MIDTERM EXAMINATION (FALL 2009)

QUESTION 2 (21 Marks) The table on the right provides vapour liquid equilibrium data for an unknown pure Substance X. It has a critical temperature and pressure of 325 K and 5 MPa respectively. The critical density is 0.1 kg/m3. Use the data provided to answer the questions below. Vapour Pressure (MPa) 0.2 2 4 T (K) 205 250 300 VL VV 3 (m /kg) (m3/kg) 2 40 3 25 5 15

(a) Draw a P-V phase diagram. Be sure to include the isotherms, and label the liquid, vapour, gas and two-phase regions, critical point, as well as the bubble and dew point curves. P, MPa

Gas Bubble 5 point curve 4 3 2 1 Liquid Dew point curve Vapour

300 K 275 K 250 K

205 K 5 10 15 20

Liquid-Vapour 25 30 35 40 V, m3/kg

(b) What is the mass (in kg) of 1 m3 of Substance X at a temperature of 250 K and a pressure of 1.99 MPa? What about the mass (in kg) of 1 m3 of substance X at 250 K and 2.01 MPa? 1m3 = 0.333 kg At P = 2.01 MPa, T = 250 K, there is only liquid. V 3 m3/kg: m X = 3 m3 /kg

1m3 = 0.04 kg At P = 1.99 MPa, T = 250 K, there is only vapor. V 25 m /kg: m X = 25 m3 /Kg (c) Substance X is maintained at a temperature of 275 K and a pressure of 2 MPa.
3

(i) What is the vapour pressure (in MPa) of Substance X under these conditions? 1 At T=275 K (blue dashed isotherm), the vapour pressure is 3 MPa

(ii) If specific volume is isobarically decreased to 10 m3/kg, what is the new equilibrium temperature? Isobaric indicates that pressure remains constant. At V = 10 m3/kg and P = 2 MPa, T = 250 K (d) A mass of 1 kg of Substance X occupies a volume of 9.95 m3 at a temperature of 340 K. (i) Name each phase present.

Since T > Tc, the only phase present is a gas. (ii) The temperature of Substance X is decreased while maintaining a constant specific volume. Estimate the pressure (in MPa) at which a new phase will appear. What is this new phase?

9.95 m3 m3 = 9.95 . If you decrease T while holding V constant, you will see a phase 1 kg kg change once you hit the critical isotherm. Since you are located to the left of the critical point (because your specific volume is less than the critical specific volume), and the critical isotherm in this region goes up and to the left relative to the critical point, the pressure in the system will be just slightly greater than 5 MPa. Since the specific volume is lower than the critical specific volume, the new phase will be a liquid. V=
(e) 1 kg of Substance X is held at 300 K. The volume occupied is 10 m3. (i) What is the system pressure (in MPa) under these conditions? 1

10 m 3 m3 = 10 V= 1 kg kg
At this specific volume and a temperature of 300 K, the pressure will be 4 MPa. (ii) What is the mass (in kg) of the liquid phase under these conditions?

L VL = 5 m3 /kg Vmix = 10 m3 /kg

V VV = 15 m3 /kg

Short answer: Since Vmix is exactly in between VL and VV, half of the contents should be liquid and half should be vapour. Thus mass of liquid = (1 kg)/2 = 0.5 kg. Long answer: Use the lever rule. mL = mTotal
VV Vmix VV VL
m3 kg m3 (155) kg

= (1 kg)

(1510)

= 0.5 kg

(iii) The pressure of Substance X is isothermally decreased to 2.0 MPa. Name the phase(s) present at equilibrium.

The only phase present will be a vapour phase

(f) How many degrees of freedom remain at the critical point? Explain your answer. 1 F=CP+2 C = 1 (pure substance) P = 2 (liquid and vapour)

F = 1 2 + 2 = 1. However, you are constrained by the fact that the density of the liquid and vapour phases vary infinitesimally at the critical point (essentially, L=V). This uses up the final degree of freedom. Thus, the degrees of freedom remaining are zero. (g) A rigid cylinder with a volume of 0.15 m3 contains a total of 10 g of liquid and vapor at equilibrium. The vapor phase specific volume is 25 m3/kg. (i) What is the temperature and pressure of Substance X in the cylinder? 1 The only place where a vapour and liquid can exist at equilibrium, with the specific volume of the vapour phase equaling 25 m3/kg is at T = 250 K and P = 2 MPa. (ii) 2.5 g of Substance X isothermally leaks out from the cylinder before the leak is fixed. What is the system pressure (in MPa) at this new condition? If some of the substance leaks out, the total mass in the vessel will decrease, causing the overall specific volume in the vessel to increase. m new = 10 g 2.5 g = 7.5 g = 0.0075 kg

