Name: Lanoline C.

Toring Date Performed: February 28, 2020

Section: 7L Date Submitted: March 6, 2020

Group No.: 2

Exercise 4

Vapor Pressure of a Liquid

I. Introduction

Vapor pressure is the pressure formed by evaporating a liquid in a closed container

(1). It is the pressure of the vapor which is in equilibrium with a liquid. Liquid- vapor equilibrium

is attained when the rates of condensation and evaporation are equal.

Vapor pressure is dependent on temperature and intermolecular forces of attraction

(IMFA). For IMFA and vapor pressure, the relationship is inversely proportional which means

that the stronger the IMFA, the lower the vapor pressure. This is because less of the liquid

phase can overcome the forces which bind the substance and are then able to vaporize. It is

the other way around for the dependence of vapor pressure with temperature. An increase in

the temperature until the critical temperature results to an increase in the vapor pressure.

Critical temperature is defined as the temperature at which liquid surface disappears and

above which a liquid does not exist no matter how high the pressure applied (2). This can be

explained by the fact that due to enough amount of energy being supplied, liquid molecules

are able to escape and vaporize.

The relationship between vapor pressure and temperature is described by the

Clausius-Clapeyron equation. Four assumptions are applied in order to derive this equation.

The first assumption is that equilibrium exists between the liquid and gas phases of acetone

and methanol. This can be shown by:

µv = µl (4-1)

where µv = chemical potential of the vapor phase

µl = chemical potential of the liquid phase

The Clausius-Clapeyron equation was derived from the Clapeyron equation

 ̅
̅ Δvap H
dP ΔS
= ̅= ̅ (4-2)
dt ΔV TΔV

̅ = molar enthalpy of vaporization

where Δvap H

T = temperature in Kelvin

P = vapor pressure

̅ = molar volume change during vaporization

ΔV

The second assumption states that the vapor behaves as an ideal gas. It provides an

equation of state that eliminates the volume of gas a variable as shown by:

̅ v = RT
ΔV (4-3)
P

The third assumption states that the molar volume of the liquid may be neglected in

comparison with the molar volume of the vapor. From this, the molar volume of liquid is

eliminated from the equation.

̅= V
ΔV ̅ l ≈ RT
̅v - V (4-4)
P

Rearranging equation (4-2) and substituting (4-4) yields the Clausius-Clapeyron

equation
̅
d ln P Δvap H
= 2 (4-5)
dt RT

According to the last assumption, the enthalpy of vaporization is independent of

temperature. From this assumption, simple integration of equation (4-5) can be done which

results to

P2 ̅
Δvap H 1 1
ln =- ( - ) (4-6)
P1 R T2 T1

or
̅
ΔvapH
ln P = - (4-7)
RT

Therefore, satisfying the above-mentioned assumptions, a plot of ln P versus 1/T is

̅
Δvap H
linear with a slope of - .
R

This exercise aims to: 1) determine the relationship between vapor pressure and

temperature in a liquid-vapor system; 2) calculate the enthalpy of vaporization of a substance

from vapor pressure-temperature data; and 3) compare the trend in vapor pressure of

structurally similar liquids.

II. Materials and Methods

Using the isoteniscope assembly shown below, the vapor pressures for both acetone

and methanol were determined. The set-up was composed of manometer, thermometer,

water-bath, isoteniscope, heat source and a 3-way stopcock.

Figure 4.1. The isoteniscope assembly.

The isoteniscope was cleaned with acetone and rinsed with the experimental liquids,

acetone and methanol. The main bulb was then filled with half-full of the same liquid. It was

ensured that there also has liquid in the U-trap. Small amount of grease was applied on the

tip of the container before it was attached to the assembly. The vacuum pump was turned on

with all holes closed. The system was tested for leaks. A little vacuum was applied to the

system and the mercury levels in the manometer were observed. Change in manometer levels

indicated if there were leaks. The 3-way stopcock was adjusted. The system was then

evacuated for 2-3 minutes to remove all air between the liquid trap and the bulb containing

acetone or methanol. Then, air was admitted to the stopcock until the liquid levels in both arms

of the U-tube were equal. The vapor pressures at different temperatures 20° below that of the

normal boiling point of acetone (56°C) and methanol (65°C) at 2° intervals were obtained. This

was done both for increasing and decreasing temperatures. The holes of the 3-way stopcock

were opened before the vacuum pump was turned off.

