Calculation of the Equilibrium Constant for the Dissociation of Propionic Acid Vapor

August Rothenberger

Partners: Stephen Nagle and Andrew Cleek

Department of Chemistry, The Pennsylvania State University, University Park, PA 16802

Abstract ...........................................................................................................................................

Propionic acid vapor was heated and the pressure recorded at regular intervals. The

dissociation constant for propionic acid vapor at standard conditions was calculated to be

7.62*10-6 ± 7.30*10-4 atm. The entropy of dissociation was calculated to be 699 J/K*mole and

compared to the theoretical Sackur-Tetrode translation entropy of 200 J/K*mole to find the

calculated value with 250% discrepancy. The discrepancy was attributed to an error in procedure

not allowing for proper calculation of the initial dimer pressure.

Introduction ....................................................................................................................................

In the gaseous phase, propionic acid can adopt either a dimer or monomer form due to

hydrogen bonding, shown below in Figure 1.1

Figure 1. Dissociation of Propionic Acid Vapor

The rate constant of the above dissociation, KP, can be calculated by measuring how the system

pressure changes with temperature. Due to Avogadro’s gas law, a mole of monomer would

contain twice as many molecules and have double the pressure as a mole of dimer. KP can be

expressed in terms of partial pressures at low pressure as:

𝑃 2
( 𝑃𝑀0 )
𝐾𝑃 = ⁄𝑃𝐷 (1)
𝑃0
where PM and PD are the partial pressures of the monomer and dimer, respectively, and P0 is the

standard state pressure, 1.0 atm.1

If a number α, between 0 and 1, represents the degree of dissociation of the dimer, PM and

PD can be written as:

𝑃𝑀 = (2𝛼⁄1 + 𝛼 )𝑃 (2)

𝑃𝑀 = (1 − 𝛼⁄1 + 𝛼 )𝑃 (3)

where the term in parentheses represents the mole fraction of monomers and dimers,

respectively.1 Equations 2 and 3 can be substituted into Equation 1 to generate:1

2
𝐾𝑃 = (4𝛼 ⁄1 − 𝛼 2 ) 𝑃 (4)

If the moles of dimer (nD), pressure (P), volume (V), and temperature (T) are known at

equilibrium, then the total number of gas molecules equals:1

𝑛𝐷 (1 + 𝛼) = 𝑃𝑉⁄𝑅𝑇 (5)

The pressure observed if there was no dissociation at equilibrium, Pi, equals:1

𝑛𝐷 𝑅𝑇⁄
𝑃𝑖 = 𝑉 (6)

Substituting Equation 6 into Equation 5 allows us to generate the relationship:1

(1 + 𝛼) = 𝑃⁄𝑃 (7)
𝑖

If Equation 7 is substituted into Equation 4, the resultant simplified expression can be written:1

4(𝑃 − 𝑃𝑖 )
𝐾𝑃 = ⁄2𝑃 − 𝑃 (8)
𝑖

Standard thermodynamic quantities of free energy (ΔG°), enthalpy (ΔH°), and entropy

(ΔS°) can be obtained from their thermodynamic relationships.1

∆𝐺° = −𝑅𝑇(ln 𝐾𝑃 ) (9)

 ∆𝐻°⁄ = −𝑑(ln 𝐾𝑃 )⁄ (10)
𝑅 𝑑(1/𝑇)

(∆𝐻° − ∆𝐺°)⁄
∆𝑆° = 𝑇 (11)

The theoretical method for predicting the translational component for entropy is defined by the

Sackur-Tetrode equation.

∆𝑆°𝑆−𝑇 = 2𝑆𝑀 − 𝑆𝐷 (12)

𝑆⁄ = 2.303 [− log 𝑃 − 5 log 𝑇 + 3 log(𝑀) − 0.5053] (13)

𝑅 2 2

SM and SD are the entropy components of the monomer and dimer, respectively, and M is the

molecular mass of each species.1

Experimental ..................................................................................................................................

A vessel of propionic acid was massed at 44.3236±0.0001 g. The vessel was connected to

an evacuated Schlenk line system so the propionic acid vapor would be transferred to a 3.4 L

bulb by diffusion until the system reached an equilibrium pressure of 2.43±0.005 torr. There was

no leak in the system. The bulb was then sealed and the propionic acid vessel again massed at

44.2666±0.0001g to determine the amount of acid vapor in the bulb. The temperature of the bulb

was increased at a constant rate of 1°C per 2 minutes and the pressure recorded every 1±0.1°C to

a precision of ±0.2% torr. Once the temperature reached 55°C, the temperature was more rapidly

increased to 65°C with pressure recorded every 1°C.

Results and Discussion...................................................................................................................

