Mole Fraction

moles of target substance divided by total moles involved

The symbol for the mole fraction is the lower-case Greek letter
chi, .: solute is an example.
Example #1: 0.100 mole of NaCl is dissolved into 100.0
grams of pure H2O. What is the mole fraction of NaCl?
Solution:
100.0 g / 18.0 g mol1 = 5.56 mol of H2O
Add to the 0.100 mol of NaCl = 5.56 + 0.100 = 5.66 mol total
Mole fraction of NaCl = 0.100 mol / 5.66 mol = 0.018
What is the mole fraction of the H2O?
5.56 mol / 5.66 mol = 0.982
By the way, another way to figure out the last substance is
1.00 minus (the total of all other mole fractions). In this case
1.00 - 0.018 = 0.982. Remember that all the mole fractons in
the solution should total up to one.
Notice that the mole fraction has no units on it and is written
as a decimal value. Do not change it to percent.
Note of caution: you could see the term "mole percent." It is
simply the mole fraction mltiplied by 100. For example, in the
problem just below, the mole fraction of cinnamic acid is
0.2885. Its mole percent would be 28.85%.
Example #2: A solution is prepared by mixing 25.0 g of
water, H2O, and 25.0 g of ethanol, C2H5OH. Determine the
mole fractions of each substance.
Solution:
1) Determine the moles of each substance:
H2O 25.0 g / 18.0 g/mol = 1.34 mol
C2H5OH 25.0 g / 46.07 g/mol = 0.543 mol
2) Determine mole fractions:
H2O 1.34 mol / (1.34 mol + 0.543 mol) = 0.71
C2H5OH 0.543 mol / (1.34 mol + 0.543 mol) = 0.29
Example #3: A solution contains 10.0 g pentane, 10.0 g
hexane and 10.0 g benzene. What is the mole fraction of
hexane?
Solution:
1)
pentane: C5H12
hexane: C6H14
benzene: C6H6
2) When you have the moles of each, add them together.
3) Then, divide the moles of hexane by the total.
Example #4: The molality of an aqueous solution of sugar
(C12H22O11) is 1.62m. Calculate the mole fractions of sugar and
water.
Solution:
1.62 mol / (1.62 mol + 55.50868 mol) = 0.028357 = 0.0284
4) You can calculate the mole fraction of the water by
subtraction.
Example #5: How many grams of water must be used to
dissolve 100.0 grams of sucrose (C12H22O11) to prepare a 0.020
mole fraction of sucrose in the solution?
3) Determine grams of water:
14.308 mol x 18.015 g/mol = 258.0 g
Example #6: Surprisingly, water (in the form of ice) is
slightly soluble in liquid nitrogen. At -196 C, (the boiling
point of liquid nitrogen) the mole fraction of water in a
saturated solution is 1.00 x 10-5. Compute the mass of water
that can dissolve in 1.00 kg of boiling liquid nitrogen.

Solution:
1) Use the definition of mole fraction to set up the following:
water = moles water / (moles water + moles nitrogen)
1.00 x 10-5 = x / (x + 71.3944041)
I'm going to carry some guard digits until the end of the
calculation.
(1.00 x 10-5) (x) + 7.139440411 x 10-4 = x
0.99999x = 7.139440411 x 10-4
x = 7.139511806 x 10-4 mol of H2O
3) Calculate grams of water from moles of water:
7.139511806 x 10-4 mol x 18.0152 g/mol = 1.2862 x 10-2 g
1.29 x 10-2 g (to three sf)
Example #7: What is the mole fraction of cinnamic acid in a
mixture that is 50.0% weight urea in cinnamic acid (urea =
60.06 g/mol; cinnamic acid = 148.16 g/mol)
Solution:
1) Let us assume 100.0 g of this mixture are present.
Therefore:
50.0 g is urea
50.0 g is cinnamic
2) Convert grams to moles:
urea: 50.0 g / 60.06 g/mol = 0.8325 mol
cinnamic acid: 50.0 g / 148.16 g/mol = 0.3375 mol
3) Determine mole fraction of cinnamic acid:
0.3375 mol / 1.1700 mol = 0.2885

