Anda di halaman 1dari 12

The Clausius-Clapeyron Equation

Some brief notes on the units:


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:

with the following values:


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

x = 24327 J/mol = 24.3 kJ/mol

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)

Hvap = 31.4 kJ/mole

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

P2 = 760.0 mmHg T2 = 68.73 C = 341.88 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:

with the following values:


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.

Calculating Bubble & Dew Points for Ideal Mixtures


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.

The bubble and dew points can be defined as:


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

- Partial pressure of component A

PoA

- Vapour pressure of component A

xA

- Liquid mole fraction of component A

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

- Total System Pressure

yA

- Vapour mole fraction of component A

Dew Point Calculation


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.

Example Calculation: Estimating the Dew Point


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

Table 1: Dew Point Calculation temperature iteration


As can be seen in the table above, the dew point for this mixture at atmospheric pressure is just
over 53oC.

Bubble Point Calculation


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.

Example Calculation: Estimating the Bubble Point


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

Table 2: Bubble Point Calculation temperature iteration


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.