The 1st Law of Thermodynamics Notes
The 1st Law of Thermodynamics Notes
The 1st Law of Thermodynamics Notes
McMullen
For a gas, the change in its internal energy, ΔU, is directly proportional to the change in its temperature measured
in Kelvin. This means that ΔU only reflects a change in the kinetic energy of the gas molecules. The potential
energy cannot change except when there is a phase change: liquid to solid or liquid to vapor.
The current statement of this law places an emphasis on the internal energy of the gas. The law states that the
internal energy of a gas can be increased in one of two ways: by the addition of heat or by work being done on the
system by an external agent. Remember that during compressions, as the volume of the gas decreases its
temperature (except in isothermal processes) increases - representing a subsequent increase in the internal energy
of the system. Thus work done on the system by an external agent as the piston is pressed down causing the
volume to decrease is negative. Conversely, if the gas expands the piston, work is positive since the internal energy
of the gas decreases as the temperature decreases.
combined
gas law
PV
diagrams
W = - ∫P dV
expanding
+
W = nRT [ln(V2÷V1)] W = PΔV 0 W = ΔU
-compressed
Q
- temp dec Q = -W Q = nCPΔT Q = nCVΔT 0
+ temp inc
ΔU
- temp dec 0 ΔU = nCVΔT ΔU = nCVΔT ΔU = nCVΔT
+ temp inc
ΔU = Q + W ΔU = Q + W ΔU = Q + W ΔU = Q + W
ΔU = 0 nCVΔT = nCPΔT - ΔU = Q ΔU = W
1st Law Q = -W PΔV
since no work is done, the since no heat can be added or
as the gas expands, heat since PΔV = nRΔT internal energy of the gas removed, any work done is at the
must be added nCVΔT = nCPΔT - nRΔT increases with the addition of expense of the internal energy of the
CP = CV + nR heat gas
ΔS ΔS = nR [ln(V2÷V1)] ΔS = nCP [ln(T2÷T1)] ΔS = nCV [ln(T2÷T1)] 0
State Variables
When examining PV graphs, state variables are ones that always maintain a constant value at a given position on a PV graph. These
variables are:
P, V, T, U, and S
Recall from the ideal gas law that PV = nRT. If n, the amount of gas, does not change, then PV ∝ T. We can use this relationship to
determine how the temperatures at different positions on a PV-diagram would compare. For example, on the PV-diagram shown below,
we can determine that the temperature at point A is lower than the temperature at point B by comparing their "PV" products. Since the
volume at point A is smaller than the volume at point B, A's "PV" product would be less than the "PV" product for point B. Note that the
same type of argument could tell us that the temperature at point C is also lower than that at point B since C's "PV" product would be
less than B's because of C's lower pressure value. We cannot compare the temperatures at point A and point C without having specific
scales on the x- and y-axes.
Since the internal energy of a gas is directly proportional to its temperature, we can conclude that the internal energy
of the gas at point B is greater than at either points A or C.
When the gas expands isobarically along path AB, the internal energy of the gas should decrease. Since the
temperature at point B is higher, we know that heat must have been added to the system. During the isochroic
process BC, no work was done on the gas since its volume remained unchanged. However, we know that heat must
have been released from the system since the temperature at point C is less than that at point B. The final compression along path CA
returns the gas to its starting position, that is, to its original state values of pressure, volume, temperature, internal energy, and entropy.
As a general rule of thumb, you can compare the entropies at two positions by knowing whether heat has been added (S increases) or
heat has been removed (S decreases). In our diagram, entropy increased along path AB and decreased along path BC.
Note that heat (Q) and work (W) are NOT state variables. Heat is the energy transferred between states - from a warm body to a cooler
body as a result of their temperature differential. Work is done whenever the energy content of a system changes.
For the closed path, ABCA, the first law reduces to Q = - W since ΔU = 0. Don't forget that changes in all state variables (ΔP, ΔV, ΔT,
and ΔS) are also equal to 0 whenever you make a complete cycle around a PV diagram.