Dpto.

Ciencia e Ingeniería de Materiales e Ingeniería Química

Chemical Basis of Engineering
Problem Set T3

Worked Examples

1. Estimate the molar heat of vaporisation of a liquid whose vapour pressure doubles
when the temperature is raised from 85 ºC to 95 ºC.

Solution:

P1 ∆H v 1 1
ln =  − 
P2 R  T2 T1 
1  ∆H v  1 1   − 7.59 × 10 −5 
ln  =  −1 −1
 −  = ∆H 
v −1

−1 
 2   8.314 JK mol  368K 358K   8.314 JK mol 
∆H v = 7.59 × 10 4 Jmol −1 = 75.9 kJmol −1

2. What is the vapour pressure of a mixture of 0.127 mol sugar and 100.0 g water at 25
ºC? Consider Pwater (25 ºC) = 28.8 Torr.

Solution:

Since this refers to solution, where water is the solvent and sugar is the solute, Raoult´s
law must be used (PH2O,solution = XH2OP0H2O). P0H2O is the vapour pressure of pure water.

 −1 
100 g / 18gmol 
n H 2O  
X H 2O = = = 0.98
nsugar + n H 2O  −1 
0.127 mol + 100 g / 18 gmol 
 
PH 2O , solution = 0.98 × 28.8 Torr = 28.2 Torr

You can observe that there is a very little change from the vapour pressure of pure
water, this is typical. Vapor pressure of a solvent decreases in presence of a non-volatile
solute.

3. What is the vapor pressure of a mixture of 3.44 g FeF2 in 75.00 g water at 20 ºC?

Solution:

If the solute is an ionic compound in water, you must use the moles of ions rather than
the moles of compound as the moles of solute in the calculation of mole fraction. Recall
that colligative properties depend on the number of particles in solution. When an ionic
compound dissolves in water, the particles are ions, not the formula unit.
The vapor pressure of water at 20 ºC is 17.5 Torr. Since FeF2 is a soluble, ionic
compound, when 1 mol of the compound dissolves, it makes 1 mol of Fe2+ and 2 moles
of F-. So the mole fraction is:

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 Dpto. Ciencia e Ingeniería de Materiales e Ingeniería Química
Chemical Basis of Engineering
Problem Set T3

 −1 
 75 g / 18gmol 
n H 2O  
X H 2O = =
n Fe 2 + + n F + + n H 2O    
 3.44 g 1 molFe2+   3.44 g 2 molF −   −1 
 −1
× + −1
×  +  75 g / 18gmol 
 93.85 gmol 1 molFeF2   93.85 gmol 1 molFeF2   
   
X H 2O = 0.9742

PH 2O, solution = 0.9742 × 17.5 Torr = 17.0 Torr

4. Calculate the osmotic pressure at 25 ºC of a solution formed by a solute of 1200 g

mol-1 molecular weight if 0.3 g of this solute were dissolved in water being the final
volume of 250 mL. What will be the value of the freezing point depression? Consider that
the density of the solution is 1 g cm-3. Kf=1.86 ºC kg-1 mol-1.

Solution: a) π=0.024 atm; ΔTC=1.86·10-3 ºC

a)

Π = MRT

0.3 g × 1 mol
1200 g
M= = 10 −3 molL−1
0.25 L

Π = 10 −3 molL−1 × 0.082 atmLmol −1 K −1 × 298 K = 0.024 atm

b)

∆T f = T f − T f0 = m × K f

1 g
mass( solution) = 250 cm 3 × = 250 g and mass( solvent) = 250 g − 0.3 g = 249.7 g
1 cm −3

0.3 g × 1 mol
1200 g
m= = 10 −3 molkg −1 ⇒ ∆T f = 1.86 º Ckgmol −1 × 10 −3 molkg −1 = 1.86 ⋅ 10 −3 º C
0.2497 kg

5. A phase diagram of bismuth is shown below. Indicate: a) How many triple points are
there? What are their coordinates and what phases coexist? b) The coordinates of the
critical point in this diagram, if possible. c) What would it happen if at a constant
temperature 500 K, we raise the pressure from 5 to 80 kbar? And what if at a constant
pressure of 40 kbar we decrease the temperature from 700 K to room temperature?