Vnew =

0.15 m3 m3 = 20 0.0075 kg kg

Since the leak occurred isothermally, you will still be in the two phase region, and your pressure will remain at 2 MPa. (iii) The cylinder described in (g)(ii) starts to leak again until only vapour remains in the cylinder. If the temperature remains constant during this entire process, calculate the mass (in g) of Substance X remaining in the cylinder at equilibrium. 2 Since the temperature remains constant during this new leak, you will be moving along the T = 250 K isotherm. If the leak continues until only vapour is left, this means the specific volume in the container will be on the dew point curve at 25 m3/kg. The volume of the cylinder = 0.15 m3 Thus, the mass inside the cylinder at this condition is:

 3 0.15 m 1000 g = 6g mass = m3 1 kg 25 kg

QUESTION 3 (20 Marks) You are provided with a Solid-Liquid phase diagram (P = 1 atm) for binary mixtures of components A and B. Component A has a molar mass of MA=20 kg/kmol and component B has a molar mass of MB=60 kg/kmol. Use the information provided to answer the questions below:

(a) What are the melting points of pure A and pure B? 2 Melting point of component A = 900C Melting point of component B = 800C (b) Are A and B completely miscible, partially miscible or immiscible? 1 Partially Miscible

(c) A mixture consisting of 3 kg of A and 12 kg of B is held at a temperature of T = 1000C. Name the phases present and their corresponding masses. 2

 12 kg Mass of B mass percent B in mixture = (100 % ) = 3kg + 12kg (100% ) = 80% Total Mass of mixture At this composition and T=1000oC, you would have 15 kg of liquid.

(d) The mixture in part (c) is cooled to a new equilibrium temperature of T = 600C. (i) Name the phases present. 1 L + S2 (ii) 1 State the mass composition of each phase present. Mass composition of the liquid phase: 60 mass% B Mass composition of the S2 phase: 86 mass% B

(iii) Determine the mass (in kg) of the solid phase present under these conditions. 2 In order to solve this, you need to use the lever rule L xL = 0.6 xmix = 0.8 S2 xS2 = 0.86

mS2 = mTotal xmixx L = (15 kg) 0.860.6 = 11.54 kg

S2 L

0.80.6

(iv) Determine the molar composition of the solid phase present under these conditions. 3 Total Mass of solid phase = 11.54 kg Mass of component A in solid phase = (0.14)(11.54 kg) = 1.616 kg Mass of component B in solid phase = (0.86)(11.54 kg) = 9.924 kg

Moles of component A in the solid phase = (1.616 kg)/( 20 kg/kmol) = 0.0808 kmol Moles of component B in the solid phase = (9.924 kg)/(60 kg/kmol) = 0.1654 kmol Therefore molar composition of the solid phase:
0.0808 kmol Moles of A mol % A in mixture = (100 % ) = (100% ) = 33% Total Moles 0.0808 kmol 0.1654 kmol +

Therefore mol% B in the mixture = 100% - 33% = 67% (e) Determine the minimum mass (in kg) of component A that needs to be added to the mixture described in part (c) in order to ensure that only a liquid exists in the vessel at 600oC. 3 In this case, we are being asked, how much component A needs to be added to reach a mixture composition of 60 mass % B, which is the minimum amount of A that needs to be added to the mixture described in part (c) so that only a liquid exists at 600oC. Initial conditions: Mass of A = 3 kg Mass of B = 12 kg Assume that you add P kg of component A to the mixture Mass of A = (3+P) kg Mass of B = 12 kg Mass composition of mixture = 60 mass% B.

Add: Final Conditions:

Mass of B (100 % ) = 60% Total Mass

12 kg (3 + P) kg +12 kg (100 % ) = 60%

Solving for P: P = 5 kg. Thus, 5 kg of component A must be added to the mixture

(f) For the mixture described in part (e), you drop the temperature to the eutectic temperature. Calculate the degrees of freedom remaining at this point (explain your answer). 2 Eutectic temperature is 500 K. F = C-P+2 Therefore F = 2-3+2 = 1 C=2 P=3

However, you have used one 1 degree of freedom by fixing the pressure at P = 1 atm Thus, the actual degrees of freedom remaining is zero. (g) For the mixture described in part (f), list the composition of each phase present. 3 Liquid composition: S1 composition: S2 composition: 50 mass% component A, 50 mass% component B 80 mass% component A, 20 mass% component B 30 mass% component A, 70 mass% component B