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Pascal's Law in Gases

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Pascal's law or Pascal's principle, enunciated almost 400 years ago, has been of utmost importance in a wide variety of scientific and engineering disciplines. Currently physics textbooks describe Pascal's law as follows: "A change in the pressure applied to an enclosed incompressible fluid is transmitted undiminished to every portion of the fluid and to the walls of its container." Such phenomenon can be explained based on the propagation of external forces at a molecular level via intermolecular repulsion (following Newton's third law of motion). In the case of gases, such propagation of forces does not take place directly, although external forces do influence the pressure of a gas by changing the momentum of the molecules hitting the walls. There is, therefore, a relationship not necessarily identical to that stated in Pascal's law. However, under certain conditions, Pascal's law remains as a fairly good approximation for gases. For example, the International Standard Atmosphere model has assumed that the atmosphere is an ideal gas following Pascal's law, with satisfactory results.
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Pascals Law in Gases
Hugo Hernandez
ForsChem Research, 050030 Medellin, Colombia
hugo.hernandez@forschem.org
doi:
Abstract
Pascal’s law or Pascal’s principle, enunciated almost 400 years ago, has been of utmost
importance in a wide variety of scientific and engineering disciplines. Currently physics
textbooks describe Pascal’s law as follows: A change in the pressure applied to an enclosed
incompressible fluid is transmitted undiminished to every portion of the fluid and to the walls of
its container.Such phenomenon can be explained based on the propagation of external forces
at a molecular level via intermolecular repulsion (following Newton’s third law of motion). In
the case of gases, such propagation of forces does not take place directly, although external
forces do influence the pressure of a gas by changing the momentum of the molecules hitting
the walls. There is, therefore, a relationship not necessarily identical to that stated in Pascal’s
law. However, under certain conditions, Pascal’s law remains as a fairly good approximation for
gases. For example, the International Standard Atmosphere model has assumed that the
atmosphere is an ideal gas following Pascal’s law, with satisfactory results.
Keywords
Blaise Pascal, Equivalent Pressure, Hydrostatic Equilibrium, Ideal Gases, Incompressible Fluids,
Intermolecular Forces, Non-ideal Gases, Repulsion
1. Introduction
In the 17th century, Galileo Galilei was asked by a fountain master of the time why a suction
pump (operating with the siphon principle) could not be used with water beyond a maximum
height of 32 feet. Galileo explained it using the notion of resistenza del vacuo (vacuum
resistance), derived from Aristotle’s horror vacui theory. Not completely convinced from his
own explanation, Galileo assigned the problem to one of his disciples: Evangelista Torricelli.
Pascals Law in Gases
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Torricelli scaled-down this effect using mercury instead of water (almost 13.6 times heavier),
finding a maximum siphon height of just 760 mm. His experiments, which rejected Galileo’s
original hypothesis by demonstrating that air (and not vacuum) exerted pressure on the liquid,
also gave rise to the invention of the barometer around 1643. In 1647, Blaise Pascal, a French
mathematician, religious philosopher and physicist, became aware of Torricelli’s experiments
and decided to reproduce and improve them [1].
Pascal results and findings can be found in different publications, including his Traités de
l’Equilibre des Liqueurs, et de la Pesanteur de la Masse de l’Air(“Treatises on the equilibrium of
liquids, and on the gravity of the mass of air). The first chapter of his treatise on the
equilibrium of liquids was entitled Que les Liqueurs pesent suivant leur hauteur(“That liquids
weight according to their height) [2]. This statement, which will later be known as Pascal’s
law, is the principle of operation of the hydraulic press, invented more than a century later [3],
and other machines.
Mathematically, Pascal’s law can be expressed as follows
§
:

(1.1)
where  is the difference in pressure between two different heights of a fluid (also
known as hydrostatic pressure), is the mass density of the fluid, is the gravitational
acceleration, and  is the corresponding height difference. Please note the change
in the order of the pressure and height differences. Considering height as positive in the
direction from the ground to the atmosphere, and considering differential changes in height,
the mathematical (differential) representation of Pascal’s law becomes:

(1.2)
A modern interpretation of Pascal’s law is [4]: A change in the pressure applied to an enclosed
incompressible fluid is transmitted undiminished to every portion of the fluid and to the walls of
its container. Mathematically this is: 󰇛󰇜
(1.3)
§
Pascal originally considered the weight (related to the pressure at the bottom) of the same liquid when
the level in the container changes. Later it was extended to consider the pressure of a column of liquid at
different positions, resulting in the famous expression (Eq. 1.1).
Pascals Law in Gases
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The pressure at a certain depth below the surface of a liquid is the sum of the external
pressure 󰇛󰇜 and the hydrostatic pressure 
**
. Thus, a change in the external
pressure acting on the contained incompressible liquid, results in a pressure change at depth :
󰇛󰇜
(1.4)
Pascal’s law can be used in a wide variety of situations. It is the operating principle of different
hydraulic machines and hydraulic components, and is also useful in the design of liquid
containers, dams, ships, submarines, and scuba diving equipment, just to mention a few.
Pascal’s law, along with the ideal gas equation, is a key principle of the International Standard
Atmosphere (ISA) model [5]. In this model, the change in temperature with decreasing altitude
(lapse rate) is assumed constant for each layer of the atmosphere, and the corresponding
pressure profile is obtained assuming that the atmosphere is at hydrostatic equilibrium. Thus,
from Pascal’s law (Eq. 1.2) and the ideal gas equation:



(1.5)
where is the average molecular mass of air, is Boltzmann constant, and is the absolute
temperature. Since is assumed to change linearly with respect to altitude (constant lapse
rate), Eq. (1.5) becomes: 
 
󰇛󰇜
(1.6)
where is the absolute temperature on the ground, and is the constant lapse rate (at the
troposphere). Solving Eq. (1.6) yields:
󰇛󰇜

(1.7)
The air in this model is also assumed to be dry, dust-free, and at rest with respect to Earth. This
hypothetic approximate model of the atmosphere has been used for calibrating pressure
altimeters, and for the design of rockets and aircrafts [6].
**
The depth of liquid below the surface is related to the height by: , where is the level of
liquid in the container.
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However, considering that Pascal investigated liquids, and also from the modern definition of
Pascal’s law we realize that it is limited to enclosed incompressible fluids (which exclude gases),
then the following question emerges: Is it safe to extrapolate Pascal’s law to gases, and
particularly, to ideal gases? Please notice that the ISA model also assumes that air is an ideal
gas, and also that the atmosphere is not enclosed or contained by rigid walls.
2. Molecular Interpretation of Pascal’s Law in Liquids
Before discussing the applicability of Pascal’s law in gases, this principle will be analyzed from a
molecular perspective. Let us consider an incompressible fluid (liquid) confined in a
impermeable solid container with constant cross-section as depicted in Figure 1. Gravity, of
course, is acting in the vertical downward direction. A specific part of the container is zoomed
in, only to find that the fluid is composed of molecules (represented by spheres). Assuming
that the system is at rest (hydrostatic equilibrium), the average net force acting on the
molecules of the fluid is zero. Since gravity is permanently acting on each molecule, such
equilibrium of forces is only possible if the intermolecular forces exactly compensate gravity, as
illustrated in Figure 2 (considering only two layers of molecules). Of course, the magnitude of
the forces will change continuously, but on average they should be zero in all directions at
equilibrium.
Figure 1. Schematic representation of an incompressible fluid (blue) confined in a cubic
container (only edges shown in black). Left: Macroscopic scale. Right: Molecular scale.
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Figure 2. Forces acting on the molecules of a liquid (cyan circles), considering only two layers of
molecules. Green arrows: Gravity. Red arrows: Intermolecular repulsion forces. Black arrows:
Normal force (repulsion force between the fluid molecule and the solid wall). Blue arrows:
Additional external forces. Left plot: No additional external forces considered. Right plot:
Additional external forces considered.
The molecules at the top of Figure 2 compensate the gravitational force acting on them due to
the repulsion forces of the molecules below them. On the other hand, the molecules at the
bottom of the container compensate the gravitational force acting on them plus the repulsion
forces of the upper molecules, thanks to the repulsion of the solid wall. Now, since at
equilibrium the vertical components of the repulsive forces at the top molecules correspond to
the gravitational force () but with opposing direction, then by Newton’s third law (action-
reaction) the repulsive force perceived by the molecules at the bottom will correspond to the
weight of the upper molecules. Adding the repulsive forces to their own gravitational force,
the net force acting on the solid wall is the sum of all the molecules above it. By adding more
layers of molecules, the result is the same: The gravitational force (weight) of the upper
molecules is transmitted to the lower molecules as a result of intermolecular repulsions.
Mathematically, the magnitude of the total force acting on the solid wall at the bottom
() would be expressed as follows:

(2.1)
where is the number of molecules in the container. Now, since the mass density of the fluid
is given by: 


(2.2)
Pascals Law in Gases
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where is the volume of incompressible fluid in the container, is the cross-section area at the
bottom of the container, and is the height of fluid, then Eq. (2.1) becomes:
 
(2.3)
Finally, since the pressure is defined as force per unit area 󰇛󰇜, we get:
 
