Beruflich Dokumente
Kultur Dokumente
Nathaly Murillo
Aaron Reinicker
Physical Chemistry I
Chem 445-021
Experiment 6
Vapor Pressure of a Pure Liquid
Abstract
somewhat close to the literature value of ∆Hvap =35.21 kJ/mol. Using the Antoine
equation the heat of vaporization was calculated to be ∆Hvap = 50.085 + 0.351 kJ/mol.
The Antoine Equation provides a better fit for the experimental data since most of the
residuals are 0 or extremely close to the experimental data when compared to the
Clausius-Clapeyron equation. Two trials were performed. The second trial appeared to be
more accurate since the values of its Antoine coefficients (A = 8.754, B = 2025.15, C =
The Antoine coefficients for trial 1 were calculated as: (A = 10.75, B=3926.05, C =
434.57).
Introduction
In this experiment, the vapor pressure of methanol was measured. Vapor pressure
of a pure compound is an intensive property that is independent of the amounts of the two
phases (gas and liquid) as long as both are present. It is defined as the pressure of a
system in which the gas of a substance is in dynamic equilibrium with its liquid form.
increases as a function of applied pressure, it was necessary to record the vapor pressure.
The vapor pressure of the system was measured using a MKS Baratron pressure gauge in
equation relating the variation of vapor pressure with temperature was used to analyze the
results:
(1)
The above equation is known as the Clausius-Clayeron equation and was used
equation 1, P represents the vapor pressure of the liquid, T represents the temperature in
Kelvin, and ΔHvap stands for the molar heat of vaporization for methanol.
Equation 1 will give an accurate fit to vapor pressure data over a wide range of
temperatures, as long as the temperature is well below the critical temperature. This will
cause compensating errors in the analysis, and therefore a more accurate equation is
required to consider the variation of vapor pressure with temperature. Hence the
following equation, the Antoine equation, was used to give a more elaborate method for
(2)
A, B, and C in the Antoine equation are empirical constants obtained from a fit to the
data.
Procedure
Ice was packed around the glass trap. Next, the constant temperature bath was set
to 24oC. Once the isoteniscope cooled from being in the oven, the bulb was filled
approximately three-fourths of the way with methanol. The isoteniscope was clamped
into the constant temperature bath and then connected to the vacuum pump. The vacuum
pump was turned on and pressure was slowly reduced until the vaporization pressure. The
vapor pressure was reached when the methanol boiled vigorously and after several
evacuations, the pressure equilibrated back to the previous reading. No methanol was
allowed to enter into the U-tube part of the isoteniscope during these evacuations. Once
the vapor pressure was discovered, methanol was allowed to enter the U-tube of the
isoteniscope. Methanol in the tube was leveled by increasing, opening the system to the
The constant bath temperature was then increased by various increments. During
the temperature increase the level of the methanol fluctuated, so; pressure was again
increased or decreased as needed. After the temperature became constant and the
methanol leveled, the pressure was recorded. Temperature was increased until methanol’s
boiling point was reached, 64.7 oC and the pressure was then at atmospheric pressure,
approximately 760 torr. The system was then returned to room temperature and pressure.
Finally, the methanol was removed from the isoteniscope. This procedure was then
repeated for a second trial, however; the temperature of the constant temperature bath
temperature, pressure, and the natural log of the pressure for both runs. With this data,
Figure 1 is produced showing the relationship temperature (in degrees Celsius) and
pressure. This plot is used to determine if our data, though from different trials, are
related. Ideally, the two trials will form one monotonically increasing curve. The data
Figure 2 shows the linear relationship between the natural log of pressure and
inverse temperature (in Kelvin). This relationship yields the parameters for the Clausius-
Clapeyron equation, the molar heat of vaporization is 33.104 +/- 0.968 kJ/mol, fairly
close to the literature value of 35.21 kJ/mol, and a y-intercept, A’, of 8.0067+/- .049.
pressure from the Clausius-Clapeyron equation, and the difference between the
equation 6, parameters for the Antoine Equation, A, B, and C, were calculated using
Regression in Excel. The parameter for the Antoine Equation A, B, and C in the first trial
were 10.75, 3926.05, and 434.57 respectively, for the second trial: A = 8.754, B =
2025.15, C = 280.549. Once the Antoine parameters for the trials were found, Table 2
includes the pressure calculated using the Antoine equation and the difference between
the experimental pressure, a plot of the residuals. Figure 3b displays the same
information only the data used in the second trial. No systematic error seems to be
prevalent in the second trial. However, the first trial seems to show signs of clustering
and an increasing trend in the later data points; these results indicate a bias. This bias also
explains why Figure 1 is not a smoother curve. In general, the Antoine Equation yielded
smaller residuals meaning the calculated value was more similar to the experimental
values. This means that the Antoine Equation is a better model and fits the data closer.
The calculated values for the Antoine Equation were compared to the literature
value for methanol, A = 8.07240, B = 1574.990, C = 238.870. The second trial yielded
results that are more accurate. The inaccuracy of the first trial is due to a systematic error
The boiling point of methanol is 64.7 oC, found on the methanol bottle used in the
experiment. The calculated boiling point, at 760 torr, using the Figure 2b, the Clausius-
Clapeyron method, is 64.4 oC. Using Antoine Equation parameters found: Trial 1 equals
64.3 oC and Trial 2 equals 64.3 oC. Both equations obtain reasonable results.
