Laws of thermodynamics Zeroth law of thermodynamics: If two systems are in thermal equilibrium with a third system, they must

be in thermal equilibrium with each other. First law of thermodynamics: It is usually formulated by stating that the change in the internal energy of a closed system is equal to the amount of heat supplied to the system, minus the amount of work performed by the system on its surroundings. In other words, it states that during an interaction between a closed system and its surroundings, the amount of energy gained by the system must be equal to the amount of energy lost by the surroundings. Second law of thermodynamics asserts that processes occur in a specific direction. It is derived from two classical statements: Clausius statement and Kelvin-Planck statement. Clausius statement: No process is possible whose sole result is the transfer of heat from a body of lower temperature to a body of higher temperature. Heat cannot spontaneously flow from cold regions to hot regions without external work being performed on the system, which is evident from ordinary experience of refrigeration, for example. In a refrigerator, heat flows from cold to hot, but only when forced by an external agent, the refrigeration system Kelvin-Planck statement: no heat engine can have a thermal efficiency of 100% i.e. all heat supplied cannot be converted to work. Even under ideal conditions, heat engine must reject heat to low temperature sink. Recall: Internal energy: sum of microscopic forms of energy (latent, Sensible, chemical, nuclear ) Enthalpy; h=u + PV Enthalpy is a measure of the total energy of a thermodynamic system. It includes the internal energy and the flow energy that is the amount of energy needed to push fluid into and out of the system. Flow work/ energy amount of energy required to make room for it by displacing its environment and establishing its volume and pressure. Equilibrium means a state of balance. Thermal equilibrium: all temperatures of interest are constant (unchanging in time and uniform in space). Mechanical equilibrium: constant pressure Chemical equilibrium: no change in chemical composition Phase equilibrium: constant mass in each phase

A thermodynamic system is in thermodynamic equilibrium when it is in thermal equilibrium, mechanical equilibrium, radiative equilibrium, and chemical equilibrium i.e. there are no net flows of matter or of energy, no phase changes, and no unbalanced potentials (or driving forces), within the system. Third law??