Determination of Pi

The initial pressure can be calculated by Equation 6. However, no temperature value was

recorded when the propionic acid vapor was allowed to expand into the bulb. If the initial

temperature is assumed to be 298.15K, the calculation is as follows:

44.3236 − 44.266𝑔 𝑎𝑡𝑚 ∗ 𝐿

𝑔 ∗ 0.0821 ∗ 298.15𝐾
74.05 𝐾 ∗ 𝑚𝑜𝑙 ⁄
𝑃𝑖 = 𝑚𝑜𝑙
3.4𝐿 = 0.00554 𝑎𝑡𝑚

This value does not make sense, since it is larger than the first recorded pressure in the bulb is

2.43 torr, or 0.00320 atm. Pi is the pressure if there is no dissociation, so it cannot be larger than

a measured data points where dissociation must occur. In all subsequent calculations, Pi will be

assumed to be 2.43 torr in order to construct data that obeys the correct kinetic and

thermodynamic trends.

Calculation of the Propionic Acid Dissociation Constant, Kp

To use the appropriate calculations, the pressure was converted to atmospheres (atm) and

the temperature converted the Kelvin (K).

1
𝑃𝑎𝑡𝑚 = 𝑃𝑡𝑜𝑟𝑟 ∗ 760 𝑡𝑜𝑟𝑟/𝑎𝑡𝑚 (14)

1 2
∆𝑃𝑎𝑡𝑚 = √760 + 𝑃𝑡𝑜𝑟𝑟 2 (15)

𝑇𝐾 = 𝑇℃ + 273.15 (16)

∆𝑇𝐾 = 0.01 (17)

Again, the rate constant for the dissociation of propionic acid is determined as:

4(𝑃 − 𝑃𝑖 )2⁄
𝐾𝑝 = 2𝑃𝑖 − 𝑃 (8)
The uncertainty for Kp will be determined in parts to simplify the calculation. First, the

uncertainty of numerator is determined.

𝑎 = (𝑃 − 𝑃𝑖 ) (18)

∆𝑎 = √∆𝑃2 + ∆𝑃𝑖 2 (19)

𝑏 = 4(𝑃 − 𝑃𝑖 )2 = 4𝑎2 (20)

∆𝑏 = 2 ∗ 𝑏 ∗ ∆𝑎⁄𝑎 (21)

The uncertainty of the denominator is given by:

𝑐 = 2𝑃𝑖 − 𝑃 (22)

∆𝑐 = √22 ∗ ∆𝑃𝑖 2 + ∆𝑃2 (23)

Finally, the uncertainty of Kp is calculated as:

2 2
∆𝐾𝑝 = 𝐾𝑝 √∆𝑏 ⁄𝑏 2 + ∆𝑐 ⁄𝑐 2 (24)

2
√∆𝑃 2 +∆𝑃𝑖 2
⁄ 2
(2∗4(𝑃−𝑃𝑖 )2 ∗ (𝑃−𝑃𝑖 ))
√ (√22 ∗∆𝑃𝑖 2 +∆𝑃2 )
∆𝐾𝑝 = 𝐾𝑝 + (25)
(4(𝑃−𝑃𝑖 )2 )2 (2𝑃𝑖 −𝑃)2

Due to the large number of data points, all data tables for recorded and calculated values are

provided in the supporting information section.

Calculation of Standard Enthalpy, Entropy, and Free Energy of Dissociation

A plot can be constructed to obey Equation 10 by taking the natural logarithm of Kp and

the inverse of T for all values, provided below in Figure 2.

 Ln(Kp) versus 1/T
0.00295 0.003 0.00305 0.0031 0.00315 0.0032 0.00325 0.0033 0.00335 0.0034
0

-2

-4
y = -28572x + 84.046
-6 R² = 0.9733
Ln(Kp)

-8

-10

-12

-14
1/T (K^-1)

Figure 2. Plot of ln(Kp) versus 1/T to determine reaction enthalpy

A linear regression is performed using the LINEST function in Excel with a 95% confidence

interval. The results of the regression are provided in Table 1.

Table 1: Linear Regression for Figure 2

m -2.86E+04 8.40E+01 b
Sm 8.63E+02 2.75E+00 Sb
R^2 9.73E-01 4.63E-01 Sy

According to Equation 10, the negative slope of the curve is equal to the standard enthalpy ΔH°

divided by the gas constant.

