Review of Thermodynamics

MODULE 1.1
ALLAN TROY SALAZAR
Outline of Presentation
▪ 1st Law of Thermodynamics: Equivalence of Heat and Work and the Conservation of Energy
▪ Internal Energy, I
▪ Pressure – Volume (PV) Work
▪ Enthalpy, H
▪ 2nd Law of Thermodynamics: Inevitable Increase of Entropy, S
▪ Efficiency
▪ Carnot Cycle
▪ Heat Capacity
▪ Entropy
▪ Gibbs Function * Gibbs Energy (G)
▪ Thermodynamic Efficiency
Thermodynamics and Geothermal Systems
▪ Effective use of geothermal energy requires ability to move and convert heat
efficiently.
▪ Some instances, heat is used to do work - > generation of electricity
▪ Heat is concentrated or dissipated
▪ Regardless of application, an understanding of the behavior of fluids and
materials when heated or cooled, and the implication for energy balances, is
the foundation for achieving an economically successful outcome for any
geothermal applications
Thermodynamic Properties
Mass and Weight - The mass (m) of a body is the measure of the amount of material present in that body.
The weight (wt) of a body is the force exerted by that body when its mass is accelerated in a gravitational
field.
The specific volume (n) of a substance is the total volume (V) of that substance divided by the total mass
(m) of that substance (volume per unit mass).
The density (d) of a substance is the total mass (m) of that substance divided by the total volume (V)
occupied by that substance (mass per unit volume).
Specific gravity (S.G.) is a measure of the relative density of a substance as compared to the density of
water at a standard temperature. In the International System of Units (SI Units), the density of water is 1.00
g/cm3 at the standard temperature.
◦ Therefore, the specific gravity (which is dimensionless) for a liquid has the same numerical value as its density in units
of g/cm3. Since the density of a fluid varies with temperature, specific gravities must be determined and specified at
particular temperatures.
 Temperature and Its Measurements
Temperature is a measure of the molecular activity of a substance. The greater the movement of
molecules, the higher the temperature. It is a relative measure of how "hot" or "cold" a
substance is and can be used to predict the direction of heat transfer.
Temperature Scales

Temperature scales normally employed for

measurement purposes are Fahrenheit (F)
and Celsius (C) scales.

These scales are based on a specification of

the number of increments between the
freezing point and boiling point of water at
standard atmospheric pressure.
Pressure and its measurements
Pressure is a measure of the force exerted per unit area on the boundaries of a substance (or
system). It is caused by the collisions of the molecules of the substance with the boundaries of
the system.

As molecules hit the walls, they exert forces

that try to push the walls outward. The forces
resulting from all of these collisions cause the
pressure exerted by a system on its
surroundings.
Equivalence of Heat & Work and
the Conservation of Energy
1 ST LAW OF THERMODYNAMICS
 Conservation of Energy – Historical Development of Concept
1750’s - Engineering community intrigued by repeatedly observed fact that doing work on
material generate heat.
• Benjamin Thompson noted that in making canon, boring into metal results in metal being hot
• Humphry Davy demonstrated that work and heat are directly related.
1842 – Julius Meyer published a seminal paper that the concept of conservation of
energy, as embodied in the equivalence of heat and mechanical work
1847 – Herman von Helmholtz – develop a mathematical basis for the concept.
1849 – James Prescott Joule, thorough experimental and observational work was
presented to the Royal Society paper “On the Mechanical Equivalent of Heat”
➢ These achievements establish the concept that mechanical work and heat are
equivalent and that, invariable energy is conserve
➢ This principle become the First Law of Thermodynamics
“Energy can neither be created nor be destroyed”
“All forms of energy are equivalent”
 Internal Energy, (E)
➢ Most rigorous description of the energy in a system relies on a
concept of Internal Energy, E – It is a characteristic of a specific
defined system
➢ SYSTEM - can be cylinder of gas, bottle of water, bar of steel,
or a rock - > anything that can be physically describe by
parameter of state such as P, V, & T.
➢ If a system is completely isolated from its surroundings (closed
system, then at any given set of condition, P and T, the
Internal Energy ( E) of the system is fixed and depends only on
the properties of the material of which the system is
composed.
➢ E, will change solely in response to changes in state
parameters of P and T
➢ If the condition to which the system is subject are change
either by making heat (Q) into it or by doing work on it, the
Internal Energy ( E) must also be change.
 Internal Energy, (E)
➢“The change in internal energy is equal to the internal energy
in the system in its final state (Ef) minus the initial internal
energy (Ei)
▪ This equation is profoundly important→ it established the
significance of knowing the E at the end points of a process
that affects the system.
▪ It is the difference of between end points that determine how
much energy is required to heat space, generate power or cool
room.
▪ It emphasize that the pathway that was followed to get from
the initial state to final state has absolutely no significance for
the change in the internal energy