The atmospheric pressure and room temperature were also recorded.

 From the gathered data, linearization was done by plotting Pgas vs 1/T for both

increasing and decreasing temperatures. Molar enthalpy of vaporization was determined.

Compressibility factor at conditions corresponding to the highest and lowest temperature were

̅ and
also calculated. The compressibility factor was then accounted and value for Δvap H

recalculated.

III. Results and Discussion

Table 4.1. Data on the atmospheric conditions.

Room temperature, °C 26

Atmospheric pressure, mmHg 748.03

Corrected atmospheric pressure, mmHg 744.53

Table 4.2. Change in Hg levels of manometer at different temperatures for acetone.

Sample: Acetone
Increasing Temperature Mode Decreasing Temperature Mode
Temperature, K hfinal, Δh, mmHg Temperature, hfinal, mmHg Δh, mmHg
mmHg K
309.15 459 0 329.15 458 0
311.15 470 22 327.15 483 50
313.15 462 6 325.15 504 92
315.15 459 0 323.15 523 130
317.15 467 16 321.15 530 144
319.15 458 -2 319.15 536 156
321.15 458 -2 317.15 534 152
323.15 462 6 315.15 494 72
325.15 458 -2 313.15 513 110
327.15 458 -2 311.15 534 152
329.15 458 -2 309.15 487 58

Table 4.3. Determination of vapor pressure at different temperatures for acetone.

Sample: Acetone
Increasing Temperature Mode Decreasing Temperature Mode
Temperature, K Δhcorr, Pgas, mmHg Temperature, Δhcorr, Pgas, mmHg
mmHg K mmHg
309.15 0 748.03 329.15 0 748.03
311.15 21.89704 726.13296 327.15 49.766 698.264
313.15 5.97192 742.05808 325.15 91.56944 656.46056
315.15 0 748.03 323.15 129.3916 618.6384
317.15 15.92512 732.10488 321.15 143.32608 604.70392
319.15 -1.99064 750.02064 319.15 155.26992 592.76008
321.15 -1.99064 750.02064 317.15 151.28864 596.74136
323.15 5.97192 742.05808 315.15 71.66304 676.36696
325.15 -1.99064 750.02064 313.15 109.4852 638.5448
327.15 -1.99064 750.02064 311.15 151.28864 596.74136
329.15 -1.99064 750.02064 309.15 57.72856 690.30144
Table 4.4. Change in Hg levels of manometer at different temperatures for methanol.
Sample: Methanol
Increasing Temperature Mode Decreasing Temperature Mode
Temperature, K hfinal, Δh, mmHg Temperature, hfinal, mmHg Δh, mmHg
mmHg K
318.15 481 0 338.15 492 0
320.15 471 -20 336.15 500 16
322.15 468 -26 334.15 499 14
324.15 464 -34 332.15 525 66
326.15 475 -12 330.15 524 64
328.15 461 -40 328.15 504 24
330.15 465 -32 326.15 487 -10
332.15 458 -46 324.15 499 14
334.15 464 -34 322.15 529 74
336.15 458 -46 320.15 519 54
338.15 457 -48 318.15 533 82

Table 4.5. Determination of vapor pressure at different temperatures for methanol.

Sample: Methanol
Increasing Temperature Mode Decreasing Temperature Mode
Temperature, K Δhcorr, Pgas, mmHg Temperature, Δhcorr, Pgas, mmHg
mmHg K mmHg
309.15 0 748.03 329.15 0 748.03
311.15 -19.9064 767.9364 327.15 15.92512 732.10488
313.15 -25.87832 773.90832 325.15 13.93448 734.09552
315.15 -33.84088 781.87088 323.15 65.69112 682.33888
317.15 -11.94384 759.97384 321.15 63.70048 684.32952
319.15 -39.8128 787.8428 319.15 23.88768 724.14232
321.15 -31.85024 779.88024 317.15 -9.9532 757.9832
323.15 -45.78472 793.81472 315.15 13.93448 734.09552
325.15 -33.84088 781.87088 313.15 73.65368 674.37632
327.15 -45.78472 793.81472 311.15 53.74728 694.28272
329.15 -47.77536 795.80536 309.15 81.61624 666.41376

