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Heat Capacity of Ortho-

Para Hydrogen
Spin isomer of hydrogen was first proposed by Werner Heisenberg and Friedrich Hund in 1927.
Taking into consideration para-hydrogen was first synthesized by Paul Harteck and Karl Friedrich
Bonhoeffer in 1929. The main idea is based on that relative spin coordinate changes the energy
distribution and results in two kind of hydrogen; para and ortho. (Spin Isomer, 2017)

Abstract
ERŞAN AKALAR

Advisor: Sadi Turgut


Introduction

The main observed value in physics is the energy. It is also taken consideration during
all calculations to understand conditions and to evaluate them. For example, in
thermodynamics, there is a strong relation between energy and entropy. Throughout this
relation, macroscopic quantities such as heat capacity can be calculated. However, as the
energy scale is changed, the necessary calculations are also needed to be revised. To
calculate heat capacity for hydrogen, there are two approaches, one for the high
temperatures and the other is for lower temperatures.

In this project, the aim is to obtain the heat capacity of hydrogen at different energy
scales; from zero -0- kelvin to -let’s say- 1000 kelvin. As we change the energy scale, we see
that the necessary calculation differs respectively. At low temperatures, quantum
mechanical approach to energy gives the correct
answer compatible with observed quantities, whereas
at higher temperatures, somehow, quantum
mechanical approach vanishes by leaving its place to
classical approach. At quantum level, spin of hydrogen
atoms is playing role to determine the heat capacity.
When spins of atoms are in the same direction, it is
called ortho-hydrogen, in the opposite condition; it is
called para-hydrogen. https://en.wikipedia.org/wiki/Spin_isomers_of_hydrogen

The effect of variety of hydrogen molecule is observed throughout energy difference


of spin isomers. Para-hydrogen which is the anti-parallel spin direction is ground state with
respect to ortho-hydrogen. Therefore, at lower temperatures, para-hydrogen is dominant
against ortho-hydrogen. Actually, all hydrogen molecules can be found at ground state. As
temperature increases, hydrogen molecule gets excited and turns into ortho-hydrogen. This
change turns to be as if there are two different types of gases. That is why; the heat capacity
change is affected by these two states. However, at high temperatures, not all hydrogen gas
turns into ortho-hydrogen. That is the interesting point, since actually; we expect at very
high temperatures all hydrogen molecules to be excited. This does not happen, because
probabilities behave classically at high temperatures and all states are equally probable.
Therefore, by the addition rule of spins, there is one state of para-hydrogen and there are
three states of ortho-hydrogen. At room temperatures, the ratio of para-hydrogen to ortho-
hydrogen is 1:3.
Theory:

The Hamiltonian of hydrogen molecule in general is

P21 P22
H=( + )+V bound (|r 1−r 2|)
2m 2 m

(Simply, kinetic energies of two atoms and bounding potential energy for outside frame of
reference) For relative coordinates, the Hamiltonian is

P2cm p2
H=( + )+V bound (|r 1−r 2|)
2mtotal 2 μ

P2cm ħ❑2 l (l+1 ) 1


H= ( 2m total
+
2 μr 2 )
+V minimum (|r 1−r 2|) + ħω(n+ )
2

1
Since V minimum∧ħω are constants, we can omit them.
2

After this point, we are not interested in translational motion of center of mass and
vibrational energy modes. The former has not got effect on the symmetry of wave function
and the latter has very higher excitation energies than rotational energy level. Therefore, we
are interested in rotational energy levels. In addition to this, rotational motion invokes the
inversion of fermions and resulting in relative angular momentum values regarding to
symmetry of the wave function. It is expected that fermions under inversion of origin show
anti-symmetric wave property, which is

Ψ ( r 1 , r 2 )=−Ψ ( r 2 , r 1 )

¿ Ψ (r , θ) ⟩ =Rvibration ( r) φlm (θ , ɸ) ¿ S , ms ⟩ (In center of mass frame)

What is the role of spin is clear when we investigate the symmetry of wave function.
Since hydrogen atoms are fermions, they have one-half spin value and they cannot be found
at the same energy level like bosons. The summation of the spin is

|S1−S 2|<S Total < S 1+ S 2 ; → 0<S Total < 1


For singlet states STotal =0 ; one anti-symmetric wave function, m s =0

1
Ψ s= (¿ ↑↓ ⟩−¿ ↓↑ ⟩ )
√2
For triplet states STotal =1 ; three symmetric wave functions, m s =−1 ,0 ,+1
1
Ψ t= ( ¿ ↑↓ ⟩ + ¿ ↓↑ ⟩ )
√2
These ms values determine the degeneracy of the rotational energy states.