\
Raoult's Law: The Effect of Nonvolatile Solutes on Vapor
Pressure

To make a solution, you need a solvent and a solute. Usually

(but not always), liquid water is the solvent and some solid
substance (sugar, for example) is the solute.
Notice the word "nonvolatile" in the title. The volatility of a
substance refers to the readiness with which it vaporizes.
Generally speaking, substances with a boiling point below 100
C are considered volatile and all others are called nonvolatile.
Ethyl alcohol and pentane are examples of volatile substances;
sugar and sodium chloride are considered nonvolatile.
The presence of a solute leads to a colligative property called
the "lowering of the vapor pressure of the solution" when
compared to the vapor pressure of the pure solvent. This is not
a nice, tidy name like osmosis, but then again, life itself is not
always nice and tidy either. There is enough of a difference
between the types (volatile and nonvolatile) of solutes to merit
treating them separately.
Here is the difference:
(a) solutions with a nonvolatile solute produce a vapor which
is pure solvent
(b) solutions with a volatile solute produce a vapor which is a
mixture of both solvent and solute.
Another way to express this difference:
(a) a nonvolatile solute does not appear as a component of the
vapor above the solution.
(b) a volatile solute does appear as a component of the vapor
above the solution.
You will discover, if you have not already, that the second type
of solution (composed of two volatile components) is more
complicated. Thus, teachers like to ask the second type on the
test, especially as a calculational problem as opposed to a
multiple-guess choice question.
One last point: in all discussions concerning vapor pressure,
the vapor is always in contact with the solution. ALWAYS!
The whole basis to the concepts presented here is that the
vapor and the solution are in equiibrium with each other. To do
this, they must be in contact.
Often, to a teacher, this is such as obvious point that they
forget to state it. If you read this and your teacher has not yet
stated the above in class, you might consider asking in class
(in a very nice tone of voice) if these problems always assume
that the vapor is in contact with the solution.
The goal to the above is to get the teacher to tell the whole
class about this important, but forgotten, point. You don't need
to tell your classmates, your goal is to (in a nice way) get the
teacher to do so.
In the mid-1800s, it was discovered that the vapor pressure of
a solution was lowered and that the amount was more-or-less
proportional to the amount of solute. In the early 1880s,
Francios Marie Raoult was able to determine the equation
which governs this property:
Psolution = (solvent) (Psolvent)
The capital P stands for the vapor pressure and is the lower
case Greek letter chi. It stands for the mole fraction, in this
case of the solvent. The P is the vapor pressure of the pure
solvent, which is usually (but not always) water.
Not unsuprisingly, the above law is called Raoult's Law.
By the way, you might ask if there are any "real world"
applications for the lowering of the vapor pressure of a
solution when compared to the pure solvent. I'm glad you
asked:

"Solutions of certain salts are in equilibrium with a particular

relative humidity less than 100%. So saturated solutions of
salts like sodium chloride and nitrite are typically used to
calibrate RH meters."
and
"Vapor pressure osmometry for molecular weight
determination. Commercial equipment gets by with a few
microliters of solvent."
I copied both those statements from the USENET group
sci.chem many years ago.
Tutorial Problems
Example #1: If 0.340 mol of a nonvolatile nonelectrolyte are
dissolved in 3.00 mol of water, what is the vapor pressure of
the resulting solution? (The vapor pressure of pure water is
23.8 torr at 25.0 C.)
Solution:
1) Calculate the mole fraction of the solvent (NOT the solute):
solvent = 3.00 mol / (0.340 mol + 3.00 mol)
solvent = 0.8982
2) Calculate the vapor pressure:
Psolution = (solvent) (Psolvent)
Psolution = (0.8982) (23.8)
Psolution = 21.4 torr
There's a key word in the above problem and it is
'nonelectrolyte.' It turns out that many substances (called
electrolytes) ionize in solution. This creates more particles in
solution than would be if the substance did not ionize, thus
lowering the vapor pressure more than would be expected.
However, we'll do two more nonelectrolyte problems first.
Sucrose is a very popular nonelectrolyte. It does not ionize in
water and its van 't Hoff factor is equal to one. (The van 't Hoff
factor comes into play with eletrolytes. Make sure you go
learn about it if you are not aware of its existence.)
Also, notice that the word 'nonvolatile' is used below. Make
sure you know what it means. If you're not sure, go back and
review the discussion above.
Example #2: 210.0 g of the nonvolatile solute sucrose
(C12H22O11) is added to 485.0 g of water at 25.0 C. What will
be the pressure of the water vapor over this solution? (The
vapor pressure of pure water is 23.8 torr at 25.0 C.)
Solution:
1) Determine moles of water and sucrose:
water: 485.0 g / 18.0152 g/mol = 26.92171 mol
sucrose: 210.0 g / 342.3014 g/mol = 0.61349 mol
2) Determine the mole fraction of the solvent:
solvent = 26.92171 mol / (26.92171 mol + 0.61349 mol) =
0.9777
3) Using Raoult's Law, determine the vapor pressure:
Psolution = (solvent) (Psolvent)
Psolution = (0.9777) (23.8)
Psolution = 23.3 torr
Example #3: The vapor pressure of water above a solution of
water and a nonvolatile solute at 25.0 C is 19.3 mm Hg. What
is the mole fraction of the solute? (The vapor pressure of pure
water is 23.8 torr at 25.0 C.)
Solution:
1) Use Raoult's Law:

Psolution = (solvent) (Psolvent)

