Vapour pressure

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Vapour pressure

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1) The natural log term on the left-hand side is unitless. It does not matter what units of pressure

you use; the only restriction is that P1 and P2 must be expressed using the same pressure unit.

2) The unit on the temperature term will be K1. The unit on R is J mol1 K1.

3) The K1 in the temperature term will cancel with the K1 associated with R.

4) This means that the unit on H must be J/mol. This then makes the right-hand side unitless.

Below, I plan to just solve a few problems. If you want more on this equation please see here.

Or, fire up Teh Great Googlizer.

Problem #1: Determine Hvap for a compound that has a measured vapor pressure of 24.3 torr at

273 K and 135 torr at 325 K.

Solution:

1) Let us use the Clausius-Clapeyron Equation:

P1 = 24.3 torr T1 = 273 K

P2 = 135 torr T2 = 325 K

2) Set up equation with values:

ln (135/24.3) = (x / 8.31447) (1/273 minus 1/325)

1.7148 = (x / 8.31447) (0.00058608)

1.7148 = 0.000070489x

Problem #2: A certain liquid has a vapor pressure of 6.91 mmHg at 0 C. If this liquid has a

normal boiling point of 105 C, what is the liquid's heat of vaporization in kJ/mol?

Solution:

1) Let us use the Clausius-Clapeyron Equation:

ln (P1 / P2) = (H / R) (1/T2 - 1/T1)

with the following values:

P1 = 6.91 mmHg T1 = 0 C = 273.15 K

P2 = 760.0 mmHg T2 = 68.73 C = 378.15 K

2) Set up equation with values:

ln (6.91/ 760) = (x / 8.31447) (1/378.15 minus 1/273.15)

-4.70035 = (x / 8.31447) (-0.0010165)

4.70035 = 0.00012226x (notice I got rid of the negative signs)

x = 38445 J/mol = 38.4 kJ/mol

Problem #3: Carbon tetrachloride has a vapor pressure of 213 torr at 40.0 C and 836 torr at

80.0 C. What s the enthalpy of vaporization in kJ/mol?

Solution:

1) Let us rearrange the Clausius-Clapeyron Equation:

ln (P1/P2) = (-Hvap/R) x (1/T1 - 1/T2)

Hvap = [-R x ln (P1/P2)] / (1/T1 - 1/T2)

2) Insert values and solve:

Hvap = [(-8.314 J/mole K) x ln (213 torr / 836 torr)] / (1/313.15 K - 1/353.15 K)

Problem #4: The molar enthalpy of vaporization of hexane (C6H14) is 28.9 kJ/mol, and its

normal boiling point is 68.73 C. What is the vapor pressure of hexane at 25.00 C?

Solution:

1) Let us use the Clausius-Clapeyron Equation:

ln (P1 / P2) = - (H / R) (1/T1 - 1/T2)

with the following values:

P1 = x

T1 = 25.00 C = 298.15 K

2) Set up equation with values:

ln (x / 760) = - (28900 / 8.31447) (1/298.15 minus 1/341.88)

ln (x / 760) = - 1.4912

x /760 = 0.2251

x = 171 torr

Comment: note that no pressure is given with the normal boiling point. This is because, by

definition, the vapor pressure of a substance at its normal boiling point is 760 mmHg.

Not indicating the above in this type of question is common. You have been warned!

Problem #5: What is the vapor pressure of benzene at 25.5 C? The normal boiling point of

benzene is 80.1 C and its molar heat of vaporization is 30.8 kJ/mol. Answer in units of atm

Solution:

1) Let us use the Clausius-Clapeyron Equation:

ln (x / 1.00) = (30800 / 8.31447) (1/353.25 minus 1/298.65)

Comment: I used the form of the equation shown in this image:

I assigned the unknown value to be associated with P2. That puts x in the numerator and a 1.00 in

the denominator, making my calculation a bit easier.

2) Let us calculate:

ln (x / 1.00) = (3704.385) (-0.000517545)

ln x = -1.9172

x = 0.147 atm

Comment: I used 273.15 to convert Celsius to Kelvin. It's normal to use 273. I just decded to

walk on the wild side for a moment.

Problem #6: The normal boiling point of Argon is 83.8 K and its latent heat of vaporization is

1.21 kJ/mol. Calculate its boiling point at 1.5 atmosphere.

