The student Mustafa Rahman

Polyatomic Gas

Linear & non-linear polyatomic

molecules

Types of polyatomic molecules

 9.4 The Polyatomic Gas

9.4.1 Rotational Contribution.

9.4.2 Vibrational Contribution.

9.4.3 Property Calculations for Polyatomic Molecules.

9.4.4 Example.

9.4.5 Summary.
 9.4 The Polyatomic Gas
The evaluation of thermodynamic properties for a gaseous assembly composed
of polyatomic molecules depends on whether the associated molecular structure is
linear or nonlinear.

For linear molecules, the atoms are arranged along a single Cartesian
coordinate; examples are CO2, N2O, and C2H2.
Purely geometrical considerations restrict‫ت قيد‬linear polyatomics to two rotational
degrees of freedom (as for diatomics), while nonlinear polyatomics exhibit three
such degrees of freedom.

for a polyatomic molecule composed of n individual atoms, the number of

vibrational modes must be 3n − 5 for the linear case and 3n − 6 for the nonlinear
case, as summarized in Table 4.9.
 Each vibrational mode of a polyatomic molecule designates an
inter nuclear distance or angle whose oscillation reflects a local
electronic potential; however, is much too difficult to handle from
‫ا لتع املم ع ن م وذج‬a quantum mechanical viewpoint; therefore, as for the

diatomic case, we seek a simpler model reflecting available

spectroscopic data.
On this basis, we employ‫ن ستخدم‬the harmonicoscillator model,
thus fostering ‫ت ع زيز‬complete separation of energy modes. A fully
complex model, including any rovibrational coupling, must
obviously be employed for more rigorous‫اكثر دقة‬calculations
Assuming complete mode separation, the molecular partition
function for a polyatomic molecule follows Eq is giving:
 The translational contribution, similar to that for a diatomic
molecule, is given by
Where the total mass, m, is simply the sum
of all atomic masses composing the
molecule.
Therefore, we conclude that the contribution of the translational mode to thermodynamic
properties is the same for a polyatomic molecule as for the monatomic gas.

For nearly all polyatomics, the energy ascribed to the first excited electronic level is
sufficiently high that only the ground electronic state is necessary for most property
calculations. Hence, from Eq. (9.15), the electronic partition function becomes

So that, from Eqs. (4.36–4.42), the resulting contribution

to thermodynamic properties is nonzero only for the
entropy and free energies. The required electronic
degeneracy can be obtained, as usual, from the term symbol
associated with the ground electronic state.
 9.4.1 Rotational Contribution)‫ت أثير (م سا مه ة‬

For a polyatomic molecule, the rotational contribution to thermodynamic

properties clearly depends on whether the molecule is linear or nonlinear.
As indicated previously‫ك م ا ه و م بينس ابقا‬, a linear polyatomic has the same two
rotational degrees of freedom as for a diatomic molecule. In addition, because of the
greater mass of typical polyatomic species, invariably T/θr > 30 so that the
rotational partition function, following Eq. (9.26), becomes
(9.79)

The symmetry factor in Eq (9.79) reflects the chemical structure of a linear

polyatomic; thus, as examples:
σ = 1 for N2O (N–N–O) and σ = 2 for CO2 (O–C–O).
Based on the diatomic case, the characteristic rotational temperature, θr , is given by Eq.
(9.23), except that the moment of inertia must be evaluated from
where xi represents the distance of each constituent
atom from the molecule’s center of mass
 Thus, from Eq. (9.79), the rotational contributions to the internal
energy and specific heat for a linear polyatomic are
(9.80).

(9.81).

In comparison to the linear polyatomic, the nonlinear polyatomic has three rotational
degrees of freedom and thus three principal moments of inertia:

where xi , yi , and zi are atomic distances from the

molecule’s center of mass, as determined via the usual
formulation,

For our purposes, we need only recall that the principal coordinates can ordinarily be established by
defining one of the three Cartesian axes to be along a line of symmetry within the molecular structure.
 Based on possible relations among the magnitudes of the principal moments of inertia, we may
define three types of polyatomic molecules, as listed in Table 9.5. For the simple spherical top (Ix = Iy =
Iz), quantum mechanics can be applied to determine rotational energies and degeneracies, as for the
diatomic molecule. The result is

Hence, from Eq. (4.12), the associated rotational partition

function becomes
 Similarly, for the asymmetric top, we find that

(9.82).

where, from Eq. (8.2), each characteristic temperature specifying rotational motion about a single
Cartesian coordinate can be related to a rotational constant, Bei , and thus to a moment of inertia, Iei , for
a given principal coordinate via