Solution:

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 Dpto. Ciencia e Ingeniería de Materiales e Ingeniería Química
Chemical Basis of Engineering
Problem Set T3

a) 5 triple points (A, B, C, D, E)

b) It is not possible to determine the coordinates of the critical point, as the liquid-vapor
equilibrium region is not included in this diagram.
c)

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 Dpto. Ciencia e Ingeniería de Materiales e Ingeniería Química
Chemical Basis of Engineering
Problem Set T3

Proposed Exercises

6. Consider two 5 L-tanks, A and B, connected by a valve. While closed, the tank A has
0.2 moles of N2 gas at 20 ºC. The tank B is filled with as many litres of O2 as those
obtained from the thermal decomposition of 100 g of potassium chlorate at 20 °C (Not
balanced reaction: KClO3 (s) → KCl (s) + O2 (g)).
a) What is the total pressure in each tank meanwhile the valve is closed?
b) What are the partial and total pressures after opening the valve?
Data: M(K) = 39.1; M(Cl) = 35.5; M(O) = 16; R = 0.082 atm L mol-1 K-1.

Solution: (Balance reaction.) a) PA = 0.961 atm; PB = 5.88 atm; b) PT = 3.42 atm.

7. Consider a 10 L vessel which contains CH4(g) at 10ºC and 446 Torr partial pressure
and oxygen gas at 10 ºC at 652 Torr. A spark starts the reaction:
CH4(g) + O2(g) → CO2(g) + H2O(l) (not balanced)
and it proceeds up to full conversion. If final temperature is 40 ºC, what is the final
pressure in the vessel? Fact: Water vapour pressure at 40 ° C is 55.324 Torr.
Data: R = 0.082 atm L mol-1 K-1.

Solution: (Balance reaction.) P=0.715 atm

8. Consider three containers A, B and C which volumes are 1, 2.6 and 2.2 liter,
respectively. Container A has 0.7 g of nitrogen at a pressure of 550 Torr; container C has
1.5 g of Ar at 400 Torr and B is empty by the time the experiment starts. a) Which are
the temperatures of containers A and C?; b) If the temperature of container B is 100 ºC
what is its final pressure if the content of A and C is completely transferred to B?; c)
Calculate the partial pressures of each of the gases in container B.
Data: M(N) = 14; M(Ar) = 39.95; R = 0.082 atm L mol-1 K-1.

Solution: a) TA = 80.2 ºC; TC = 103 ºC; b) P = 0.74 atm; c) PN2 = 0.294 atm; PAr =
0.441 atm

9. The normal boiling point of acetone, an important laboratory and industrial solvent, is
56.2 ºC and its enthalpy of vaporization is 25.5 kJ mol-1. At what temperature does
acetone have a vapor pressure of 375 mmHg?
Data: R = 8.314 J mol-1 K-1.

Solution: Use Clausius-Clapeyron equation. T = 306 K.

10.The vapor pressures of benzene and acetone at 50 °C are 271 and 603 Torr,
respectively. Determine: a) The vapor pressure of an ideal mixture consisting of equal
parts by weight of benzene and acetone at 50 °C and b) the mole fraction of acetone in
the vapour phase.
Data: M(acetone) = 58 g mol-1, M(benzene) = 78 g mol-1.

Solution: Raoult’s and Dalton’s. a) P=461 Torr; b) Yacetone=0.75

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 Dpto. Ciencia e Ingeniería de Materiales e Ingeniería Química
Chemical Basis of Engineering
Problem Set T3

11. Determine the composition of a mixture of acetone and toluene (assuming an ideal
behaviour) which boils at 80 ºC considering that their vapor pressures at this
temperature are 1610 and 290 mmHg, respectively.

Solution: xacetone = 0.356.

12. The minimum concentration of oxygen in water required for highest living
organisms (fishes) is 4 mg O2 L-1. Calculate: a) the partial pressure of O2 required for
keeping fishes alive at 20 ºC; b) the atmospheric pressure that would yield this partial
pressure of O2 assuming that about 21 % of the atmosphere is oxygen.
Data: M(O2) = 32 g mol-1; KH(O2, 20 ºC) = 1.3·10-3 mol L-1 atm-1.

Solution: a) 0.1 atm (Henry’s law); b) 0.48 atm.