19.3 = (x) (23.8)
x = 0.811
Example #4: Calculate the vapor pressure of water above a
solution at 35.0 C that is 1.600 m fructose, C6H12O6. (The
vapor pressure of pure water at 35.0 C is 42.2 mmHg.)
Solution:
1) From the molality, we know this:
1.600 mol of fructose is dissolved in 1.000 kg of water.
2) Determine moles of water:
1000 g / 18.015 g/mol = 55.5093 mol of H2O
3) Determine mole fraction of solvent:
55.5093 / (55.5093 + 1.600) = 0.97198
4) Using Raoult's Law, the vapor pressure above the solution
is:
(42.2 mmHg) (0.97198) = 41.0 mmHg
Example #5: The vapor pressure of pure methanol, CH3OH,
at 30. C is 160. torr. How many grams of the nonvolatile
solute glycerol, C3H5(OH)3, must be added to 116. g of
methanol to obtain a solution with a vapor pressure of 127.
torr?
Solution:
1) Write an expression for the mole fraction of the solvent
(methanol):
116. g divided by 32.0416 g/mol = 3.6203 mol
set mol of glycerol equal to x
solvent = 3.6203/(3.6203 + x)
2) Solve for 'x' with Raoult's Law:
127 torr = (solvent) (Psolvent)
127 = (3.6203/(3.6203 + x)) times 160. torr
Algebra!
x = 0.940708 mol
3) Convert moles to grams:
0.940708 mol is the amount of glycerol, so use its molar mass
0.940708 mol times 92.0932 g/mol = 86.6 g (to three sig figs)
PRACTICE PROBLEMS
Problem #1: What is the vapor pressure of an aqueous
solution that has a solute mole fraction of 0.1000? The vapor
pressure of water is 25.756 mmHg at 25 C.
Solution:
solvent = 1.0000 - 0.1000 = 0.9000
Use Raoult's Law:
Psolution = (solvent) (Psolvent)
x = (0.900) (25.756)
x = 23.18 mmHg
Problem #2: The vapor pressure of an aqueous solution is
found to be 24.90 mmHg at 25 C. What is the mole fraction
of solute in this solution? The vapor pressure of water is
25.756 mm Hg at 25 C.
Solution:
Use Raoult's Law:
Psolution = (solvent) (Psolvent)
24.90 = (x) (25.756)
x = 0.966765 (this is the solvent mole fraction)
solute = 1 - 0.966765 = 0.033235
solute = 0.03324
Problem #3: How many grams of nonvolatile compound
B (molar mass= 97.80 g/mol) would need to be added to 250.0
g of water to produce a solution with a vapor pressure of

23.756 torr? The vapor pressure of water at this temperature is

42.362 torr.
Solution:
We will assume that B does not ionize in solution.
1) Determine mole fraction of solvent that produces a solution
vapor pressure of 23.756 torr:
Psolution = (solvent) (Psolvent)
23.756 torr = (x) (42.362 torr)
x = 0.5608
2) Determine moles of compound B needed to produce the
above solvent mole fraction:
0.5608 = 13.88 / (13.88 + B)
7.7839 + 0.5608B = 13.88
0.5608B = 6.0961
B = 10.87 mol
3) Determine mass of B
10.87 mol times 97.80 g/mol = 1063 g
Comment: this is a completely ridiculous amount to dissolve
in 250.0 g of water, but that's not the point. The point is to
solve the problem.
Problem #4: At 29.6 C, pure water has a vapor pressure
of 31.1 torr. A solution is prepared by adding 86.8 g of "Y", a
nonvolatile non-electrolyte to 350. g of water. The vapor
pressure of the resulting solution is 28.6 torr. Calculate the
molar mass of Y.
Solution:
1) Use Raoult's Law to determine mole fraction of the solvent:
Psolution = (solvent) (Psolvent)
28.6 torr = (solvent) (31.1 torr)
solvent = 28.6 torr / 31.1 torr
solvent = 0.91961415
2) Use the mole fraction and the moles of water to determine
the moles of Y:
350. g / 18.015 g/mol = 19.428254 mol
0.91961415 = 19.428254 / (19.428254 + x) <--- x equals the
moles of Y dissolved
(0.91961415) (19.428254 + x) = 19.428254
17.8665 + 0.91961415x = 19.428254
0.91961415x = 1.561754
x = 1.69827 mol
3) Calculate molar mass of Y:
86.8 g / 1.69827 mol = 51.1 g/mol (to three sig figs)
Problem #5: The vapor pressure of pure water is 23.8
mmHg at 25.0 C. What is the vapor pressure of 2.50 molal
C6H12O6
Solution:
1) Covert the molality to a mole fraction. First, calculate total
moles:
2.50 m C6H12O6 = 2.50 mol / 1.00 kg H2O
1000 g / 18.015 g/mol = 55.51 mol
55.51 mol + 2.50 mol = 58.01 mol
2) We need the mole fraction of water:
55.51 / 58.01 = 0.9569
3) Use Raoult's law:
Psolution = (solvent) (Psolvent)
Psolution = (0.9569) (23.8 mmHg) = 22.8 mmHg
Problem #6: How many grams of testosterone , C19H28O2,
a nonvolatile, nonelectrolyte (MW = 288.4 g/mol), must be
added to 207.8 grams of benzene to reduce the vapor pressure
to 71.41 mm Hg? (Benzene = C6H6 = 78.12 g/mol. The vapor
pressure of benzene is 73.03 mm Hg at 25.0 C.)
Solution:
Use Raoult's law:

Psolution = (Psolvent) (solvent)

