1. The Clausius Inequality Expressions of inequality/equality relating to heat flow at a fixed temperature. The expression is required for the derivation of an equation for entropy – which is our next main topic. Derived from a “thought experiment” using Carnot engines acting in a series.

2. Volume Pressure a b d T1T1 Q1Q1 Carnot Cycle Q2Q2 T2T2 c Q=0

3. Heat Flows in a Carnot Cycle Hot Reservoir, T 1 Cold Reservoir, T 2 C W Q1Q1 Q2Q2

4. Such that One could also consider the small amount of reversible heat flow  Q rev that flows at a temperature T at each point in the cycle. The net heat flow is equal to the sum of the differential flows: For a Carnot cycle, some of the heat into the cycle is converted to work so that Q 1 > Q 2. We also know that From the definition of an integral, we find for the entire cycle that But is this generally true for any cycle?

5. Derivation of the Clausius Inequality Principal reservoir C1C1 T1T1 Auxiliary reservoirs W1W1 Q1Q1 Q1Q1 Working substance in a cycle 1 2

6. Derivation of the Clausius Inequality Principal reservoir C1C1 T1T1 W1W1 Q1Q1 Q1Q1 Working substance in a cycle 1 2 W2W2 Q2Q2 Q2Q2 C2C2 T2T2 3 Add N Carnot engines in total Composite System

7. Analysis of Composite Device The total heat supplied by the reservoir to the composite device in a cycle with N engines is: In an entire cycle,  U for the working substance and the composite device is 0. Then the First Law says:  U = 0 = W + Q An important conclusion is that Q = -W. The total work done by the composite device in a cycle is

8. Derivation of the Clausius Inequality Principal reservoir Composite system i N i N Q= - W Q = -W > 0 Violates Kelvin statement of the 2nd Law! What can be allowed?

9. Derivation of the Clausius Inequality Principal reservoir Composite system Q W Q= - W < 0 Allowed:

10. Derivation of the Clausius Inequality Principal reservoir Composite system Q = - W = 0 Q W Allowed: (Sum of +ve and –ve  Q and  W)

11. Results Allowed by Second Law Q < 0 or Q = 0, thus But, so we can divide by In the limit of small  Q i, we can integrate over the entire cycle: where T o is the temp. of the reservoir (external heat source) and the circle represents integration over the entire cycle. Clausius Inequality

12. Reversible Cycles If the cycle at the centre of the composite device is reversible, then it can be run in reverse. The opposite result is then obtained. In the composite device, work is done ON the system, and heat is given OFF to the reservoir. Q W Allowed: 0  Q = - W

13. Reversible Cycles Thus, there are restrictions on Q when the cycle is operated in reverse. But the cycle can still also be operated in the forward direction such that: Only one solution satisfies both requirements for forward and reverse cycles: Integrating: In a reversible process, the temperature of the system and reservoir are equal: T. Clausius Equality