Name:

SID:

GSI/Section:

Chemical Engineering 141: Thermodynamics Spring 2013

Tuesday, April 2nd, 2013 Midterm 2 70 minutes 115 points total Use of phone devices is not permitted Return your equation sheets with the exam Show your work

Problem 1 30 points total

Problem 2 35 points total

Problem 3 50 points total

Total Exam Score

1. Steam is initially (state 1) at T = 100 C and P = 0.5 atm. The saturation pressure of steam at this temperature is 1 atm. Then, the pressure is isothermally increased to P = 50 atm (state 2). Assume that the steam obeys the following equation of state Z = 1 + BP/RT with B = 10 L/mol. The molar volume of liquid water is 18 cm3/mol. Gas constant R = 0.08206 L*atm/mol*K (a) Below is the P-T phase diagram for water. On the graph, identify the phases and the initial and final states 1 and 2.

Final

Initial

A sublimation/deposition curve B fusion/melting curve C evaporation/condensation curve D triple point E critical point

(b) What is the fugacity of the system at the final state?

ln ! = ln ! =

"

P 0

( Z ! 1)

dP BP where Z = 1 + P RT

BP RT At the point where the steam is in equilibrium with liquid water BP sat ln ! sat = RT sat ! =1.386 Now, as the pressure continues to increase, we need to use the Poynting factor. We assume that the liquid phase molar volume is a very weak function of P in this temperature range and can obtain the following expression: " V ( P ! P sat ) % sat sat fwater ( P = 50 atm ) = P ! water exp $ ' RT # & fwater = 1.426 atm

(c) If the saturation pressure of steam at 120 C is 1.96 atm, calculate the !H the information provided in this problem? Clearly state your assumptions.

vap

of water given

R = 8.314 J/mol*K dP sat !H lv = dT T !V lv Assume molar volume of liquid is negligible compared to molar volume of gas. ( !V lv ~ V v ) RT Assume vapor behaves as an ideal gas ( V v = sat ) P
dP sat !H lv !H lv = = dT TV v T " RT % $ sat ' #P & sat lv dP !H = dT sat P RT 2 "H lv # 1 & d (ln P sat ) = ! d% ( R $T '

# & % sat sat ( d (ln P ) ln P " ln P1 ( !H lv = " R = "R% 2 1 1 d (1 / T ) % ( " % ( T T $ ' 2 1 # & J % ln(1.96 atm ) " ln(1atm ) ( lv !H = "8.314 = 41 kJ/mol 1 1 ( mol * K % " $ 393K 373K '
sat

More rigorous method of solving:

dP sat !H lv = dT T !V lv

Assume molar volume of liquid is negligible compared to molar volume of gas. ( !V lv ~ V v ) Molar volume of vapor can be found from Z = 1 + BP/RT. V = RT/Psat + B dP sat !H lv = " RT % dT T $ sat + B ' #P & lv Re-arrange to get !H on one side " RT 2 % dP sat RT 2 dP sat dP sat !H lv = $ sat + BT ' = sat + BT P dT dT #P & dT Pull in the P and T terms where you can d (ln P sat ) dP sat lv !H = " R +B d (1 / T ) d (ln T ) Plug in the two points you know: (1 atm, 373K) and (1.96 atm, 393K)

ln P2sat " ln P1sat P2sat " P1sat !H = " R +B 1 " 1 ln T2 " ln T1 T2 T1

lv

!H lv = "8.314

J ln(1.96 atm ) " ln(1atm ) L 1.96 atm " 1atm 100 J + 10 * 1 1 mol * K mol ln 393K " ln 373K 0.987 L * atm " 393K 373K

!H lv = 41 kJ/mol + 18.6 kJ/mol = 59.6 kJ/mol

2. A student wanted to make 100 mL of a 25% by volume ethanol solution in water, so he combined 25 mL of pure ethanol with 75 mL of water. The molar volume of a water-ethanol mixture at 25C can be described by the equation:

V = a * (xethanol) + b * xethanol + c

where xethanol is the mole fraction of ethanol in the solution. The density of ethanol is 0.789 g/mL and its molecular weight is 46 g/mol. The density of water is 1 g/mL and its molecular weight is 18 g/mol.

(a) (15 points) At 25C, a solution with xethanol = 0.3 has a molar volume of 28.3 mL/mol. Use this additional information to determine the values of a, b and c in the equation above.

(b) (5 points) Draw the molar volume of the water-ethanol mixture in the V-xethanol graph below, and show the: (i) Molar volume of the students solution (Vsolution) (ii) Molar volume of pure ethanol and water (Vethanol, Vwater) (iii) Partial molar volume of ethanol in the students solution

!"

#"

(c) (10 points) Calculate the partial molar volume of ethanol and water after the student combined 25 mL ethanol and 75 mL water.

After substitution and simplification:

! !! = !!! + 2!!! + ! + ! ! !! = !!! + ! x1=xethanol

 Using these expressions and the values derived in part a:

(d) (5 points) Calculate the final total volume of the solution after the student combines 25 mL ethanol and 75 mL water.

!"

#"

Can also be calculated from: Vt= n*V Vt= (4.16 mol +0.42 mol)*(21 mL/mol) Vt= 96 mL

 3. You have a refrigeration system that operates via the vapor compression cycle, with the evaporator operating at -20C and the condenser at 40C. Ammonia is used as the refrigerant. A data table and a chart are provided for the properties of ammonia. If any interpolation is required, please show work. When using the graph, make sure your thought-process is evident.

(a) Draw the cycle on a P vs. H diagram and label H1, H2, H3, and H4. Label the y-axis with the pressures of the condenser and the evaporator.

(b) Determine the COP. Assume the compressor functions adiabatically and reversibly.

(c) Calculate the required refrigerant flow rate for 1 ton of refrigeration. 1 ton of refrigeration = 3.517 kW (kW [=] kJ/s).

(d) Calculate the compressor power (kW) requirement at this flow rate.

(e) When the temperature difference between the condenser and the evaporator is large (i.e. when freezing rather than refrigerating), the use of a flash tank becomes beneficial. The vapor compression cycle with a flash tank is shown below.

Saturated liquid exiting the condenser (at the pressure of the condenser found in part A) is throttled to 529 kPa in the flash tank, at which point some of the liquid is converted to vapor. This vapor can no longer be of use in the evaporator. Thus, exiting the flash tank we have two streams: a saturated liquid stream and a saturated vapor stream, both at 529 kPa. The saturated vapor (2) is compressed by a secondary compressor to the pressure of the condenser, where it joins the stream exiting the primary compressor. The saturated liquid (4) is throttled to the evaporator pressure (found in part A), at which point it enters the evaporator. The mass flow rates are 0.000511 kg/s through the secondary compressor and 0.00285 kg/s through the primary compressor. Draw and label the modified vapor compression cycle on a P vs. H diagram. If values remain the same, use the same labels as in part A. Use H1, H2, H3, and H4 for any new values in the altered cycle. Label the y-axis with numerical pressure values.

(f) Calculate the COP for the altered cycle. Assume the compressors function adiabatically and reversibly.

(g) Determine the overall power requirement for the altered cycle.

(h) What are some of the advantages and disadvantages of using a flash system?