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Boyles Law
Boyle's law shows that, at constant temperature, the product of an ideal gas's pressure and volume is always
constant. It was published in 1662. It can be determined experimentally using a pressure gauge and a
variable volume container. It can also be found through the use of logic; if a container, with a fixed number
of molecules inside, is reduced in volume, more molecules will hit the sides of the container per unit time,
causing a greater pressure.
As a mathematical equation, Boyle's law is: P1V1 P2V2 , where P is the pressure (Pa), V the volume (m3) of a
gas.
Charles's law
Charles's Law, or the law of volumes, was found in 1787 by Jacques Charles. It says that, for an ideal gas at
constant pressure, the volume is directly proportional to its temperature.
V1 V2
, where V is the volume (m3) of a gas and T is the temperature in Kelvin of a gas.
T1 T2
Gay-Lussac's law
Gay-Lussac's law, or the pressure law, was found by Joseph Louis Gay-Lussac in 1809. It states that the
pressure exerted on a container's sides by an ideal gas is proportional to its temperature.
P1 p 2
Avogadro's law
Avogadro's law states that the volume occupied by an ideal gas is proportional to the number of moles (or
molecules) present in the container. This gives rise to the molar volume of a gas, which at STP is 22.4 dm3
(or litres).
V V
The relation is given by: 1 2 , where n is equal to the number of moles of gas (the number of molecules
n1 n2
divided by Avogadro's Number which is 6.021023/mol) and V is the volume (m3) of a gas.
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Where
P= Pressure in Pascals (Pa)
V= Volume in m3
T= Temperature in Kelvin
n = number of moles
R = universal gas constant = 8.3145 J/mol K
N = number of molecules
k = Boltzmann constant = 1.38066 x 10-23 J/K = 8.617385 x 10-5 eV/K
k = R/NA
NA = Avogadro's number = 6.0221 x 1023 /mol
Example 1: Find the volume occupied by 1 mol of an ideal gas at standard temperature of 273 K and
pressure of 1.013105 Pa.
Example 2: A car tyre contains 0.02m3 of air at 27C and a pressure of 3105Pa. What is the mass of the air
in the tyre? (Molar mass of air =28.8 g)
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Thermodynamics
Thermodynamics, which began as an effort to increase the efficiency of steam engines in the early 1800s,
can be thought of as the study of the relationship between heat transferred to or from an object, and the work
done on or by an object. Both heat and work deal with the transfer of energy, but heat involves energy
transfer due to a temperature difference.
The four laws of thermodynamics summarize the most important facts of thermodynamics. They define
fundamental physical quantities, such as temperature, energy, and entropy, to describe thermodynamic
systems and they describe the transfer of energy as heat and work in thermodynamic processes.
Experimentally reproducible distinction between heat and work is at the heart of thermodynamics, and about
processes in which this distinction cannot be made, thermodynamics has nothing to say.
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Pressure-Volume Diagrams (PV diagrams) are useful tools for visualizing the thermodynamic processes of
gases. These diagrams show pressure on the y-axis, and volume on the x-axis, and are used to describe the
changes undergone by a set amount of gas. Because the amount of gas remains constant, a PV diagram not
only tells you pressure and volume, but can also be used to determine the temperature of a gas when
combined with the ideal gas law. A Sample PV diagram is shown below, showing two states of the gas, state
A and state B.
In transitioning from state A to state B, the volume of the gas increases, while the pressure of the gas
decreases. In the transition from state B to state A, the volume of the gas decreases, while the pressure
increases. Because the work done on the gas is given by U=-PV, you can find the work done on the gas
graphically from the PV diagram by taking the area under the curve. Because of the positive/negative sign
convention, as the volume of gas expands the gas does work (U is negative), and as the gas compresses,
work is done on the gas (U is positive).
Example 3: 5000 joules of heat is added to a closed system, which then does 3000 joules of work. What is
the net change in the internal energy of the system?
Example 4: A liquid is changed to a gas at atmospheric pressure (101,325 Pa). The volume of the liquid was
510-6 m3. The volume of gas is 510-3 m3. How much work was done in the process?
Example 5: Using the PV diagram below, find the amount of work required to transition from state A to B,
and then the amount of work required to transition from state B to state C.
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In exploring ideal gas state changes, there are a number of state changes in which one of the characteristics
of the gas or process remain constant, and are illustrated on the PV diagram below.
In an adiabatic process, heat flow (Q) is zero. Applying the first law of thermodynamics, if Eint =Q+U, and
Q is 0, the change in internal energy of the gas must be equal to the work done on the gas (Eint =U).
In an isobaric process, pressure of the gas remains constant. Because pressure is constant, the PV diagram
for an isobaric process shows a horizontal line. Further, applying this to the ideal gas law, you find that V/T
must remain constant for the process.
In an isochoric process, the volume of the gas remains constant. The PV diagram for an isochoric process is
a vertical line. Because U=-PV, and V=0, the work done on the gas is zero. This is also reflected
graphically in the PV diagram. Work can be found by taking the area under the PV graph, but the area under
a vertical line is zero. Applying this to the ideal gas law, you find that P/T must remain constant for an
isochoric process.
In an isothermal process, temperature of the gas remains constant. Lines on a PV diagram describing any
process held at constant temperature are therefore called isotherms. In an isothermal process, the product of
the pressure and the volume of the gas remain constant. Further, because temperature is constant, the
internal energy of the gas must remain constant.
Example 6: An ideal gas undergoes an adiabatic expansion, doing 2000 joules of work. How much does the
gass internal energy change?
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Example 7: Heat is removed from an ideal gas as its pressure drops from 200 kPa to 100 kPa. The gas then
expands from a volume of 0.05 m3 to 0.1 m3 as shown in the PV diagram below. If curve AC represents an
isotherm, find the work done by the gas and the heat added to the gas.
Entropy
Entropy is a thermodynamic property that can be used to determine the energy available for useful work in a
thermodynamic process, such as in energy conversion devices, engines, or machines. Such devices can only
be driven by convertible energy, and have a theoretical maximum efficiency when converting energy to
work. During this work, entropy accumulates in the system, which then dissipates in the form of waste heat.
In classical thermodynamics, the concept of entropy is defined phenomenological by the second law of
thermodynamics, which states that the entropy of an isolated system always increases or remains constant.
Thus, entropy is also a measure of the tendency of a process, such as a chemical reaction, to be entropically
favored, or to proceed in a particular direction. It determines that thermal energy always flows
spontaneously from regions of higher temperature to regions of lower temperature, in the form of heat.
These processes reduce the state of order of the initial systems, and therefore entropy is an expression of
disorder or randomness. This picture is the basis of the modern microscopic interpretation of entropy in
statistical mechanics, where entropy is defined as the amount of additional information needed to specify the
exact physical state of a system, given its thermodynamic specification. The second law is then a
consequence of this definition and the fundamental postulate of statistical mechanics.
Thermodynamic entropy has the dimension of energy divided by temperature, and a unit of joules per kelvin
(J/K) in the International System of Units.
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