Essential

Thermo 322 Vocab Sheet

System: any part of the universe we choose to study; it may have real (eg, a capped test tube) or
imaginary boundaries and these boundaries may be rigid or mobile (as in a piston). Careful
choice of your system can make the problem much easier (eg, choose a closed system if poss.).

State: the condition in which the system exists (eg, temp, pressure, number of moles of
substance); in thermodynamics, this will often refer to the state at which equilibrium exists. a
condition which is time-invariant and reproducible.

Surroundings: once you choose the system and its boundaries, everything else becomes the
surroundings. Realistically, this may be the part of the universe that is affected by changes in
the system.

Closed system: this system does not exchange mass with its surroundings, but may exchange
work and heat. Thus the energy, P, T, V may change but the mass of the system remains fixed.

Open system: this system does exchange mass with its surroundings. Here, the boundaries may
be defined as a specific volume in space through which mass may enter and leave, or an actual
container, say a length of pipe with reactants flowing in and products flowing out.

Isothermal system: a process which occurs at constant temperature (T1 = T2) and can apply to
both open and closed systems. To maintain an isothermal state, it is usually necessary to
exchange heat with the surroundings.

Adiabatic system: a process occurs in either an open or closed system without exchanging heat
with its surroundings (Q = 0). Commonly also termed perfectly insulated.

Isolated system: a system that exchanges neither heat nor mass nor work with its
surroundings; eg, a chemical reaction occurring in an insulated vessel of constant volume.

State variable: the terms state variable, state property, property are used interchangeably and
refer to a variable whose value depends on the state in which the system exists. Between two
states, the change in a state variable is always the same, regardless of the path taken. Temp,
pressure, volume & internal energy are all state variables.

Path variable: properties whose value depends on the path travelled by the system. This only
has meaning when applied to a process in which the path taken is specified; key path variables
are work (W) and heat (Q).

Extensive property: the value depends on the size of the system and are additive. For example,
volume: if you double the number of particles, keeping T and P constant, the volume of an ideal
gas will double; if a system has multiple parts, the volume of each part can be added to
determine the total system volume.

Intensive property: these properties do not depend on the size of the system, for instance, T, P,
specific volume (=V/n), density (=m/V). When the system is homogeneous, extensive variables
will often be rendered intensive by dividing by the size of the system (eg, number of moles);
this is indicated by a bar over the variable.

Work (W): work can the energy used to move an object over a specified distance (W = F*d =
mad), PV work used to maintain or change the volume of a system [W = (PV)], but also shaft
(mechanical) or electrical work. Our convention is that work done by a system on its
surroundings will decrease the energy of the system, while work done by the surroundings on
the system will increase the energy of the system.

Heat (Q): heat is transferred when two bodies of different temperature are in constant (see 0
law of thermo). Common calculations: Q = m*cp*T or Q/t = h*A*T (ChE 353).

Reversible/ Irreversible processes:

From: Kyle, Chemical & Process Thermodynamics, Prentice Hall