EXERCISES.

THERMODYNAMICS OF MIXTURES

1. Using the data from literature that you deem appropriate and knowing that for blood
the observed freezing point is -0.52oC.

a-) Determine the boiling point of blood

b-) Calculate the osmotic pressure at 25oC.
c-) Determine the value of the vapor pressure exerted by the solution blood

2. Un recipiente está dividido en dos compartimientos. Uno contiene 3,0 moles H2a 1.0
atm y 25.0oC; the other compartment contains 1.0 mol of N2at 3.0 atm and 25.0oC. Calculate
the change in free energy and the change in entropy of mixing when the division is removed.
Asuma ideal behavior.

3. If 100g of ethanol dissolves 0.225g of solid anthracene at 40oC y 0.463g at 60oC.

a-) Find the Hsunof anthracene in ethanol at infinite dilution.

b-) Knowing that the Hfus= 6.6 kcal/mol for the solute what does the difference represent between
Hfusy Hsol?.

4. a-) What is the Henry's constant for CH?3Cl and H2The 25oC, if the partial pressure of the
Methyl chloride varies according to its composition based on the following data:

PMethyl chloride(mm) 205,2 363.2 756.1 945.9

mMethyl chloride(mol/kg) 0.029 0.051 0.106 0.131
b-)With the available data, I could calculate the vapor pressure of CH.3Cl pure?
Explain your answer.

5. The heights recorded in an osmometer of polyvinyl chloride solutions in

cyclohexanone at 298 K are presented in the Table. The pressures must be expressed in
terms of the heights reached by the solution with a density of 0.980 g/cm3in balance with the
osmotic pressure. With that information, determine the molecular weight of the polymer.

c g/cm3 1,0 2.0 4.0 7.0 9.0

h cm 0,28 0,71 2,01 5,10 8,00

6. The cryoscopic depression observed when dissolving 0.5g of benzoic acid is 50g of acetone.
is Tc = 0.197 but if dissolved in 50g of benzene the decrease is 0.2100Knowing
that the cryoscopic constants are 2.40 K-kg/mol and 5.12 K-kg/mol for acetone and the
benzene respectively, calculate the molecular weight of the solute in each case. Explain the
differences if they are present.

7. For a mixture of ethyl iodide-ethyl acetate at 50 0C, to find the coefficients

of activity of the two components based on the symmetric reference system (Law of
Raoult) and based on the asymmetric system (solvent according to Raoult's Law) and solute according to

(Henry's Law). Assume that the iodide is the solute. The experimental data are:

Xyod 0,0 0.0579 0.1095 0,1918 0,23530 0.37180 0.5478

Pyod(mm) 0,0 28.0 52.7 87.7 105.4 155.4 213.3
Pac(mm) 280.4 266.1 252.3 231.4 220.8 187.9 142.2

Xyod 0.6349 0.8253 0,9093 1.00

Pyod 239.1 296.9 322.5 353.4
Pac 122.9 66.6 38.2 0,0

8. Calculate the osmotic pressure of a 3.0 molal sucrose solution in water at 300C. The
the vapor pressure of the solution is 29.675 mm and that of water is 300It is 31,824 mm. The
The densities of water and the solution at that temperature are 0.9957 and 1.230 g/cm³.3respectively and the
The molecular weight of sucrose is 342 g/mol.

9. The solubility of ice in glycerol at -0.300C is XH= 0.99971. The HVof H2O (l) is
9.72 kcal/mol at the normal boiling temperature

a-) Find the cryoscopic depression of a glycerol solution in ice with concentration Xthe
0.00029.
What is the boiling point of the previous solution?

10. The melting point of white phosphorus is 440C and his Hfuseit is 600 cal/mol.

a-) Calculate its ideal solubility in a solvent at 250C

b-) The HsunThe phosphorus in n-heptane at infinite dilution is 4.1 kcal/mol at 25. 0C. Find the
solubility of phosphorus in n-heptane at 400C if the real solubility at 250C is Xp 0.0124

11. When an electrolyte completely dissociates in a solvent, the effective number of

Particles in solution are different from the number of undissociated particles. Consequently, when
study the colligative properties of electrolyte solutions the concentration must
to refer to the total concentration of ions in solution. This total concentration is
equal to the concentration of the undissociated electrolyte multiplied by the number of ions it dissociates into

dissociates. Thus, for an electrolyte:

 M nz Xnz n  Mz  n  Xz

n = n+ + n- total number of ions and their effective molality due to all particles in
solution will be.

mef= n mMX MX = undissociated electrolyte

It is then had:
Tc= Kc mef= Kc(n mMX)
Tb= Kbmef= Kb (n mMX)

RT RT
Cef (nC) M Molecular Weight
M MX M MX

Considering the above and if you know that common salt costs $3.60/Kg and calcium chloride
$2.76/Kg, decide which of these salts is more suitable to add to the paths in
winter and prevent the formation of ice.