Clearly, both the symmetric and spherical tops can be considered special cases of the asymmetric
top, so that the rotational partition function for all three cases can be determined via Eq. (9.82).
As usual, the symmetry factor must be calculated from structural considerations so as to correct for
any repeated counting of indistinguishable configurations. In essence ‫جوهر‬, the symmetry factor
indicates ‫ ي شير‬the number of ways that a molecule can be rotated to achieve‫ت ح قيق‬the same orientation
in three-dimensional space.
Typical examples are given in Table 9.6, with structural clarifications provided for NH3, CH4, and
C6H6 in Fig. 9.4.
 Regardless of‫ب غضا لنظر عن‬the symmetry factor, Eq. (9.82) indicates that
the rotational contributions to the internal energy and specific heat
for a nonlinear polyatomic are

Therefore, we find that, compared to the linear polyatomic of Eqs. (9.80) and (9.81), the
rotational mode for a nonlinear polyatomic contributes an additional RT/2 to the internal
energy and an additional R/2 to the specific heat.

In otherward, the rotational contribution to internal energy and heat capacity for both linear and
nonlinear polyatomics is in exact agreement with that expected from classical equipartition theory
 9.4.2 Vibrational Contribution

According to Table 9.4, linear and nonlinear polyatomics contain 3n–5 and 3n–6 vibrational
modes, respectively. Unfortunately‫ل س وء ا حل ظ‬, because of the plethora‫وفرة‬of such modes for large
polyatomics, their identification is hardly straightforwardً ‫ا‬ ‫ض‬
‫ ب ا لكاد ي بدو وا ح‬.

However, by choosing special coordinates labeled normal coordinates, the kinetic and
potential energy terms become pure quadratics so that we can ensure simple harmonic
motion.

In particular, the specification of pure harmonic motions supported by a given molecular

structure is called normal mode analysis, as described for a simple linear triatomic in Appendix
L.
 The purpose from normal mode analysis is identification‫ديد‬ ‫ت ح‬of the
independent vibrational modes for any polyatomic molecule.

Significantly, displacement along the identified normal coordinates causes all nuclei to move
in phase with the same harmonic frequency.
Hence, we can model the inherently‫ط بيعته ا‬complex vibration of a polyatomic molecule with
the same harmonic oscillator equations that we previously used for the diatomic molecule.
Operating again with the zero of energy at the ground vibrational level, we have from Eq.
(9.47)
(9.86). (9.47).

where m is 3n - 5 for a linear and 3n - 6 for a nonlinear polyatomic. From Eq. (8.2), the
characteristic vibrational temperature for each normal mode is

(9.87).
 where ωei is a so-called normal frequency (cm-1) and the rotational
constants Bei, these normal vibrational frequencies are usually
obtained from the analysis of spectroscopic data.

we find from Eqs. (9.48) and (9.49) that the vibrational contributions to the internal energy
and heat capacity, respectively, for any polyatomic molecule are

(9.48).
(9.88).

(9.49)
(9.89).

Each term of Eqs. (9.88) or (9.89) entails an independent characteristic temperature.

the required θvi values are based on Eq. (9.87) and tabulated
values of ωei, as elaborated for CO2 and H2O in Fig. 9.5. Typically,
for a linear triatomic such as CO2, we identify a symmetric stretch
mode, an asymmetric stretch mode, and two identical bending
modes.
 9.4.3 Property Calculations for Polyatomic Molecules

As for the monatomic and diatomic cases, separation of energy modes implies that we may
determine thermodynamic properties for polyatomic gases by summing over the contributions
from each energy mode. As an example, the internal energy for a nonlinear polyatomic can be
evaluated by summing the translational contribution from Eq. (9.6), the rotational
contribution from Eq. (9.84), and the vibrational contribution from Eq. (9.88), thus
obtaining

For the entropy, we must carefully allocate contributions from the translational and the three
internal energy modes, so that from Eqs. (8.14) and (8.15), we have

(9.90)
9.4.4 Example.
 summary

In summary, given the knowledge established in this chapter, analogous expressions could
be obtained for any thermodynamic property‫خاص ية‬of an ideal gas by using appropriate‫من اس ب‬
contributions relevant to monatomic, diatomic, linear polyatomic, or nonlinear polyatomic
molecules.

Training\ Answer briefly an following

points?

• Linear & non-linear polyatomic molecules.

• Types of polyatomic molecules.

• Contributions of polyatomic molecules.

Thank you very much for
listening