71.41 = (73.03) (2.66 / (2.66+x))
71.41 = 194.2598 / (2.66+x)
71.41 = 194.2598 / (2.66+x)
194.2598 = 189.9506 + 71.41x
71.41x = 4.3092
x = 0.0603445 mol
288.4 g/mol times 0.0603445 mol = 17.4 g (to three sig figs)
Problem #7: At 25.0 C, the vapor pressure of benzene
(C6H6) is 0.1252 atm. When 10.00 g of an unknown nonvolatile substance is dissolved in 100.0 g of benzene, the
vapor pressure of the solution at 25.0 C is 0.1199 atm.
Calculate the mole fraction of solute in the solution, assuming
no dissociation by the solute.
Solution:
1) Because solute is non-volatile, the vapor of the solution
contains only benzene. All of the unknown substance remains
in solution. Assuming an ideal mixture, the vapor pressure of
the solution is given by Raoult's Law:
Psolution = (Psolvent) (solvent)
2) The mole fraction of benzene in this mixture is:
Psolution = (Pbenzene) (benzene)
benzene = Psolution / Pbenzene
= 0.1199 atm / 0.1252 atm
= 0.9576677
3) The mole fractions of the components in any mixture sum
up to unity. So, for this solution:
benzene + solute = 1
Hence:
solute = 1 - benzene
= 1 - 0.9576677 = 0.04233
Problem #8: What is the vapor pressure at 25.0 C of a
solution composed of 42.71 g of naphthalene (a non-volatile
compound, MW = 128 g/mol) and 40.65 g of ethanol (MW =
46.02 g/mol). (The vapor pressure of pure ethanol at 25.0 C is
96 torr. )
Solution:
1) The vapor pressure of this kind of solvent is related to the
mole fraction of the solvent and its pure vapor pressure:
vapor pressure of the solution = mole fraction of solvent times
vapor pressure of the pure solvent
This is known as Raoult's Law.
2) Calculating:
moles naphthalene ---> 42.71 g / 128 g/mol = 0.334 mol
moles ethanol ---> 40.65 g / 46.02 g/mol = 0.883 mol
mole fraction ethanol ---> 0.883 / (0.883 + 0.334) = 0.726
vapor pressure of solution ---> 96 torr times 0.726 = 70. torr
Problem #9: A nonvolatile organic compound Z was used
to make up a solution. Solution A contains 5.00 g of Z
dissolved in 100. g of water and has a vapor pressure of 754.5
mmHg at the normal boiling point of water. Calculate the
molar mass of Z.
Solution:
1) Use Raoult's Law to determine mole fraction of the solvent:
Psolution = (solvent) (Psolvent)
754.5 torr = (solvent) (760.0 torr)
Note: 760.0 torr is the vapor pressure of water at its normal
boiling point, 100 C
solvent = 754.5 torr / 760.0 torr
solvent = 0.99276316
2) Use the mole fraction and the moles of water to determine
the moles of Z:

100. g / 18.015 g/mol = 5.55093 mol

0.99276316 = 5.55093 / (5.55093 + x) <--- x equals the moles
of Z dissolved
x = 0.040464 mol
3) Calculate molar mass of Z:
5.00 g / 0.040464 mol = 124 g/mol (to three sig figs)
Problem #10: What is the molality of an aqueous
solution of urea, CO(NH2)2, if the vapor pressure above the
solution is 22.83 mmHg at 25 C? Assume that urea is nonvolatile. The vapor pressure of pure water is 23.77 mmHg at
25 C
Solution:
Psoln = (Psolvent) (mole fraction of solvent)
22.83 = (23.77) (x)
x = 0.960 (this is the mole fraction of water)
mole fraction of urea = 0.040
Let us assume a total of 1.000 mole of solvent and solute is
present.
Change 0.960 mole to grams of water:
0.960mol times 18.015 = 17.2944 g
Calculate molality:
0.040 mol / 0.0172944 kg = 2.31 m
Problem #11: Calculate the mass of propylene glycol
(C3H8O2) that must be added to 500. grams of water to reduce
the vapor pressure by 4.75 mmHg at 40.0 C.
Solution:
Look up the vapor pressure of water at 40.0 C. It is 55.3
mmHg.
Use Raoult's Law to get the mole fraction of the solvent:
50.55 mmHg = (55.3 mmHg) (x)
x = 0.9141
The 50.55 comes from 55.3 minus 4.75.
The mole fraction of the solute is 0.0859
Let's set up a mole fraction calculation:
(x / 76.0942) divided by [(x / 76.0942) + (500. / 18.0152)] =
0.0859
The x / 76.0942 is the mole of C3H8O2, the 500. / 18.0152 is
the mol of water and the sum of the two (inside the square
brackets) is the total mol in the solution.
Solve for x.
Problem #12: What is the vapor pressure of water above a
solution in which 32.5 g of glycerin (C3H8O3) are dissolved in
125. g of water at 343 K? The vapor pressure of pure water at
343 K is 233.7 torr.
Solution:
The vapor pressure is proportional to the mole fraction in the
solution.
moles glycerin = 32.5 g / 92.19 g/mol = 0.3525 moles
moles water = 125 g / 18.0 g/mol = 6.944
total moles = 7.2965 mol
mole fraction of water = 6.944 mol / 7.2965 mol = 0.9516
(0.9516) (233.7 torr) = 222.4 torr
Problem #13: A solution is prepared by dissolving 396 g of
sucrose in 624 g of water at 30.0 C. What is the vapor
pressure of this solution? (The vapor pressure of water is
31.82 mmHg at 30.0 C.)
Solution:
1) Determine moles of solute and solvent:
396 g / 342.2948 g/mol = 1.1569 mol
624 g / 18.015 g/mol = 34.6378 mol

2) Determine mole fraction of the solvent:

34.6378 mol / (34.6378 mol + 1.1569 mol) = 0.96768
3) Determine vapor pressure:
x = (31.82 mmHg) (0.96768) = 30.8 mmHg (to three sig figs)
Problem #14: Calculate the vapor pressure of a solution made
by dissolving 21.80 g of glucose (molar mass = 180.155
g/mol) in 460.0 g of H2O at 30.0 C. (The vapor pressure of
the pure solvent is 31.82 mmHg at 30.0 C.)
Solution:
1) Determine moles of solute and solvent:
21.80 g / 180.155 g/mol = 0.1210 mol
460.0 g / 18.015 g/mol = 25.5343 mol
2) Determine mole fraction of the solvent:
25.5343 mol / (25.5343 mol + 0.1210 mol) = 0.9952836
3) Determine vapor pressure:
x = (31.82 mmHg) (0.9952836) = 31.67 mmHg (to four sig
figs)
Problem #15: The vapor pressure of carbon tetrachloride
(CCl4) at 50.0 C is 0.437 atm. When 7.42 g of a pure
nonvolatile substance is dissolved in 100.0 g of carbon
tetrachloride, the vapor pressure of the solution is 0.411 atm.
Calculate the molar mass of the solute.
Solution:
0.411 atm = (0.437 atm) (x)
x = 0.9405 (this is the mole fraction of the CCl4)
100.0 g / 153.823 g/mol = 0.6501 mol
0.9405 = 0.6501 / (0.6501 + x)
0.61142 + 0.9405x = 0.6501
x = 0.041127 mol (this is the moles of the unknown substance
that was dissolved in 100.0 g of CCl4)
7.42 g / 0.041127 mol = 180. g/mol
Problem #16: At 27.0 C, the vapor pressure of pure water is
23.76 mmHg and that of an aqueous solution of urea is 22.97
mmHg. Calculate the molality of urea in this solution.
Solution:
Psolution = Psolvent times mole fraction of the solvent
22.97 = (23.76) (x)
x = 0.96675
Let's dissolve some urea in 1.00 mole of water. The mole
fraction of the water is:
0.96675 = 1 / (1+x)
where x is the number of moles of urea and 1+x is the total
moles in the solution.
x = 0.0344 mole of urea
0.0344 mol / 0.0180 kg = 1.91 molal
Notice that 1 mole of water equals 18.0 g = 0.0180 kg

Raoult's Law: Vapor Pressure and Volatile Solutes (in

Ideal Solutions)
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:
Psolution = PA A + PB B
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
(Pcy = 97.6 torr) and 2.50 mol acetone (Pac = 229.5 torr).
What is Ptotal, the total vapor pressure, above this solution?
Solution:
1) Calculate the mole fraction of each substance:
cyclohexane 1.40 mol / (1.40 mol + 2.50 mol) =
0.358974359
acetone 2.50 mol / (1.40 mol + 2.50 mol) = 0.641025641
2) Use Raoult's Law:
Ptotal = Pcy cy + Pac ac
x = (97.6 torr) (0.358974359) + (229.5) (0.641025641)
x = 35.03589744 + 147.1153846 = 182.15 torr = 182 torr (to 3
sf)
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.
This is important because it allows us to calculate the
composition (using mole fractions) of the vapor. How? Divide
each component's vapor pressure by the total vapor pressure.
Here's the calculation for the example:
for cyclohexane 35.0359 torr / 182.15 torr = 0.19
for acetone 147.1154 torr / 182.15 torr = 0.81
(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 =
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 (when using 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
CH2Cl2 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:
1) Calculate the mole fraction of each substance:
CH2Cl2 0.0400 mol / (0.0400 mol + 0.0800 mol) = 0.333
CH2Br2 0.0800 mol / (0.0400 mol + 0.0800 mol) = 0.667
2) Use Raoult's Law:
Psolution = PCl Cl + PBr Br
Psolution = (133 torr) (0.333) + (11.4 torr) (0.667) = 44.289 torr +
7.604 torr = 51.893 torr
I won't round off here because I want to go to the mole
fractions in the vapor.
3) Calculate mole fractions in vapor:
CH2Cl2 44.289 / 51.893 = 0.8535
CH2Br2 7.604 / 51.893 = 0.1465
I actually did the second mole fraction by subtraction (1 minus
0.8535).
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:
1) Calculate the mole fraction of each substance:
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.)
C10H16 50.00 g / 136.2364 g/mol = 0.36701 mol
C10H18O 50.00 g / 154.2512 g/mol = 0.32415 mol
C10H16 = 0.36701 mol / (0.36701 mol + 0.32415 mol) = 0.531
C10H18O = 0.32415 mol / (0.36701 mol + 0.32415 mol) = 0.469
2) Use Raoult's Law:
Psolution = PC10H16 C10H16 + PC10H18O C10H18O
Psolution = (100.3 torr) (0.531) + (9.8 torr) (0.469) = 53.2593 torr
+ 4.5962 torr = 57.8555 torr
3) Calculate mole fractions in vapor:
C10H16 53.2593 / 57.8555 = 0.9206
C10H18O 4.5962 / 57.8555 = 0.0794