Solution:

1) Let us use the Clausius-Clapeyron Equation:

ln (P1 / P2) = - (H / R) (1/T1 - 1/T2)

with the following values:

P1 = 1.0 atm T1 = 83.8 K

P2 = 1.5 atm T2 = x

2) Set up equation with values:

ln (1.0/ 1.5) = - (1210 / 8.31447) (1/83.8 minus 1/x)

0.405465 = 145.53 (0.011933 minus 1/x)

0.405465 = 0.17366 minus 145.53 / x

0.231805 = -145.53 / x

Problem #7: Chloroform, CHCl3has a vapor pressure of 197 mmHg at 23.0 C, and 448 mmHg

at 45.0 C. Estimate its heat of vaporization and normal boiling point.

Solution:

1) Let us use the Clausius-Clapeyron Equation:

ln (P1 / P2) = - (H / R) (1/T1 - 1/T2)

with the following values:

P1 = 197 mmHg T1 = 296 K

P2 = 448 mmHg T2 = 318 K

2) Set up equation to solve for the enthalpy of vaporization:

ln (197 / 448) = - (x / 8.31447) (1/296 minus 1/318)

x = 29227.66 J = 29.2 kJ

3) Let us use the Clausius-Clapeyron Equation:

ln (P1 / P2) = - (H / R) (1/T1 - 1/T2)

with the following values:

P1 = 760 mmHg T1 = x

P2 = 448 mmHg T2 = 318 K

4) Set up equation to solve for the normal boiling point:

ln (760 / 448) = - (29227.66 / 8.31447) (1/x minus 1/318)

0.5285252 = - 3515.2764 (1/x minus 1/318)

0.5285252 = 11.05433 minus (3515.2764 / x)

10.5258048 = 3515.2764 / x

x = 334 K

You might be interested in a collection (from the literature) of enthalpy of vaporization values

for chloroform. The author of the above problem (not the ChemTeam!) obviously used the fourth

of the four listed values. Interestingly, Wikipedia uses the 31.4 value.

Problem #8: A 5.00 L flask contains 3.00 g of mercury. The system is at room temperature of

25.0 C. By how many degrees should we increase the temperature of the flask to triple the

mercury vapor pressure. The enthalpy of vaporization for mercury is 59.11 kJ/mol?

Solution:

1) Let us use the Clausius-Clapeyron Equation:

P1 = 1 T1 = 298 K

P2 = 3 T2 = x

Comment: I don't care what the actual vapor presssure value is at either temperature. I just care

that it triples in value from P1 to P2. Wy can I do this? Because I will be using a ratio of P2 to P1.

I only care that that ratio is 3.

3) Set up equation with values:

ln (3/1) = (59110 / 8.31447) (1/298 minus 1/x)

1.0968 = 7109.2926 (1/298 minus 1/x)

1.0968 = 23.8567 minus 7109.2926/x)

x = 312.4 K = 39.4 C

Clicking this link will take you to a NIST paper that has a table of calculated mercury vapor

pressures. See page 20.

Also, notice the kinda, sorta vapor pressure assumption. I assumed that only some of the 3.00 g

of Hg evaporated at 25 C. That's a fair assumption, I would think.

February 14, 2013 mycheme

When a liquid mixture begins to boil, the vapour does not normally have the same composition

as the liquid. The components with the lowest boiling point (i.e. the more volatile) will

preferentially boil off. Thus, as the liquid continues to boil, the concentration of the least

volatile component drops. This results in a rise in the boiling point. The temperatures over

which boiling occurs set the bubble and dew points of the mixture.

1. The bubble point is the point at which the first drop of a liquid mixture begins to vaporize.

2. The dew point is the point at which the first drop of a gaseous mixture begins to condense.

For a pure component, the bubble and dew point are both at the same temperature its boiling

point. For example, pure water will boil at a single temperature (at atmospheric pressure, this is

100oC).

For ideal mixtures (i.e. mixtures where there are no significant interactions between the

components), vapour-liquid equilibrium is governed by Raoults Law and Daltons Law.

Raoults Law

Raoults Law states that the partial pressure of a component, PA, is proportional to its

concentration in the liquid. So for component A,

Where:

PA

PoA

xA

Daltons Law

Daltons Law states that the total pressure is equal to the sum of the component partial pressures.