(2.4)
This expression closely resembles Pascal’s law, but we are still missing something. The
molecules at the top of the fluid can also be exposed to additional (external) forces as can be
seen in the right scheme in Figure 2. In this case, the external force will increase the repulsion
forces between fluid molecules, and also will increase the normal repulsion forces at the
bottom wall. In other words, the external force propagates in the direction of the force by
increasing the magnitude of the intermolecular repulsive forces found along the path of the
force. This effect is described by the modern formulation of Pascal’s law, when using the
expression undiminished transmission of the changes in pressure’ (or changes in external
forces). Furthermore, the molecules close to the side walls will also be pushed towards those
walls, also resulting in a lateral (isotropic) transmission of the pressure.
This analysis could be easily extended to solid systems, concluding that Pascal’s law should also
be valid for solids. Of course, the pressure inside most solid systems cannot be easily
determined, but in certain solid systems it is possible (imagine for example particles of sand or
any other solid material). The main differences between solid and liquid systems at the
molecular level are that the motion of molecules at the solid state is more constrained than at
the liquid state, and that molecular contact of liquids with the walls is more homogeneous.
However, the transmission of force by intermolecular repulsion also takes place in solids. In the
following section, the case of gas systems will be considered.
3. Pascal’s Law in Gases
3.1. Molecular Analysis of Pascal’s Law in Gases
Let us now imagine a similar situation for a container filled with a gas. The molecular
representation at the bottom wall is presented in Figure 3. Given that gas molecules are less
crowded, repulsion forces are only present when molecules collide between them, or when
they hit the walls.
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Figure 3. Forces acting on the molecules of a gas (purple circles). Green arrows: Gravity. Red
arrows: Intermolecular repulsion forces. Black arrows: Normal force (repulsion force between
the fluid molecule and the solid wall). Blue arrow: Additional external force.
First, we can see that repulsive forces emerging during molecular collisions have no direct
effect on the pressure of the wall, since those forces cannot propagate at such low densities.
The same thing occurs with external forces, they are not propagated. Since equilibrium (local
equilibrium at the molecular level) cannot be reached, those forces will have an effect on the
speed and direction of the molecules. Now, a small fraction of molecules will be hitting the wall
at a certain instant. The number of molecules hitting the wall is the molecular flux, which mainly
depend on the molecular density, but also on the temperature of the system and the relative
macroscopic motion of the gas [7]. In our case, since the gas is completely confined there is no
relative macroscopic motion of the gas, or in other words, the gas is static or at rest. On the
other hand, the resulting normal repulsive force at any wall will be determined by the
momentum of the collision. Faster and heavier molecules will result in larger repulsion forces,
thus increasing the pressure at the walls. Thus, mass and gravity have an important influence
on the pressure at the walls, but not related to the transmission of the weight through the gas,
but as a result of the increased molecular momentum when colliding with the walls.
The previous analysis clearly indicates that Pascal’s law cannot be directly extended to gas
systems. This does not necessarily mean that density, gravity and height of gas have no effect
on pressure.
3.2. Ideal Gas under Constant Force Model
Let us consider an ideal gas system contained in an impermeable thermally-insulated container,
subject to a constant force. The cross-section of the container, perpendicular to the external
Pascals Law in Gases
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force, is constant. Before the force is applied, the distribution of molecular positions is
assumed uniform, and the distribution of molecular speeds is assumed to follow the Maxwell-
Boltzmann distribution. For this particular system, it is possible to approximately estimate the
local density, temperature and pressure profiles in the direction of the external force that will
be obtained at equilibrium [8]. Particularly, the local (equivalent
††
) pressure is given by the ideal
gas equation:
󰇛󰇜󰇛󰇜󰇛󰇜
(3.1)
where 󰇛󰇜 and 󰇛󰇜 are the local equilibrium molecular density and absolute temperature
at depth from the top of the container, is the total height of the container, is the initial
absolute temperature of the system, and is the molecular diameter. The equivalent
pressure at a certain height was found to be identical to the pressure exerted on the walls at
the same height (pressure isotropy).
Additionally, the local equilibrium temperature  and local molecular density are given by [8]:
󰇛󰇜

󰇡
󰇢
󰇡
󰇢
󰇡
󰇢󰇧

󰇡
󰇢󰇨

󰇧
󰇡
󰇢󰇡
󰇢
󰇨󰇧
󰇡
󰇢󰇨

󰇧
󰇡
󰇢󰇨
󰇡
󰇢
(3.2)
󰇛󰇜󰇯󰇭
󰇮󰇧󰇧
󰇨󰇨󰇰
(3.3)
Where is the overall molecular density in the container.
Thus, the change in local pressure with respect to depth will be:

󰇛󰇜
 󰇛󰇜

(3.4)
where 
 is known as the lapse rate.
††
The term equivalent pressure indicates that forces (pressure) only appear when a physical barrier is
imposed on the system (e.g. the walls of the container or the pressure measurement device). The
internal pressure of an ideal gas is zero (or negligible), since no significant intermolecular forces are
present [7].
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Given the complexity of Eq. (3.2), instead of presenting a general expression for the lapse rate
let us consider two different scenarios: 1) Lab-scale dimensions 󰇡
󰇢, and 2) Atmosphere-
scale dimensions 󰇡
󰇢. In the first scenario, a very rough approximation of the lapse rate
is:

 
󰇡
󰇢

󰇡
󰇢

󰇡
󰇢

(3.5)
whereas for the second case we have:

 





(3.6)
Similarly, the change in molecular density with respect to depth will be given by:


󰇧
󰇨

󰇧󰇧
󰇨󰇨󰇛󰇜

(3.7)


󰇛󰇜󰇧
󰇨󰇛󰇜

(3.8)
The local change in pressure then becomes:

󰇛󰇜
󰇡
󰇢

󰇡
󰇢

󰇡
󰇢
󰇧
󰇨

󰇧󰇧
󰇨󰇨

(3.9)
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
󰇛󰇜





󰇛󰇜󰇧
󰇨

(3.10)
Clearly, the rate of change in the pressure of ideal gases under an external force with respect
to depth (or with respect to height by reversing the sign) is not constant, as in the case of
liquids (Pascal’s law). However, gravity, density and depth show an important effect on the
rate of pressure change.
A graphical comparison between the results obtained for air using Eq. (3.4) and those expected
using Pascal’s law (Eq. 1.5) is presented in Figure 4. Different values of 
are considered. For
greater accuracy, especially at intermediate values of 
, instead of using the analytical
approximations given in Eq. (3.9) and (3.10), the rate of pressure change is obtained by
numerically differentiating Eq. (3.2).
Figure 4. Relative rate of pressure change 󰇡
󰇢 as a function of the relative depth 󰇡
󰇢 for
different values of the ratio 
. Pascal’s law (black solid line) is included for comparison.
Even considering that the results obtained by the ideal gas under constant force model are just
approximate, it is possible to conclude that Pascal’s law is, in general, not valid for ideal gases.
For relatively small containers, the pressure changes are small but much larger than those
predicted by Pascal’s law. However, in the middle section of the container the rate of pressure
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change remains relatively constant, resembling Pascal’s law but with a proportionality factor.
For very large containers (or large systems), the pressure changes are large but usually smaller
than those predicted by Pascal’s law. For intermediate values of 
󰇛󰇜, Pascal’s law
can be considered a fairly good approximation, particularly in the middle and top sections of
the container.
In 1965, Yalamov and Derjagin [9] found, using the mathematical approach proposed by James
Clerk Maxwell [10], that pressure anisotropy emerges in gases formally violating Pascal’s law.
However, they did not observe anisotropy experimentally, attributing this effect to an
incomplete mathematical formulation of Maxwell [11]. Their experiments were performed in
very small systems ( in height), subject to large temperature gradients
(). They experimentally validated the pressure anisotropy of gases, one
component of Pascal’s law, but their results did not allow verifying the validity of Eq. (1.5).
3.3. Pascal’s Law in Non-ideal Gases
As the density of a gas increases, the average distance between molecules is reduced. At some
point, when the average intermolecular distance approaches the radius of action of the
molecules, non-ideal gas behavior emerges [12]. At this point, a weak but permanent
interaction between molecules will be present, which will partially transfer gravitational and
other external forces. Thus, as the average intermolecular distance is reduced in the non-ideal
gas, it is expected that the rate of pressure change approaches Pascal’s law. Non-ideal gas
behavior can be considered as an intermediate state between ideal gases and liquids. At a
specific instant, some molecules will behave as ideal gases and some other almost as liquids
(transferring forces via intermolecular repulsion), depending on the local molecular densities. If
we consider that a fraction of molecules  behave as ideal gas molecules while the remaining
show a liquid-like behavior, then the rate of pressure change of a non-ideal would be
approximately given by:


󰇛󰇜
(3.11)
where 󰇡
󰇢 is given by Eq. (3.4).
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4. Conclusion
Pascal’s law is a physical principle used for many important applications in science and
engineering, indicating that external forces (or pressure) applied to contained incompressible
fluids are transmitted or propagated through the fluid. This occurs because external forces are
balanced by intermolecular repulsive forces.
In gases, however, forces (and particularly weight) cannot be directly transmitted as predicted
by Pascal’s law. Of course, the mass density of the gas and the external acceleration determine
the pressure changes in the system because they influence the momentum of the molecules
colliding with the walls, but not as the result of intermolecular force propagation. Thus, gases
do not strictly follow Pascal’s law.
The International Standard Atmosphere model, while being a good approximation for
describing the behavior of the atmosphere based on physical principles such as the ideal gas
equation and Pascal’s law, cannot be considered a rigorous first-principles model because using
Pascal’s law in this system might be phenomenologically erroneous.
Acknowledgments
The author gratefully acknowledges Prof. Jaime Aguirre (Universidad Nacional de Colombia)
for fruitful discussions and for reviewing and proof-reading the manuscript.
This research did not receive any specific grant from funding agencies in the public,
commercial, or not-for-profit sectors.
References
[1] Loeffel, H. (1987). Blaise Pascal 16231662. Birkhauser Verlag, Basel.
[2] Pascal, B. (1663). Traites de l'equilibre des liqueurs, et de la pesanteur de la masse de l'air.
Chez Guillaume Desprez, Paris.
[3] Bramah, J. (1795). Obtaining and Applying Motive Power. British Patent No. 2045.
[4] Walker, J. (2018). Fundamentals of Physics Halliday & Resnick. Extended 11th Ed. John Wiley
& Sons, Hoboken. p. 393.
[5] ISO 2533:1975 (1975). Standard Atmosphere. International Organization for Standardization.
Pascals Law in Gases
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www.forschem.org
[6] Cavcar, M. (2000). The international standard atmosphere (ISA). Anadolu University,
Turkey. http://www.academia.edu/download/52648552/ISAweb.pdf
[7] Hernandez, H. (2019). Calculation of Molecular Fluxes and Equivalent Pressure in Ideal
Gases. ForsChem Research Reports, 4, 2019-03. doi: 10.13140/RG.2.2.35898.44483.
[8] Hernandez, H. (2020). Effect of External Forces on the Macroscopic Properties of Ideal
Gases. ForsChem Research Reports, 5, 2020-07. doi: 10.13140/RG.2.2.33193.21608.
[9] Yalamov, Ya. I. & Deryagin, B. V. (1965). К ВОПРОСУ О ТЕМПЕРАТУРНЫХ НАПРЯЖЕНИЯХ В
НЕОДНОРОДНО НАГРЕТЫХ ГАЗАХ (Stresses due to temperature in unevenly heated gases).
Dokl. Akad. Nauk SSSR, 161 (3), 572574.
[10] Maxwell, J. C. (1879). VII. On stresses in rarified gases arising from inequalities of
temperature. Philosophical Transactions of the royal society of London, (170), 231-256.
[11] Deryagin, B. V. & Rabinovich, Ya. I. (1965). ЭКСПЕРИМЕНТАЛЬНАЯ ПРОВЕРКА
ПРИМЕНИМОСТИ ЗАКОНА ПАСКАЛЯ В НЕОДНОРОДНО НАГРЕТЫХ ГАЗАХ (Experimental
test of the validity of Pascal’s law in unevenly heated gases). Dokl. Akad. Nauk SSSR, 162 (1),
5053.
[12] Hernandez, H. (2017). Clausius’ molecular sphere of action in crowded systems: Non-ideal
gas behavior. ForsChem Research Reports, 2, 2017-11. doi: 10.13140/RG.2.2.36384.07681.
... Mathematical expressions for ideal gases are obtained [51].  In gases, forces (and particularly weight) cannot be directly transmitted, and thus, gases do not strictly follow Pascal's law [53]. This idea is also supported by experimental results [56]. ...
... This idea is also supported by experimental results [56]. An alternative analytical expression describing the effect of mass density and external acceleration on pressure changes in presented [53]. This result, based on the conservation of momentum, is used to derive a new barometric formula without recurring to the hydrostatic pressure assumption based on Pascal's law [58]. ...
... While this useful theorem is not new, it represented an important personal paradigm change as it was not previously known by the author. In 5 th place we find the analysis of the validity of Pascal's law in gases [53], reaching the (now evident to the author) conclusion that forces are not directly transmitted through gases as in the case of liquids and solids, and therefore Pascal's law is not valid for gases § § . 4 th place was given to the mechanistic model of liquid evaporation having a single parameter (cohesion temperature), representing an alternative to the empirical Antoine equation (with three parameters) for describing vapor pressure [93,99]. ...
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The current report celebrates the 100 th report published by ForsChem Research, as well as the 7 th year since the beginning of the ForsChem Research Project. In this publication, a brief review of the evolution of ForsChem Research is presented, highlighting the most important contributions published in ForsChem Research Reports. A graphical bibliometric analysis is also included to illustrate the evolution of the works published during its first 7 years, and their impact as measured by ResearchGate (RG) stats. In addition, a selection of the author's top 10 favorite reports is presented. Finally, a brief outline is exposed about the plans for ForsChem Research in the future.
... Pascal's law was originally proposed for describing pressure differences in liquids [2], and has been shown unsuitable for gases [3,4]. In gases, the increase in pressure as the altitude decreases is not directly caused by the weight of the column of gas, as indicated by Pascal's law. ...
... Even more, the increase in atmospheric pressure close to the surface is even larger than the pressure increase expected by the increased weight of air. However, under certain conditions gases can behave approximately as a Pascal fluid [3]. ...
