First Law of Thermodynamics and Entropy

The First Law of Thermodynamics can be written in different ways. For example, the First Law is applied
differently for a process in which the volume stays constant and for a process in which the pressure stays
constant.
In an isometric (or isovolumetric) process, the volume of the system remains constant (∆V = 0). Since there is
no change in volume, the work done by the system equals zero according to definition. The internal energy of
the system depends only on heat transfer into or out of the constant volume system. When the First Law of
Thermodynamics is applied to an isometric process, it becomes:

An isobaric process is one in which the system's pressure is fixed (∆P= 0). Although the pressure remains
constant, we are unable to eliminate any terms; both W and Q will apply to this process because volume
increases. Therefore, the First Law when applied to an isobaric process remains essentially the same:

In an adiabatic process, there is no transfer of heat to or from the system. Other characteristics such as the
pressure, volume, and temperature of the system may vary. However, no heat transfer into or out of the
process takes place. Many students tend to confuse heat and temperature. It is easy to make the mistake of
assuming that if there is a temperature change, there has been a transfer of heat, and vice versa. But notice
that during an adiabatic process, the temperature of the system changes due to internal fluctuations of the
system itself, and not as a result of heat lost or gained from the surroundings. Since no heat is exchanged,
then ∆Q = 0. Thus, the internal energy of the system depends only on the work done by the system:

During an isothermal process, the temperature of the system is held constant (∆T= 0). For this type of process,
we will assume that we are dealing with an ideal gas. If the temperature of this system is fixed, then its internal
energy also remains constant, since the internal energy of an ideal gas depends only on the temperature.
Therefore, ∆U = 0, and the First Law becomes:

A cyclic process, as you can probably tell from the name itself, occurs when the changes in the system form a
cycle. In other words, the initial state and the final state of the system are the same. Diagrammatically, a cyclic
process is represented as a closed path. It is called an open cycle if the process does not end at initial
conditions. The work done by the system equals the area within the curve. As you learned in the definition of
the First Law, the internal energy of a system depends on the initial and final states of that system. If the initial
state and the final state are equal, then there is no change in energy. This means that ∆U = 0, and we can
derive the equation:

In an isometric process, the volume of the system __________. Remains constant (∆V = 0)
During an isothermal process, the temperature of the system __________. Is held constant (∆T= 0)
In a cyclic process___________.There is no change in energy
By definition, enthalpy, usually symbolized as H, is the sum of internal energy plus the product of the pressure
of the gas in the system times its volume. The change of enthalpy occurring during a process is equal to the
initial enthalpy minus the final enthalpy.
∆H = Hinitial - Hfinal
or
∆H = U + PV
The enthalpy of a system is defined in terms of the internal energy, pressure, and volume of the gas in the
system. Enthalpies of steam and water are shown in steam tables.
H = U + PV/J
J = Joule constant, 778 ft-lbf/Btu
Heat causes increased motion of the molecules in the working fluid, such as steam. If the steam is enclosed in
a container, the motion of the molecules causes them to collide with the walls of the container. The collisions
result in the steam exerting a pressure on the container. As more heat is added, the molecular motion of the
gas increases and, if the volume of the container does not change, the pressure increases. The pressure-
volume energy of the steam, as the name implies, is the result of its pressure and volume. Pressure-volume
energy is a form of heat energy.
EXAMPLE
Find the pressure-volume energy of steam at a pressure of 100 psia and a specific volume of 4.4310 ft3/lbm.
Step 1. Convert 100 psi to pounds per square foot (psf):
100 psi × 144 in2/ft2 = 14400 psf
Step 2. Multiply 14400 psf × specific volume 4.4310 ft3/lbm = 63806.4 ft
Step 3. Divide 63806.4 ft by 778 ft-lbf/Btu = 82 Btu

Enthalpy is given the symbol ________. H

The enthalpy of a gas such as steam can be defined in terms of the _________. Internal energy plus its
pressure-volume energy
The heat capacity of a substance is the amount of heat required to raise the temperature of a defined amount
by one degree. The temperature of a body depends on the average vibrational energy of the body's molecules
while the total amount of heat in a body depends on the temperature, weight, and type of material composing
the body.
The specific heat of a substance is defined as the ratio of the heat capacity of the substance divided by the
heat capacity of the same weight of water.
The ease with which a substance gains or loses heat can also be described in terms of its molar heat capacity,
which is the heat required to raise the temperature of one mole of the substance by 1°C.
In the metric system, the units of molar heat capacities are therefore either cal/mol-°C or cal/mol-K.
In the SI system the units of molar heat capacities are J/mol-K.
In the English system, the units are Btu/mol-F.
Specific heat ratios are generally recorded without units. For example, turpentine requires 0.4260 Btu to raise 1
pound of the substance 1°F.