Thus for component A, its partial pressure, PA, is proportional to its mole fraction in the gas

phase:

Where

PTotal

yA

The dew point is the temperature at which a gas mixture will start to condense. For an ideal

mixture, we can use Daltons and Raoults Laws to calculate the dew point. By combining the

two equations, we can calculate the liquid mole fractions for a given vapour composition, i.e.:

Calculating the dew point is iterative. Firstly we guess a temperature which allows us to calculate

the vapour pressure Po for each component (the vapour pressures of pure components can be

calculated using the Antoine Equation Antoine Coefficients for many components are

presented elsewhere on this site).

The pure component vapour pressures can then be used to calculate the liquid mole fraction for

each component, x, using the above equation. The sum of all the liquid mole fractions should add

up to 1 at the dew point. If the sum is greater than 1, the temperature guess is too low. If the sum

is less than 1, the temperature guess is too high. Adjust the temperature until the liquid mole

fractions add up to 1.

A gas has the following composition: 75mol% n-pentane, 20mol% n-hexane, 5mol% n-heptane.

What is its Dew Point at atmospheric pressure (760 mmHg)?

The normal boiling points of pentane, hexane and heptane are 36oC, 69oC and 98oC respectively,

so the dew point at atmospheric pressure will lie within this temperature range. As a first guess,

take a temperature of 40oC.

The vapour pressure of each component can be estimated using their Antoine Equation (see our

separate article). So at 40oC, the vapour pressure of each component is as follows:

Assuming ideal behaviour, the liquid mole fractions at the dew point can be calculated using:

Thus

Adding the liquid mole fractions together gives: 0.655 + 0.542 + 0.409 = 1.606. This is greater

than 1, meaning that 40oC is below the dew point. Re-guessing the temperature at 50oC, 58oC,

53oC and 54oC:

Temperature

40oC

50oC

58oC

53oC

54oC

xPentane

0.655

0.475

0.374

0.434

0.421

xHexane

0.542

0.374

0.283

0.336

0.325

xHeptane

0.409

0.267

0.194

0.237

0.227

Total

1.606

1.116

0.851

1.006

0.972

As can be seen in the table above, the dew point for this mixture at atmospheric pressure is just

over 53oC.

The bubble point is the temperature at which a liquid mixture will start to boil. As with a dew

point calculation, we can use Daltons and Raoults Laws to calculate the bubble point. By

combining the two equations, we can calculate the vapour mole fractions for a given liquid

composition, i.e.:

Again, as with the dew point, calculating the bubble point is iterative. Firstly we guess a

temperature which allows us to calculate the vapour pressure Po for each component. This is then

used to calculate the vapour mole fraction for each component, y, using the above equation. The

sum of all the vapour mole fractions should add up to 1 at the bubble point. If the sum is greater

than 1, the temperature guess is too high. If the sum is less than 1, the temperature guess is too

low. Adjust the temperature until the vapour mole fractions add up to 1.

A liquid has the following composition: 75mol% n-pentane, 20mol% n-hexane, 5mol% nheptane. What is its Bubble Point at atmospheric pressure (760 mmHg)?

The normal boiling points of pentane, hexane and heptane are 36oC, 69oC and 98oC respectively,

so the bubble point at atmospheric pressure will lie within this temperature range. As a first

guess, take a temperature of 40oC.

The vapour pressure of each component can be estimated using their Antoine Equation (see our

separate article). So at 40oC, the vapour pressure of each component is as follows:

Assuming ideal behaviour, the vapour mole fractions at the bubble point can be calculated using:

Thus

Adding the vapour mole fractions together gives: 0.857 + 0.074 + 0.006 = 0.937. This is less

than 1, meaning that 40oC is below the bubble point. Re-guessing the temperature at 50oC, 45oC,

42oC and 41oC:

Temperature

40oC

50oC

45oC

42oC

41oC

yPentane

0.857

1.183

1.011

0.918

0.888

yHexane

0.074

0.107

0.089

0.080

0.077

yHeptane

0.006

0.009

0.008

0.007

0.006

Total

0.937

1.299

1.108

1.005

0.971

As can be seen in the table above, the bubble point for this mixture at atmospheric pressure is

just under 42oC.

Non-ideality

As noted above, this calculation method assumes that the mixture obeys Raoults Law and

Daltons Law. This is not always the case. In particular, Raoults Law is often not followed when

the components are polar or dissimilar. Where the solution is not ideal, more complicated

calculation methods are required. This is outside the scope of this short article.

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