Example #4: At a certain temperature, the pure vapor

pressures of benzene (C6H6) and toluene (C7H8) are Pben = 94.6
torr and Ptol = 29.1 torr. What are the mole fractions of
benzene and toluene, ben and tol in both the liquid and vapor
phases above a mixture where the total vapor pressure is Ptot =
82.0 torr?
Solution:
1) Raoult's Law for a solution of two volatiles is this:
Ptotal = Pben ben + Ptol tol
82.0 = (94.6) (x) + (29.1) (1 - x)
82.0 = 94.6x + 29.1 - 29.1x
52.9 = 65.5x
x = 0.8076336 <--- the mole fraction of benzene in the
solution
1 - x = 0.1923664 <--- the mole fraction of toluene in the
solution
2) The mole fractions in the vapor are as follows:
benzene:
(94.6) (0.8076336) = 76.4 torr <--- partial pressure of benzene
in the vapor
76.4 torr / 82.0 torr = 0.9317
toluene (can be done by subtraction also)
(29.1) (0.1923664) = 5.59786 torr <--- partial pressure of
toluene in the vapor
5.59786 torr / 82.0 torr = 0.06827
The fact that the two calculated mole fractions add up to
0.9997 is due to rounding errors along the way.
Example #5: Calculate the vapor pressure of a solution of
74.0 g of benzene (C6H6) in 48.8 g of toluene (C7H8) at 25.0
C. The vapor pressure of benzene is 95.1 torr and of toluene
is 28.4 torr at this temperature.
Solution:
1) Determine moles of benzene and toluene:
benzene ---> 74.0 g / 78.1134 g/mol = 0.94734 mol
toluene ---> 48.8 g / 92.1402 g/mol = 0.52963 mol
2) Determine the mole fraction of each substance:
benzene ---> 0.94734 mol / (0.94734 mol + 0.52963 mol) =
0.6414
toluene ---> 1 - 0.6414 = 0.3586
3) Raoult's Law for a solution of two volatiles is this:
Ptotal = Pben ben + Ptol tol
Ptotal = (95.1) (0.6414) + (28.4) (0.3586)
Ptotal = 61.0 torr + 10.2 torr = 71.2 torr
4) Although not asked for, you can proceed to the composition
of the vapor:
benzene vapor mole fraction ---> 61.0 / 71.2 = 0.85674
toluene vapor mole fraction ---> 1 - 0.85674 = 0.14326
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.
Problem #1: At 333 K, substance A has a vapor pressure of
1.0 atm and substance B has a vapor pressure of 0.20 atm. A
solution of A and B is prepared and allowed to equilibrate with
its vapor. The vapor is found to have equal moles of A and B.
What was the mole fraction of A in the original solution?
Solution:

1) We know these statements are true:

PA = PA A
and
PB = PB B
2) Equal moles of A and B in the vapor means PA = PB.
Therefore:
PA A = PB B
3) We set A = x and B = 1 - x. Substituting, we obtain:
(1.0) (x) = (0.20) (1-x)
x = 0.17
If the question had asked for the mole fraction of B, it would
be 1 - 0.17 = 0.83 atm.
Problem #2: 30.0 mL of pentane (C5H12, d = 0.626 g/mL, v.p.
= 511 torr) and 45.0 mL of hexane (C6H14, d = 0.655 g/mL,
v.p. = 150. torr) are mixed at 25.0 C to form an ideal
solution.
a) Calculate the vapor pressure of this solution.
b) Calculate the composition (in mole fractions) of the vapor
in contact with this solution.
Solution:
1) Calculate (then add) moles of pentane and hexane:
pentane:
(0.626 g/mL) (30.0 mL) = 18.78 g
18.78 g / 72.15 g/mol = 0.26029 mol
hexane:
(0.655 g/mL) (45.0 mL) = 29.475 g
29.475 g / 87.1766 g/mol = 0.338107 mol
total moles = 0.26029 mol + 0.338107 mol = 0.598397 mol
2) Calculate mole fractions:
pentane 0.26029 mol / 0.598397 mol = 0.435
hexane 0.338107 mol / 0.598397 mol = 0.565
3) Calculate total pressure (the answer to part a):
Ptotal = PP P + PH H
x = (511 torr) (0.435) + (150. torr) (0.565)
x = 222.285 torr + 84.75 torr
x = 307.035 torr (to three sf, it is 307 torr)
4) Calculate composition of the vapor (the answer to part b)
pentane 222.285 torr / 307.035 torr = 0.724
hexane 84.75 torr / 307.035 torr = 0.276
The substance with the higher vapor pressure (because of the
weaker intermolecular forces) is present in the vapor to a
larger mole fraction than it is present in the solution.
Problem #3: What is the vapor pressure (in mmHg) of a
solution of 4.40 g of Br2 in 101.0 g of CCl4 at 300 K? The
vapor pressure of pure bromine at 300 K is 30.5 kPa and the
vapor pressure of CCl4 is 16.5 kPa.
Solution:
1) Calculate moles, then mole fraction of each substance:
bromine 4.40 g / 159.808 g/mol = 0.027533 mol
CCl4 101.0 g / 153.823 g/mol = 0.6566 mol
Br2 0.027533 mol / 0.684133 mol = 0.040245
CCl4 0.6566 mol / 0.684133 mol = 0.959755
2) Calculate total pressure:
Ptotal = PBr2 Br2 + PCCl4 CCl4
x = (30.5 kPa) (0.040245) + (16.5 kPa) (0.959755)
x = 1.2275 + 15.8360 = 17.0635 kPa
3) Convert to mmHg:
17.0635 kPa x (760.0 mmHg / 101.325 kPa) = 128 mmHg (to
three sig fig)

