温可逆T1 = 298.15K p1= 303975Pa1、恒温可逆压缩W = nRT ln ( p1 / p0 ) = 8.314×298.15J× ln3 = 2.73 kJW = ?U = nCV, m (T2 – T0) = 2.5 ×8.314 ×(408.1-298.15)J = 2.29 kJ例理想气体n = 1 molCV, m =2.5R　γ = 1.4T0 = 298.15K p0 = 101325PaT2 = ？ p2= 303975Pa2、绝热可逆V0 = 24.46dm33、绝热不可逆1、恒温可逆T3 = ？ p3= 303975PaT1 = 298.15K p1= 303975Pa?U = WnCV, m (T3 – T0) = - p环 （ V3 – V0）= - p3 V3 + p3 V02.5nR (T3- T0) = -nR T3+ nR T0 ( p3 / p0 )= ······· = 468KW = ?U = nCV, m (T3 – T0) = ······· = 3.53 kJ例pV1V理想气体n = 1