Fundamentals of Chemical Engineering Thermodynamics (MindTap Course List)
Fundamentals of Chemical Engineering Thermodynamics (MindTap Course List)
1st Edition
ISBN: 9781111580704
Author: Kevin D. Dahm, Donald P. Visco
Publisher: Cengage Learning
Question
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Chapter 6.6, Problem 23P

(A)

Interpretation Introduction

Interpretation:

The heat added to the gas.

Concept Introduction:

The analogous time-independent form of energy balance for the gas is written as:

Δ{M(U^+V22+gh)}=[min(H^in+Vin22+ghin)mout(H^out+Vout22+ghout)+WS+WEC+Q]

Here, time is t, total mass is M, specific internal energy is U^, velocity is V, acceleration due to gravity is g, height is h, initial mass flow is min, initial specific enthalpy is H^in, initial velocity is Vin, initial height of the gas is hin, final mass flow is mout, final height of the gas is hout, shaft work is added to the system is WS, work is added to the system through expansion or contraction of the system is WEC, and total heat added throughout the process is Q.

(A)

Expert Solution
Check Mark

Explanation of Solution

The analogous time-independent form of energy balance for the gas is written as:

Δ{M(U^+V22+gh)}=[min(H^in+Vin22+ghin)mout(H^out+Vout22+ghout)+WS+WEC+Q]        (1)

Neglecting the potential and kinetic energy for a closed system with no shaft work and no expansion work, equation (1) can be rewritten as:

Δ{N(U_)}=QΔU=Q        (2)

Here, number of moles is N, and molar internal energy is U_.

The equation for the change in internal energy (dU_) is,

dU_=(U_2U_2ig)+(U_2igU_1ig)(U_1U_1ig)U_2U_1=(U_2U_2ig)+(U_2igU_1ig)(U_1U_1ig)        (3)

Here, molar internal energy at state 2 is U_2, molar internal energy at state 1 is U_1, and molar internal energy for an ideal gas state at state 2 and 1 is U_2ig,andU_1ig respectively.

To calculate the residual molar internal energy (U_R),

U_R=U_U_ig=V_=,T=TV_=V_,T=T{T(δP/δT)V_P}dV_        (4)

Here, molar volume is V_, temperature is T, pressure is P, change in pressure and temperature at constant molar volume is (δP)V_,and(δT)V_ respectively.

Partially differentiate the Van der Waals equation to obtain (δP/δT)V_.

P=RTV_baV_2(δP/δT)V_=RV_b

Here, gas constant is R, Van der Waals parameter is a,andb.

Substitute RV_b for (δP/δT)V_, and RTV_baV_2 for P in Equation (4).

U_U_ig=V_=,T=TV_=V_,T=T{T(δP/δT)V_P}dV_=V_=,T=TV_=V_,T=T{T(RV_b)(RTV_baV_2)}dV_=V_=,T=TV_=V_,T=T{aV_2}dV_=aV_

The expression for the change in internal energy (dU_) of an ideal gas is:

dU_=CVdT=CV(T2T1)

Here, constant volume heat capacity for ideal gas is CV, change in temperature is dT, final temperature is T2, and initial temperature is T1.

Substitute 2.5R for CV, 600K for T2, and 300K for T1, 8.314J/Kmol for R.

dU_=CVdTdU_=2.5R(600K300K)dU_=2.5(8.314J/Kmol)(600K300K)U_2U_1=6,235.5J/mol(1kJ/mol/1,000J/mol)=6.235kJ/mol

Substitute 6.235kJ/mol for U_2U_1, aV_ for (U_2U_2ig),and(U_1U_1ig) in Equation (3).

U_2U_1=(U_2U_2ig)+(U_2igU_1ig)(U_1U_1ig)6.235kJ/mol=[aV_]+(U_2igU_1ig)[aV_]6.235kJ/mol=(U_2igU_1ig)

Calculate the change in molar internal energy (ΔU).

ΔU=N(U_2igU_1ig)        (5)

Substitute 10moles for N, and 6.235kJ/mol for (U_2igU_1ig) in Equation (5).

ΔU=10moles(6.235kJ/mol)=62.35kJ

Substitute 62.35kJ for ΔU in Equation (2).

ΔU=Q62.35kJ=Q

The heat added to the gas is 62.35kJ.

