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Vapor Pressure and Molecular Weight of a Pure Liquid

Purpose The purpose of this lab is to measure the enthalpy and entropy of vaporization of n-pentane. You will also determine the molecular weight of pentane. A secondary purpose is to familiarize you with the operation of a vacuum line.

Introduction

Vapor pressure and enthalpy of vaporization are important properties of a volatile substance. Vapor pressures are needed to understand distillation and other separation techniques. The enthalpy of vaporization is necessary to predict the change in boiling point with pressure. The enthalpy and entropy of vaporization are needed to calculate the enthalpy, absolute entropy, and Gibb's free energy of formation of gaseous substances. These thermodynamic variables are also important measures of intermolecular interactions. Vapor pressures are most accurately measured with an isoteniscope, Figure 1a. A small bulb holding the substance is attached to a open-end manometer. The sample bulb and the open-end manometer are both held in a constant temperature bath. The vapor pressure of the liquid is measured by adjusting the pressure in the ballast bulb so that the level of the manometer is the same in both arms. Then the pressure in the sample bulb is the same as in the ballast bulb, and the pressure of the ballast bulb is then recorded. The advantage of the isoteniscope is that the liquid and vapor of the sample are both kept at the constant temperature.

sample open-end manometer
sample
open-end
manometer

pressure transducer

pressure transducer
pressure transducer
Vapor Pressure and Molecular Weight of a Pure Liquid Purpose The purpose of this lab is
sample
sample
Vapor Pressure and Molecular Weight of a Pure Liquid Purpose The purpose of this lab is
ballast
ballast

to vacuum

to vacuum

constant temperature bath

constant temperature bath

a. Isoteniscope

b. Vacuum line

Figure 1. Vapor pressure measurement: (a) isoteniscope, (b) vacuum line. In a vacuum line part of the vapor is at room temperature, causing a temperature gradient.

A less accurate, but more common method for measuring vapor pressures is a vacuum line, Figure 1b. Vacuum lines are used in handling gases and air or moisture sensitive compounds. Inorganic chemists often use vacuum lines for synthesis and characterization. For simple compounds, vapor pressure and enthalpy of vaporization are often used for quick characterization of unknowns. Therefore, a vacuum line is an important piece of laboratory apparatus that every chemist should know how to use.

Vapor Pressure

2

In a vacuum line, the vapor pressure of the substance is directly measured by the pressure transducer. In other words, the substance comes in direct contact with the pressure measurement device, since there is no intervening open-end manometer. Therefore, most of the vapor is at a different temperature than the liquid. This temperature gradient makes true equilibrium impossible to establish, and also the properties of the gas are different in different parts of the vacuum line. These effects cause systematic errors in the vapor pressure measurement. However, the speed and convenience of using the vacuum line method usually outweigh these errors. The procedure for the vacuum line is very simple. The sample is placed in a constant temperature bath; after the pressure stabilizes, the pressure is recorded. To give you some practice in using the vacuum line, you will also experimentally determine the molecular weight of the substance using a vapor density measurement.

Theory The relationship between vapor pressure and temperature is given by the Clausius-Clapeyron equation:

ln (

p

2

p

1

) =

-

vap H m

R

(

1

T 2

1

- T 1 )

(1)

The assumptions used in the derivation of eq. 1 are that the vapor behaves as an ideal gas, the molar volume of the liquid is much smaller than the vapor, and the enthalpy of vaporization is independent of temperature. For this experiment we need to relax the assumption that the vapor behaves ideally. We also need to consider the effects of the assumption that the enthalpy of vaporization is independent of temperature. Please review the derivation of the Clapeyron equation in your text. The Clapeyron equation applies to the equilibrium vapor pressure curve:

dp

dT

=

S m

vap

vap

V m

(2)

where vap S m and vap V m are the change in molar entropy and molar volume for the phase

transition (vapor -liquid). At equilibrium the vaporization process is reversible and isothermal so that the entropy of vaporization is:

vap S m =

vap H m / T

(3)

Substituting eq. 3 into eq. 2 and assuming that the volume of the liquid is negligible compared to

the vapor so that vap V m = V m , the molar volume of the vapor, gives

dp

dT

=
=

vap H m

T V m

(4)