𝐽 𝐽
∆𝐻° = 𝑚 ∗ 𝑅 = 2.86 ∗ 104 𝐾 ∗ 8.314 𝑚𝑜𝑙∗𝐾 = 2.38 ∗ 105 𝑚𝑜𝑙

Uncertainty is calculated by:

𝐽
∆(∆𝐻°) = √(8.63 ∗ 102 )2 ∗ (8.314)2 = 7.2 ∗ 103 𝑚𝑜𝑙

Additionally, we are able to solve for KP at 25.0°C using the best-fit line for Figure 2.
1
𝐾𝑃 = 𝑒^(2.86 ∗ 104 ln(𝑎𝑡𝑚) 𝐾 ∗ 298.15 𝐾 + 84.0 ln(𝑎𝑡𝑚)) = 7.62 ∗ 10−6 𝑎𝑡𝑚
 2
1
∆𝐾𝑃 = (7.62 ∗ 10 −6 ) √ 4 2
∗ (−2.86 ∗ 10 ) ∗ ( ) = 7.30 ∗ 10−4 𝑎𝑡𝑚
298.15

Equations 9 and 11 can be used to calculate ΔG° and ΔS° for each temperature. The

uncertainty calculations are provided below. Data tables are provided in supporting information

∆(∆𝐺°) = 𝑅 ∗ 𝑇 ∗ ∆𝐾𝑃 /𝐾𝑃 (26)

1 2 2
∆(∆𝑆°) = 𝑇 √(∆(∆𝐻°)) + (∆(∆𝐺°)) (27)

Deviation from Theoretical Values

From literature,2 the thermodynamic values for standard enthalpy and entropy for

dissociation of propionic acid are:

𝐽
∆𝐻° = 6.36 ∗ 104 ± 837 𝑚𝑜𝑙𝑒

𝐽
∆𝑆° = 151 𝐾∗𝑚𝑜𝑙𝑒

At standard conditions, the free energy of dissociation is:

𝐽 𝐽 𝐽
∆𝐺° = ∆𝐻° − 𝑇∆𝑆° = 6.36 ∗ 104 𝑚𝑜𝑙𝑒 − 298.15𝐾 ∗ 151 𝐾∗𝑚𝑜𝑙𝑒 = 1.86 ∗ 104 ± 837 𝑚𝑜𝑙𝑒

The experimentally determined value of entropy is best compared to the translational

component of entropy, theoretically calculated by the Sackur-Tetrode method described by

Equations 12 and 13. Equation 13 is clarified below.1

5 3
𝑆𝑀 = 𝑅 ∗ 2.303 [− log 𝑃 + 2 log 𝑇 + 2 log 74.08 − 0.5053]

5 3
𝑆𝐷 = 𝑅 ∗ 2.303 [− log 𝑃 + 2 log 𝑇 + 2 log 148.16 − 0.5053]

The results are included in Supporting Information, but the results were averaged to obtain the

following values of ΔS°S-T.

𝐽
∆𝑆°𝑆−𝑇 = 200 𝐾∗𝑚𝑜𝑙𝑒
The averaged calculated and Sackur-Tetrode values of entropy have a difference of:

𝐽 𝐽
|(200 − 699) 𝑚𝑜𝑙𝑒| = 499 𝐾∗𝑚𝑜𝑙𝑒

from which it is possible to calculate the deviation in our experimental procedure.

𝐽
499 𝐾∗𝑚𝑜𝑙𝑒
%𝐷𝑒𝑣𝑖𝑎𝑡𝑖𝑜𝑛 = ( ⁄ 𝐽 ) ∗ 100% = 250%
200 𝐾∗𝑚𝑜𝑙𝑒

This deviation can be attributed to the improper calculation of the initial pressure Pi used

in all calculations in the report. In order to properly calculate the thermodynamic quantities, the

initial temperature should have been taken when the propionic acid vapor was allowed to enter

the bulb under vacuum conditions. The initial pressure used for our calculations is larger than the

actual Pi value, which is why our value for standard entropy of reaction is much larger than the

theoretical value.

General Discussion

According to the results found in Table 3, KP increases with temperature. This agrees

with the expected result, since it requires energy to break the hydrogen bonds holding the dimer

together. At higher temperature, a greater monomer (product) concentration is present in the

bulb, leading to a larger equilibrium constant, which is defined as product concentration over

reactant concentration. Le Chatelier’s principle also applies since the reaction is endothermic,

and as the temperature of the system is increased, more product will be formed.

The standard dissociation enthalpy and entropy contribute to the free energy in different

ways. The enthalpy, ΔH°, is a measure of the heat required from the environment for the reaction

to progress, positive in our case since bonds are broken. Enthalpy is independent of temperature

since heat is a form of energy, the temperature is related to how quickly the heat flows from the
environment to the system. Entropy is the measure of disorder as the reaction progresses,

positive since the number of molecules increases. Entropy increases with temperature since

disorder is measured as a number of system microstates; higher temperature correlates to faster

translational, rotational, and vibrational microstates of the system.

A typical hydrogen bond energy for an O-H---O system is about 21 kJ/mole.3 The

measured enthalpy of dissociation in our experiment was 237 kJ/mole. The dimer has two

hydrogen bonds, so the system would have an enthalpy of 42 kJ/mole, but this does not nearly

account for deviation of the calculated value. An explanation for the deviation of our procedure

can be found above.