... Thus, it is not the purpose to change the mathematical model but only to change its interpretation. Furthermore, the larger rate of change in pressure compared to Pascal's law is consistent with previous theoretical developments [3,13] as well as experimental results [4]. ...
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Barometric formulas are important mathematical equations used to understand and predict the behavior of the atmosphere pressure at different altitudes. Since the first development by Pierre-Simon de Laplace in the 18th century, the fundamental assumptions leading to barometric formulas have been considering air as an ideal gas at steady-state, and considering atmospheric pressure as a hydrostatic pressure following Pascal’s law. Being rigorous however, gases do not follow Pascal’s law since the molecules are on average so far from each other that they cannot transmit the weight of their neighboring molecules in the vertical direction. For this reason, a new barometric formula has been derived without recurring to the hydrostatic pressure assumption. Instead of Pascal’s law, the conservation of momentum is used to describe the effect of gravity on the vertical molecular density profile. Then, after determining the temperature profile (which can be derived by solving the energy conservation equation, or can be empirically obtained), the molecular density profile can be solved, and the vertical pressure profile can be directly obtained from the ideal gas equation. The barometric formula obtained, which is almost equivalent to the current barometric formula used by the standard atmospheric model (the US Standard Atmosphere of 1976), was tested considering a set of experimental barometric measurements reported from different locations worldwide. Even though only a slight difference is obtained, the new expression no longer requires assuming atmospheric pressure as hydrostatic. The wide success of previous barometric formulas can be explained by the fact that the pressure drop predicted by the conservation of momentum deviates by less than 4% from Pascal’s law. Finally, a multicomponent model of air was considered, which allows the estimation of atmospheric composition changes with altitude.
... A molecular model of an enclosed ideal gas subject to a constant external force [1] was used in a previous report [2] to show that Pascal's law does not describe the behavior of pressure differences in gases. Of course, several simplifying assumptions were necessary for obtaining the mathematical model. ...
... A graphical comparison of the model predictions assuming Pascal's law and the experimental results obtained is presented in Figure 7 where Pascal's law inadequacy can be clearly seen. Since the observed accelerations are smaller than those predicted using Pascal's law, it can be concluded that the actual air pressure difference is larger than that predicted by Pascal's law, in qualitative agreement with an alternative model described in a previous report [2]. ...
... The experimental results presented in this report indicate that Pascal's law does not correctly describe the pressure differences in atmospheric air, supporting the idea that pressure changes in the vertical direction are the result of differences in molecular velocities and densities, rather than the direct effect of the weight of the gas. The true behavior seems to be much more complicated than that predicted by Pascal's law [2]. ...
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Pascal's law, while originally proposed for liquids, has usually been considered valid also for gases. However, the fact that the molecules in a gas are separated from each other beyond their spheres of action most of the time, does not allow the direct transmission of the weight of the gas in the vertical direction. Undoubtedly, the mass of gas and the gravitational acceleration influence the pressure of the gas, but not according to Pascal's law. Although a previously reported mathematical model of the motion of gas molecules supports this idea, an additional experimental verification is presented in this report. The validation of Pascal's law in gases is done considering the effect of differential air pressure on the acceleration of a body during free fall, particularly for low-density bodies. The free fall experiments were done considering four boxes (made of paper) of different sizes and densities, showing significantly lower free fall accelerations (p-value), compared to the predictions obtained assuming the validity of Pascal's law in gases.
... All other gravitational effects will be neglected. The pressure difference between the bottom and the top of the gas is also considered negligible [9]. However, there is a difference between the horizontal and vertical position of the piston, but it is kinematic and not energetic. ...
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The First Law of Thermodynamics represents the principle of energy conservation applied to the interaction between different macroscopic systems. The traditional mathematical description of the First Law (e.g.) is rather simplistic and lack universal validity, as it is only valid when several implicit assumptions are met. For example, it only considers mechanical work done associated with a change in volume of a system, but completely neglects other types of work. On the other hand, it employs the concept of entropy which is not only ambiguous but also implies only heat associated with a temperature difference, neglecting other types of heat transfer that may take place at mesoscopic and/or microscopic levels. In addition, it does not consider mass transfer effects. In the previous report of this series, a more general representation of the First Law is obtained considering different conditions and different types of interactions between the systems. In this report, the expression previously obtained is applied to different representative examples, involving macroscopic systems with no volume change, gas systems with volume change, and even a case where mass transfer between the systems takes place.