For a real gas, the compressibility factor z is given as

z =

pV m

RT

Solving for the volume of the vapor gives

(5)

Vapor Pressure

3

V

m = zRT / p

(6)

Substituting eq 6 into eq. 4 and rearranging gives

d

ln p

vap H m

dT

=

zRT 2

or

d ln p

d 1/T

=

-

vap H m

z R

(7)

Assuming that the enthalpy of vaporization is constant over the temperature range of the

experiment and integrating eq. 7 gives the Clausius-Clapeyron equation under the assumption

that the vapor behaves as a real gas

ln ( p p 2

1

) =

-

vap H m

z R

(

1

T 2

1

- T 1 )

(8)

Therefore, a plot of ln p versus 1/T will yield a straight line of slope - vap H m / z R.

The value of z can be determined from standard tables as follows. Experimental measurements

of the compressibility factor, z, are difficult near the liquid-vapor coexistence curve.

Extrapolation of experimental values to the liquid-vapor coexistence region has been completed,

based on the Law of Corresponding States and other theoretical considerations 1 . The results for

a few substances are shown in Figure 3. The plot is given in terms of the reduced temperature, T r ,

where T r =T/T C , where T C is the critical temperature of the substance.

1.00 z(pentane) 0.98 z(water) z(benzene) 0.96 0.94 Z 0.92 0.90 0.88 0.86 0.4 0.5 0.6 0.7
1.00
z(pentane)
0.98
z(water)
z(benzene)
0.96
0.94
Z
0.92
0.90
0.88
0.86
0.4
0.5
0.6
0.7
0.8

Tr

Figure 3. The compressibility factor, z, as a function of reduced temperature along the liquid-

vapor coexistence curve. The curves are calculated using tabulated polynomial coefficients from

Pitzer, et. al. 1 .

Vapor Pressure

4

Finally, we must consider the effect of the temperature dependence of the enthalpy. Please

review in your text that the temperature dependence of the enthalpy of a reaction is

r H T2 = r H T1 + r C p (T 2 - T 1 )

(9)

where r C p is the difference in heat capacity of products minus reactants. For this phase

transition the product is the vapor and the reactant is the liquid. If r C p is large, eq. 8 will not

hold and the plot of ln p versus 1/T will show some curvature instead of being a straight line.

The entropy of vaporization is also an important quantity. The standard state (1 atm) entropy

change can be determined by calculating the enthalpy of vaporization at the normal boiling point

using eq. 9 and then using eq. 3 at the normal boiling point. However, this calculation gives the

entropy change at the normal boiling point, not at 298K as is usually desired. Please review in

your text that the temperature dependence of the entropy of a reaction is

r S T2 = r S T1 + r C p ln (T 2 / T 1 )

(10)

with r C p as defined above. Eq. 10 can be used to calculate the entropy of vaporization at any

temperature (assuming r C p is constant over the temperature range).

Procedure

The vapor pressure curve will be determined by isolating a sample in a vacuum line and

measuring the vapor pressure directly on an electronic pressure sensor while changing the

temperature using constant temperature baths. The constant temperature baths are "slush" baths

made by freezing an organic solvent using liquid nitrogen, LN 2 , to produce a "milk shake"

consistency slush. Since the slush is an equilibrium mixture of a pure liquid and its solid phase,

the bath temperature will be held constant at the normal melting point. Below are listed some

common slush baths.

Slush Bath Temperatures (from Dodd and Robinson 2 )

0°C

-22.9°C

water-ice

carbon tetrachloride

-45.2°C chlorobenzene

-63.5°C chloroform

-83.6°C ethylacetate

The molecular weight of a gas can be determined using its vapor density and the ideal gas law.

Vapor density is measured by filling a bulb of known volume and weight with a vapor and

determining the weight of the vapor by difference. Knowing the weight of the vapor and the

volume, pressure, and temperature allows the calculation of the molecular weight using

PV=nRT.

Procedure Outline

A diagram of the vacuum line for this experiment is shown in Figure 2. The cold finger is used

to protect the vacuum pump. The cold finger is immersed in a dewar of liquid nitrogen, which

condenses any vapors so that they don't reach the pump. The circle symbols with X's through

Vapor Pressure

5

them symbolize stopcocks. The sample is held in the glass sample tube. The gas density bulb is

removed for weighing on an analytical balance (however, a mechanical balance must be used so

make sure that you know how to use a mechanical analytical balance before you come to lab).

