Vol.

6, 2021-03

The Effect of Chemical Reactions on the Barometric Formula

Hugo Hernandez
ForsChem Research, 050030 Medellin, Colombia
hugo.hernandez@forschem.org

doi: 10.13140/RG.2.2.26938.72649

Abstract

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.

Keywords

Atmospheric reactions, Barometric formula, Chemical reactions, Energy conservation, Lapse

rate, Pascal’s law, Troposphere

1. Introduction

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 steady-
state, 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). In addition, no chemical reactions were assumed to
occur in the atmosphere. However, this is not an accurate assumption since many different
reactions involving air molecules are permanently taking place in the atmosphere. Thus, the

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 The Effect of Chemical Reactions
on the Barometric Formula
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

purpose of the current report is to analyze and discuss the effect of chemical reactions on the
barometric formula.

By assuming the following linear profile for the atmospheric temperature ( ):

( ) ( )
(1.1)

the alternative multicomponent barometric formula previously developed (neglecting chemical

reactions) predicts the following molecular density ( ̃) and equivalent pressure ( ) [4] profiles:

( )
̃( ) ̃ ( )

(1.2)

( ) ( )∑ ̃ ( )

(1.3)

where is a constant lapse rate (negative temperature gradient), is the altitude with respect
to the ground, ̃ is the molecular density of component (in a mixture of components), is
the molecular mass of the -th component, is Boltzmann constant,
is the gravitational acceleration, is a mean molecular velocity
correction factor [1], and the subscript indicates an arbitrary reference point (usually the
ground).

2. Analyzing the Effect of Chemical Reactions

In order to begin to understand the effect of chemical reactions in the atmosphere, a simple
hypothetical reversible reaction is considered:

(2.1)
where and are molecular species present in the atmosphere.

This reversible reaction can be modeled by the following rate equations:

( ) ( )̃ ( )
(2.2)
( ) ( )̃ ( )
(2.3)

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 The Effect of Chemical Reactions
on the Barometric Formula
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

where and are the reactions rates for the forward and backward reactions, respectively,
and and are the corresponding reaction rate coefficients. This hypothetical reaction
represents the reversible decomposition of one molecule of species into two molecules of
species . Assuming only thermal effects, the reaction rate coefficients can be represented by
general Arrhenius expressions [5], as follows:

( ) ( ) ( )

(2.4)

( ) ( ) ( )

(2.5)
where are kinetic parameters.

In order to simplify the model, let us assume only components in the air mixture ( ). In
this case, component represents an inert species.

Following the previous derivation of the barometric formula [1], the steady-state balance of
momentum for each component in a horizontal atmospheric section of volume , assuming
a symmetrical vertical velocity distribution, yields:

( ) ( )
̃( )
(2.6)

where and represent the net molecular flux of species across the horizontal plane in the
upward and downward direction respectively, and is the average molecular speed of
species at altitude . The effect of the chemical reaction on the momentum balance is
neglected considering the symmetry of the velocity distribution assumed, and also assuming
that momentum is conserved during the reaction inside the control volume.

The molecular flux corresponds to:

( ) ̃ ( ) ( )
(2.7)
( ) ̃ ( ) ( )
(2.8)

where ̃ and ̃ are the molecular densities of species immediately above and below the
horizontal section at altitude , respectively.

Considering the Maxwell-Boltzmann distribution assumption with a limiting-velocity correction

factor [1]:

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 The Effect of Chemical Reactions
on the Barometric Formula
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

(2.9)

√ √

(2.10)
then Eq. (2.6) can be expressed as:

̃ ̃ ̃
(̃ ̃ )

(2.11)

On the other hand, the balance of molecules of species in a horizontal atmospheric section of
volume yields:
( ) ( )
( )̃ ( ) ( )̃ ( )
(2.12)
or equivalently,
̃ ̃
(̃ ̃ ) √ ( ̃ ̃ )

(2.13)

where and represent the relative stoichiometric coefficients of species for each
reaction.

Combining Eq. (2.11) and (2.13) results in:

̃ ̃
√ ( ̃ ̃ ) ( ̃ ̃ )

(2.14)

Neglecting the differences in density at both sides of the differential region we can obtain the
following approximation:

̃
( )̃ √ ( ̃ ̃ )

(2.15)
which can be expressed as the following integral:

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 The Effect of Chemical Reactions
on the Barometric Formula
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

̃
̃
∫ ∫
̃ ( )̃ ( ̃ ̃ )
√
(2.16)

Particularly for the reaction considered we have: , ,

. Given that for a reversible chemical reaction , then Eq. (2.16) can be
alternatively expressed as:
̃
̃
∫ ∫
̃ ( )̃ ( ̃ ̃ )
√
(2.17)

For any inert species ( in this case) Eq. (2.17) can be solved resulting in:

̃ ( )
( ) ∫ ( ) ( ) ( )
̃ ( )
(2.18)
or equivalently,
( )
̃ ̃ ( )

(2.19)
which is identical to Eq. (1.2).

