Mechanical equilibrium

Mechanical equilibrium is related to pressure, and a system is in mechanical equilibrium if

there is no change in pressure at any point of the system with time. However, the pressure may
vary within the system with elevation as a result of gravitational effects.
For example, the higher pressure at a bottom layer is balanced by the extra weight it must carry,
and, therefore, there is no imbalance of forces. The variation of pressure as a result of gravity
in most thermodynamic systems is relatively small and usually disregarded.

Chemical equilibrium
System is in chemical equilibrium if its chemical composition does not change with time, that
is, no chemical reactions occur. A system will not be in equilibrium unless all the relevant
equilibrium criteria are satisfied.
Thermal equilibrium
A system is in thermal equilibrium if the temperature is the same throughout the entire system,
as shown in Fig. 1–27. That is, the system involves no temperature differential, which is the
driving force for heat flow.

Thermodynamic state
Consider a system not undergoing any change. At this point, all the properties can be measured
or calculated throughout the entire system, which gives us a set of properties that completely
describes the condition, or the state, of the system. At a given state, all the properties of a
system have fixed values. If the value of even one property changes, the state will change to a
different one. In Fig. 1–26 a system is shown at two different states.
Thermodynamics deals with equilibrium states. The word equilibrium implies a state of
balance. In an equilibrium state there are no unbalanced potentials (or driving forces) within
the system. A system in equilibrium experiences no changes when it is isolated from its
surroundings.

PROCESSES AND CYCLES

Any change that a system undergoes from one equilibrium state to another is called a
process.and the series of states through which a system passes during a process is called the
path of the process (Fig. 1–29). To describe a process completely, one should specify the initial
and final states of the process, as well as the path it follows, and the interactions with the
surroundings.

Quasi-static/quasi-equilibrium process
When a process proceeds in such a manner that the system remains infinitesimally close to an
equilibrium state at all times, it is called a quasi-static,or quasi-equilibrium, process.A quasi-
equilibrium process can be viewed as a sufficiently slow process that allows the system to
adjust itself internally so that properties in one part of the system do not change any faster than
those at other parts.
This is illustrated in Fig. 1–30. When a gas in a piston-cylinder device is compressed suddenly,
the molecules near the face of the piston will not have enough time to escape, and they will
have to pile up in a small region in front of the piston, thus creating a high-pressure region
there. Because of this pressure difference, the system can no longer be said to be in equilibrium,
and
this makes the entire process nonquasi-equilibrium. However, if the piston is moved slowly,
the molecules will have sufficient time to redistribute, and there will not be a molecule pileup
in front of the piston. As a result, the pressure inside the cylinder will always be nearly uniform
and will rise at the same rate at all locations. Since equilibrium is maintained at all times, this
is
a quasi-equilibrium process.

It should be pointed out that a quasi-equilibrium process is an idealized process and is not a
true representation of an actual process. But many actual processes closely approximate it, and
they can be modeled as q uasi-equilibrium with negligible error. Engineers are interested in
quasi-equilibrium processes for two reasons. First, they are easy to analyze; second, work-
producing
devices deliver the most work when they operate on quasi-equilibrium processes. Therefore,
quasi-equilibrium processes serve as standards to which actual processes can be compared.
Process diagrams plotted by employing thermodynamic properties as coordinates are very
useful in visualizing the processes. Some common properties that are used as coordinates are
temperature T, pressure P, and volume V (orspecific volume v). Figure 1–31 shows the P-V
diagram of a compression process of a gas.

Note that the process path indicates a series of equilibrium states through which the system
passes during a process and has significance for quasi-equilibrium processes only. For
nonquasi-equilibrium processes, we cannot characterize the entire system by a single state, and
thus we cannot speak of a process path for a system as a whole. A nonquasi-equilibrium process
is denoted by a dashed line between the initial and final states instead of a solid line.

The prefix iso- is often used to designate a process for which a particular property remains
constant.
An isothermal process, for example, is a process during which the temperature T remains
constant;
An isobaric process is a process during which the pressure P remains constant;
An isochoric (or isometric) process is a process during which the specific volume v remains
constant.