The pressure sensor is a very accurate (±0.3%) electronic sensor, which has an internal

diaphragm that flexes to change the capacitance of the sensor. The capacitance is converted to a

corresponding pressure reading by a digital readout. An outline of the procedure is:

  • 1. Evacuate the manifold and immerse the cold finger in LN 2, , weigh the evacuated gas

density bulb. The exact volume of the bulb is etched in the glass.

  • 2. Fill the sample tube with n-pentane.

  • 3. Freeze the pentane with liquid nitrogen and remove any air from the tube.

  • 4. Immerse the sample tube in a series of slush baths and measure the vapor pressure.

  • 4. At the last temperature fill the gas density bulb with pentane vapor.

  • 5. Determine the weight of the vapor in the gas density bulb.

  • 6. To finish up at the end of the day: evacuate the gas density bulb and manifold.

  • 7. Turn off the pump and remove the cold finger.

Caution:

Don't over-tighten the stopcocks. Close the stopcock until the o-ring appears to "wet" the

glass valve seat, then tighten no furthur. If the stopcock doesn't have o-rings (the valve at

the top of the cold trap is of this type), close the stopcock until the teflon appears to

"wet" the glass valve seat.

The halogenated hydrocarbons used for slush baths are suspected carcinogens.

Always work in the hood and wear gloves when handling these compounds.

To

pump

Pressure Sensor S1 S2 S3 S4 S5 Sample Tube Gas Density Bulb Cold Finger
Pressure
Sensor
S1
S2
S3
S4
S5
Sample
Tube
Gas Density
Bulb
Cold Finger

Figure 2. Vacuum line.

Vapor Pressure

6

Detailed Procedure: Gases behave in a very predictable way-- they expand to fill the accessible

space. The detailed directions given below shouldn't replace your common sense about how to do

the experiment. Make sure you know what each stopcock does and why you open and close them

when you do. You shouldn't need to refer to these directions while you are doing the experiment.

  • 1. Turn on the vacuum pump and pressure sensor at least 3 hours before you begin. The 3 hours

is to pump down the vacuum line and to allow the electronics to warm up. Make sure S1, S2, S4,

and S5 are open.

  • 2. Close S4 and S5. Remove the gas density bulb and weigh by hanging the bulb from the hook

at the top of a mechanical analytical balance. You will have to remove the balance pan to avoid

exceeding the weight limit on the balance. Make sure that you know how to use a mechanical

analytical balance before you come to lab.

  • 3. Replace the gas density bulb on the vacuum line and open S4 and S5. Wait for the line to

return to 0.0 mmHg pressure.

  • 4. Close S2 and add 3 mL of n-pentane to the sample bulb. Replace the sample bulb on the

vacuum line.

  • 5. Using LN 2 freeze the pentane in the sample bulb, then open S2. Freezing the sample keeps the

vacuum system from pumping away the liquid while air is being removed from the sample tube.

  • 6. When the pressure returns to 0.0 mmHg close S1 and warm the sample until it thaws.

  • 7. Look up the vapor pressure of n-pentane in the CRC Handbook before you come to lab, so that

you know how cold the first bath can be. Vapor pressures less than 2 mmHg are difficult to

measure on our vacuum line.

  • 8. Prepare the coldest slush bath first. To prepare a slush bath alternately add the slush solvent

and LN 2 to a small dewar flask with rapid stirring. Add small amounts of solvent and LN 2

repeatedly to avoid forming a solid mass of frozen solvent. Repeat your additions until you have

sufficient slush to cover the sample bulb. The slush should have a milk-shake consistency. If the

slush is too thin, all the solid will melt before the sample measurement can be made. If the slush

is too thick, the sample tube will break when you move the dewar upwards around the sample.

Always work in the hood and wear gloves when handling these compounds.

  • 9. Place the first slush bath around the sample. Wait for the pressure to stabilize and record the

pressure. Pressure readings should take about 5 minutes to stabilize.