(B)

Interpretation Introduction

Interpretation:

The heat added to the container.

(B)

Expert Solution
Check Mark

Explanation of Solution

Rewriting Equation (2):

ΔU=Q=MC^VdT=MC^V(T2T1)        (6)

Here, mass is M, and constant volume heat capacity on mass basis is C^V.

Substitute 10kg for M, 1.5J/gK for C^V, 600K for T2, and 300K for T1 in Equation (6).

ΔU=Q=(10kg)(1.5J/gK)(600K300K)Q=(10kg)[(1.5J/gK)(1,000gkg)](300K)Q=4,500,000J(1kJ/1,000J)Q=4,500kJ

The heat added to the container is 4,500kJ.

(C)

Interpretation Introduction

Interpretation:

The change in entropy of the gas.

Concept Introduction:

The residual entropy (S_R) is given by:

S_R=S_S_ig=RlnZ+V_=,T=TV_=V_,T=T{(δP/δT)V_(R/V_)}dV_

Here, molar volume is V_, temperature is T, change in pressure and temperature at constant molar volume is (δP)V_,and(δT)V_ respectively, and gas constant is R.

(C)

Expert Solution
Check Mark

Explanation of Solution

The equation for the change in entropy (dS_) is:

dS_=(S_2S_2ig)+(S_2igS_1ig)(S_1S_1ig)S_2S_1=(S_2S_2ig)+(S_2igS_1ig)(S_1S_1ig)

Here, molar entropy at state 2 is S_2, molar entropy at state 1 is S_1, and molar entropy for an ideal gas state at state 2 and 1 is S_2ig,andS_1ig respectively.

The residual entropy (S_R) is given by:

S_R=RlnZ+V_=,T=TV_=V_,T=T{(δP/δT)V_(R/V_)}dV_        (7)

Partially differentiate Van der Waals equation to find (δP/δT)V_.

P=RTV_baV_2(δP/δT)V_=RV_b

Here, gas constant is R, Van der Waals parameter is a,andb.

Substitute RV_b for (δP/δT)V_ in Equation (7).

S_S_ig=RlnZ+V_=,T=TV_=V_,T=T{(δP/δT)V_(R/V_)}dV_=RlnZ+V_=,T=TV_=V_,T=T{RV_bRV_}dV_=RlnZ+[Rln(V_b)RlnV_]V=V=V=RlnZ+Rln[V_bV_]

  =Rln[Z+V_bV_]=Rln[P(V_b)RT]

Using Van der Waals expression, calculate the initial volume (V_1).

P1=RT1V_1baV_12

Here, initial pressure is P1.

Substitute 5bar for P1, 83.14barcm3/Kmol for R, 300K for T1, 8×105cm6bar/mol2 for a, and 100cm3/mol for b.

5bar=(83.14barcm3/Kmol)(300K)V_1100cm3/mol8×105cm6bar/mol2V_12V_1=5,057cm3/mol

The number of moles and volume remains constant so this value will also apply at final state. Therefore, the final volume is

V_1=V_2=5,057cm3/mol

The final pressure (P2) can be calculated using the expression:

P2=RT2V_2baV_22

Substitute 5,057cm3/mol for V_2, 83.14barcm3/Kmol for R, 600K for T1, 8×105cm6bar/mol2 for a, and 100cm3/mol for b.

P2=(83.14barcm3/Kmol)(600K)5,057cm3/mol100cm3/mol8×105cm6bar/mol2(5,057cm3/mol)2=10.03bar

Write the expression of the parameter S_2igS_1ig.

S_2igS_1ig=CVln(T2/T1)+Rln(V_2/V_1)

Here, constant volume heat capacity for ideal gas is CV

Substitute 8.314J/molK for R, 600K for T2, 300K for T1, 5,057cm3/mol for V_1,andV_2, 2.5R for CV.