Conclusion ......................................................................................................................................

The dissociation constant for propionic acid vapor at standard conditions was calculated

to be 7.62*10-6 ± 7.30*10-4 atm by heating the vapor at constant volume. Our calculations have a

discrepancy of 250% from the accepted values, attributed to improper proper calculation of the

initial dimer pressure Pi.

Sample Calculations.......................................................................................................................

All sample calculations below are for the data point recorded at 27.0°C
1
𝑃𝑎𝑡𝑚 = 2.49 𝑡𝑜𝑟𝑟 ∗ 𝑡𝑜𝑟𝑟 = 3.28 ∗ 10−3 𝑎𝑡𝑚 (14)
760
𝑎𝑡𝑚

1 2
∆𝑃𝑎𝑡𝑚 = √760 + (2.49 ∗ .002)2 = 6.55 ∗ 10−6 𝑎𝑡𝑚 (15)

𝑇𝐾 = 27.0℃ + 273.15 = 300.15 𝐾 (16)

∆𝑇𝐾 = √0.012 = 0.01 𝐾 (17)

 4(3.28∗10−3 𝑎𝑡𝑚−3.20∗10−3 𝑎𝑡𝑚)2
𝐾𝑝 = = 7.99 ∗ 10−6 𝑎𝑡𝑚 (8)
2∗3.20∗10−3 𝑎𝑡𝑚−3.28∗10−3 𝑎𝑡𝑚

𝑎 = (3.28 ∗ 10−3 𝑎𝑡𝑚 − 3.20 ∗ 10−3 𝑎𝑡𝑚) = 7.89 ∗ 10−5 𝑎𝑡𝑚 (18)

∆𝑎 = √(6.55 ∗ 10−6 )2 + (6.39 ∗ 10−6 )2 = 9.16 ∗ 10−6 𝑎𝑡𝑚 (19)

𝑏 = 4 ∗ (7.89 ∗ 10−5 𝑎𝑡𝑚)2 = 2.49 ∗ 10−9 𝑎𝑡𝑚2 (20)

−6
∆𝑏 = 2 ∗ 2.49 ∗ 10−9 ∗ 9.16 ∗ 10 ⁄7.89 ∗ 10−5 = 5.78 ∗ 10−9 𝑎𝑡𝑚2 (21)

𝑐 = 2 ∗ 3.20 ∗ 10−3 𝑎𝑡𝑚 − 3.28 ∗ 10−3 𝑎𝑡𝑚 = 3.12 ∗ 10−3 𝑎𝑡𝑚 (22)

∆𝑐 = √22 ∗ (6.55 ∗ 10−6 𝑎𝑡𝑚)2 + (6.39 ∗ 10−6 𝑎𝑡𝑚)2 = 1.44 ∗ 10−3 𝑎𝑡𝑚 (23)

(5.78∗10−9 )2 (1.44∗10−3 )2
∆𝐾𝑝 = 7.99 ∗ 10−6 √(2.49∗10−9 )2 + (3.12∗10−3 )2 = 1.85 ∗ 10−6 𝑎𝑡𝑚 (24)

𝐽 𝐽
∆𝐺° = −8.314 𝑚𝑜𝑙∗𝐾 ∗ 300.15 𝐾 ∗ (ln 7.99 ∗ 10−6 𝑎𝑡𝑚) = 2.93 ∗ 104 𝑚𝑜𝑙 (9)

10−6 𝐽
∆(∆𝐺°) = −8.314 ∗ 300.15 𝐾 ∗ 1.85 ∗ ∗ 10−6 = 5.79 ∗ 102 𝑚𝑜𝑙 (26)
7.99

𝐽 𝐽
(2.38 ∗ 105 𝑚𝑜𝑙 − 2.93 ∗ 104 𝑚𝑜𝑙 )⁄ 2 𝐽
∆𝑆° = 300.15 𝐾 = 6.94 ∗ 10 𝐾∗𝑚𝑜𝑙 (11)

1 𝐽
∆(∆𝑆°) = 300.15 √(7.2 ∗ 103 )2 + (5.79 ∗ 102 )2 = 2.31 𝐾∗𝑚𝑜𝑙 (27)

𝐽 5 3
𝑆𝑀 = 8.314 𝑚𝑜𝑙∗𝐾 ∗ 2.303 [− log 3.24 ∗ 10−3 + 2 log 300.15 + 2 log 74.08 − 0.5053] (13)

𝐽 𝐽
𝑆𝑀 = 2.10 ∗ 102 𝐾∗𝑚𝑜𝑙 𝑆𝐷 = 2.73 ∗ 102 𝐾∗𝑚𝑜𝑙

𝐽 𝐽 𝐽
∆𝑆°𝑆−𝑇 = 2 ∗ 2.10 ∗ 102 𝐾∗𝑚𝑜𝑙 − 2.73 ∗ 102 𝐾∗𝑚𝑜𝑙 = 1.47 ∗ 102 𝐾∗𝑚𝑜𝑙 (12)

Supporting Information ................................................................................................................