Table 4.6. Plotted values in the determination of molar heat of vaporization of acetone.
Sample: Acetone
Increasing Temperature Mode Decreasing Temperature Mode
-1
ln Pgas 1/T, K ln Pgas 1/T, K-1
6.587733139 0.003213884 6.617443084 0.003038129
6.595923782 0.003153082 6.548597255 0.003056702
6.617443084 0.003173092 6.486862616 0.003075504
6.620100726 0.003133323 6.427520934 0.003094538
6.620100726 0.00311381 6.40473895 0.00311381
6.38478973 0.003133323
 6.625
6.62
6.615
6.61
ln Pgas

y = -297.1x + 7.5463
6.605 R² = 0.5583
6.6
6.595
6.59
6.585
0.0031 0.00312 0.00314 0.00316 0.00318 0.0032 0.00322
1/T (1/K)

Figure 4.2. ln Pgas vs. 1/T plot of acetone for increasing temperature.

6.65

6.6

6.55

6.5
ln Pgas

6.45

6.4
y = -2477.4x + 14.122
6.35 R² = 0.947

6.3
0.00302 0.00304 0.00306 0.00308 0.0031 0.00312 0.00314
1/T (1/K)

Figure 4.3. ln Pgas vs. 1/T plot of acetone for decreasing temperature.
Table 4.7. Plotted values in the determination of molar heat of vaporization of methanol.
Sample: Methanol
Increasing Temperature Mode Decreasing Temperature Mode
ln Pgas 1/T, K-1 ln Pgas 1/T, K-1
6.617443084 0.003143171 6.630661222 0.003066074
6.643706917 0.003123536 6.598639156 0.003084992
6.651453417 0.003104144 6.513788293 0.003104144
6.661689612 0.003084992 6.542879255 0.003123536
6.633284012 0.003066074 6.501910739 0.003143171
6.669298578 0.003047387
 6.677
6.667
6.657
ln Pgas

6.647
6.637 y = -356.52x + 7.7495
R² = 0.4532
6.627
6.617
0.00295 0.003 0.00305 0.0031 0.00315
1/T (1/K)

Figure 4.4. ln Pgas vs. 1/T plot of methanol for increasing temperature.

6.605
ln Pgas

6.555
y = -1622.1x + 11.593
R² = 0.7974
6.505

6.455
0.00295 0.003 0.00305 0.0031 0.00315
1/T (1/K)

Figure 4.5. ln Pgas vs. 1/T plot of methanol for decreasing temperature.
Table 4.8. Linear Regression Analysis for the determination of the molar heat of vaporization
(ΔvapH) of acetone for increasing temperature mode and decreasing temperature mode.
Parameter Value
Increasing Temperature Decreasing Temperature
r 0.7471947537 0.9731392501
slope -297.1 -2477.4
y-intercept 7.5463 14.122
Experimental ΔvapH, kJ/mol 2.4700894 20.5971036

Table 4.9. Linear Regression Analysis for the determination of the molar heat of vaporization
(ΔvapH) of methanol for increasing temperature mode and decreasing temperature mode.
Parameter Value
Increasing Temperature Decreasing Temperature
r 0.6732013072 0.892972564
slope -356.52 -1622.1
y-intercept 7.7495 11.593
Experimental ΔvapH, kJ/mol 2.96410728 13.4861394

Table 4.10. Literature values (ΔvapH and van der Waals constants) of acetone.
Parameter Value
ΔvapH, kJ/mol 31.3
a, Pa m6/mol2 160.2 x 10-2
b, m3/mol 112.4 x 10-6
Table 4.11. Literature values (ΔvapH and van der Waals constants) of methanol.
Parameter Value
ΔvapH, kJ/mol 35.2
a, Pa m6/mol2 94.72 x 10-2
b, m3/mol 65.84 x 10-6

Table 4.12. Determination of compressibility factor, Z and Δ vapH (with Z) of acetone at highest
and lowest temperature
Z ΔvapH, kJ/mol
Increasing Temperature Mode
Highest Temp (321.15 K) 0.9998630356 2.469751086
Lowest Temp (311.15 K) 0.9998577235 2.469737964
Decreasing Temperature Mode
Highest Temp (329.15 K) 0.9998707054 20.59444051
Lowest Temp (319.15 K) 0.9998902352 20.59484276

Table 4.13. Determination of compressibility factor, Z and ΔvapH (with Z) of methanol at highest
and lowest temperature
Z ΔvapH, kJ/mol
Increasing Temperature Mode
Highest Temp (328.15 K) 0.9999187558 2.963866463
Lowest Temp (318.15 K) 0.9999173507 2.963862299
Decreasing Temperature Mode
Highest Temp (326.15 K) 0.9999207606 13.48507077
Lowest Temp (318.15 K) 0.9999263684 13.48514639