➢There are an infinite number of pathways that could be

followed that would achieve the same results regardless of the
complexity of the path followed
 Pressure – Volume Work (PV)
The conclusion that is inescapable is that any change in the
internal energy of a system is solely the result of work (w) done
to the system, or that the system perform, and any heat (q)
added to or taken from the system

Mechanical work is performed when a force applied to a point,

surface, or volume results in displacement of that point,
surface, or volume.

By convention, mechanical work done on a system is positive,

whereas work done by a system is negative. Work performed is,
therefore, equivalent to the difference in volume between the
two states:
 Enthalpy, (H)
in a process in which no change in volume occurs, no
mechanical work is performed and any change in
internal energy is solely related to heat added to or
removed from the system:

The subscript v is used to indicate heat at constant

volume; similarly, a subscript p would refer to a constant
pressure condition. If, however, a change in volume
occurs at constant pressure and heat is also added to or
removed from the system, the change in internal energy
is

The heat added to or removed from the system at

constant pressure is called the enthalpy (H) and the
change in enthalpy (ΔH ) that is realized when moving
from one state to another is defined as
Inevitable Increase of Entropy
2 ND LAW OF THERMODYNAMICS
Efficiency, e
At the same time as the concept of conservation of energy was being formulated, advances in
steam engine technology were flourishing.
1769, James Watt, building on early work of Thomas Savery, Thomas Newcomen, and others,
had developed the steam engine to the point that it began to be the dominant driver of the
Industrial Revolution.
The issue was how much work could be done for a given amount of heat?
The ideal, of course, would be a situation in which all of the energy contained in a given amount
of heat would be converted to work with 100% efficiency.

e is the efficiency. For the ideal case, e = 1.0 and q = − w.

Carnot Cycle
1824, Nicolas Léonard Sadi Carnot, a French engineer, provided the definitive conceptualization
that allowed efficiency to be rigorously determined.
Carnot’s conceptualization of the problem was further developed by Èmile Clapeyron and Rudolf
Clausius, such that by the 1850s the concept was available in the form we generally use today.
To understand the fundamentals behind the Carnot cycle, the concept of equilibrium must be
appreciated. From a thermodynamic perspective, a system has achieved an equilibrium state if it
does not change spontaneously from the state it is in.
A Carnot engine is an imaginary engine that cycles through a series of four steps. At the end of
the fourth step, the engine returns to its initial state.
In reality, it is impossible to carry out a series of completely reversible (i.e., equilibrium) steps,
because achieving complete equilibrium requires that no pressure or temperature gradients
develop during the action of the engine.
The only means by which such a state can be achieved is if each step is carried out infinitely
slowly. Hence, the Carnot engine is an ideal that cannot be realized.
 Carnot Cycle
The engine is composed of a gas-filled cylinder with a frictionless
piston. The gas we will consider follows the ideal gas law

Isothermal Process – keeps the temperature constant

Adiabatic Process - change in state parameters (P and T), and therefore the change in
internal energy (ΔE ) is only a function of the work done on the system
 Heat Capacity (C )
➢ Noted that different materials require different amounts of heat in
order to achieve a specific change in temperature.
➢ IF same amount of heat were added to two different materials, each
material would reach a different temperature.
➢ If these two materials were placed in contact, the warmer material Rearranging, C x dT = dq
would cool down and the cooler would warm up by absorbing the
warmer material’s heat
At Constant Pressure
➢ The quantity that represented this phenomenon ultimately became
known as the heat capacity (C), is expressed in joules per gram for
each degree of temperature change (J/g-K).
➢ changes in volume and changes in pressure affected the heat At Constant Volume
capacity, so it became a standard to specify heat capacity either at
constant pressure (Cp) or at constant volume (Cv).
The mathematical expression for the general relationship for heat capacity and
heat is
 Entropy (S)
In Carnot cycle, we are confronted by the fact that we have started at
some initial condition for which there is no history.
Heat In
The process that brought the Carnot cycle to the P, V, T at which it Work done
begins is not specified system