... Is Earth actually rotating? Why wind velocities don't match the expected speed of Earth, considering that momentum is not easily transmitted through gases [11], as it can be evidenced by their low viscosity values? Why doesn't Earth leave a tail of atmosphere like comets do? ...
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This is a continuation of the fictional dialogue taking place by Descartes' hypothetical characters (Eudoxius, Epistemon and Polyander). In this opportunity, the discussion revolves around the common confusion between models and reality. Knowledge is built upon models, which are approximate representations of reality. However, it is practically impossible for us to determine the correctness of those models, and therefore, we will never know for sure which model is an accurate description of reality. Unfortunately, scientific models taught in schools and universities are tacitly assumed by most students (and educators) to be our reality, and this misconception limits scientific progress. For this reason, students, educators and scientists are invited to continuously and openly question all of our current scientific paradigms, even when those paradigms can be regarded as "universally accepted truths".
... Recently, an alternative derivation of the barometric formula was obtained without the hydrostatic assumption for the pressure of air [1], but taking into account that in reality Pascal's law is not valid for gases [2,3]. The barometric formula was obtained assuming air at steadystate, with a normal distribution of vertical molecular velocities at each altitude, and using only conservation equations (particularly, introducing the conservation of momentum instead of the hydrostatic pressure assumption). ...
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The classical barometric formula used in atmospheric models is derived neglecting the presence of chemical reactions in the atmosphere. However, many chemical reactions are continuously taking place either promoted by sunlight or simply by the thermal motion of the molecules. In this report, the effect of chemical reactions on the barometric formula will be modeled and discussed. Such effect is not only related to individual molecular concentration profiles but also to thermal profiles when the heat of reaction is considered. The derivation of the model is based on a simple reversible chemical reaction, but it is also generalized for any arbitrary set of chemical reactions taking place in the system. Even under the steady-state assumption, the differential equations obtained do not provide a direct analytical solution and therefore, they must be numerically integrated. A particular example is presented for illustrating the model obtained but also the numerical solution method.
... supercritical fluid, liquid or solid), suitable for the transmission of forces by contact through the entire body, whereas the other body must be elastic. In ideal gases, such transmission of forces is not possible [29], and therefore, energy transfer as work between two gas bodies cannot take place. Let us picture the interface between an ideal gas and a solid body, both at the same temperature ( Figure 22). ...
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A dynamic model of a piston engine is presented based on the original engine proposed by Carnot in 1824. The dynamic model simulation can be used to analyze the Carnot cycle under carefully controlled ('reversible') conditions, as well as the operation of the engine under 'irreversible' conditions. The results obtained for the Carnot cycle are, in general, in agreement with the analytical results predicted by thermodynamic theory. The main difference observed is that the entropy change during a full cycle was negligible but not exactly zero. In fact, the entropy change at the end of the cycle can only be exactly zero if the whole process is adiabatic. In addition, different 'irreversible' scenarios were found that resulted in negligible total entropy change (considering also the surroundings), thus showing that it is not an exclusive property of 'reversible' systems. Different thermodynamic notions including energy, heat, work, reversibility, entropy, the Second Law of Thermodynamics, and engine efficiency, are discussed and explained, in order to get a better understanding from the results obtained.
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Conventional thermodynamic and transport properties of ideal gases have been widely investigated in the absence of external forces (or in the presence of external forces with a negligible effect). However, when the potential energy provided by external forces acting on the molecules of an ideal gas overcomes their thermal kinetic energy, relevant changes in the properties of the system are expected. In that case, non-constant local temperature, density and pressure profiles in the direction of the force are obtained. Local differences with respect to such forced equilibrium profiles will drive the transport of mass and energy. A net heat flux from a colder to a warmer region is therefore possible, which would not be observed under "normal" conditions without significant external forces. The external force is also capable of increasing the overall temperature of the system, since the potential energy provided by the force becomes kinetic energy at the molecular level. In this report, a mathematical description of the molecular position and velocity distribution in the presence of external forces is derived from the fundamental equations of motion, and assuming an initial Maxwell-Boltzmann distribution of molecular velocities and a uniform distribution of molecular positions. Particularly, approximate mathematical expressions of these distributions are proposed for practical purposes. These distributions are then used to obtain the local temperature, density and pressure profiles in the direction of the force. The results obtained, while being approximate, might provide an alternative for modeling different phenomena involving gases under the effect of relevant external forces (e.g. atmospheric models).