Table 4.14. Percent error of experimental ΔvapH of acetone for increasing temperature mode
and decreasing temperature mode.
Percent error (%)
Increasing Temperature Mode -92.10834058
Decreasing Temperature Mode -34.19455719

Table 4.15. Percent error of ΔvapH with incorporated compressibility factor of acetone for
increasing temperature mode and decreasing temperature mode.
Percent error (%)
Increasing Temperature Mode
Highest Temp (321.15 K) -92.10942145
Lowest Temp (311.15 K) -92.10946337
Decreasing Temperature Mode
Highest Temp (329.15 K) -34.20306548
Lowest Temp (319.15 K) -34.20178031

Table 4.16. Percent error of experimental ΔvapH of methanol for increasing temperature
mode and decreasing temperature mode.
Percent error (%)
Increasing Temperature Mode -91.57924068
Decreasing Temperature Mode -61.68710398
Table 4.17. Percent error of ΔvapH with incorporated compressibility factor of methanol for
increasing temperature mode and decreasing temperature mode.
Percent error (%)
Increasing Temperature Mode
Highest Temp (328.15 K) -91.57992482
Lowest Temp (318.15 K) -91.57993665
Decreasing Temperature Mode
Highest Temp (326.15 K) -61.69013987
Lowest Temp (318.15 K) -61.68992502

The isoteniscope method was used to determine the vapor pressure of the sample

liquids, acetone and methanol respectively. The molar heat of vaporization was also obtained

experimentally using the Clausius-Clapeyron equation. The assumptions made and their

effect on the experimental value of ΔvapH will be explained.

The vapor pressures of acetone and methanol were expressed as Δh that corresponds

to the difference in the readings in the manometer (h2-h1). The barometric reading and

manometer readings were corrected since an increase in temperature leads to the expansion

of the mercury inside the barometer. The formula used for correcting the pressure is shown

by:

PC = PB (1-1.8 x 10-4 TR) (4-8)

After correcting the pressures, Pgas values were calculated by the formula

Pgas = Patm – Δh (4-9)

When one end of the U-tube is connected to a gas supply, changes in the levels of the liquid

can be observed to the pressure exerted by the gas. For the set-up, equation (4-9) can be

explained by the fact that when the gas pressure is lower than the atmospheric pressure, Δh

will be negative since there will be a decrease in the height for the arm exposed to atmospheric

pressure (3).

Relationship between the vapor pressure and temperature is explained by the

Clausius-Clapeyron equation. From this, the natural logarithm of the pressures of the two

samples were plotted versus the inverse of their temperatures in order to get a curve with the
̅
Δvap H
slope - . In the experiment, it was observed that the values gathered were erroneous
R

where the pressure recorded will suddenly have a steep increase then will decrease again.
The obtained values for ΔvapH had very great deviations from the literature values which led

to errors ranging from 35% to 90%. From the ln P vs 1/T plots, it was observed that the

decreasing temperature mode gave values closer to the literature value. At decreasing

temperature, heat is being released naturally as vapor condenses. Enthalpy effect is dominant

in this mode which explains why it gave better results. On the other hand, at increasing

temperature, heat is being added in order to overcome IMFA, to supply kinetic energy and to

maintain vapor temperature. Entropy effect is a lot more dominant in this mode rather than

enthalpy. It gave erroneous effects due to fluctuations. Heat addition has more immediate

effect at the increasing T mode particularly when rapid boiling occurs.

The molecular structures of the sample liquids must also be taken into account when

determining the vapor pressure. Generally, substances with higher molecular weight will have

lower vapor pressures and therefore a higher molar enthalpy of vaporization. Between acetone

and methanol, acetone has a greater molecular weight so it is expected to have a higher ΔvapH,

but due to sources of error, the results deviated from what is expected. For substances with

higher molecular weight, more heat is required to supply the kinetic energy of molecules.

There is a lower tendency to escape to gas phase. Furthermore, methanol exhibits hydrogen

bonding which also implies higher IMFA.

Temperature affects the vapor pressure of a liquid in a directly proportional

relationship. This is because the average kinetic energies of molecules increase (4). This also

means that higher amount of molecules acquire sufficient energy to escape from the liquid.