13. During production, nitric acid (HNO3) forms an azeotrope with water (H2O) as
shown in the diagram. According to the phase diagram, determine:
a) The phases present in each region.
b) The boiling temperature of both pure components. Indicate which one is the most
volatile.
c) The boiling temperature of a mixture containing 40% HNO3.
d) The composition of the liquid in equilibrium with the vapor containing 90% H2O.
e) Is it possible to obtain pure HNO3 from mixtures containing 40% HNO3 and 80%
HNO3? If so, would it be part of the condensed vapor or part of the residue?

120

110
Temperature (ºC)

100

90

80

0 10 20 30 40 50 60 70 80 90 100

% weight nitric acid

Solution: b) Tb(H2O) = 100 ºC y Tb(HNO3) = 86 ºC; c) 110 ºC; d) 25% HNO3; e) Only
starting from 80% HNO3 and by fractional distillation. Pure HNO3 would be part of the
distillate because the system shows an azeotrope with maximum boiling point.

14. How many grams of sugar (C6H12O6) should be dissolved in 500 cm3 of water so
that the resulting solution has a vapor pressure of 148.9 mmHg at 60 ºC? The density of
water at 60 ºC is 0.9971 g cm-3 and its vapor pressure at 60 °C is 149.38 mmHg.
Data: M(C) = 12; M(H) = 1; M(O) = 16.

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 Dpto. Ciencia e Ingeniería de Materiales e Ingeniería Química
Chemical Basis of Engineering
Problem Set T3

Solution: 17 g of sugar.

15. A 0.500 g sample of hemoglobin was dissolved in H2O to prepare 100 mL of

solution. At 25 °C the osmotic pressure of the solution was 1.35 mmHg, what is the
approximate molecular weight of hemoglobin?
Data: R = 0.082 atm L mol-1 K-1.

Solution: 6.9·104 g mol-1.

16. A reaction mixture for the combustion of SO2 was prepared opening a faucet that
connects two separate chambers: one with a volume of 2.125 L full of SO2 at 0.75 atm,
and the other with 1.5 L at 0.5 atm filled with O2; the two gases are stored at 80 ºC.
Determine: a) Which is the molar fraction of SO2 in the mixture, the total pressure and
the partial pressures before the reaction; b) Once the reaction has finished and assuming
it is completely displaced to the right, which are the molar fractions in the mixture and
the total final pressure?
2 SO2 (g) + O2 (g) ⇔ 2 SO3 (g)
Data: R = 0.082 atm L mol K-1.
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Solution: a) xSO2 = 0.68, PT = 0.647 atm, PSO2 = 0.44 atm, PO2 = 0.207 atm; b) xSO2 =
0.05, PT = 0.44 atm.

17. Consider the phase equilibrium diagram of helium. This noble gas behaves as a
super-fluid (without viscosity) in its He (II) state. Using the diagram below indicate:
a) The maximum temperature at which
He (II) can behave as a superfluid.
b) The minimum pressure for helium to
be in solid state.
c) The normal boiling temperature of
He(I).
d) Is it possible that helium in its solid
state sublimes?
e) The triple points of the diagram and
the phases in equilibrium.
f) Which of the two liquid phases of
helium, He (I) or He (II), is denser?
Explain your reasoning.

Solution: a) ∼2 K; b)∼20 atm; c) ∼4.5 K; d)

No; e) There are two triple points: (1) 25
atm; 1.7K (Solid ↔ He(I) ↔ He(II)); (2)
0.05 atm; 2.2 K: (He(I) ↔ He(II) ↔ Vapor)
f) He(I).

18. Calculate the molar mass of the substances that were used as solutes in the
following solutions: a) 231 g of water and 31.4 g of terbutyl alcohol, with freezing point
of –3.36 ºC (Kf = 1.86 ºC Kg mol-1); b) 71.7 g of ethanol and 3.63 g of aspirine, with

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 Dpto. Ciencia e Ingeniería de Materiales e Ingeniería Química
Chemical Basis of Engineering
Problem Set T3

boiling point of 78.74 ºC (Kb = 1.22 ºC Kg mol-1); c) 31.8 g de ethylene bromide and
3.24 g de anthracene, with a freezing point of 3.3 ºC (Kf = 11.8 ºC Kg mol-1).
Data: Tb (ethanol) = 78.4 ºC; Tf (ethylene bromide) = 10 ºC.