Problem #4: A solution has a 1:3 ratio of cyclopentane to

cyclohexane. The vapor pressures of the pure compounds at
25 C are 331 mmHg for cyclopentane and 113 mmHg for
cyclohexane. What is the mole fraction of cyclopentane in the
vapor above the solution?
Solution:
1) mole fractions for each substance:
cyclopentane: 1/4 = 0.25
cyclohexane: 3/4 = 0.75
Note: one part cyclopentane and three parts cyclohexane
means four total parts to the solution, hence four in the
denominator.
2) total pressure above the solution is:
Ptotal = PCP CP + PCH CH
x = (331) (0.25) + (113) (0.75)
x = 82.75 + 84.75 = 167.5 mmHg
3) mole fraction of cyclopentane in the vapor:
82.75 mmHg / 167.6 mmHg = 0.494
To 2 sig figs, write 0.49
Problem #5: Acetone and ethyl acetate are organic liquids
often used as solvents. At 30.0 C, the vapor pressure of
acetone is 285 mmHg and the vapor pressure of ethyl acetate
is 118 mmHg. What is the vapor pressure at 30.0 C of a
solution prepared by dissolving 25.0 g of acetone in 22.5 g of
ethyl acetate?
Solution:
1) Determine moles of each compound in solution:
acetone: 25.0 g / 58.08 g/mol = 0.43044 mol
ethyl acetate: 22.5 g / 88.10 g/mol = 0.25539 mol
2) Determine mole fraction for each compound in solution:
acetone: 0.43044 mol / 0.68583 mol = 0.62762
ethyl acetate: 1 - 0.62762 = 0.37238
3) Determine vapor pressure of vapor above solution:
P = (0.62762) (285 mmHg) + (0.37238) (118 mmHg)
P = (178.872) + (43.941) = 222.813 mmHg
P = 223 mmHg (to three sig figs)
Special bonus question: determine the composition (expressed
in mole fraction) of the vapor above this solution.
Solution:
acetone: 178.872 / 222.813 = 0.8028
ethyl acetate: 1 - 0.8028 = 0.1972
Note how the vapor is richer than the solution in the
component with the higher vapor pressure. This is the basis
for fractional distillation.
Problem #6: A solution containing hexane and pentane has a
pressure of 252.0 torr. Hexane has a pressure at 151.0 torr and
pentane has a pressure of 425.0 torr. What is the mole fraction
of pentane?
Solution:
Ptotal = PH H + PP P
252 = (151) (1 - x) + (425) (x)
x = 0.3686
Problem #7: The vapor pressure above a solution of two
volatile components is 745 torr and the mole fraction of
component B (B) in the vapor is 0.59. Calculate the mole
fraction of B in the liquid if the vapor pressure of pure B is
637 torr.
Solution:
1) Find partial pressure of B in vapor:

Ppartial, B = Ptotal, vapor B

x = (745) (0.59)
x = 439.55 torr
2) Determine mole fraction of B in solution that gives above
partial pressure:
PB = PB B
439.55 = (637) (x)
x = 0.69
We could calculate the vapor pressure of pure A, if we so
desired. The solution is left to the reader. The answer is 1454.5
torr.
Notice also, that the vapor is richer than the solution in A, the
more volatile component. In the solution, the mole fraction of
A is 0.21 and in the vapor it is 0.41.
Problem #8: Bromobenzene (MW: 157) steam distills at 95
C. Its vapor pressure at 95 C is 120 mmHg.
a. What is the vapor pressure of water at 95 C?
b. How many grams of bromobenzene would steam distill
with 20 grams of water?
Solution:
1) For part a, Teh Google yields:
633.9 mmHg
2) The Wikipedia page for steam distillation says:
"When a mixture of two practically immiscible liquids is
heated while being agitated to expose the surfaces of both the
liquids to the vapor phase, each constituent independently
exerts its own vapor pressure as a function of temperature as if
the other constituent were not present."
3) The total pressure of the vapor phase is:
633.9 + 120 = 753.9 mmHg
4) The mole fraction of the water vapor:
633.9 / 753.9 = 0.8408
5) This means:
20/18.0 = 1.11 moles of water represents 0.8408 of the vapor
also, please note that the mole fraction of the bromobenzene
is:
1 minus 0.8408 = 0.1592
6) Set up a ratio and proportion:
1.11 is to 0.8408 as x is 0.1592
x = 0.148728 mol
23.35 g of bromobenzene
Problem #9: Given that the vapor above an aqueous solution
contains 18.3 mg water per liter at 25.0 C, what is the
concentration of the solute within the solution in mole
percent? Please assume ideal behavior.
Solution:
1) We need to know the pressure exerted by the vapor:
0.0183 g / 18.015 g/mol = 1.01582 x 10-3 mol
PV = nRT
(x) (1.00 L) = (1.01582 x 10-3 mol) (0.08206) (298 K)
x = 2.4841 x 10-2 atm
2) Let's convert the pressure to mmHg:
2.4841 x 10-2 atm times 760 mmHg/atm = 18.9 mmHg
3) We look up the vapor pressure for water at 25 C:
23.8 mmHg
4) Now, we use Raoult's Law:
18.9 = (23.8) (solvent)
solvent = 0.794
solute = 1 minus 0.794 = 0.106