Table 2 includes the measured values for the experiment and their conversions to

standard units. Uncertainties are also included.

 Table 2: Measured Values
T (°C) ΔT (°C) P (torr) ΔP (torr) P (atm) ΔP (atm) Pi (atm) ΔPi (atm) T (K) ΔT (K)
2.50E+01 1.00E-01 2.43E+00 4.86E-03 3.20E-03 6.39E-06 3.20E-03 6.39E-06 2.98E+02 1.00E-01
2.60E+01 1.00E-01 2.46E+00 4.92E-03 3.24E-03 6.47E-06 3.20E-03 6.39E-06 2.99E+02 1.00E-01
2.70E+01 1.00E-01 2.49E+00 4.98E-03 3.28E-03 6.55E-06 3.20E-03 6.39E-06 3.00E+02 1.00E-01
2.80E+01 1.00E-01 2.50E+00 5.00E-03 3.29E-03 6.58E-06 3.20E-03 6.39E-06 3.01E+02 1.00E-01
2.90E+01 1.00E-01 2.54E+00 5.08E-03 3.34E-03 6.68E-06 3.20E-03 6.39E-06 3.02E+02 1.00E-01
3.00E+01 1.00E-01 2.56E+00 5.12E-03 3.37E-03 6.74E-06 3.20E-03 6.39E-06 3.03E+02 1.00E-01
3.10E+01 1.00E-01 2.60E+00 5.20E-03 3.42E-03 6.84E-06 3.20E-03 6.39E-06 3.04E+02 1.00E-01
3.20E+01 1.00E-01 2.64E+00 5.28E-03 3.47E-03 6.95E-06 3.20E-03 6.39E-06 3.05E+02 1.00E-01
3.30E+01 1.00E-01 2.67E+00 5.34E-03 3.51E-03 7.03E-06 3.20E-03 6.39E-06 3.06E+02 1.00E-01
3.40E+01 1.00E-01 2.72E+00 5.44E-03 3.58E-03 7.16E-06 3.20E-03 6.39E-06 3.07E+02 1.00E-01
3.50E+01 1.00E-01 2.76E+00 5.52E-03 3.63E-03 7.26E-06 3.20E-03 6.39E-06 3.08E+02 1.00E-01
3.60E+01 1.00E-01 2.80E+00 5.60E-03 3.68E-03 7.37E-06 3.20E-03 6.39E-06 3.09E+02 1.00E-01
3.70E+01 1.00E-01 2.84E+00 5.68E-03 3.74E-03 7.47E-06 3.20E-03 6.39E-06 3.10E+02 1.00E-01
3.80E+01 1.00E-01 2.92E+00 5.84E-03 3.84E-03 7.68E-06 3.20E-03 6.39E-06 3.11E+02 1.00E-01
3.90E+01 1.00E-01 2.98E+00 5.96E-03 3.92E-03 7.84E-06 3.20E-03 6.39E-06 3.12E+02 1.00E-01
4.00E+01 1.00E-01 3.06E+00 6.12E-03 4.03E-03 8.05E-06 3.20E-03 6.39E-06 3.13E+02 1.00E-01
4.10E+01 1.00E-01 3.12E+00 6.24E-03 4.11E-03 8.21E-06 3.20E-03 6.39E-06 3.14E+02 1.00E-01