Solution: a) 75.2 g mol-1; b) 181.7 g mol-1; c) 181 g mol-1.

19. Considering the data in the table, build the boiling point/molar fraction diagrams for
the liquid and the vapor in a mixture of two components (ideal behaviour). The normal
boiling points of these compounds are 76.7 y 113 ºC.

If we heat an equimolecular solution up to 95 ºC, calculate the composition of the

condensed fraction and liquid, together with the evaporated percentage.

Solution: liquid: XCCL4 = 0.42; condensed: YCCl4= 0.68;

%Vapor = 31%; levers rule for a mixture of two components A and B in two phases α
and β: Xα = (c-b)/(a-b); where Xα is the ratio of phase α; c is the ratio of component B
(for example CCl4) in the whole system (0.5 in this case); b is the ratio of B in phase β; a
is the ratio of B in phase α.

20. Consider a solution with 17 g of a non-volatile solute in 85 g of benzene at 25 ºC.

The vapor pressure of the solution is 0.11 atm. Calculate the molar fraction and the
molar mass of the solute.
Data: Pº (Benzene, 25ºC) = 0.125 atm. M(Benzene) = 78.1 g/mol.

Solution: Xsolute = 0.12; M (solute) = 114.55 g/mol.

21. Triple point of a pure substance has coordinates: 260 K and 0.4 atm. Critical
pressure and temperature are, respectively, 1.8 atm and 315 K and its normal melting
point is 250 K. If vapor pressure of such substance at 240 K is 0.2 atm, reason next
questions:
a) Draw approximately the phase diagram indicating the regions of different phases
of matter and the points given as data.
b) Order reasonably the density of phases shown in the diagram.
c) Is it possible to sublimate the substance at reduced pressure of 0.35 atm?
d) Is it possible to find the substance in liquid phase at 373 K? Reason your answer.
Solution: b) L > S > V; c) Yes, there is a phase boundary between solid and vapor
phases; d) No. It’s beyond the critical point and kinetic energy is too high. At that
temperature it’s a supercritical fluid.

22. Consider a mixture of chloroform, P0(chloroform, 20 ºC) = 158.6 Torr and heptane
P0(heptane, 20 ºC) = 40 Torr with a mole fraction in heptane in the liquid of 0.288.

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 Dpto. Ciencia e Ingeniería de Materiales e Ingeniería Química
Chemical Basis of Engineering
Problem Set T3

Estimate the vapor pressure of the mixture and calculate what the mole fraction of
heptane is in the vapor phase at 20 ºC.

Solution: PT = 124.4 Torr; YHeptane = 0.0926.

23. A solution contains 102 g of sugar, C12H22O11, in 375 g of water. Determine the
vapor pressure lowering at 25 ºC.
Data: M(O) = 16; M(H) = 1; M(C) = 12; P0(H2O, 25 ºC) = 23.8 mmHg.

Solution: 0.333 mmHg.

24. Glycogen is a polymer of glucose (repetitive units of C6H12O6) of variable molecular

weight which animal cells use to store glucose. When cells need energy they use the
glycogen, which releases glucose units that are transported by the blood. 130 mg of
glycogen were dissolved in 0.85 mL of water and the osmotic pressure of resulting
solution, at 25 ºC, was 0.36 mmHg. How many units of glucose has the glycogen?
Data: M(C) = 12; M(O) = 16; M(H) = 1; R = 0.082 at Lmol-1K-1= 8.314 J mol-1K-1; 1 atm
= 760 mmHg.

Solution: Calculate the molar mass of the polymer and divide it by the molar mass of
the monomer (glucose): 43802 units of glucose.

25. In Winter, in very cold places, to prevent the formation of ice on roads, NaCl
powder is spread. Due to the corrosion problems caused by Cl- ions, the replacement of
NaCl by SiO2 is intended. For a given weight of the two proposed salts (100 g) dissolved
in 3 kg of water, which of them exert their antifreeze action more effectively? (Take into
account that NaCl acts as an electrolyte and in these concentrations has a value for the
Van´t Hoff factor of i = 1.85 and SiO2 is a non-electrolyte).
Data: M(NaCl) = 58.45 g mol-1; M(SiO2) = 60.1 g mol-1; Kf = 1.86 ºC kg mol-1.

Solution: NaCl presents antifreeze action more effectively.

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