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10 Examples
15 problems
The key point to remember about solutions with two (or more) volatile components?
All the components are represented in the vapor that is in contact with the solution.
This is important:
ALL the components.
In a solution with a nonvolatile solute, only the pure vapor of the solvent is present
above the solution. 100% of the nonvolatile solute stays in solution, none of it enters
the vapor above the solution.
By the way, at this introductory level, we will only discuss solutions with two volatile
components. More complex solutions (with three or more volatile components) are
discussed at a level beyond the scope of the ChemTeam's mission. Also, note the
presence of the word 'ideal' in the title. We will discuss the real behavior of solutions
in a different tutorial.
The key equation to use is Raoult's Law, but in a slightly expanded form from how it
is first presented:
The subscripts A and B stand for the two different volatile substances in the solution.
Example #1: A solution is composed of 1.40 mol cyclohexane (Pcyo = 97.6 torr) and
2.50 mol acetone (Paco = 229.5 torr). What is Psolution, the total vapor pressure, above
this solution?
Solution:
There is something very important about the above calculation for the vapor pressure
of the solution. It is that we also know the vapor pressures of the two components of
the vapor.
(By the way, we know that pressure is directly proportional to the number of moles
from consideration of the Ideal Gas Law.)
A key point about the above result is this: the vapor is richer in the component with
the higher vapor pressure than the solution. In our example, the acetone in the solution
had χ = 0.64, but acetone's mole fraction in the vapor equals 0.81.
The component with the higher vapor pressure? There's more of it in the vapor
(expressed in mole fractions) than in the solution.
If we were to constantly sweep away the vapor from above the solution, then more of
the solution would vaporize. However, what happens then is that we would remove
(from the solution) more and more of the component with the higher vapor pressure.
This fact allows us the means to separate two volatile components in a solution and
obtain each substance in a (relatively) pure form.
The general name of the separation process that exploits volatility differences
is distillation. It is an extremely important research and industrial process.
However, please be aware that the reality is much more complex than the discussion
just above. That discussion is for another time, another class.
You might be interested to know that there are some solutions that resist distillation.
These solutions are called azeotropes. Here is the begining of the Wikipedia entry:
"An azeotrope is a mixture of two or more liquids (chemicals) in such a ratio that its
composition cannot be changed by simple distillation. This occurs because, when an
azeotrope is boiled, the resulting vapor has the same ratio of constituents as the
original mixture."
Notice how the composition of the solution and the vapor are the same. This means
that it is extremely difficult (although not impossible in some cases) to distill an
azeotrope.
Example #2: A solution is prepared by mixing 0.0400 mol CH 2Cl2 and 0.0800 mol of
CH2Br2 at 25 °C. Assuming the solution is ideal, calculate the composition of the
vapor (in terms of mole fractions) at 25 °C. At 25 °C, the vapor pressures of pure
CH2Cl2 and pure CH2Br2 are 133 and 11.4 torr, respectively.
Solution:
2) Use Raoult's Law (I'll use a mid-dot rather than parenthesis to show the
multiplication):
Psolution = PClo· χCl + PBro· χBr
I won't round off here because I want to go to the mole fractions in the vapor.
3) Calculate mole fractions in vapor:
Example #3: C10H16 and C10H18O are two of the many compounds used in perfumes
and cosmetics to provide a fresh pine scent. At 69.0 °C the pure substances have
vapor pressures of 100.3 torr and 9.8 torr, respectively. What is the composition of the
vapor in terms of mole fractions above a solution containing equal masses of these
compounds at 69.0 °C? Assume ideal behavior.
Solution:
Assume 50.00 g of each substance. (You can pick any mass of each substance, just as
long as they are equal. Just like Henry Ford and the Model A: you can have any color
of car, just as long as it was black.)
Psolution = PC10H16o χC10H16 + PC10H18Oo χC10H18O
Solution:
Psolution = Pbenzo χbenz + Ptoluo χtolu
52.9 = 65.5x
benzene:
(94.6) (0.8076336) = 76.4 torr <--- partial pressure of benzene in the vapor
(29.1) (0.1923664) = 5.59786 torr <--- partial pressure of toluene in the vapor
The fact that the two calculated mole fractions add up to 0.9997 is due to rounding
along the way. Three sig figs gives 1.00.
Solution:
1) Determine moles of benzene and toluene:
Psolution = Pbenzo χbenz + Ptoluo χtolu
4) Although not asked for, you can proceed to the composition of the vapor:
Notice I didn't pay too much attention to sig figs. Just remember to calculate with
minimal rounding-off and then round off to the correct number of sig figs at the end.
Be aware that the other mole fraction is obtained by subtraction. Round off the first
mole fraction to the proper number of sig figs, then perform the "one minus"
operation.
Example #6: What is the ideal vapor pressure of a solution which contains 4.401
moles of C6H6 and 1.623 moles of CCl4 at 20.00 °C? The vapor pressure of pure
CCl4 at 20.00 °C is 91.32 mmHg and C6H6 is 74.61 mmHg.
Solution:
1) Mole fractions:
2) Raoult's Law
Psolution = PC6H6o χC6H6 + PCCl4o χCCl4
Example #7: Acetone and methanol form an ideal solution. At 25 °C, the vapor
pressure of pure acetone is 30.784 kPa and that of methanol is 16.958 kPa. Calculate
the mole fraction of methanol in a solution that boils at 25 °C and 25.130 kPa.
Solution:
χacet + χmeth = 1
2) Therefore:
χacet = 1 − χmeth
Psolution = χacet Paceto + χmeth Pmetho
χmeth = 0.11843
Example #8: Liquids A and B form an ideal solution. The vapor pressure of pure A is
0.700 atm at the normal boiling point of a solution prepared from 0.250 mole of B and
0.650 mole of A.What is the vapor pressure of pure B at this temperature?
Solution:
0.650
χA = ––––––––––– = 0.72222
0.250 + 0.650
0.250
χB = ––––––––––– = 0.27778
0.250 + 0.650
The value for χBcould have also been arrived at by doing 1 minus the value for χA.
Psolution = PA + PB
Psolution = χA· PAo + χB· PBo
In the problem, the term 'normal boiling point' allows us to set the vapor pressure of
the solution as 1.00 atm.
4) Solve for χB:
Example #9: Heptane and octane form an ideal solution. At 40 °C, the vapor pressure
of heptane is 91.5 torr and the vapor pressure of octane is 31.2 torr. A solution is made
of 5.32 g heptane and 8.80 g octane. Calculate the mole fraction of octane is the vapor
above the solution at 40 °C.
Solution:
0.0530885
χhept = ––––––––– = 0.4080
0.1301261
0.0770376
χoct = ––––––––– = 0.5920
0.1301261
The value for χoctcould have also been arrived at by doing 1 minus the value
for χhept.
3) Raoult's Law for two volatile components and solve for P solution:
Psolution = χhept· Phepto + χoct· Pocto
Example #10: Two liquids, A and B, form an ideal solution. The solution boils at 22
°C and 0.255 atm. The vapor pressure of pure A is 0.192 atm at 22 °C and the vapor
pressure of B is 0.311 atm, also at 22 °C. Determine the mole fraction of each solution
component.
Solution:
Psolution = χA· PAo + χB· PBo
0.056 = 0.119χA
Solution:
1) Let the mole fractions be x (the volatile solute) and 1 − x (the water). Using
Raoult's Law:
134.46x = 2.06
4) You can double-check that the ratio and proportion is correct. Here is the mole
fraction calculation for water:
15 problems