4.20E+01 1.00E-01 3.17E+00 6.34E-03 4.17E-03 8.34E-06 3.20E-03 6.39E-06 3.15E+02 1.00E-01
4.30E+01 1.00E-01 3.23E+00 6.46E-03 4.25E-03 8.50E-06 3.20E-03 6.39E-06 3.16E+02 1.00E-01
4.40E+01 1.00E-01 3.34E+00 6.68E-03 4.39E-03 8.79E-06 3.20E-03 6.39E-06 3.17E+02 1.00E-01
4.50E+01 1.00E-01 3.41E+00 6.82E-03 4.49E-03 8.97E-06 3.20E-03 6.39E-06 3.18E+02 1.00E-01
4.60E+01 1.00E-01 3.47E+00 6.94E-03 4.57E-03 9.13E-06 3.20E-03 6.39E-06 3.19E+02 1.00E-01
4.70E+01 1.00E-01 3.53E+00 7.06E-03 4.64E-03 9.29E-06 3.20E-03 6.39E-06 3.20E+02 1.00E-01
4.80E+01 1.00E-01 3.61E+00 7.22E-03 4.75E-03 9.50E-06 3.20E-03 6.39E-06 3.21E+02 1.00E-01
4.90E+01 1.00E-01 3.68E+00 7.36E-03 4.84E-03 9.68E-06 3.20E-03 6.39E-06 3.22E+02 1.00E-01
5.00E+01 1.00E-01 3.79E+00 7.58E-03 4.99E-03 9.97E-06 3.20E-03 6.39E-06 3.23E+02 1.00E-01
5.10E+01 1.00E-01 3.92E+00 7.84E-03 5.16E-03 1.03E-05 3.20E-03 6.39E-06 3.24E+02 1.00E-01
5.20E+01 1.00E-01 4.00E+00 8.00E-03 5.26E-03 1.05E-05 3.20E-03 6.39E-06 3.25E+02 1.00E-01
5.30E+01 1.00E-01 4.08E+00 8.16E-03 5.37E-03 1.07E-05 3.20E-03 6.39E-06 3.26E+02 1.00E-01
5.40E+01 1.00E-01 4.23E+00 8.46E-03 5.57E-03 1.11E-05 3.20E-03 6.39E-06 3.27E+02 1.00E-01
5.50E+01 1.00E-01 4.37E+00 8.74E-03 5.75E-03 1.15E-05 3.20E-03 6.39E-06 3.28E+02 1.00E-01
5.70E+01 1.00E-01 4.55E+00 9.10E-03 5.99E-03 1.20E-05 3.20E-03 6.39E-06 3.30E+02 1.00E-01
5.90E+01 1.00E-01 4.72E+00 9.44E-03 6.21E-03 1.24E-05 3.20E-03 6.39E-06 3.32E+02 1.00E-01
6.10E+01 1.00E-01 4.90E+00 9.80E-03 6.45E-03 1.29E-05 3.20E-03 6.39E-06 3.34E+02 1.00E-01
6.30E+01 1.00E-01 5.07E+00 1.01E-02 6.67E-03 1.33E-05 3.20E-03 6.39E-06 3.36E+02 1.00E-01
6.50E+01 1.00E-01 5.26E+00 1.05E-02 6.92E-03 1.38E-05 3.20E-03 6.39E-06 3.38E+02 1.00E-01
Table 3 contains the calculated value of Kp and the thermodynamic quantities.

