Chapter 2 Second law of thermodynamics.pptVIP

Chapter 2 Second law of thermodynamicsThe problem: direction and limitation of a reaction.Limitation: 反应进行的程度，平衡时 的情况，(K,转化率，平衡时各物质的浓度)。Requirements: P174 §2.1 The common characteristics of spontaneous change ***Spontaneous process: The process occurs naturally without help of external force. For example: ①向真空膨胀 Q=W=ΔU=0,逆过程:W0→Q,但 不能恢复原状,不可逆。 ②热由高→低 逆过程需制冷作功 ③水由高→低 逆过程需抽水做功 ④Zn(s)+CuSO4=Cu(s)+ZnSO4，电解 The properties of spontaneous process: ① It has a certain direction. ② athwart process can not take place spontaneously. ③ Irreversible process. §2.2 The second law of thermodynamics 一、Statements in Chinese 1.不可能把热从低温物体传到高温物体，而不引起其他变化。--Clausius— 2.不可能从单一热源取出热使之完全变为功，而不引起其他变化。--Kelvin— 3. The second kind of perpetual motion machine can not be constructed. The second kind of perpetual motion machine: a device that operates in cycles and that converts heat into work without producing some other change in the surroundings. 4. All spontaneous processes are irreversible. §2.3 Carnot theoremCarnot theorem：所有工作在同温热源和同温冷源间的热机， 其效率都不可能超过可逆机的效率。 证明： 高温热源T2 I—任意机，R—卡诺机， 让 I和R作功的绝对值相等。ηI =W/Q1’ ηR =W/Q1  假定：ηI ηR 则：W/Q1’ W/Q1 → Q1Q1’ 净结果：低温热源给出热：Q1-W- (Q1’-W)= Q1-Q1’ 高温热源得到热：Q1-Q1’0 热从低温物体传到高温物体，而没引起其他变化。  违反了Clausius的说法，所以，假定是不成立的。  Process 1: reversible isothermal expansion at T1Process 2: reversible adiabatic expansion.Process 3: reversible isothermal compression at T2 Process 4: reversible adiabatic compression 对任意可逆循环：Σ ( QQ i / T ) R = 0  在此基础上定义熵： Σ ( δ Q i / T ) R = 0 量纲: J /Ｋ∵可逆热具有定值，只与始末态有关，与中间经过的途径无关。