As we move through the cycle from beginning to end, we add and System does
subtract heat and the system does work or has work done on it. work
As a result, the enthalpy of the gas is changing. All of the changes in
temperature are a function of the heat capacity of the gas in our
cylinder, but the heat content at the beginning of our cycle is never
involved in doing work and we can never use it. Heat Out
Furthermore, because the Carnot cycle is an idealized, reversible system
that is unattainable in real life, there is a certain amount of heat that we
simply cannot access—moving through a real-life cycle, we will
inevitably lose some heat through friction and conduction that can
never be used for useful work.
A measure of this unattainable heat that is present at the initial state of
our system as well as that lost in the process of moving through the
cycle is called entropy.
 Entropy (S)
Definition of entropy states that any differential change in the heat a system
contains, at a given temperature, leads to a change in the entropy of the system.
One way to conceptualize this relationship is to consider the temperature–entropy
of Carnot cycle
At the initial point in the cycle, the temperature and entropy are fixed (as are the
pressure and volume). When heat is reversibly added to the system as work is
done at constant temperature (dq/T), hence, entropy increase.
In step 2, as the gas adiabatically expands, the temperature drops. Because there is
no change in the heat content, dq is 0 and there is no change in the entropy.
Steps 3 and 4 are the exact reverse of steps 1 and 2, respectively, and the system
returns to the same entropy and temperature it initially had.
In reality, the entropy of the universe within which the engine exists has
increased.
This is apparent the fact that the addition and removal of heat was done using Once the two thermal reservoirs have reached the
external heat reservoirs. The higher-temperature reservoir loses some heat with same temperature, regardless of how that happens,
each cycle, and the lower-temperature reservoir gains heat.
they are no longer of any use for doing work, and
Once this happens, no more work can be done because Δq/qin approaches 0, the entropy of the system has reached its maximum
which is the same thing as saying the efficiency approaches 0. state.
 Gibbs Function and Gibbs Energy
▪ As discussed in“Carnot Cycle”, when one defines the initial state of the
Carnot cycle, there is no need to specify how that initial state was achieved.
▪ It would be impossible to independently determine how the system achieved
its current, initial state because the physical system contains no information
that records the system’s history.
▪ It is not possible to determine the actual, absolute internal energy of a Heat In
substance or system—the best we can do is determine how the internal
energy changes as the system evolves from its current initial state to some Work done
other state. system

▪ We can also determine whether or not two systems (whether they be System does
minerals, rocks, liquid, and gas, or any other pair of materials or substances) work
are in equilibrium, and what the absolute differences are in their respective
heat contents.
▪ Two systems that have the same temperature, and are therefore in
thermodynamic equilibrium, are incapable of doing work without some Heat Out
external action being taken.
▪ If, however, they are not at the same temperature, they can be a source of
useful energy.
▪ To determine the amount of available energy that can be extracted for
useful work, the difference in the heat contents of the systems must be
evaluated.
 Gibbs Function and Gibbs Energy
To compare states, we must have a means of comparing the energy contained in one substance or system
with that in another.
Consider the Carnot cycle and how the internal energy changes.
It is evident that there are three fundamental attributes that contribute to the energy in that system at any
point along the cycle—
➢ the energy that exists in the system at the initial set of conditions before the cycle begins,
➢ the energy the system acquires or gives up along an isothermal path, and
➢ the energy it acquires or gives up along an adiabatic path.

In 1876, J. Willard Gibbs defined a function that mathematically described the energy contained in such a
system and how that energy is affected by changes in temperature and pressure.
The Gibbs function follows from the discussions above regarding the first and second laws of
thermodynamics.
 Thermodynamic Efficiency
Because steps 2 and 4 in our Carnot engine were conducted adiabatically, there is no heat added
to or removed from the system in these steps.

This expression represents the thermodynamic efficiency of the

engine (all temperatures are expressed in Kelvin).

This relationship has profound implications for the

thermodynamic efficiency of any geothermal application.
 Temperature & Efficiencies in Geothermal Reservoir
Systems

In real life, the actual thermodynamic efficiencies that are achieved are influenced by
additional factors.

One such factor is the depth at which the working fluid resides and the resulting pressure
change that it experiences when it is brought to the surface and utilized for power
generation

To understand the implications of this process for geothermal systems, the

thermodynamic properties of water must be considered.
The entropy of a system approaches a constant value as
the temperature approaches absolute zero
3 RD LAW OF THERMODYNAMICS