Table 3: Calculated Values

Ln(Kp) 1/T ΔG° (J/mol) Δ(ΔG°) (J/mol) ΔS° (J/Kmol) Δ(ΔS°) (J/Kmol) Sm Sd ΔSS-T
-1.18E+01 3.35E-03 2.92E+04 3.16E+05 6.99E+02 2.34E+00 2.10E+02 2.73E+02 1.47E+02
-1.31E+01 3.34E-03 3.27E+04 1.15E+03 6.85E+02 2.29E+00 2.10E+02 2.73E+02 1.47E+02
-1.17E+01 3.33E-03 2.93E+04 5.79E+02 6.94E+02 2.31E+00 2.10E+02 2.73E+02 1.47E+02
-1.14E+01 3.32E-03 2.86E+04 4.99E+02 6.94E+02 2.30E+00 2.10E+02 2.73E+02 1.47E+02
-1.05E+01 3.31E-03 2.64E+04 3.21E+02 6.99E+02 2.31E+00 2.10E+02 2.73E+02 1.47E+02
-1.02E+01 3.30E-03 2.56E+04 2.74E+02 6.99E+02 2.31E+00 2.10E+02 2.73E+02 1.47E+02
-9.61E+00 3.29E-03 2.43E+04 2.12E+02 7.01E+02 2.31E+00 2.10E+02 2.73E+02 1.47E+02
-9.17E+00 3.28E-03 2.33E+04 1.74E+02 7.02E+02 2.30E+00 2.10E+02 2.73E+02 1.47E+02
-8.89E+00 3.27E-03 2.26E+04 1.53E+02 7.02E+02 2.29E+00 2.10E+02 2.73E+02 1.47E+02
-8.48E+00 3.26E-03 2.17E+04 1.29E+02 7.03E+02 2.29E+00 2.10E+02 2.73E+02 1.47E+02
-8.21E+00 3.25E-03 2.10E+04 1.14E+02 7.03E+02 2.28E+00 2.10E+02 2.73E+02 1.47E+02
-7.96E+00 3.23E-03 2.05E+04 1.03E+02 7.02E+02 2.27E+00 2.10E+02 2.73E+02 1.47E+02
-7.73E+00 3.22E-03 1.99E+04 9.43E+01 7.02E+02 2.26E+00 2.10E+02 2.73E+02 1.47E+02
-7.34E+00 3.21E-03 1.90E+04 8.05E+01 7.02E+02 2.26E+00 2.10E+02 2.73E+02 1.47E+02
-7.07E+00 3.20E-03 1.84E+04 7.29E+01 7.02E+02 2.25E+00 2.10E+02 2.73E+02 1.46E+02
-6.76E+00 3.19E-03 1.76E+04 6.49E+01 7.02E+02 2.24E+00 2.09E+02 2.72E+02 1.46E+02
-6.54E+00 3.18E-03 1.71E+04 6.02E+01 7.02E+02 2.23E+00 2.09E+02 2.72E+02 1.46E+02
-6.37E+00 3.17E-03 1.67E+04 5.69E+01 7.01E+02 2.22E+00 2.09E+02 2.72E+02 1.46E+02
-6.18E+00 3.16E-03 1.62E+04 5.34E+01 7.00E+02 2.21E+00 2.09E+02 2.72E+02 1.46E+02
-5.85E+00 3.15E-03 1.54E+04 4.82E+01 7.00E+02 2.21E+00 2.09E+02 2.72E+02 1.46E+02
-5.66E+00 3.14E-03 1.50E+04 4.55E+01 7.00E+02 2.20E+00 2.09E+02 2.72E+02 1.46E+02
-5.50E+00 3.13E-03 1.46E+04 4.35E+01 6.99E+02 2.19E+00 2.09E+02 2.72E+02 1.46E+02
-5.34E+00 3.12E-03 1.42E+04 4.17E+01 6.98E+02 2.18E+00 2.09E+02 2.72E+02 1.46E+02
-5.14E+00 3.11E-03 1.37E+04 3.96E+01 6.97E+02 2.17E+00 2.08E+02 2.72E+02 1.45E+02
-4.97E+00 3.10E-03 1.33E+04 3.80E+01 6.96E+02 2.16E+00 2.08E+02 2.71E+02 1.45E+02
-4.70E+00 3.09E-03 1.26E+04 3.58E+01 6.96E+02 2.15E+00 2.08E+02 2.71E+02 1.45E+02
-4.39E+00 3.08E-03 1.18E+04 3.35E+01 6.96E+02 2.15E+00 2.08E+02 2.71E+02 1.45E+02
-4.19E+00 3.08E-03 1.13E+04 3.24E+01 6.96E+02 2.14E+00 2.08E+02 2.71E+02 1.45E+02
-4.00E+00 3.07E-03 1.08E+04 3.13E+01 6.95E+02 2.13E+00 2.08E+02 2.71E+02 1.45E+02
-3.61E+00 3.06E-03 9.82E+03 2.96E+01 6.96E+02 2.13E+00 2.08E+02 2.71E+02 1.45E+02
-3.21E+00 3.05E-03 8.75E+03 2.82E+01 6.97E+02 2.12E+00 2.07E+02 2.70E+02 1.44E+02
-2.57E+00 3.03E-03 7.06E+03 2.67E+01 6.98E+02 2.11E+00 2.07E+02 2.70E+02 1.44E+02
-1.62E+00 3.01E-03 4.48E+03 2.56E+01 7.02E+02 2.11E+00 2.07E+02 2.70E+02 1.44E+02
#NUM! 2.99E-03 #NUM! 2.46E+01 #NUM! #NUM! 2.07E+02 2.70E+02 1.44E+02
#NUM! 2.97E-03 #NUM! 2.38E+01 #NUM! #NUM! 2.07E+02 2.70E+02 1.44E+02
#NUM! 2.96E-03 #NUM! 2.31E+01 #NUM! #NUM! 2.06E+02 2.69E+02 1.43E+02
Average 6.99E+02 2.23E+00 2.09E+02 2.72E+02 1.46E+02
The error propagation for KP is included in Table 4.