A system is said to have undergone a cycle if it returns to its initial state at the end of the
process. That is, for a cycle the initial and final states are identical.
TEMPERATURE AND THE ZEROTH LAW OF THERMODYNAMICS
Although we are familiar with temperature as a measure of “hotness” or “coldness,” it is not
easy to give an exact definition for it. Based on our physiological sensations, we express the
level of temperature qualitatively with words like freezing cold, cold, warm, hot, and red-hot.
However, we cannot assign numerical values to temperatures based on our sensations alone.
Furthermore, our senses may be misleading. A metal chair, for example, will feel much colder
than a wooden one even when both are at the same temperature.
Fortunately, several properties of materials change with temperature in a repeatable and
predictable way, and this forms the basis for accurate temperature measurement. The
commonly used mercury-in-glass thermometer, for example, is based on the expansion of
mercury with temperature. Temperature is also measured by using several other temperature-
dependent properties. It is a common experience that a cup of hot coffee left on the table
eventually cools off and a cold drink eventually warms up. That is, when a body is brought into
contact with another body that is at a different temperature, heat is transferred from the body
at higher temperature to the one at lower temperature until both bodies attain the same
temperature (Fig. 1–34). At that point, the heat transfer stops, and the two bodies are said to
have reached thermal equilibrium. The equality of temperature is the only requirement for
thermal equilibrium. equality of temperature is the only requirement for
thermal equilibrium.

zeroth law of thermodynamics states that if two bodies are in thermal equilibrium with a third
body, they are also in thermal equilibrium with each other. It may seem silly that such an
obvious fact is called one of the basic laws of thermodynamics. However, it cannot be
concluded from the other laws of thermodynamics, and it serves as a basis for the validity of
temperature measurement. By replacing the third body with a thermometer, the zeroth law can
be restated as two bodies are in thermal equilibrium if both have the same temperature reading
even if they are not in contact.
Thermometry
It may be defined as the act of measuring temperature with accuracy and precision. A property
or characteristic which changes its value as a function of temperature is called thermometric
property and corresponding substance is known as thermometric substance.
Temperature scales
Temperature scales enable us to use a common basis for temperature measurements, and
several have been introduced throughout history. All temperature scales are based on some
easily reproducible states such as the freezing and boiling points of water, which are also called
the ice point and the steam point, respectively. A mixture of ice and water that is in equilibrium
with air saturated with vapor at 1 atm pressure is said to be at the ice point, and a mixture of
liquid water and water vapor (with no air) in equilibrium at 1 atm pressure is said to be at the
steam point.

In Celsius scale the temperature of ice and steam points are fixed at 0 C and 100 C. There are
100 degrees between the ice point and steam point
In Fahrenheit scale, the temperature of ice and steam points are 32 F and 212 F. There are 180
degrees between the ice point and the steam point.

Methods of measurement

Liquid in glass thermometer:

These thermometers use liquids as the thermometric substance and change in the lengh of liquid
column in the capillary with heat interactions is the characteristics used for temperature
measurement. Usually mercury and alcohol are used in these type of thermometers. The figure
below shows mercury in glass thermometer. It consists of a vertical tube with graduations
marked on it to show the temperature, one end of which is connected to a thermometric bulb.
A small quantity of mercury is filled in a capillary tube. Mercury has lower specific heat and
hence absorbs little heat from the body or source. When the bulb is brought in contact with a
hot system, there is change in volume of mercury which results in rise or fall of mercury level
in the capillary tube. The length of liquid column is used as a thermometric property and is a
measure of temperature.

A small quantity of liquid enclosed in a glass capillary is called Liquid in glass thermometer.
In this type, the expansion of the liquid is used as the thermometric property.
𝐿
𝑇(𝐿) =273.16(𝐿 )
𝑝
Where L & 𝐿𝑝 are thermometric properties (Length). (Details will be shown in next section).

Gas thermometers
Thermocouple: When two wires of different materials are joined at their ends with different
temperatures existing at the two junctions, an electro motive force (emf) generated. The
generated emf may be used as a measure of the temperature of one junction, if the temperature
at the other junction is known.
A thermocouple circuit is made up from joining two wires A and B made of dissimilar metals.
Due to Seeback effect, a net e m f is generated in the circuit which depends on the difference
in temperature between the hot and cold junctions is, therefore, a thermometric property of the
circuit. This e m f can be measured by a micro voltmeter to a high degree of accuracy. The
metal pairs used are copper-constantan, chromel- alumel and platinum- platinum- rhodium.

ℇ = a + bt + ct2 + dt3

Electrical Resistance Thermometer: In the resistance thermometer, the change in resistance

of a metal wire due to its change in temperature is the thermometric property. The wire,
frequently, platinum, may be incorporated in a Wheatstone bridge circuit. The platinum
resistance thermometer measures temperature to a high degree of accuracy and sensitivity,
which makes it suitable as a standard for the calibration of other thermometers.

R = R0 (1 + At + Bt2) where R0 is the resistance of the platinum wire when it is surrounded by

melting ice and A, B are constants.