In the case of species and , Eq. (2.17) become:

̃
̃
∫
̃ ( )) ( )̃
( √ ( ) ̃ √ ( )

(2.20)
̃
̃
∫
̃ ( )̃ ( )̃
√ ( ) ( )̃ √ ( )

(2.21)

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 The Effect of Chemical Reactions
on the Barometric Formula
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

Unfortunately, it is no longer possible to separate variables in order to obtain an analytical

solution unless the system is exactly at chemical equilibrium at each altitude (valid only when
each horizontal section is a closed system). That is when:

( ) ( )̃ ( ) ( ) ( )̃ ( )
(2.22)

Any situation beyond such chemical equilibrium condition will result in a vertical density profile
which is not easily obtained analytically, as a result of the complexity of the equations involved.
Furthermore, if we consider the heat of reaction in an energy balance, the vertical temperature
profile will also be affected, complicating even more the results.

Thus, instead of analytically solving the problem we will focus on the steady-state solution
obtained numerically. One simple approximation is using Euler’s numerical integration method.
Of course, improved methods for the numerical solution of ordinary differential equations
(Runge-Kutta, Adams-Bashforth, etc. [6]) can be used but their algebraic representation
complexity increases. Thus, Euler’s approach is used only for illustration purposes. If we know
the ground-level atmospheric composition (or the composition at any reference altitude), then
we can just proceed to integrate vertically in order to obtain the composition profiles.

3. Numerical Solution neglecting the Heat of Reaction

Neglecting the effect of the heat of reaction on the temperature profile of the atmosphere,
and using Euler’s method as a representative numerical integration approach, we can
transform Eq. (2.17) into:

̃( ) ̃( ) (( )̃ √ ( ̃ ̃ ))

(3.1)

This expression can be generalized for any set of chemical reactions taking place in the
atmosphere as follows:

̃( ) ̃( ) (( )̃ √ ∑ )

(3.2)
where represents the rate of the -th reaction determined at altitude . This rate can be a
function of temperature, light intensity or any other source of energy promoting the reaction.

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 The Effect of Chemical Reactions
on the Barometric Formula
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

For the reacting species in the example of the previous Section we get (from Eq. 2.20 and 2.21):

̃ ( ) ̃ ( ) (( √ )̃ √ ̃ )

(3.3)

̃ ( ) ̃ ( ) (( )̃ √ ̃ √ ̃ )

(3.4)

while for the inert species, Eq. (2.19) is used. Finally, the temperature profile is given by Eq. (1.1).
As an example, let us consider the arbitrary conditions summarized in Table 1 and Table 2. The
concentration profiles obtained in the presence and in the absence of reaction are presented in
Figure 1.

Table 1. Physicochemical properties of the different species considering the reaction

Property \ Species A B C
(g/mol) 32 16 28
-1 2 0
̃ (mol/m ) 3
10 10 10

Table 2. Kinetic parameters of the forward and backward reactions considering the reversible
reaction
Parameter Forward reaction Backward reaction
20 s-1 1×10-6 m3/(mols)
0 1
15 kJ/mol 10 kJ/mol

The concentration profiles shown in Figure 1 correspond to those required to match the
arbitrarily pre-defined ground-level composition. In the absence of chemical reaction, the
concentration of the heavier species is lower at high altitudes compared to the lighter species.
However, in the presence of reactions, this situation might change, as illustrated by the
particular example considered. Of course, the heat of reaction was neglected, and the
temperature profile was assumed linear as described by Eq. (1.1).

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 The Effect of Chemical Reactions
on the Barometric Formula
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

Figure 1. Concentration profiles for a 3-component system with (solid lines) and without
(dotted lines) considering the reaction. Blue: Species A. Red: Species B. Green: Inert
species C. Neglecting heat of reaction.