10. Remove the slush bath. Check to make sure that solid remains in the slush. If available, use a

platinum resistance thermometer to check the slush bath temperature. If the thermometer isn't set

up, just use the table above to determine the temperature. Return the slush bath solvent to its

original container for reuse.

Vapor Pressure

7

11.

Gently wipe the outside of the sample bulb with a paper towel to avoid contamination of the

next slush bath. Go on to the next slush baths. A large beaker of cold water can also be used for

temperatures close to room temperature.

12.

At the last temperature, you should also do the gas density measurement. To do the density

measurement, open S4 and S5 to allow vapor to fill the gas density bulb. After you have recorded

the vapor pressure, use a thermometer to measure the air temperature near the gas density bulb

(the gas IN the density bulb is at room temperature, not at the temperature of the liquid. So you

will need the room temperature to calculate the molecular weight). Close S4 and S5 and gently

remove the gas density bulb from the vacuum line. Weigh the filled gas density bulb as you did

 

before.

To finish up at the end of the day:

13.

Cool the sample bulb with LN 2 to condense all the pentane vapor back into the sample bulb.

Close S2.

14.

Replace the gas density bulb on the vacuum line. Open S1, S4, and S5 and bring the pressure

to 0.0 mmHg.

15.

Close S1, turn off the vacuum pump, and unscrew the cold finger. The cold finger won't

come all the way off, but the trapped solvents will be able to evaporate anyway.

16.

Replace the balance pan on the analytical balance. Replace the solvents in the solvent storage

cabinet.

Calculations

Make a plot according to eq. 8. Use the average temperature of your runs to calculate T r and

then read z from Figure 3. Determine vap H m from the slope of your plot and z. This vap H m

will correspond to the average temperature of your runs. To calculate vap H m at the normal

boiling point, 309.2K, use eq. 9. The heat capacity of gaseous pentane is 120.2 J mol -1 K -1 (Table

2.11 in Atkins 3 ). The heat capacity of liquid pentane is not available in standard tabulations, but

the change in heat capacity for vaporization is a remarkably linear function of the number of

carbon atoms, for hexane through decane 4 . The extrapolated value for pentane of vap C p is

-47.26 J mol -1 K -1 . At the normal boiling point, vap H m = vap m since the vapor pressure is

one atmosphere.

To calculate the standard entropy of vaporization of n-pentane at 298K, use the

vap m(309.2K) you calculated above and eq. 3 to calculate vap m at the normal boiling point.

Then use eq. 10 to calculate vap m(298.2K) .

Use the ideal gas law to determine the molecular weight of pentane from the weight of the

vapor in the gas density bulb, the vapor pressure, and the volume and temperature of the gas

bulb. Don't be disappointed if your results vary 20% or so from the calculated value. Gas density

measurements are expected to give rough estimates only. Note that you don't need to calculate

the density of the gas, just use PV=nRT directly.

Make sure to answer the following questions in your discussion:

Vapor Pressure

8

  • 1. Do you see any evidence that vap H m is temperature dependent over your temperature range?

  • 2. How does your vap m compare with other substances? Does n-pentane obey Trouton's rule?

  • 3. If you were able to measure the slush bath temperatures, how close to the tabulated values

were the slush bath temperatures? What could cause any discrepancies?

  • 4. Why is vap C p negative?

  • 5. Compare vap m to tabulated values. Does the temperature correction in eq. 9 have an

important effect?

Literature Cited

  • 1. Pitzer, K. S.; Lippmann, D. Z.; Curl, Jr., R. F.; Huggins, C. M.; and Petersen, D. E., J. Amer.

Chem Soc., 1955, 77, 3433.

  • 2. Dodd, R. E.; Robinson, P. L. , Experimental Inorganic Chemistry, Elsevier Publishing C.,

Amsterdam, 1957, 56.

  • 3. Atkins, P. W., Physical Chemistry, 5th Ed., Freeman, New York, NY, 1994.