When ice is heated, the heat that initially enters the system is used to raise the temperature of the ice to its
melting temperature (0°C or 32°F). As additional heat is added the ice begins to melt. As the ice melts, the
temperature remains constant. The amount of heat required to transform the ice from its solid state to its liquid
state is called the latent heat of fusion. Once the ice has completely melted, the temperature of the water
slowly increases as more heat is added. Once the water starts to boil, the heat that enters the sample is used
to convert the liquid into steam and the temperature of the sample remains constant until all the liquid
evaporates. The amount of heat required to vaporize the liquid is the latent heat of vaporization.

The heat capacity of a substance is the amount of heat required to raise the temperature of a defined amount
by one __________. degree
In the English system, the units of molar heat capacities are_________. Btu/lb-deg F
The amount of heat required to convert ice to liquid is called the __________. Latent heat of fusion
Thermodynamics is concerned with transformations of energy, and the laws of thermodynamics describe the
bounds in which these transformations are observed to occur. The First Law states that energy is conserved in
all instances. However, it does not help us understand why energy transformations take place in the
mechanism that they do, only that they can. The Second Law addresses this concern.
The First Law treats heat and work as equal terms that are simply added in an energy balance. However,
experience shows that heat and work are two distinctly different quantities. The entire quantity of work energy
can be transformed into heat. On the other hand, only a portion of the available heat can be converted into
work energy.
One statement associated with the Second Law of Thermodynamics is that heat always flows from a high
temperature object to a lower temperature object and never in the reverse direction. This suggests that heat
itself has not only a magnitude or size but also depends on temperature. The relationship of temperature to the
quality of heat is evident from the increase in efficiency with which heat may be converted into work as the
temperature of the source is increased. The available energy to perform work in a power plant cycle increases
as the pressure and temperature of the steam in the boiler increases. This is a key concept to understanding
why the most efficient power plants operate at the highest pressures and temperatures. In other words, it is not
important how much thermal energy (enthalpy) is in the steam from the boiler, but rather how much of the
energy is useable by the turbine. This concept is directly associated with statements in the Second Law of
Thermodynamics.
The Second Law addresses __________. Why energy transformations take place
The Second Law also addresses___________. The direction of heat transfer between two bodies (substances)
based on their relative temperatures
The First Law treats heat and work as __________. "Equal" terms
The flow of heat depends on__________. A difference in temperature

No system can operate in such a way that its only effect is to convert heat completely into work. 100%
efficiency is not possible in converting heat into work. However, the greater amount of heat energy (enthalpy)
in the steam that is pressure-volume energy (versus internal energy), the greater the useable energy content,
and therefore the more efficient the turbine cycle.
The pressure-volume energy of steam is quantified by the term entropy – the higher the entropy, the less
useable energy the steam will have.
AND
Any process which consists solely in the transfer of heat from one temperature to a higher one is impossible.
To transfer heat from a lower temperature source to a higher temperature source requires external work. This
is why we cannot use the tremendous amount of heat energy in the exhaust steam from the LP turbine
entering the condenser to heat feedwater entering the boiler.

Physically, entropy, given the symbol S, is a measure of molecular order, or more to the point, the state of
disorder.
In general, we want our main steam to have a low entropy and a high enthalpy. This effectively means main
steam conditions that are high pressure and high temperature. Steam under these conditions will have a high
amount of useable thermal energy for conversion to mechanical energy in the turbine.

This can be seen on a temperature-entropy (T-s) diagram for a simple, non-reheat unit. On the diagram:
 a-b represents pump power
 b-c is regenerative feedwater heating and the boiler economizer
 c-d shows the latent heat added to the water in the waterwall tubes to vaporize the water
 d-e is the superheater
 e-f steam expansion through an ideal turbine, exhausting into a condenser
 f-a is the latent heat removed from steam in the condenser
The area below a-f represents the heat rejected by the condenser to the circulating water, while the usable
energy available in the cycle is represented by the white area within the envelope a-b-c-d-e-f-a.
With this in mind, let's compare a higher pressure cycle (abcdef), to a lower pressure cycle (abc'd'e'f'). Note
what happens in the lower pressure, higher entropy cycle: there is less usable energy (the area on the diagram
within the envelope). The higher pressure, lower entropy cycle has more area within the envelope, and
therefore more usable energy.
Once again, when the steam entropy is lower, more energy is available to do work by the turbine. As entropy
increases, less energy is available to do work.

Entropy is given the symbol __________. s

Steam entropy levels that are __________ are essential to efficient energy conversion by the steam turbine.
lower