Chemistry · Ch 7 — Thermodynamics
Mathematical Statement of the First Law
Mathematical Statement of the First Law
Starting from the general first-law statement (7.7), four special cases -- each corresponding to one of the process types from Section 7.2.3 -- simplify the equation considerably.
Case 1: Cyclic process (isothermal expansion of an ideal gas around a full cycle). Since the system returns exactly to its starting state, ; substituting into (7.7) gives -- during a cyclic process, the heat absorbed by the system exactly equals the work done BY the system.
Case 2: Isochoric process (, no volume change, hence no expansion work possible). Starting from and setting gives simply -- at constant volume, all the heat supplied to the system goes directly into raising its internal energy, none of it diverted into P-V work.
Case 3: Adiabatic process (, no heat exchange at all). Substituting into (7.7): -- the fall in a system's internal energy during an adiabatic process is exactly equal to the work it does on its surroundings (there being no heat available to replace the lost energy).
Case 4: Isobaric process (constant pressure). Here -- part of the heat absorbed by the system is spent doing P-V expansion work against the constant external pressure, and the rest is added to the system's internal energy.
Worked example (Problem 7.1). A gas in a frictionless piston-cylinder expands against a constant external pressure of 1 atm, from an initial volume of 5 L to a final volume of 10 L, absorbing 400 J of heat from its surroundings in the process. Since heat is given to the system ( J) and work is done by the system as it expands (using the isobaric-case formula): …
Worked out. A gas in a frictionless piston-cylinder expands against a constant external pressure of 1 atm from L to L, absorbing J. . Using J: J. …