  • 4. Linear extrapolation for the following data derived from Dean, J. A. Lange's Handbook of

Chemistry, 14th Ed., McGraw-Hill,Inc., New York, NY, 1992. Table 6.1.:

n-alkane

vap C p,m ( J mol -1 K -1 )

hexane

-52.014

heptane

-58.805

octane

-60.261

nonane

-66.954

decane

-72.785

Vapor Pressure and Enthalpy of Vaporization

When a liquid is placed in a container, and the container is sealed tightly, a portion of the liquid

will evaporate. The newly formed gas molecules exert pressure in the container, while some of

the gas condenses back into the liquid state. If the temperature inside the container is held

constant, then at some point equilibrium will be reached. At equilibrium, the rate of condensation

is equal to the rate of evaporation. The pressure at equilibrium is called vapor pressure, and will

remain constant as long as the temperature in the container does not change.

This equilibrium relationship between vapor and liquid can be derived from the thermodynamic

master equation.

(1)

dG

=

VdP – SdT

If the liquid and vapor phases are at equilibrium with one another, then G = 0. Rearranging the

master equation and substituting in the equation for the change of entropy for vaporization gives

a general equation for phase transitions:

(2)

(3)

S = H vap / T

dP =

H

m,Trans

T

V

m

dT

Equation (3) can be solved by making the assumption that the enthalpy of transition is

independent of T & P, and that the change in volume can be attributed solely to the ideal gas

volume. With these assumptions in place, the Clausius-Clapeyron equation describes how

vapor pressure changes with changes in temperature, as well as describes how the enthalpy of

vaporization affects those changes.

(4)

ln

P

2

− ∆ H

    T 1

2

T 1    

1

vap

P

1

R

=

P = vapor pressure, T is Kelvin temperature, H vap is the molar enthalpy of vaporization, and R

is the universal gas constant (in units of J/K*mol).

If we let P 1 and T 1 be fixed and equal to the values for “standard” conditions (P o = 1bar, T o

vap =

“standard boiling point”), then equation (4) can be re-written for other T & P conditions as

(5)

(6)

Gentry, 2007

ln

P

=

− ∆ H

vap

RT

+

C

C = constant =

+ ∆ H

vap

o

RT

vap

+ ln(

P

o

)

(solving for T o , P o =1bar)

Theoretical equations are only as good as the assumptions made to derive them. In this case, the

three principal assumptions are that:

1) H vap is constant, independent of both T and P,

2) The volume of the liquid is negligible compared to the volume of the gas, and

3) V is given by the volume of an ideal gas.

If the gases do not obey the ideal gas law, then we must correct the Clausius-Clapeyron equation

using a “real gas” equation such as compressibility.

(7)

(8)

Z V actual / V ideal

or

V actual = Z · nRT/P

ln

P

=

− ∆ H

vap

Z

RT

+

C

One method we can use to estimate the compressibility factor is the Berthelot equation.

(9)

Z =

1

+

9 PT

c

128 P T

c

1

T

6

c

T

2

where T c and P c are the critical temperature and pressure of the liquid taken from the literature.

[for example, http://webbook.nist.gov/chemistry]

It should be pointed out that the Clausius-Clapeyron equation also assumes that H vap is

independent of temperature. In reality we know that the enthalpy of transition changes as you

move away from the standard vaporization temperature. This is due to there being differences in

the heat capacities for solids and liquids.

(10)

H

vap

(

T

)

= ∆

H

o

vap

+

T

T

o

(

C

p vapor

,

C

p liquid

,

)dT

We will be applying the assumption of H vap =constant over only a small temperature range, so

errors due to the assumption should be small.

- 2 -

OBJECTIVES

In this experiment, you will introduce a specific volume of a volatile liquid into a closed vessel,

and measure the pressure in the vessel at several different temperatures. Since there will be

residual air in the vessel as well, you will need to use Dalton’s Law of Partial Pressure to extract

the vapor pressure from the observed pressure.

By analyzing your measurements, you will be able to calculate the relationship between P vap and

T and calculate the H vap of the liquid.

OBJECTIVES In this experiment, you will introduce a specific volume of a volatile liquid into a

PROCEDURE 1

Figure 1

  • 1. Obtain and wear safety glasses. CAUTION: The alcohol used in this experiment is flammable. Be sure that there are no open flames in the room during the experiment. Notify your teacher immediately if an accident occurs.

  • 2. Connect a Gas Pressure Sensor to Channel 1 of the Vernier computer interface. Connect a Temperature Probe to Channel 2 of the interface. Connect the interface to the computer with the proper cable.

