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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:
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
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:
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.
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
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.
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
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.
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
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.