It is known that singlet has anti-symmetric spin function, so to protect its property ℓ
values should be even. For triplet states, they are symmetric spin functions, so l values
should be odd number. For example, under inversion with respect to origin, θ becomes θ−π
andɸ+ π. Therefore, φ ml ( θ , ɸ )=φml ( θ−π , ɸ+ π ) gives plus (+) forl=2 n, minus (-) forl=2 n+1. (
n=0,1,2,3 …) (Spin Isomer of Hydrogen, Wikipedia)

After this point, to obtain heat capacity, we need to find partition function.
2
−ħ l (l +1)

Z=∑ ( 2l+1)e
2 I kB T
, (2 l+ 1) term comes for m l values. There are (2 l+ 1) times
l

degeneracy. However, this partition function is valid only we think that hydrogen atoms are
spinless and distinguishable particles. For the otherwise condition, we have to split partition
function as Z singlet and Ztriplet according to their ℓ values. Therefore;
2 2
−ħ l (l +1) −ħ l (l +1)
2 k BT I 2 k BT I
Z singlet = ∑ (2l+1)e and Ztriplet = ∑ (2l+1)e
l=even l=odd

Z=Z singlet +Z triplet

ℓ values are important as temperature changes. They represent the energy split of
rotational energy levels. This energy level should be evaluated in accordance with the energy
scale in which the gas exists. For example, if we think that we are in energy scale of room
temperature, energy splitting of rotational levels is not distinguishable; since their difference
is so small than heat energy of room that they may be account the same. That is why, the
summations turns into an integral changing variable is ℓ. In other words, all rotational energy
Pn
probabilities turn out to be equal at room temperatures. ( =1)
Pn−1
2
∞ ħ l (l +1)
−β
2I 2 I k BT
Z=∫ ¿ ¿2l+1 ¿ e d l= for spinless partition function
0 ħ2

d2 F
Then, to find heat capacity; F=−k B T ln z => C v =−T => C v =k B
dT2
For singlet state, partition function is

2
∞ ħ l (l +1)
−β
2I 2 I k BT
Z singlet =∫ ¿ ¿ 2l+1 ¿ e d l=
0 ħ2

For triplet state, partition function is


2
∞ ħ l (l +1)
−β 6 I kBT
Ztriplet =∫ 3 ¿ ¿2l+1 ¿ e 2I
the multiple three comes from the ms values,
d l=
0 ħ2
there are three degeneracy for triplet state.

2 I k BT
Z singlet ħ2 1
= = It is seen by this equation that the proportion of 1 to 3 is because of
Z triplet 6 I k B T 3
2
ħ
compound spin states.

Unlike high temperatures, for low temperatures, the calculation differs. Since our
energy scale becomes comparable to the rotational energy levels of hydrogen molecule,
each energy level has different contribution to probability, which means that we cannot
Pn
accept probabilities as equal. ( ≠1) Therefore, summation over ℓ values protects its
Pn−1
form. To find heat capacity, again we need partition function, but this time we find C v as
ΔU
.
ΔT

E n e− β E
n

Δ U will be calculated by mean energy value. U average =∑ En Pn=∑ . Therefore,


n n Z
2
∂U σ e
C v= = , as numeric values.
∂ T K B T2

Data and Conclusion:

With this formula, we expect a graph that at high temperature it will show a constant
heat capacity.

The graph of heat capacity of spinless hydrogen gas is Figure 1a. This is only dependent on
rotational excitation energy.
The graph of para and ortho hydrogen is Figure b and Figure c, respectively. As seen from
figure b, approximately 200 kelvin, heat capacity is dominated by para-hydrogen which
means para-hydrogen is more effective than ortho-hydrogen. Also, Figure d shows that at
low temperature ratio goes to infinity, since there is almost not ortho-hydrogen contribution
to heat capacity. That is expected result, since at low temperature, all hydrogen gas turns
into para-hydrogen state, which is the ground state.

12 12 Heat
Heat capacity-
capacity- Temperaturefor
Temperature
Para-Hydrogen
10 10

8 8

6
6(Joule*NA/Kelvin)
Cv
Cv (Joule*NA/Kelvin)

4 4

2 2

0
0 Temperature (Kelvin)
0
0
2
2
4
4 Temperature
6 (Kelvin)
6
8
8
10
10
12
12

Figure a

Figure b
9
Heat capacity- Temperature for
Ortho-Hydrogen
8

4
Cv (Joule*NA/Kelvin)
3

0 Temperature (Kelvin)
0 200 400 600 800

Figure c

12 Ratio of Cv (Para/Ortho) - Temperature

10

0
Temperature (Kelvin)
0 2 4 6 8 10 12

Figure d
References:

 Revolvy, L. (n.d.). "Spin isomers of hydrogen" on Revolvy.com. Retrieved June 05, 2017,
from https://www.revolvy.com/topic/Spin%20isomers%20of
%20hydrogen&item_type=topic
 Spin isomers of hydrogen. (2017, May 11). Retrieved June 05, 2017, from
https://en.wikipedia.org/wiki/Spin_isomers_of_hydrogen

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