  • 3. Use the clear tubing to connect the white rubber stopper to the Gas Pressure Sensor. (About one-half turn of the fittings will secure the tubing tightly.) Twist the white stopper snugly into the neck of the Erlenmeyer flask to avoid losing any of the gas that will be produced as the liquid evaporates (see Figure 1). Important: Close the valve on the white stopper.

  • 4. Obtain a small amount of ethanol. Draw 3 mL of ethanol into the 20 mL syringe that is part of the Gas Pressure Sensor accessories. Make sure there is no air present. Thread the syringe onto the two-way valve on the white stopper (see Figure 1). Do not place the flask in the water bath yet.

  • 5. Start the Logger Pro program on your computer. Open the file “34 Vapor” from the

Advanced Chemistry with Vernier folder.

- 3 -

  • 6. Click

6. Click to begin data collection. Your first measurement will be of the pressure of the

to begin data collection. Your first measurement will be of the pressure of the

air in the flask and the room temperature. Place the Temperature Probe near the flask. When

the pressure and temperature readings stabilize, click

6. Click to begin data collection. Your first measurement will be of the pressure of the

to record the readings.

  • 7. Add ethanol to the flask.

    • a. Open the valve below the syringe containing the 3 mL of ethanol.

    • b. Push down on the plunger of the syringe to inject the ethanol and quickly close the valve.

    • c. Carefully remove the syringe from the stopper so that the stopper is not moved.

  • 8. Monitor the pressure and temperature readings. When the readings stabilize, click

  • .
    .
    • 9. Carefully move the stoppered flask to a 1 liter beaker that you will use as a temperature bath. Include a magnetic stir bar so that the liquid can be mixed during the later warming process. AFTER putting the flask in the beaker, add water and ice to cover the flask up to the top gas level.

    Place the Temperature Probe in the ice bath as well. Monitor the pressure and

    temperature readings. When the readings stabilize, click

    .
    .

    Note: make sure that the pressure went down when you chilled the apparatus in the ice bath.

    If the temperature remained relatively unchanged, then you may have a leak in your system.

    • 10. Use the hot plate to slowly start warming your water bath. Take temperature/pressure measurements every 3-5ºC.

    *** Note the word “slowly”… you want to insure enough time

    that the temperature of the liquid and vapor inside the flask remains in equilibrium with the

    temperature of the surrounding water bath.

    Also, remove any floating ice cubes prior to

    warming otherwise there may be a temperature gradient between the temperature probe and

    the surface of the liquid.

    • 11. Repeat Step 12 until you your temperature approaches 40°C. Do not warm the water bath beyond 40°C because the pressure increase may pop the stopper out of the flask. If you must remove some of the water in the bath, do it carefully so as not to disturb the flask. Let me repeat that. The stoppers on the flasks are not very secure. The easiest way to have problems is to let gas escape from the stoppers. This will occur if there is too much jostling, especially at higher temperatures where there is excess pressure inside the flask.

    • 12. After you have completed your readings, click

    6. Click to begin data collection. Your first measurement will be of the pressure of the

    to end the data collection. Record the

    various temperatures and pressures in your lab book. Do not exit Logger Pro until your data

    are recorded.

    - 4 -

    DATA ANALYSIS

    • 1. Since air was present in the flask before the ethanol was added, the observed pressure inside the flask was a combination of air pressure and ethanol vapor pressure.

    We measured P air

    before adding the ethanol. However we did this at room temperature. You will need to

    adjust P air for the changes in temperature. Assume that the air followed the ideal gas law and

    that the volume remained constant.

    Calculate the resultant vapor pressures for ethanol (in bar) as a function of temperature.

    • 2. The Clausius-Clapeyron equation says that a plot of ln(P) vs. (1/T) should have a linear relationship with one another.

      • (a) What are the expected parametric expressions for the slope and the intercept for your data?

      • (b) Using linear regression, obtain your experimental values for slope and intercept and use the slope to calculate your experimental heat of vaporization.

  • 3. Compare your experimental heat of vaporization to a literature value for ethanol

  • 4. Use the Clausius-Clapeyron equation to extrapolate your data and find the “normal boiling point”. How does your number compare to the literature value? Comments?