S_2igS_1ig=(2.5R)ln(T2/T1)+Rln(V_2/V_1)S_2igS_1ig={[(2.5)(8.314J/molK)][ln(600K/300K)]+(8.314J/molK)[ln(5,057cm3/mol/5,057cm3/mol)]}=[(2.5)(8.314J/molK)][ln(600K/300K)]+0=14.40J/molK(1kJ/molK/1,000J/molK)=0.0144kJ/molK

The change in molar entropy (dS_gas) of gas is:

dS_gas=S_2S_1=Rln[P2(V_2b)RT2]+S_2igS_1igRln[P1(V_1b)RT1]        (8)

Substitute 8.314J/molK for R, 600K for T2, 300K for T1, 5,057cm3/mol for V_1,andV_2 respectively, 5bar for P1, 100cm3/mol for b, 10.03bar for P2, and 0.0144kJ/molK for S_2igS_1ig in Equation (8).

dS_gas={(8.314J/molK)ln[10.03bar(5,057cm3/mol100cm3/mol)(8.314J/molK)(600K)]+(0.0144kJ/molK)(8.314J/molK)ln[5bar(5,057cm3/mol100cm3/mol)(8.314J/molK)(300K)]}={(8.314J/molK)ln[10.03bar(4,957cm3/mol)(4,988.4J/mol)]+(0.0144kJ/molK)(8.314J/molK)ln[5bar(4,957cm3/mol)(2,494.2J/mol)]}=0.0144kJ/K

The change in entropy (ΔS) of gas is calculated by using the expression,

ΔSgas=N(dS_gas)

Substitute 10moles for N, and 0.0144kJ/K for dS_gas.

ΔSgas=10moles(0.0144kJ/K)=0.144kJ/K

Hence, the change in entropy (ΔSgas) is 0.144kJ/K.

(D)

Interpretation Introduction

Interpretation:

The change in entropy of the universe.

Concept Introduction:

The formula to calculate the change in entropy of the universe (ΔSuniverse) is given by:

ΔSuniverse=ΔSgas+ΔScontainer+ΔSfurnace

Here, change in entropy of the gas is ΔSgas, change in entropy of the container is ΔScontainer, and change in entropy of the furnace is ΔSfurnace.

Write the expression of the change in entropy of the container (ΔScontainer).

ΔScontainer=dQrevT

Here, change in reversible heat is dQrev.

(D)

Expert Solution
Check Mark

Explanation of Solution

The formula to calculate the change in entropy of the universe (ΔSuniverse) is given by:

ΔSuniverse=ΔSgas+ΔScontainer+ΔSfurnace        (9)

Write the expression of the change in entropy of the container (ΔScontainer).

ΔScontainer=dQrevT        (10)

Substitute MC^VdT for dQrev in Equation (10).

ΔScontainer=MC^VdTT        (11)

Integrating Equation (11), we get,

ΔScontainer=T1T2MC^VTdT=MC^Vln(T2/T1)        (12)

Here, mass is M.

Substitute 10kg for M, 1.5J/gK for C^V, 600K for T2, and 300K for T1 in Equation (13).

ΔScontainer=(10kg)(1.5J/gK)[ln(600K/300K)]=(10kg){(1.5J/gK)(1,000g/1kg)(1kJ/1,000J)}[ln(600K/300K)]=10.39kJ/K

Assuming the furnace as a heat reservoir, calculate the change in entropy of the furnace (ΔSfurnace)

ΔSfurnace=QfurnaceT        (13)

Here, heat added or removed from furnace is Qfurnace.

The heat added or removed from furnace (Qfurnace) is given by the expression:

Qfurnace=(Qgas+Qcontainer)        (14)

Here, heat added or removed from gas and container is Qgas,andQcontainer respectively.

Substitute 62.35kJ for Qgas, and 4,500kJ for Qcontainer in Equation (14).

Qfurnace=(62.35kJ+4,500kJ)=4,562.35kJ

Substitute 4,562.35kJ for Qfurnace, and 600K for T in Equation (13).

ΔSfurnace=QfurnaceT=4,562.35kJ600K=7.6039kJ/K

Substitute 0.144kJ/K for ΔS_gas, 10.39kJ/K for ΔScontainer, and 7.6039kJ/K for ΔSfurnace in Equation (9).

ΔSuniverse=ΔSgas+ΔScontainer+ΔSfurnace=0.144kJ/K+10.39kJ/K+(7.6039kJ/K)=2.930kJ/K

The change in entropy of the universe (ΔSuniverse) is 2.930kJ/K.

(E)

Interpretation Introduction

Interpretation:

What aspect of this process is irreversible?

(E)

Expert Solution
Check Mark

Explanation of Solution

The large variation between the initial and final temperature is the irreversible aspect of this process.

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