The assumptions of the Clausius-Clapeyron equation are not always valid and these

also limit the accuracy of the values of ΔvapH. From the third assumption (4-4), the molar

volume of the liquid is not totally negligible. This assumption is only applicable in the low-

pressure region because the molar volume of the liquid is only a few tenths of a percent of the

molar volume of the vapor (5). Another is the fourth assumption that states that the ΔvapH is

independent of temperature. This is because Cp is a function of temperature. This can be

shown by:
 dH = (∂H/ ∂T)p dT + (∂H/ ∂P)T dP

∫dH = ∫ Cp dT + ∫(∂H/ ∂P)T dP

ΔH = h2 – h1 = ∫ Cp dT + ∫(∂H/ ∂P)T dP (4-10)

From this, it can be observed that ΔvapH is not entirely independent of temperature. Many

substances show small differences in the ΔvapH in temperatures near room conditions but as

the temperature of some substances approach their critical temperatures, the values for their

ΔvapH approaches zero.

The gas does not behave ideally because the idealizing conditions which are low

pressure and high temperature were not attained in the experiment. This is why the

compressibility factor, Z must be incorporated in the recalculation of ΔvapH. It helps to correct

the non-ideality of the gas. From the experiment, all the Z values were all near 1, thus the

assumption on the ideality of the gas is valid.

Another method that can be used to determine the enthalpy of vaporization of a liquid

is by calorimetry. In this method, a known mass of the liquid which is to be tested is vaporized

in a special vaporization vessel in a current of air. By calorimetry, the quantity of heat absorbed

which is also the enthalpy of vaporization can be determined (6).

Some applications of this experiment are distillation of volatile substances,

manufacturing processes which depend on humidity conditions, and solvent recovery.

IV. Summary and Conclusions

There are many methods available in determining the vapor pressure of liquids. The

most commonly used of these is the isoteniscope method which was employed in the

experiment.

The Clausius-Clapeyron equation describes the variation of vapor pressure with

temperature. The derivation of this equation is guided by four assumptions. However, some

of them lead to errors in the results gathered in the experiment. Corrections were done in order

to obtain more accurate ΔvapH values.

 From the graphs of ln P versus 1/T for both increasing and decreasing temperature

modes, a linear relationship is observed with negative slopes. Therefore, vapor pressure

increases as temperature increases.

The vapor pressure is also affected by IMFA and molecular weights of liquids. For

stronger IMFA, there is a stronger attraction between molecules so there is a lesser tendency

to escape to gas phase. Then, the vapor pressure will be lower. An example is oxygen and

methanol having almost the same molecular weights but since methanol exhibits dipole-dipole

interaction aside from London dispersion forces, its vapor pressure is lower. For molecular

weight, higher molecular weight also lowers the vapor pressure of a substance.

Overall, it can be concluded that the isoteniscope method is an effective way of

determining vapor pressures of liquid. However, it should be remembered that the

assumptions in the Clausius-Clapeyron equation are not always valid especially the

negligence of the molar volume of liquid and the independence of the ΔvapH from temperature.

Accounting the compressibility factor helps in correcting the non-ideality of the gas.

V. Sample Calculations

VI. Literature Cited

1. Vapor Pressure [Internet]. Indiana: Purdue University. Vapor pressure; n.d. [cited 2020

Mar 5]. Available from:

https://www.chem.purdue.edu/gchelp/liquids/vpress.html#:~:text=Vapor%20Pressure&

text=The%20vapor%20pressure%20of%20a%20liquid%20varies%20with%20its%20tem

perature,following%20graph%20shows%20for%20water.&text=As%20the%20temperatur

e%20of%20a,decreases%20as%20the%20temperature%20decreases.

2. Atkins PW, De Paula JC. Physical chemistry. 9th edition. New York: W. H. Freeman Co.;

2010. 138-139

3. Bond T, Hughes C. O-level Physics Critical Guide. Updated edition. London: Yellowreef

Limited; 2013. 6-6

4. Brown TL, Eugene EL, Bursten BE, Murphy, CJ. Chemistry: The Central Science. 12th

edition. New Jersey: Pearson Prentice Hall; 2009. A-14

5. Garland CW, Nibler JW, Shoemaker DP. Experiments in Physical Chemistry. 8th edition.

New York: McGraw-Hill; 200

6. PHYWE. Determination of the Enthalpy of Vaporization of Liquids. PHYWE series of

publications. n.d. 2(4): 25