  • 5. The assumption was made that ethanol behaves like an ideal gas. Using Eqn. 9, what is the calculated compressibility, Z, for ethanol at 298K? If you use this to correct for your calculations, what is your corrected heat of vaporization? (Assume that Z stays constant over the temperature range that we looked at.)

  • 6. The assumption was made that H vap is independent of temperature. Using the literature value for the standard heat of vaporization, what is the change in H vap when going from 298K to 273K, given that the heat capacities for ethanol are C p,liq = 112 J/mol*K and C p,gas = 65.2 J/mol*K? [Note that you must first calculate each H vap compared to the standard vaporization temperature for ethanol.]

  • Reference

    1 Advanced Chemistry with Vernier

    - 5 -

    Problem 1 - Vapor Pressure and Heat of Vaporization of Liquids Problem 1 Summary

    Part 1-1: Determine the value (and uncertainty) of the vapor pressure and heat of vaporization of acetone [CAS # 67-64-1] at these temperatures:

    330, 375, 425, and 460 K

    Part 1-2: Determine the value (and uncertainty) of the vapor pressure and heat of vaporization of butyramide [CAS # 541-35-5] at these temperatures:

    415, 455, 490, and 520 K

    Introduction Vapor pressure is a fundamental thermodynamic property of a solid or liquid. It is the pressure generated at a particular temperature by pure component which has liquid (or solid) and vapor in equilibrium in a closed vessel. Its units are the usual units of pressure: engineering (psia, mm Hg (Torr), atm, bar, etc.) or SI units (Pa, kPa, MPa). The vapor pressure of a liquid increases with temperature between the triple point and the critical point. Vapor pressure gives a measure of the escaping tendency of a material. The difference in vapor pressure between chemicals is the driving force for separation by distillation: The measure of separability for an ideal mixture of two components is the relative volatility, a (1 2) , defined as,

    a (12) = Psat 1 /Psat 2

    (1)

    where Psat 1 and Psat 2 are the vapor pressures. Few liquid mixtures are ideal, so at low to moderate pressures this relative volatility equation usually contains activity coefficient terms, γ i = f i /(x i f i 0 ), in which the vapor pressure is essentially the reference fugacity, f i 0 ≈ Psat i [1]. The vapor pressure is also an important parameter in evaluating environmental and safety hazards of chemicals (e.g., evaporation rate, persistence in the soil, flash point, emissions, etc.) [2]. The most common vapor-pressure equation as a function of the temperature, T, is,

    log(Psat) = A – B/(T+C)

    (2)

    which was suggested by Antoine in 1888. High-accuracy use of the Antoine equation is restricted to a short range, typically 1 to 200 kPa. Thus the Antoine equation is often used for calculations related to atmospheric or vacuum distillations. The Antoine equation can cautiously be used to give vapor pressure data to ±15% over the temperature range where vapor pressure increases from 1 kPa to the critical pressure. The Riedel equation is,

    ln(Psat) = A + B/T + C ln(T) + D T N

    (3)

    where A, B, C, D, and N are adjustable parameters (N is usually an integer from 1 to 6). The temperature, T, must be absolute temperature, K. The Riedel equation is used to fit data over the entire liquid range from the triple point to the critical point with a precision of 0.5 to 2%. It also has the correct derivative behavior (d(lnP)/d(1/T)) over most of the liquid range.

    A second wide-range vapor-pressure equation is the Wagner equation which is given in reduced form: the temperature and pressure variables are divided by the critical temperature, Tc, and the critical pressure, Pc,

    ln(Pr) = [a + b(1-Tr) 1.5 + c(1-Tr) 3 + d(1-Tr) 6 ]/Tr

    (4)

    where Tr = T/Tc and Pr = Psat/Pc. There are many other vapor-pressure equations but the Antoine, Riedel, and Wagner equations are the three most commonly used in the chemical industry [1]. Heat of vaporization is the difference in heat content between coexisting liquid and vapor [4];

    ΔH vap = H V - H L

    (5)

    For a process where energy is absorbed or liberated at constant pressure, heat of vaporization is called enthalpy of vaporization. It usually has a maximum value at the triple point and decreases with temperature, going to zero at the critical point. Heat of vaporization is an extensive property and is usually reported in thermal units per mole (e.g., kJ/mol). The heat of vaporization can be determined from direct calorimetric measurements (rare) or derived from accurate vapor pressure data via the Clapeyron equation:

    ΔH vap = -RΔZ VL [d(lnP)/d(1/T)]

    (6)

    where ΔZ VL is the difference in compressibility factor (Z = PV/nRT) between coexisting vapor and liquid.

