Thermodynamics – Why Are Heat and Work Not State Functions of a System?

thermodynamics

Heat and work, unlike temperature, pressure, and volume, are not intrinsic properties of a system. They have meaning only as they describe the transfer of energy into or out of a system.

This is the extract from Halliday & Resnick.

My chem book writes:

Heat & work are the forms of energy in transit. They appear only when there occurs any change in the state of system and the surroundings. They don't exist before or after the change of the state.

So, heat energy is dependent on the path or the way the system changes, right? So, are they saying, for one path connecting two states, more heat energy can be liberated while for another path, less heat is released? How? For the same two states, how can there be a different amount of heat energy liberated? Is there any intuitive example to understand this?

Best Answer

Suppose you have a thermodynamic system in a state $A$. In this state it has a certain amount of internal energy, $U_A$, because internal energy is a state variable. You can determine the internal energy by knowing only the state.

Now suppose the system undergoes some process - you don't know (or care) what - that leaves it in state $B$. Again, you can determine its internal energy by knowing only the state, and that energy will be $U_B$.

Clearly, to get from state $A$ to state $B$, the system had to gain a net amount of energy $\Delta U = U_B - U_A$. That fact is true no matter what the process was. Hopefully that's all clear so far.

But hopefully it's also clear that how that energy was transferred to the system depends on the process. There are many - or, well, at least several - different ways by which energy can be transferred in or out of a system, such as electromagnetic radiation, sound, gravity, or physically pushing on something. Different processes will use different methods, or different combinations of methods (because it's possible for a process to transfer some energy by EM radiation and some by sound, for example).

We've broadly grouped these methods of transferring energy into two categories, heat and work. Generally, the methods which involve the system pushing its environment around (or vice-versa) count as work, while others count as heat. (This should make sense because you need force and a change in position to have work.) So depending on the process by which the system gets from $A$ to $B$, the amount of energy transferred by heat methods and the amount of energy transferred by work methods can vary. Any basic thermodynamics textbook will give several examples to show how the distribution of energy transfer between heat and work depends on the process.

Of course, the total amount of energy transferred through all methods is always the same: it always has to be $\Delta U$. That's just energy conservation.