12. Knowing that the Henry's constant for O2(g) in water is 4.34x104atm a 25.00C
calculate its solubility at the pressure of Bogotá and at 25.00And taking into account that the air
it contains approximately 20% O2.

13. A 0.001 m solution of PT(NH3)4Cl4in water presented a freezing point of

-0.00540C. K C H O2 = 1.86 K-mol/kg)

a-) Analyze whether the compound dissociates and, in that case, how many ions it produces.

14. When dissolving 5 g of acetic acid in 100 g of H2The observed vapor pressure was
3120 Pa and if it dissolves in 100g of benzene it is 9330 Pa.
Knowing that the vapor pressures of water and benzene are 3167.2 Pa respectively
At 9670 Pa, calculate in each case the molecular weight of acetic and discuss the results.
obtained.

15. The main solutes in seawater expressed in p.p.m. by mass are:

Cl: 18980 ppm Ca+2400

Na+: 10560 K+380
SO4:= 2700 HCO-3:140
Mg+21270 Br: 65

Knowing that KC1.86 K-kg/mol and Kb+ 0.153K-kg/mol for water, determine the point
the freezing point and boiling point of a sample of seawater from the
mentioned characteristics.

16. A 200The following density data was obtained for aqueous solutions of
CuSO4.

%CuSO4(g CuSO4/100g solution) p(g/cm3)

5 1,051
10 1,107
15 1,167
20 1,233

d CuSO43.603 g/cm3

a-) Determine the molar volume of the solution Vm and plot it as a function of XCuSO4.
b-) Calculate the excess volume for the studied mixtures.
c-) Determine the partial molar volume of CuSO for each [Link](II) and analyze its
sulfate

variation with the composition.

17. 20g of a solute is added to 100g of water at 250C. The vapor pressure of pure water
It is 23.76 mmHg. The vapor pressure of the solution is 22.41 mmHg.

a.-) Calculate the molar mass of the solute.

What mass of solute is required in 100g of water to reduce the vapor pressure to the
half the value of pure water?

18. Suppose a series of solutions is prepared using 180g of water as

solvent and the mass g of a non-volatile solute. What will be the relative decrease of the
vapor pressure if the molar mass of the solute is: 100g/mol, 200g/mol and 10000g/mol?

19. Two grams of benzoic acid dissolved in 25g of benzene, Kc4.90 kg/mol
they produce a decrease in the freezing temperature of 1.62K. Calculate the mass
molar. Compare this value with the mass obtained from the formula of benzoic acid,
C6H5COOH.

20. The heat of fusion of acetic acid is 11.72 kJ/mol at the melting point, 16.61.0C.
Calculate Kc for acetic acid.

21. The heat of fusion of water at the freezing point is 6009.5 J/mol. Calculate the
melting point of water in solutions with a molar fraction of water equal to: 1.0, 0.8,
0.6, 0.4, 0.2. Graph the values of T vs [Link].

22. For the CCl4, Kb5.03 Kkg/mol y Kc= 31.8 K kg/mol. If 3.00g of a substance in
100g of CCl4they produce an increase in the boiling point temperature of 0.60 K, calculate the
decrease in the freezing temperature, the relative decrease in pressure
vapor, the osmotic pressure at 250C and the molar mass of the substance. The density of CCl4it
1.59 g/cm3and the molar mass, 153.823 g/mol.

23. As the boiling point of the liquid depends on the pressure, Kb is a function of the
Pressure. Calculate the value of Kb for water at 750 mmHg and at 740 mmHg of pressure.
Assume that Hvaporit is constant.

24. For p-dibromobenzene, C 6H4Br2the heat of fusion is 85.8 J/g and the melting point,
860C. Calculate the ideal solubility at 250C.

For p-dichlorobenzene, C 6H4Cl2The heat of fusion is 124.3 J/g and the melting point,
52.70C. Calculate the ideal solubility at 250C.

The melting point of iodine is 113.6.0C and the heat of fusion, 15.64 kJ/mol

a.-) What is the ideal solubility of iodine at 250C?

b.-) How many grams of iodine dissolve in 100 grams of hexane at 250C?.