Table 4: Error in Kp
(P-Pi) Δ(P-Pi) 4(P-Pi)^2 Δ4(P-Pi)^2 (2Pi-P) Δ(2Pi-P) Kp ΔKp
0.00E+00 9.04E-06 0.00E+00 0.00E+00 3.20E-03 1.43E-05 0.00E+00 0.00E+00
3.95E-05 9.10E-06 6.23E-09 2.87E-09 3.16E-03 1.43E-05 1.97E-06 9.10E-07
7.89E-05 9.16E-06 2.49E-08 5.78E-09 3.12E-03 1.44E-05 7.99E-06 1.85E-06
9.21E-05 9.17E-06 3.39E-08 6.76E-09 3.11E-03 1.44E-05 1.09E-05 2.18E-06
1.45E-04 9.25E-06 8.38E-08 1.07E-08 3.05E-03 1.44E-05 2.75E-05 3.51E-06
1.71E-04 9.29E-06 1.17E-07 1.27E-08 3.03E-03 1.45E-05 3.87E-05 4.20E-06
2.24E-04 9.37E-06 2.00E-07 1.68E-08 2.97E-03 1.45E-05 6.73E-05 5.64E-06
2.76E-04 9.44E-06 3.05E-07 2.09E-08 2.92E-03 1.46E-05 1.05E-04 7.15E-06
3.16E-04 9.50E-06 3.99E-07 2.40E-08 2.88E-03 1.46E-05 1.38E-04 8.34E-06
3.82E-04 9.60E-06 5.82E-07 2.93E-08 2.82E-03 1.47E-05 2.07E-04 1.04E-05
4.34E-04 9.68E-06 7.54E-07 3.36E-08 2.76E-03 1.47E-05 2.73E-04 1.22E-05
4.87E-04 9.76E-06 9.48E-07 3.80E-08 2.71E-03 1.48E-05 3.50E-04 1.41E-05
5.39E-04 9.84E-06 1.16E-06 4.25E-08 2.66E-03 1.48E-05 4.38E-04 1.60E-05
6.45E-04 1.00E-05 1.66E-06 5.16E-08 2.55E-03 1.49E-05 6.51E-04 2.03E-05
7.24E-04 1.01E-05 2.09E-06 5.86E-08 2.47E-03 1.50E-05 8.47E-04 2.38E-05
8.29E-04 1.03E-05 2.75E-06 6.82E-08 2.37E-03 1.51E-05 1.16E-03 2.89E-05
9.08E-04 1.04E-05 3.30E-06 7.56E-08 2.29E-03 1.52E-05 1.44E-03 3.32E-05
9.74E-04 1.05E-05 3.79E-06 8.19E-08 2.22E-03 1.53E-05 1.71E-03 3.70E-05
1.05E-03 1.06E-05 4.43E-06 8.96E-08 2.14E-03 1.54E-05 2.07E-03 4.20E-05
1.20E-03 1.09E-05 5.73E-06 1.04E-07 2.00E-03 1.55E-05 2.87E-03 5.24E-05
1.29E-03 1.10E-05 6.65E-06 1.14E-07 1.91E-03 1.56E-05 3.49E-03 5.99E-05
1.37E-03 1.11E-05 7.49E-06 1.22E-07 1.83E-03 1.57E-05 4.10E-03 6.71E-05
1.45E-03 1.13E-05 8.38E-06 1.31E-07 1.75E-03 1.58E-05 4.79E-03 7.51E-05
1.55E-03 1.15E-05 9.64E-06 1.42E-07 1.64E-03 1.59E-05 5.86E-03 8.70E-05
1.64E-03 1.16E-05 1.08E-05 1.53E-07 1.55E-03 1.60E-05 6.97E-03 9.89E-05
1.79E-03 1.18E-05 1.28E-05 1.70E-07 1.41E-03 1.62E-05 9.10E-03 1.21E-04
1.96E-03 1.21E-05 1.54E-05 1.90E-07 1.24E-03 1.64E-05 1.24E-02 1.55E-04
2.07E-03 1.23E-05 1.71E-05 2.04E-07 1.13E-03 1.66E-05 1.51E-02 1.81E-04
2.17E-03 1.25E-05 1.89E-05 2.17E-07 1.03E-03 1.67E-05 1.84E-02 2.12E-04
2.37E-03 1.28E-05 2.24E-05 2.43E-07 8.29E-04 1.70E-05 2.71E-02 2.94E-04
2.55E-03 1.32E-05 2.61E-05 2.69E-07 6.45E-04 1.72E-05 4.04E-02 4.18E-04
2.79E-03 1.36E-05 3.11E-05 3.03E-07 4.08E-04 1.75E-05 7.63E-02 7.43E-04
3.01E-03 1.40E-05 3.63E-05 3.37E-07 1.84E-04 1.78E-05 1.97E-01 1.83E-03
3.25E-03 1.44E-05 4.23E-05 3.74E-07 -5.26E-05 1.82E-05 -8.03E-01 -7.11E-03
3.47E-03 1.48E-05 4.83E-05 4.11E-07 -2.76E-04 1.85E-05 -1.75E-01 -1.49E-03
3.72E-03 1.52E-05 5.55E-05 4.54E-07 -5.26E-04 1.88E-05 -1.05E-01 -8.65E-04
Acknowledgements ........................................................................................................................

Reagents, materials, and laboratory space were provided by the Penn State Chemistry

Department. Special thanks to Rebecca Katz and Prof. Bratoljub H. Milosavljevic for assistance

and guidance in writing this report.

References .......................................................................................................................................

1. Milosavljevic, B. “Lab Packet for CHEM 457 Experimental Physical Chemistry.” Fall 2018.

2. Allen, G.; Caldin, E. F. Quarterly Reviews 1953, 7, 255.

3. "Structure and energetics of the hydronium hydration shells" J. Phys. Chem. A. 111 (12):

2253–2256.