Bondoc, Kristopher Jayson C.

11 July 2012
CH 45 A: Physical Chemistry 1, Laboratory Instructor: Erwin P. Enriquez, Ph.D.

Experiment 3: Heat Capacity Ratios for Gases

Derived Data Tables (for theoretical values: with vib. contributions; without vib. contributions)

Trial 1 Trial 2
P1 P2 P3 T P1 P2 P3 T
mmHg mmHg mmHg °C mmHg mmHg mmHg °C
oxygen 29.03 753.0 7.54 25.5 23.23 753.0 6.59 25.5
nitrogen 30.33 753.0 18.98 27.0 35.79 753.0 9.27 27.0

Trial 1 Trial 2
Pcarboy1 Pcarboy2 Pcarboy3 T Pcarboy1 Pcarboy2 Pcarboy3 T
mmHg mmHg mmHg °C mmHg mmHg mmHg °C
oxygen 782.03 753.0 760.54 25.5 776.23 753.0 759.59 25.5
nitrogen 783.33 753.0 771.98 27.0 788.79 753.0 762.27 27.0

Trial 1 Trial 2
γ γ
experimental theoretical experimental theoretical
oxygen 1.3643 1.2857; 1.4000 1.4080 1.2857; 1.4000
nitrogen 2.7391 1.2857; 1.4000 1.3663 1.2857; 1.4000

Trial 3 Trial 4
P1 P2 P3 T P1 P2 P3 T
mmHg mmHg mmHg °C mmHg mmHg mmHg °C
oxygen 29.81 753.0 8.67 25.5
nitrogen 32.50 753.0 9.01 27.0 36.40 753.0 10.05 25.5

Trial 3 Trial 4
Pcarboy1 Pcarboy2 Pcarboy3 T Pcarboy1 Pcarboy2 Pcarboy3 T
mmHg mmHg mmHg °C mmHg mmHg mmHg °C
oxygen 782.81 753.0 761.67 25.5
nitrogen 785.50 753.0 762.01 27.0 789.40 753.0 763.05 25.5

Trial 3 Trial 4
γ γ
experimental theoretical experimental theoretical
oxygen 1.4261 1.2857; 1.4000
nitrogen 1.4003 1.2857; 1.4000 1.4000 1.2857; 1.4000
Absolute Uncertainties

Trial 1 Trial 2
P1 P2 P3 P1 P2 P3
cmMS mmHg cmMS cmMS mmHg cmMS
0.05 0.5 0.05 0.05 0.5 0.05

Trial 1 Trial 2
P1 P2 P3 P1 P2 P3
mmHg mmHg mmHg mmHg mmHg mmHg
0.50 0.5 0.05 0.50 0.5 0.05

Trial 1 Trial 2
Pcarboy1 Pcarboy2 Pcarboy3 Pcarboy1 Pcarboy2 Pcarboy3
mmHg mmHg mmHg mmHg mmHg mmHg
0.5 0.5 0.5 0.5 0.5 0.5

Trial 1 Trial 2
experimental γ experimental γ
1.95E-12 2.04E-12
3.84E-12 1.92E-12

Trial 3 Trial 4
P1 P2 P3 P1 P2 P3
cmMS mmHg cmMS cmMS mmHg cmMS
0.05 0.5 0.05 0.05 0.5 0.05

Trial 3 Trial 4
P1 P2 P3 P1 P2 P3
mmHg mmHg mmHg mmHg mmHg mmHg
0.50 0.5 0.05 0.50 0.5 0.05

Trial 3 Trial 4
Pcarboy1 Pcarboy2 Pcarboy3 Pcarboy1 Pcarboy2 Pcarboy3
mmHg mmHg mmHg mmHg mmHg mmHg
0.5 0.5 0.5 0.5 0.5 0.5

Trial 3 Trial 4
experimental γ experimental γ
2.03E-12 ---
1.98E-12 1.96E-12
Results and Discussion

