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Chemical Engineering 141: Thermodynamics Spring 2013

Tuesday, February 26th, 2013 Midterm 1 80 minutes 110 points total Use of phone devices is not permitted Return your equation sheet with the exam 1. (22 points) A gas obeys the following equation of state: P(V-b) = RT, b = 0.05 L/mol For your reference: R = 0.08314 L*bar/mol*K = 8.314 J/mol*K a) (9 points) Calculate the work per mole required to perform a reversible isothermal compression from state (1) to state (2) as specified below: P1 = 20 bar T1 = 400 C V2 = 0.2*V1 1. P(V-b) = RT P1 = 20 bar T1 = 400 C V1 = ? T1 = T2 = 400 C = 673K
RT RT V= + b V1 = 1 + b = P P1
0.08314 L * bar * 673K mol * K = 2.85 L/mol + 0.05 L mol 20 bar

P2 = ? T2 = 400 C V2 = 0.2V1

V2 = 0.2V1 = 0.2 * 2.85L / mol = 0.57 L / mol

L * bar 0.08314 * 673K RT2 mol * K =107.6 bar P2 = = L L V2 ! b (0.57 ! 0.05 ) mol mol !W = ! PdV
W = ! " P dV

Two ways to proceed

W = ! " P dV = ! "
V1 V2 V2 V1 V2 !b RT RT dV = ! " d (V ! b) V1 !b V !b V !b

"V ! b % W = ! RT ln $ 2 ' = 9420 J/mol # V1 ! b &

or

# RT & #1& # !1 & W = ! " P dV = ! " Pd % + b ( = ! " RTPd % ( = ! " RTP % 2 ( dP $ P ' $P' $P '
dP = RT ln( P2 / P1 ) = 9415 J/mol P 1 P b) (13 points) Calculate the work per mole required to perform an irreversible isothermal compression in a real piston that requires an additional pressure of 1 bar to overcome the effect of friction. !P = 1 bar Pext = P + !P W = RT !
P2

!W = ! Pext dV

!W = !( P + "P )dV
V2

Two ways to proceed

W = ! # ( P + "P ) dV = ! # P dV !
V1 V2 V1

V2 V1

"P dV

! " P dV = 9420 J/mol (answer from part a)

! # "P dV = !"P(V2 ! V1 ) = !(1bar )(0.57 ! 2.85L / mol )*

V1

V2

100 J = 228 J/mol L * bar

W = 9420 + 228 J/mol = 9648 J/mol or

$ RT ' W = ! # ( P + "P ) dV = ! # ( P + "P )d & + b) % P ( #1& # !1 & W = ! ) RT ( P + "P )d % ( = ! ) RT ( P + "P ) % 2 ( dP $P' $P '
P2 # 1 & dP + ! RT ("P ) % 2 ( dP P 1 $P ' P W = RT [ln( P2 / P1 ) + !P(1 / P2 " 1 / P1 )]

W=

P2

P 1

RT

W = 8.314

! 107.6 bar $ ! J 1 1 $ * 673K [ln # ' & ' 1bar # & = 9643 J/mol " 20 bar % " 107.6 bar 20 bar % mol * K

2. (23 points) Someone in lab left the valve of a pressured gas cylinder (10 atm) slightly open, allowing the gas inside to flow slowly into the room (1 atm). At this low flow rate, the rate of heat transfer with the surroundings is assumed to be fast, and the expansion process can be assumed to be isothermal, with the gas at a temperature of 300K. The gas follows the equation of state Z=1+BP/RT, with B=10 J/mol*atm. a) (10 points) Find the change in molar enthalpy of the gas as it expands isothermally into the room.

b) (8 points) Find the change in molar entropy of this process.

c) (5 points) A Mollier diagram plots entropy vs. enthalpy and could provide information that relates (a) and (b). Derive the slope of an isotherm on a Mollier diagram.

or

3. (35 points) Consider a cycle that consists of the following reversible processes, using 1 mol of an ideal gas as the working fluid: (i) Adiabatic compression from state (1) to state (2) (ii) Constant-volume heating from state (2) to state (3) (iii) Adiabatic expansion from state (3) to state (4) (iv) Constant-volume cooling from state (4) to state (1) a) (5 points) Draw the paths qualitatively on the P-V diagram below. Label each state (1), (2), (3), and (4) according to the description above. Also show the flows of heat, QH and Qc on the diagram.

b) (10 points) Calculate the values of QH, Qc, W1->2 and W3->4

c) (10 points) Show that: !! = !!

! !

Solution 1:

Solution 2:

d) (10 points) Show that the thermal efficiency of this cycle is: ! = 1 !!
!

4. (30 points) A gas is contained in a balloon at 5 atm. The balloon suddenly bursts such that the gas inside is released quickly, resulting in a change in temperature from 298K to 323K. Cv of the real gas is 1.5R and is independent of temperature. The following correlations and data can be used to predict PVT behavior of a real gas: ! = ! ! + !!! ! ! ! ! = 1 + !! !! !! = !! !! ! ! 0 . 5 0.2 !! = 0.1 ! !! = 0.1 ! !! !! !! ! ! !" ! !! = !!! ( )!! !!! !!! !! ! where Tc = 150K, Pc = 25 atm, and = 0.1 a) (10 points) What is the change in molar enthalpy of this process if the gas is assumed to be ideal?

b) (20 points) The change in molar enthalpy of this process for a real gas is 566.9 J/mol. Determine the final pressure of the real gas.