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Tompall Toone

Nathaly Murillo
Aaron Reinicker
Physical Chemistry I
Chem 445-021
Experiment 6
Vapor Pressure of a Pure Liquid

Abstract

In this experiment the vapor pressure of methanol was measured by means of a

vacuumed isoteniscope in a stirred water bath. The heat of vaporization as calculated by

the Clausius-Clapeyron equation was ∆Hvap = 33.104 + 0.968 kJ/mol, which is

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 =

280.549) were closer to the literature values (A = 8.07240, B = 1574.990, C = 238.870).

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.

Since vapor pressure strongly increases as a function of temperature and slightly

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

which it increased strongly as a function of increasing temperature. The following

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

under the assumption that the heat of vaporization is independent of temperature. In

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

finding vapor pressure as a function of temperature:

(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

atmosphere, or decreasing, turning on the vacuum, the pressure.

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

was increased at a different interval then the first trial.

Results and Analysis

Table 1 includes temperature, in both Celsius and Kelvin, inverse of both

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

yields an acceptable trend.

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.

Table 2 provides the temperature, the experimental pressure, the calculated

pressure from the Clausius-Clapeyron equation, and the difference between the

experimental pressure and the Clausius-Clapeyron calculated pressure. Next using

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 experiential pressure and the calculated Antoine pressure.


Figure 3a displays the first trials pressure differences, for both equations, verses

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

as found in Figure 3a.

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

the experimental data.

Data and Results

Table 1a: Experimental Data Trial 1

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

Table 1b: Experimental Data Trial 2

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)

Figure 1b : Pvap vs Temperature Combined

Temperature vs Pvap combined


y = 9E-05x 3 + 0.2729x 2 - 9.7997x + 234.46
800 R2 = 0.9955

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)

Figure 2b: Log(P) vs 1/T Combined

log(P) vs 1/T Combined

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

T (C) P(exp) P(calc, eq2) {|P (Exp) – P(calc) {P(exp)-P(calc)}


(torr) (torr) P(Calc)|} (torr) Antoine (torr) Antoine (torr)
24 156.6 153.8 2.8 155.3228622 1.277137833
29 191.6 192.0 0.4 192.1225483 -0.52254834
31 181.8 209.4 27.6 208.9104465 -27.11044647
34 235.3 238.0 2.7 236.5650336 -1.26503363
36 224.6 258.8 34.2 256.7803004 -32.18030041
40 300.9 305.1 4.2 301.9141984 -1.014198431
41 286.4 317.7 31.3 314.2528034 -27.85280336
46 384.2 387.5 3.3 382.9758062 1.224193832
47 372.9 402.9 30 398.2316235 -25.33162353
52 489.2 487.8 1.4 482.960722 6.239278023
53 482.3 506.5 24.2 501.7193341 -19.41933413
57 567.1 587.2 20.1 583.4231056 -16.3231056
58 620.0 609.0 11 605.6169807 14.38301927
62 693.9 702.9 9 702.1059655 -8.2059655
63.2 730.4 733.4 3 733.6059297 -3.205929664
Footnotes: Hvap = 33.104 + 0.968 kJ/mol
Antoine Coefficients (A = 10.75, B=3926.05, C = 434.57)

Figure 3a:

{P (Exp) – P(Calc)} vs. P{Exp} Combined

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:

{Pexp - Pcalc} vs. Pexp Trial 2

0 Antoine Trial 2
Pexp

0 100 200 300 400 500 600 700 800 Clausius Trial 2
-1

-2

-3

-4
{Pcalc - Pexp}

Footnote: Antoine Coefficients Trial 2: A = 8.754, B = 2025.15, C = 280.549


Trial 1: A = 10.75, B=3926.05, C = 434.57

Sample Data of Unknown Substance (Provided in Lab)

Figure 4:

Temperature vs Pressure (Data Given)


y = 0.0011x 3 - 0.1751x 2 + 10.927x - 227.85
900 R2 = 0.9999
800
700
Pressure (mmHg)

600
500 Given Data
400 Poly. (Given Data)
300
200
100
0
0 50 100 150
Temperature (C)
Figure 5:

log(P) vs. 1/T Given Data


y = -2616.4x + 9.2709
3.5 R2 = 0.9991

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

Table 3: Differences Between Experimental and Calculated Values of Given Data

T (C) Pexp Pcalc Clausius {Pexp – Pcalc} Pcalc Antoine {Pexp-Pcalc}


(torr) (torr) Clausius (torr) (torr) Antoine (torr)
45 10.2 11.15 0.9456703 10.20129881 0.001298806
50 14.1 14.94 0.839993551 14.12540212 0.025402123
60 26.0 26.15 0.144513468 25.95394561 -0.046054391
65 34.5 34.16 -0.34098393 34.50241545 0.002415447
70 45.4 44.28 -1.11607989 45.32416619 -0.075833814
75 58.9 56.98 -1.91658342 58.87914104 -0.020858959
80 75.7 72.80 -2.89684891 75.68958079 -0.010419213
85 96.4 92.38 -4.019353 96.3435099 -0.0564901
90 121.5 116.5 -5.04351836 121.4978445 -0.002155538
95 151.8 145.9 -5.91379742 151.8810803 0.081080347
100 188.2 181.7 -6.54703556 188.2955285 0.095528495
105 231.4 224.9 -6.51914055 231.6190726 0.219072553
110 282.4 276.9 -5.55109117 282.8064324 0.406432418
115 342.2 339.0 -3.19432458 342.8899252 0.689925209
120 412 413.0 0.98445244 412.9797226 0.979722649
125 492.9 500.6 7.718977445 494.2636108 1.363610759
130 586.1 604.0 17.85961595 588.0062639 1.906263913
131.6 627.93 640.7 12.78193879 620.8520501 -7.077949863
135 692.9 725.3 32.38995449 695.5480508 2.64805079
140 814.8 867.1 52.3437392 818.3033945 3.503394454
Footnote: Antoine Coefficients: A = 7.20976 + 0.06142 , B =1329.233 + 23.217 , C =
169.4521 + 2.362
Figure 6: (Pcalc – Pexp) vs Pexp for Clausius and Antoine Given Data

{Pcalc - Pexp} vs. {Pexp} Given Data

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

= 8.754, B = 2025.15, C = 280.549) are closer to the literature values (A = 8.07240, B =

1574.990, C = 238.870) then for trial 1 (A = 10.75, B=3926.05, C = 434.57) which

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:

1. NIST Chemistry Webbook. “Methyl Alcohol” U.S. Secretary of Commerce. 4

April 2008.

<http://webbook.nist.gov/cgi/cbook.cgi?Name=methanol&Units=SI&cTG=on&cTC=on

&cTP=on>

2. Wang, Nam Sun. Bubble Point /w Antoine Equation. “Computer Methods in

Chemical Engineering” 4 April 2008.

<http://dwb.unl.edu/Teacher/NSF/C14/C14Links/www.glue.umd.edu/7Ensw/ench250/bu

bpnt.htm>

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