5/3/2025 Physical Chemistry
Chapter 3. Phase equilibrium
Phase equilibrium of one-component stystem
3.1. A saturated solution of Na2SO4, with excess of the solid, is present at equilibrium with its
vapour in a closed vessel. (a) How many phases and components are present? (b) What is the
number of degrees of freedom of the system? Identify the independent variables.
3.2. Use the Clapeyron equation to estimate the slope of the solid-liquid phase boundary of
water given the enthalpy of fusion is 6,008 kJ/mol and the densities of ice and water at 0oC are
0,91671 and 0,99984 g/ml.
3.3. Densities of solid phenol and liquid phenol are 1,072 and 1,056 g/ml; enthalpy of melting
of phenol is 24,93 cal/g; crystallization temperature of phenol at 1 atm is 41oC. Determine the
melting point of phenol at 500 atm. Answer: 43,15 oC
3.4. At 0oC, enthalpy of fusion of ice water is 1434,6 cal/mol. Volume of water in solid and
liquid form are 1,098 and 1,001 ml/g, respectively. Determine the dP/dT for the melting process
and the melting temperature of ice water at 4 atm. Answer: Tfusion (4atm) = -0,0243 oC
3.5. S(rhomic), when heated, tranforms to S(monoclinic) with the volume change DV = 0,0138
ml/g. The phase transition tempearatures at 1 atm and 10 atm are 95,5 oC and 95,8 oC.
Determine enthalpy of phase transition between S(rhomic) and S(monoclinic). Given that
molecular weight of S is 32 g/mol; 1 cal = 41,3 [Link].
3.6. The vapour pressure of mercury at 20°C is 160 mPa; what is its vapour pressure at 40°C
given that its enthalpy of vaporization is 59.30 kJ/mol?
3.7. Vapour pressure of aceton at 306 K and 320 K are 346 mmHg and 556 mmHg. Determine
enthalpy of vaporization and boiling temperature of acetone.
Answer: Tb = 326 K, enthalpy of vaporization = 6592 cal/mol.
3.8. At normal condition, boiling point of water and chloroform are 1000C and 600C,
respectively. Enthalpy of vaporization are 12,0 và 7,0 kcal/mol, respectively. Determine the
temparature at which these two liquids have the same vapour pressure? Answer: 175,4oC
3.9. At 46oC, vapour pressure of liquid A is 50mmHg and that of solid A is 49,5 mmHg. At
45oC, vapour pressure of liquid A is 1 mmHg higher than that of solid A. Determine the
enthalpy of fusion, enthalpy of sublimation and melting temperature of A. Given that enthalpy
of vaporization is 9 kcal/mol and volume of A in liquid and solid form are similar.
Answer: lfusion = 2,32 [Link]–1; lsublimation = 11,32 [Link]–1; Tom = 46,9oC.
Vapour of A solid ⇌ A (solid) ⇌ A (liquid) ⇌ Vapour of A liquid
vapour pressure of A solid = vapour presure of A liquid at melting temperature of A
3.10. Given that benzene và toluene forms an ideal solution. Pure benzene boils at 80oC. At
this temperature, vapor pressure of toluene is 350 mmHg.
a) Determine partial pressure and total pressure of the solution having xbenzen= 0,2 at 80oC.
b) Determine the composition of the solution that boils at 80oC at the surrounding pressure is
500 mmHg? Answer: a) 152 mmHg; 280 mmHg; 432 mmHg; b) xbenzene = 0,366
Liquid-vapour equilibrium
5/3/2025 Physical Chemistry
3.11. At 80oC, vapor pressure of pure A and pure B is 100 and 600 mmHg, respectively.
a) Draw a diagram “pressure - composition” (P-x) of the ideal solution of A-B.
b) A solution containing 40% mol B is put into a closed vessel and there is 1/3 total mole of
solution evaporated. Determine the composition of the liquid and vapor phase at the
equilibrium. (Answer: xB = 0,261 and yB = 0,679)
3.12. Assuming that CCl4 and SnCl4 form an ideal solution. Determine the composition of a
solution boils at 100oC under atmospheric pressure of 760 mmHg and the composition of the
first bubble appeared, given that vapor pressure of CCl4 and SnCl4 are 1450 và 500 mmHg,
respectively at 100oC. (Answer: 0,274 and 0,522)
3.13. Acetone and water are miscible liquids. The vapour pressure of water and acetone are
given as follows:
t, oC 70 80
'
P!"#$%&# , mmHg 1190 1600
'
P()*+, , mmHg 235 346
a. A mixture of acetone and water (mixture A) starts to boil at 70oC (atmospheric pressure is 1
atm). Calculate the composition of the first bubble that appears? (0.55 and 0.45)
b. Heat the mixture until 80oC, there are two phases: liquid B and vapour C at the equilibrium.
Determine the composition of phase B and phase C. If mixture A has a total of 1 mole,
determine how much acetone evaporated?
(liquid B: 0.33 and 0.67; vapour C: 0.7 and 0.3; 0.42 mol acetone evaporated)
Liquid-liquid equilibrium
3.14. Phenol and water are partially miscible liquids. A mixture consists of phenol and water
has the temperature transition from one phase to two phases as follows:
% phenol 10 20 30 35 40 45 50 55 60 70
o
t ( C) 42 52 60 67 66 65 63 60 50 28
a) If 10 g phenol and 20 g water are put into a closed tube and keep at 60oC. Determine
the number of phases, composition and mass of each phase at the equilibrium.
(2 phases; 30% and 55%; 26 g water phase and 4 g phenol phase)
b) If 20 g of water was added into the tube and keep at 60oC, what will happen?
(two phases -> one phase)
3.15. Water and CCl4 are immiscible liquids. At 25oC, I2 in water has a concentration of 0.0612
g/L in equilibrium with I2 in CCl4 with concentration of 5.202 g/L. Shake well the mixture
consisting of 10 mL I2/CCl4 solution (concentration 3.2 g/L) and 150 ml distilled until
equilibrium. Determine the concentration of I2 in CCl4 phase and I2 in water phase at the
equilibrium.
(2.72 g/L and 0.032 g/L)