4. Numerical Solution considering the Heat of Reaction

When the heat of reaction is considered, the temperature profile must be updated according to
the steady-state energy (enthalpy in this case) balance equation:

(̃ ) (̃ )
∑ ∑

(4.1)

where is the enthalpy capacity of species [7,8], and is the enthalpy of the -th reaction.
An exothermic reaction will have a negative enthalpy of reaction. After some algebra, this
equation can be equivalently expressed as follows:

∑ ( ∑ )

∑ ( √ ̃ )

(4.2)

where represents the corresponding temperature lapse rate in the absence of chemical
reactions.

Using Euler’s integration approach, Eq. (4.2) becomes:

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 The Effect of Chemical Reactions
on the Barometric Formula
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

∑ ( ∑ )
( ) ( )
∑ ( √ ̃ )
( )
(4.3)
Of course, Eq. (3.2) and (4.3) must be solved simultaneously.

Considering the same example of the previous Section with , and

, and assuming a lapse rate of in the absence of chemical reactions, the
temperature profile presented in Figure 2 is obtained (starting from the same ground-level
conditions). In addition, the new concentration profiles are illustrated in Figure 3.

Figure 2. Temperature profile for a 3-component system considering the reaction (blue
solid line) and without considering the reaction (red dotted line). .

Due to a net prevalence of the forward reaction which is exothermic, the same ground-level
temperature is obtained necessarily at a larger lapse rate (more negative), and therefore, the
temperature drop with altitude is much larger.

It is also observed that the presence of the reaction affects the concentration profile of the
inert species by changing the temperature profile of the whole atmosphere. In this case, the
same ground-level concentration of the different components is achieved when the
concentration of the inert species is lower at higher altitudes in the presence of the reaction.

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 The Effect of Chemical Reactions
on the Barometric Formula
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

Figure 3. Concentration profiles for a 3-component system with (solid lines) and without
(dotted lines) considering the reaction. Blue: Species A. Red: Species B. Green: Inert
species C. Considering heat of reaction.

5. Conclusion

Even though their effect is usually neglected, chemical reactions play a key role in the vertical
distribution profile of molecules in the atmosphere. Since chemical reactions are typically
influenced by temperature, the vertical temperature profile will have an important effect on
the extent of reaction at each particular altitude. In addition, the heat of reaction influences
the temperature profile. This complex interaction between concentration and temperature at
different altitudes do not have a simple analytical solution, unless no reaction is taking place,
yielding in such case the conventional barometric expression. When chemical reactions take
place, even assuming a steady-state atmospheric condition, the vertical concentration and
temperature profiles must be obtained by numerical integration of a set of ordinary differential
equations. If the model is dynamic, the system becomes a set of partial differential equations.

This report shows the effect of chemical reactions on the differential barometric formula, and
some arbitrary examples are used to graphically illustrate such effect.

Acknowledgments

This research did not receive any specific grant from funding agencies in the public,
commercial, or not-for-profit sectors.

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 The Effect of Chemical Reactions
on the Barometric Formula
Hugo Hernandez
ForsChem Research
hugo.hernandez@forschem.org

References

[1] Hernandez, H. (2020). A Barometric Formula without the Hydrostatic Pressure Assumption.
ForsChem Research Reports, 5, 2020-14. doi: 10.13140/RG.2.2.20093.49126.

[2] Hernandez, H. (2020). Pascal’s Law in Gases. ForsChem Research Reports, 5, 2020-09. doi:
10.13140/RG.2.2.36166.09285.

[3] Hernandez, H. (2020). Testing Pascal's Law in Gases using Free Fall Experiments. ForsChem
Research Reports, 5, 2020-12. doi: 10.13140/RG.2.2.35747.89120.

[4] 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.

[5] Hernandez, H. (2019). Collision Energy between Maxwell-Boltzmann Molecules: An

Alternative Derivation of Arrhenius Equation. ForsChem Research Reports, 4, 2019-13. doi:
10.13140/RG.2.2.21596.33926.

[6] Atkinson, K., Han, W., & Stewart, D. E. (2009). Numerical solution of ordinary differential
equations. John Wiley & Sons. Hoboken, New Jersey.

[7] Hernandez, H. (2019). Collision Energy between Maxwell-Boltzmann Molecules: An

Alternative Derivation of Arrhenius Equation. ForsChem Research Reports, 4, 2019-13. doi:
10.13140/RG.2.2.21596.33926.

[8] Hernandez, H. (2020). Equivalent Degrees of Freedom, Heat Capacity and Adiabatic Index of
Non-ideal Gases. ForsChem Research Reports, 5, 2020-16. doi: 10.13140/RG.2.2.25053.84964.

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