    Assuming that the vapor phase behaves as an ideal gas (Z = 1) and the

    liquid phase compressibility factor is negligibly small, the Clapeyron equation reduces to the Clausius-Clapeyron equation:

    ΔH vap = -R[d(LnP)/d(1/T)]

    (7)

    Heat of vaporization is an important quantity in the design of heat exchangers and other chemical process units. Enthalpy of vaporization is also used to calculate the Hildebrand solubility parameters that are useful in solvent selection to determine the mutual compatibility of chemicals [1]. Experimental techniques for vapor pressure and heat of vaporization measurements have been reviewed e.g. in [3-4]. Most commercial or in- house apparatus are typically suitable for routine measurements of vapor-liquid equilibria at temperatures between ca. –30° to 200° C and pressures between ca. 0.1 kPa to less than 10 MPa. Beyond these ranges, specialized apparatus are necessary and the cost of the measurement increases significantly. In recent years, there are a growing number of industrially important chemicals whose vapor pressures and heats of vaporization need to be determined outside of the range of the ordinary apparatus (e.g., highly volatile compounds at closely subcritical conditions, low volatile compounds with high melting points, etc.). Molecular simulation could offer an attractive alternative to these difficult laboratory measurements.

    Problem Definition

    Part 1-1: Determine the vapor pressure and heat of vaporization of acetone [67-64-1] at these temperatures:

    330, 375, 425, and 460 K

    Also specify the uncertainty in the reported values.

    Part 1-2: Determine the vapor pressure and heat of vaporization of butyramide [541-35-5] at these temperatures:

    415, 455, 490, and 520 K

    Also specify the uncertainty in the reported values.

    Problem Requirements and Restrictions:

    • 1. Any force-field parameters (published or unpublished) may be used

    as long as they do not violate restriction 2 below and are reported in

    the manuscript submitted to the contest committee. Any force-field parameters published in a peer-reviewed journal by the date of the Contest announcement may be used, regardless of what experimental data were used to derive them.

    • 2. Any publicly-available physical property data may be used to fit new

    force-field parameters, excluding vapor pressure and heat of

    vaporization data at temperatures above 303 K for acetone and for butyramide.

    • 3. Computing vapor pressures at any set of temperatures, using a vapor

    pressure equation (such as those described in the Introduction) to fit

    the simulation data, and then calculating answers at the Contest state points is a permitted strategy.

    • 4. Any method, direct or indirect, may be used to determine the heat of

    vaporization from the results of the simulation. If the Clapeyron equation is used as an indirect method (instead of the Clausius-

    Clapeyron equation), the densities of the coexisting saturated liquid and saturated vapor phases must be determined from the simulation.

    Judging criteria:

    The Problem 1 numerical score will be a maximum of 100 points based

    on the weighted numerical percentage difference for the vapor pressure and heat of vaporization as described below:

    Vapor pressure

    A numerical score will be computed as the sum of the absolute values of

    the percentage difference for each of four state points from the experimental benchmark data (the benchmark data state points will include upper and lower uncertainty bounds so that answers within the uncertainty bounds will be given a “0” difference). The total score will

    be the weighted average of Part 1-1 (weight = 30) and Part 1-2 (weight = 70) subtracted from 100. A perfect score is 100.

    Heat of Vaporization

    A numerical score will be computed as the sum of the absolute values of the percentage difference for each of four state points from the benchmark data determined by ASTM Standard Practice E 2071 [5] (the benchmark data state points will include upper and lower uncertainty bounds [6] so that answers within the uncertainty bounds will be given a “0” difference). The total score will be the weighted average of Part 1- 1 (weight = 30) and Part 1-2 (weight = 70) subtracted from 100. A

    perfect score is 100. For a given state point, no credit is given if it is not calculated or deviates by more than 50 % from the corresponding experimental value. The final numerical score is the sum of the vapor pressure and the heat of vaporization scores.

    Evaluation Spreadsheet