Problem #10: An 18.2% by mass aqueous solution of an

electrolyte is prepared (molar mass = 162.2 g/mol). If the
vapor pressure of the solution is 23.51 torr, into how many
ions does the electrolyte dissociate? The vapor pressure of
water at this temperature is 26.02 torr.
Solution Overview: (1) we will calculate the mole fraction of
the solute in the 18.2% solution (2) we will calculate the mole
fraction of the solute in the solution via Raoult's Law (3) will
divide #2 by #1
1) 18.2 % means this:
18.2 g solute in 100 g of solution. Therefore, 81.8 g of water.
moles solute 18.2 g / 162.2 g/mol = 0.112207 mol
moles water 81.8 g / 18.015 g/mol = 4.5407 mol
mole fraction of solute 0.112207 mol / 4.652907 mol =
0.0241155
We might call this the 'analytical mole fraction.' It completely
ignores any dissociation that might occur, looking only at how
many moles of the solid solute were dissolved into the
solution.
2) mole fraction via Raoult's Law:
23.51 torr = (solvent) (26.02 torr)
solvent = 0.903536
solute = 0.096464
3) divide #2 by #1:
0.096464 / 0.0241155 = 4
The electrolyte dissociated into 4 ions per formula unit. An
example of such a substance would be FeCl3.
Problem #11:
1,1-Dichloroethane (CH3CHCl2) has a vapor pressure of 228
torr at 25.0 C; at the same temperature, 1,1dichlorotetrafluoroethane (CF3CCl2F) has a vapor pressure of
79 torr. What mass of 1,1-dichloroethane must be mixed with
240.0 g of 1,1-dichlorotetrafluoroethane to give a solution
with vapor pressure 157 torr at 25 C? Assume ideal behavior.
Solution:
1) State Raoult's Law:
Let Cl = 1,1-dichloroethane and F = 1,1dichlorotetrafluoroethane
Ptotal = PCl Cl + PF F
2) Substitute values and solve:
157 torr = (228 torr) (x) + (79 torr) (1 - x)
where 'x' is the mole fraction of 1,1-dichloroethane and '1 - x'
is the mole fraction of 1,1-dichlorotetrafluoroethane.
157 = 228x + 79 - 79x
149x = 78
x = 0.52349 (this is the mole fraction of 1,1-dichloroethane)
3) Set up a mole fraction equation:
0.52349 = (x / 98.9596) divided by [(x / 98.9596) + (240.0 /
170.92)]
where 'x' is the mass of 1,1-dichloroethane (which is our
answer).

However, I will solve the other mole fraction expression. (I

did solve the above equation on paper when I formatted this
answer (Nov. 16, 2011) and I did get the answer below.)
4) Use the mole fraction of 1,1-dichlorotetrafluoroethane:
0.47651 = (240.0 / 170.92) divided by [(x / 98.9596) +
(240.0 / 170.92)]
where 'x' is still the mass of 1,1-dichloroethane (which is our
answer).
The reason? One less 'x' in the above equation.
5) Algebra!
1.40416 = 0.47651x / 98.9596 + 0.6690963
0.0048152x = 0.7350637
x = 152.654864 g
Rounded to four significant figures would be 152.6 g
Problem #12: The vapor pressure of pure benzene (C6H6,
symbolized by B) and toluene (C7H8, symbolized by T) at
25.0 C are 95.1 and 28.4 torr, respectively. A solution is
prepared with a mole fraction of toluene of 0.75. Determine
the mole fraction of toluene in the gas phase. Assume the
solution to be ideal.
Solution:
1) Raoult's Law for a solution of two volatiles is this:
Ptotal = PB B + PT T
Ptotal = (95.1) (0.25) + (28.4) (0.75)
Ptotal = 23.775 torr + 21.3 torr Ptotal = 45.075 torr
2) The mole fraction of toluene in the vapor is this:
21.3 torr / 45.075 torr = 0.472545757
Rounded to three sig figs, this is 0.472.
Problem #13: 1-propanol (P1 = 20.9 torr at 25.0 C) and 2propanol (P2 = 45.2 torr at 25.0 C) form ideal solutions in all
proportions. Let 1 and 2 represent the mole fractions of 1propanol and 2-propanol in a liquid mixture, respectively. For
a solution of these liquids with 1 = 0.520, calculate the
composition of the vapor phase at 25.0 C.
Solution:
1) Use the mole fractions of each liquid to calculate the partial
pressure of that component:
vapor pressure of 1-propanol: 20.9 torr x 0.520 = 10.868 torr
vapor pressure of 2-propanol: 45.2 torr x 0.480 = 21.696 torr
(the 0.480 comes from 1 - 0.520)
2) Use the partial pressures to determine the composition of
the vapor:
total pressure of the vapor: 10.868 + 21.696 = 32.564 torr
mole fraction 1-propanol in vapor: 10.868 / 32.564 = 0.334
mole fraction 2-propanol in vapor: 1 - 0.334 = 0.666