In 100g of benzene, 70.85g of naphthalene is dissolved.10H8a 250And they dissolve

103.66 g at 350C. Assume that the solution is ideal. Calculate it. Hfusy T0 for the
naphthalene

27. If 6.00 g of urea, (NH2)2In a 1.00 L solution, calculate the pressure.

osmotic of the solution at 270C.
28. Consider a vertical tube with a cross-sectional area of 1.00 cm 2. The bottom
the tube is closed with a semipermeable membrane and 1.00g of glucose is placed in it,
C6H12O6in the tube. The closed end of the tube is submerged in pure water. The density
of the solution can be taken as 1 g/cm3and the concentration of sugar is supposed
uniform in the solution. T = 250C. Assume a negligible immersion depth.

a.-) What will be the height of the liquid level in the tube at equilibrium?
b.-) What is the osmotic pressure at equilibrium?

29. A 250C, a solution that contains 2.50g of a substance in 250 cm3of solution,
It exerts an osmotic pressure of 400 Pa. What is the molar mass of the substance?

30. The volume of NaCl solutions in water was measured at different molalities and was
found that the volume depends on the molality according to the following equation: V(cm3)=
1003+1662m+1.77m3/2+0.12m2Calculate the partial molar volume of component a
m = 0.100 mol/kg-1.

31. Consider a 5-liter container divided into two equal compartments. In one
from the compartments there is N2gas at 3 atm pressure and 250C; and in the other
compartment has H2at 1 atm of pressure and 250C. Calculate Smixby letting it be
mix the gases in the two compartments. Assume that the gases are ideal.

32. The table shows how the vapor pressure of the iodine (I) acetate mixture varies.
of style (A). A 500To find the activity coefficients of the two components at the
different compositions:

a.-) According to Raoult's law

b.-) According to Henry's law taking iodine as the solute.
 XI PITorr PATorr

0.0000 0.0 280.4

0.0579 28.0 266.1
0.1095 52.7 252.3
0.1918 87.7 231.4
0.2353 105.4 220.8
0.3718 155.4 187.9
0.5478 213.3 144.2
0.6349 239.1 122.9
0.8253 296.9 66.6
0.9093 322.5 38.2
1.0000 353.4 0

33. The following data is available for the acetone-chloroform system.

T = 28,15oC T = 25oC

%m (Ac) PT(mm) P(Ac)(mm) Pchlor(mm) %m (Ac) d (g/cm3)

100 258.8 258.8 0 100 0.78491

71.3 220.5 180.4 40.1 83.34 0.85147
55.0 202.7 133.2 69.5 66.96 0.92905
44.0 193.4 94.4 95.0 54.17 1,00050
36.0 188.5 67.9 120.6 43.70 1.06789
27.5 190.8 43.1 147.7 35.49 1,12762
14.7 201.7 23,4 178.3 27,72 1,19083
0 221.8 0 221.8 20.12 1.25927
11.59 1,34501
5,71 1,41065
0 1,47993

a) Build the graphs of total and partial pressures and include the graphs.
corresponding to ideal behavior.
b) Calculate the activity coefficients using the symmetric reference system
c) Calculate the molar volume of the mixture and from the corresponding graph, calculate the
partial molar volumes for each of the components. Verify the equation
of Gibbs-Duhem.
d) Analyze the behavior of the acetone system with the obtained results.
chloroform

34. The following density data in g cm3were obtained for the ethanol-water system.
The composition is expressed in the table as % by weight.
Error! Invalid link.
a) Calculate the molar volume of the mixture and, based on the corresponding graph, calculate
the partial molar volumes for each of the components. Verify the
Gibbs-Duhem equation.
b) Calculate the molar excess volume for the mixtures

35. The Antoine equation states that the vapor pressure can be expressed as a function of
of the temperature according to:
Log p = A - B/(t + C)

Where p is the pressure expressed in mm and t is the temperature in degrees Celsius.

Knowing that for ethanol the boiling point is 78.29oC at 760 mm and the Have a nice day

The boiling temperature is 9.260 cal/mol. Calculate the ebullioscopic constant at 560 mm.
The constants of the Antoine equation for ethanol are:
A = 16,1952 B = 3423,53 C = - 55,7152
36. The osmotic pressures of enzyme solutions in water at 298 K are indicated at
continuation.
Find the molar mass of the enzyme

c /g L-1 1,00 2,00 4,00 7,00 9,00

/(10-2kPa 2,75 6,96 19,7 50,0 78,5

36. Calculate the solubility of O2 and N2 from the air in H2O at 10°C and 30°C. Consider that the

The total pressure of the system is 560 mmHg. Use Henry's Law for gases.

T/°C kH(O2)in water 10-4atm kH(N2)in water 10-4ATM

10 3.27 6.68
30 4.75 9.24