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Molecules are in permanent motion and interaction. Even though a system might be at rest from a macroscopic point of view, it is restless at the molecular scale. Such continuous molecular motion results in the flow of molecules through space. The number of molecules crossing a boundary per unit time per unit area is denoted as a molecular flux. Three different types of boundaries are considered: Completely permeable, semi-permeable rigid and impermeable rigid boundaries. When the system is contained by rigid (impermeable or semi-permeable) boundaries such molecular flux against the walls produce a net force per unit area that is denoted as pressure. The purpose of this report is deriving mathematical expressions for estimating the molecular flux and pressure on rigid boundaries in ideal gases, using only the classical equations of motion and the distribution of molecular positions and velocities in the system. The pressure at the interior of an ideal gas system is zero because there are no forces acting on the molecules. Thus, the concept of equivalent pressure, as the pressure that would be obtained in the presence of an impermeable rigid boundary, is introduced. The mathematical results presented are based on the following general assumptions: i) Molecular collisions in the gas are negligible (ideal gas assumption). ii) There are no external forces acting on the system. iii) There is no net macroscopic motion of the gas parallel to the surface. iv) Molecular positions are uniformly distributed in the system volume. v) The orthogonal component of molecular velocity is normally distributed. vi) The system considered is large compared to the size of the molecules. The results obtained are consistent with the continuity equation. Furthermore, when the ideal gas system is at macroscopic rest, the classical ideal gas thermodynamic equation of state is obtained. In addition, three different regimes of molecular flux and pressure are observed: The thermal motion regime, the macroscopic regime and the transition regime between the first two.
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Clausius' definition of the molecular sphere of action has proved to be a valuable concept for describing and understanding the behavior of matter from a molecular point of view. In the present report, the effect of crowding on the mean sphere of action between Lennard-Jones molecules is investigated by molecular dynamics simulation. A crowding function is defined in order to quantify the effect of molecular crowding on the spheres of action. For single component systems at high temperatures, it was possible to identify three different cases of crowding: 1) an ideal gas case, where molecules do not affect the sphere of action of their neighbors, 2) a non-ideal gas case, where the molecular interaction potential of neighbor molecules interferes causing a distortion in the sphere of action, and 3) a dense case, where the sphere of action of neighbor molecules overlap, resulting in a permanent collision condition between neighbors. The results obtained can be generalized for multicomponent systems using an extension of Lorentz and Berthelot rules of mixing for calculating the overall Lennard-Jones parameters of the mixture. Using this approach, it is possible to determine the conditions for transition from the ideal gas to the non-ideal gas behavior, and also from the non-ideal gas to the dense behavior. An example is presented for air, where an extended phase-diagram is obtained, showing that the dense behavior approximately corresponds to the supercritical phase. It was found that the transition density to the dense phase corresponds to the density of the critical point of air. It is also observed that at ambient conditions, air always behave as an ideal gas.
Article
1. In this paper I have followed the method given in my paper “On the Dynamical Theory of Gases” (Phil. Trans., 1867, p. 49). I have shown that when inequalities of temperature exist in a gas, the pressure at a given point is not the same in all directions, and that the difference between the maximum and the minimum pressure at a point may be of considerable magnitude when the density of the gas is small enough, and when the inequalities of temperature are produced by small solid bodies at a higher or lower temperature than the vessel containing the gas. 2. The nature of this stress may be thus defined:— Let the distance from a given point, measured in a given direction, be denoted by h ; then the space-variation of the temperature for a point moving along this line will be denoted by d θ/ dh , and the spaced variation of this quantity along the same line by d ² θ/ dh ² .
Traites de l'equilibre des liqueurs, et de la pesanteur de la masse de l'air
  • B Pascal
Pascal, B. (1663). Traites de l'equilibre des liqueurs, et de la pesanteur de la masse de l'air. Chez Guillaume Desprez, Paris.
Obtaining and Applying Motive Power. British Patent No
  • J Bramah
Bramah, J. (1795). Obtaining and Applying Motive Power. British Patent No. 2045.
Standard Atmosphere. International Organization for Standardization. Pascal's Law in Gases
ISO 2533:1975 (1975). Standard Atmosphere. International Organization for Standardization. Pascal's Law in Gases
The international standard atmosphere (ISA)
  • M Cavcar
Cavcar, M. (2000). The international standard atmosphere (ISA). Anadolu University, Turkey. http://www.academia.edu/download/52648552/ISAweb.pdf
Experimental test of the validity of Pascal's law in unevenly heated gases)
  • B V Deryagin
  • Ya I Rabinovich
  • Экспериментальная
  • Применимости
  • Паскаля
  • Неоднородно
  • Газах
Deryagin, B. V. & Rabinovich, Ya. I. (1965). ЭКСПЕРИМЕНТАЛЬНАЯ ПРОВЕРКА ПРИМЕНИМОСТИ ЗАКОНА ПАСКАЛЯ В НЕОДНОРОДНО НАГРЕТЫХ ГАЗАХ (Experimental test of the validity of Pascal's law in unevenly heated gases). Dokl. Akad. Nauk SSSR, 162 (1), 50-53.