By the reversible adiabatic expansion method, the heat capacity ratio of the oxygen and nitrogen
gases was determined experimentally. In this method, the gas was allowed to expand adiabatically
(that is, no heat comes into/out of the system) and reversibly until the pressure has dropped from
an initial value to atmospheric pressure. Then, at constant volume, its temperature was restored back
to its initial value and the pressure was again measured. To compute for the heat capacity ratio,
pressure values were plugged in using the following equation (eq. 1):

Theoretically, the heat capacity ratio of a diatomic gas molecule can be computed in terms of
degrees of freedom that the molecule possesses. In this type of calculation, it is assumed that the gas
is perfect, so, the molar heat capacity of that gas at constant pressure is equal to the sum of its molar
heat capacity at constant volume and R. Alternatively, the heat capacity ratio can be computed as 1
plus the ratio of R and the molar heat capacity at constant volume. The molar heat capacity at
constant volume can be obtained by getting the partial derivative of the sum of molar energies per
degrees of freedom in which the corresponding contributions to the energy per mole of gas are
RT/2. The partial derivative was obtained at constant volume.

The results of the experiment revealed that the average heat capacity ratio of oxygen and nitrogen
gases are 1.3995 and 1.3889, respectively. These experimental values were computed using Eq. 1.
Then, the theoretical heat capacity ratios for both gases were also computed using the approach
involving the calculation of molar heat capacity at constant volume. The results for both gases are
1.2875 (assuming that there is vibrational contributions) and 1.4000 (assuming that there is no
vibrational contributions). The difference between these theoretical values can attest that the
vibrational contributions to the molar heat capacity at constant volume is small at a difference of
0.1125. Meanwhile, comparing the experimental values with the theoretical values, it can be seen that
the experimental values are closer than theoretical ones that were computed assuming that there is
no vibrational contributions. This observation thus affirm that those vibrational contributions are
partly negligible at relatively lower temperatures since vibrational energy is highly quantized and
strongly dependent on temperature.

Assumptions

As stated earlier, the contributions of vibrational modes are assumed to be negligible since it is only
partially “active” at ambient temperatures. Also, in attaining the second reading for the pressure, it is
assumed that the gas momentarily approached the atmospheric pressure upon opening the carboy to
the atmosphere. In line with this, it is also assumed that the method is adiabatic in a sense that the
carboy is opened to the atmosphere at a rapid rate. With this in mind, Equation 1 was derived to
compute for the heat capacity ratio. This equation was the corrected one due to the ambiguity in the
location of the boundary between the gas portion leaving and the portion staying inside the carboy.
For reference, the original derived equation for the heat capacity ratio is given by the ratio of the
natural logarithms of p1/p2 and p1/p3.
Errors and their Sources

Based on the results, it can be inferred that the deviation of the values obtained with respect to the
expected results are within the bounds of errors in uncertainties involved in measurements. As
observed though, it can be said that the reason why the experimental values are less than the
theoretical values calculated without the vibrational contributions is that the expansion made was a
little irreversible in a sense that the method was not sufficiently adiabatic because the stopper was
left open for so long. But the error due to this scenario is not that dramatic, and thus, did not affect
the results too much.

Applications

Heat capacity ratios are of great importance in engine and hydraulics industry. Turbochargers in
engines allow cars and machines to make power but inevitably, heat comes off as a by-product. To
understand the process involved in such mechanisms in turbochargers, it is needed to understand
the concept of adiabatic process. An equation used to find pressure and temperature values in the
adiabatic process of a turbocharger in engines integrates the heat capacity ratio of air.

Conclusions

It can be concluded that by adiabatic method, the heat capacity ratio for gases can be determined
efficiently. The results obtained agree with the theoretical values obtained when various modes of
degrees of freedom were taken into consideration. Though this method gives a relatively decent
results, other methods such as measuring the speed of sound through various gases can be done to
obtain more reliable results.

Calculations

Calculation for the theoretical value of the heat capacity ratio γ

With vibrational degrees of freedom,

Without vibrational degrees of freedom,

Grubbs test for the outlier (at 95% confidence level)
Using Grubbs test, the first trial result was discarded. Gcalc>Gtable.