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CAMPUS ESTADO DE MEXICO IQ2003.1 Equilibrium Thermodynamics Dr.

Ricardo Macas-Salinas
EXAMPLE PROBLEMS PRIOR THE FIRST PARTIAL EVALUATION

Problem 1. The vapor pressures of solid & liquid chlorine are given by ln P s= 24.320 ln P l =17.892 3777 T 2669 T

where P is the pressure in torr & T is the absolute temperature in K. Calculate the temperature & pressure at the triple point of chlorine Problem 2. Draw the phase diagram for oxygen using the following data: triple point = 54.3 K & 1.14 torr; critical point = 154.6 K & 37,828 torr; normal melting point = -218.4 C; and normal boiling point = -182.9 C. Hints: (1) normal conditions refer to 1 bar or 750.1 torr, (2) plot ln (P) versus T Problem 3. How many degrees of freedom has each of the following systems? (a) Liquid water in equilibrium with its vapor, (b) liquid water in equilibrium with a mixture of water vapor & nitrogen, and (3) a liquid solution of alcohol in water in equilibrium with its vapor Problem 4. A non-spontaneous process is a reversible one, false or true? Explain Problem 5. Draw the phase diagram for I2 using the following data: triple point = 113 C & 0.12 atm; critical point = 512 C & 116 atm; normal melting point = 114 C; and normal boiling point = 184 C. Hint: normal conditions refer to 1 atm.

Problem 6. The vapor pressure of methanol along the entire liquid-vapor coexistence curve can be expressed very accurately by the empirical equation: ln P = 16.758207 10.752849 3.603425 x 4.373232 x 2 2.381377 x 3 4.572199 1 x 1.7 x

where P is the pressure in bar, x = T / Tc and Tc = 512.6 K. Use this formula to show that the normal boiling point of methanol is 337.67 K. Problem 7. A system comprised of chloroform, 1,4-dioxane, and ethanol exists as a two-phase vaporliquid system at 50 C & 55 kPa. How many phase-rule variables in addition to T & P must be chosen so as to determine the composition of the two phases at equilibrium? Problem 8. Explain why an spontaneous process is irreversible, give an example

CAMPUS ESTADO DE MEXICO IQ2003.1 Equilibrium Thermodynamics Dr. Ricardo Macas-Salinas


SOLUTIONS

Problem 1. At the triple point, the two equations for the vapor pressure must be equivalent, since the solid and liquid coexist. Then: 24.320 3777 2669 =17.892 T tp T tp

24.320 17.892 T tp=2669 3777 T tp


T tp= 172.4 K

We can check this by substituting back into both expressions, and we find that ln P s= ln P l = 2.41 torr and therefore P tp =11.1 torr

Problem 2. We can use the triple point (TP) & the normal melting point (NMP) to construct the liquidsolid line and the triple point ( TP), normal boiling point (NBP), and the critical point (CP) to construct the liquid-gas line. The liquid-gas line stops at the critical point. We produce the following diagram:

CP liquid NBP gas

NMP solid TP Problem 3.

(a) The system contains a single component existing as two phases (one liquid & one vapor), thus: F = 2 + N = 2 2 + 1= 1 (b) In this case, two components are present (the addition of an inert gas to the system of water in equilibrium with its vapor changes the characteristics of the system). Again, there are two phases, thus: F = 2 + N = 2 2 + 2 =2 (c) Here N = 2 & number of phases = 2, thus: F = 2 + N = 2 2 + 2 =2

Problem 4. True, because a process is reversible when its direction can be reversed at any point by an infinitesimal change in external conditions, therefore a spontaneous process cannot be reversed.

Problem 5. We can use the triple point (TP) & the normal melting point (NMP) to construct the liquidsolid line and the triple point ( TP), normal boiling point (NBP), and the critical point (CP) to construct the liquid-gas line. The liquid-gas line stops at the critical point. We produce the following diagram:

CP

liquid solid

gas NBP

NMP

TP

Problem 6. At the normal boiling point, P = 1 atm = 1.01325 bar. If the normal boiling point of methanol is 337.67 K, then the equality below should hold when x = 337.67 / 512.6: ln ( 1.01325)=16.758207 10.752849 2 3 1.7 3.603425 x + 4.373232 x 2.381377 x + 4.572199 ( 1 x ) x

0.013163 16.758207 16.758207 2.373719 + 1.897712 0.680722+ 0.735141 therefore 0.013163 0.013163

Problem 7. The system contains three components existing as two phases (one liquid & one vapor), thus: F = 2 + N = 2 2 + 3= 3 therefore, in addition to T & P we must choose one more variable.

Problem 8. A spontaneous process is a real one; it cannot be reversed at any point due to an infinitesimal change in external conditions, therefore such a process is irreversible. Good examples of irreversible processes include: (1) friction, (2) unrestrained expansion, (3) mixing of two gases, (4) chemical reactions, etc.

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