2-First Law WorkHeat
2-First Law WorkHeat
2-First Law WorkHeat
Must focus upon infinitessimal changes in state and energy, and be Work can now be written in terms of pressure and change in volume:
able to connect the contributions of small changes in heat and work to dw ' &pex dV
the total energy
If we need to know the total work done expanding the volume of a
Work done on a system: dw system, we can integrate the above expression over the initial and final
Energy supplied as heat: dq volumes V f
m
w ' & pex dV
dU ' dq % dw Vi
w = 0
m
w ' &pex dV ' &pex (Vf & Vi ) p dp at all times during the expansion. Therefore,
Vf Vf Vf
Vi
m m m
w ' & pex dV ' & (p & dp) dV ' & p dV
If )V = Vf - Vi, then the work can be written
Vi Vi Vi
w ' &pex )V
The dpdV part disappears, since the integral of the product of two
infintessimal quantities gives another infinitessimal quantity. Thus,
The integral above is interpreted as area, as Vf
we watch work done by a gas expanding
m
against a constant pressure dw ' &pex d V ' &p dV w ' & p dV
Vi
The magnitude of work, *w*, is equal to the This is work of reversible expansion. The integral on the right can be
area beneath the line with p = pex, between evaluated with knowledge of how pressure of the defined gas depends
final and initial volumes: p, V graphs to on the volume (i.e., if we know the equation of state of the gas, p can be
calculate expansion are indicator diagrams expressed in terms of V)!
# When Vf > Vi, gas expands, and work done to expand the gas dU ' dq
causes the system to lose internal energy, w < 0
# Constant supply of energy at constant T replenishes internal energy Write dU = dqv, which implies infinitessimal change at constant volume.
# More work is done for a given change in volume at higher Thus for a measurable finite change:
temperature )U ' qV
# Pressure of confined gas needs higher opposing pressure for
reversibility - so, pressure can change but )T = 0 (continued) q > 0 (heat supplied to system) q < 0 (heat lost from system)
Heat Capacity Molar Heat Capacity
Increasing temperature increases the internal energy of a system Heat capacity is an extensive property: for instance, we know for
instance that 100 g of water has 100x the heat capacity of 1 g of water
The exact increase depends upon the heating conditions
So, we can also have an intensive property, the molar heat capacity at
Heat cannot be detected or measured directly. (There is no heat constant volume, which is a measure of heat capacity at constant
meter.) One way to determine the magnitude of a heat transfer is to volume per mole of material: CV,m
measure the work needed to bring about the same change in the
thermodynamic state of the system as was produced by heat transfer. s
There is also the specific heat capacity, CV,m , which gives us a useful
measure of heat capacity per unit mass of the sample (e.g., J K-1 g-1)
Another approach is to deduce the magnitude of a heat transfer from the
its effects; namely, a temperature change. The temperature change Generally:
resulting from a particular transfer of heat is determined by the heat
capacity of the system, which is defined as follows: Heat capacities are temperature dependent, decreasing at lower T
heat capacity (of a system): the heat required to raise the Over small ranges near room temperature, CV are almost invariant to
temperature of the system by one Kelvin changes in temperature
(or one C)