This analysis was repeated for a set of given data and the Clausius-Clapeyron and
Antoine equations were compared. Figure 4 shows the relationship between pressure and
temperature in Celsius. The given data provides an extremely nice trend. Figure 5 is used
to calculate the parameters for the Clausius-Clapeyron; Figure 5 plots natural log of
pressure verses inverse temperature. The heat of vaporization is 50.085 + 0.351 kJ/mol
and the y-intercept, A, equals 9.2709 + 0.0501. Table 3 calculates the residuals for both
the Clausius-Clapeyron and Antoine Equation (found using equation 6). The Antoine
parameters were found to be A = 7.20976 + 0.06142, B =1329.233 + 23.217, C =
169.4521 + 2.362. Figure 6 plots these residuals. The Antoine Equation provides a better
fit for the experimental data because the most of the residuals are 0 or extremely close to
Temp (C) Temp (K) 1/T (C) 1/T (K^-1) Pressure Log{P}
(torr)
24.0 297.15 0.0417 0.003365 156.6 2.195
29.0 302.15 0.0345 0.00331 191.6 2.282
34.0 307.15 0.0294 0.003256 235.3 2.372
40.0 313.15 0.0250 0.003193 300.9 2.478
46.0 319.15 0.0217 0.003133 384.2 2.585
52.0 325.15 0.0192 0.003076 489.2 2.690
58.0 331.15 0.0172 0.00302 620 2.792
63.2 336.35 0.01582 0.002973 730.4 2.864
Footnote: Vapor Pressure at air evaporation = 114.5 torr
Temp (C) Temp (K) 1/T (C) 1/T (K^-1) Pressure Log{P}
(torr)
31.0 304.15 0.0323 0.003288 181.8 2.260
36.0 309.15 0.0278 0.003235 224.6 2.351
41.0 314.15 0.0244 0.003183 286.4 2.457
47.0 320.15 0.0213 0.003124 372.9 2.572
53.0 326.15 0.0189 0.003066 482.3 2.683
57.0 330.15 0.0175 0.003029 567.1 2.754
62.0 335.15 0.0161 0.002984 693.9 2.841
Footnote: Vapor Pressure at air evaporation = 128.1 torr
Figure 1a : Pvap vs Temperature Separate Trials
Temperature vs Pvap
800
700
600
Pressure (torr)
500 Trial 1
400 Trial 2
300
200
100
0
0 20 40 60 80
Temperature (C)
700
600
Pvap (torr)
500
400 Poly. (Series1)
300
200
100
0
0 10 20 30 40 50 60 70
Temperature (C)
Figure 2a: Log(P) vs 1/T Separate Trials
log(P) vs 1/T
3.5
3
2.5
2
log(P)
Trial 1
1.5 Trial 2
1
0.5
0
0.00295 0.003 0.00305 0.0031 0.00315 0.0032 0.00325 0.0033 0.00335 0.0034
1/T (K^-1)
3 y = -1729.3x + 8.0067
2.9 R2 = 0.9995
2.8
2.7
2.6
log(P)
Series1
2.5
Linear (Series1)
2.4
2.3
2.2
2.1
2
0.0029 0.003 0.0031 0.0032 0.0033 0.0034
1/T (K^-1)
A’ = 8.0067 + 0.049
∆Hvap = 33.104 + 0.968 kJ/mol
Table 2: Differences Between Experimental and Calculated Values
Figure 3a:
20
10
{P (Exp) – P(Calc)}
0
0 100 200 300 400 500 600 700 800
-10
Clausius
Clapyron
-20
Antoine
-30
-40
P{Exp}
Figure 3b:
0 Antoine Trial 2
Pexp
0 100 200 300 400 500 600 700 800 Clausius Trial 2
-1
-2
-3
-4
{Pcalc - Pexp}
Figure 4:
600
500 Given Data
400 Poly. (Given Data)
300
200
100
0
0 50 100 150
Temperature (C)
Figure 5:
3
2.5
2
log(P)
Given Data
1.5 Linear (Given Data)
1
0.5
0
0.002 0.0022 0.0024 0.0026 0.0028 0.003 0.0032 0.0034
1/T (K^-1)
A = 9.2709 + 0.0501
∆Hvap = 50.085 + 0.351 kJ/mol
60
50
{Pcalc - Pexp} (mm Hg)
40
30
Clausius
20
Antoine
10
0
0 100 200 300 400 500 600 700 800 900
-10
{Pexp} (mm Hg)
Conclusion:
The literature value for ∆Hvap of methanol is 35.21 kJ/mol and our calculated
value was ∆Hvap = 33.104 + 0.968 kJ/mol. I think that the difference in this data was due
to the fact that we calculated two different Room Temperature Vapor Pressures when we
evacuated all the air from the system. For Trial 1 the Vapor Pressure at 24C was 114.5
torr while for Trial 2 our Vapor Pressure at 23.9C was 128.1 torr. I performed an
additional analysis on the second trial by graphing its {Pexp – Pcalc} vs. Pexp. The
second trial appears to be more accurate because the values of its Antoine coefficients (A
means that we may have brought the pressure down too low in that trial. Even with this
error, the Antoine equation still appears to be a better fit then the Clausius Clapeyron
Equation for both our experiment and the unknown data provided.
References:
April 2008.
<http://webbook.nist.gov/cgi/cbook.cgi?Name=methanol&Units=SI&cTG=on&cTC=on
&cTP=on>
<http://dwb.unl.edu/Teacher/NSF/C14/C14Links/www.glue.umd.edu/7Ensw/ench250/bu
bpnt.htm>