Office Use Only

Monash University

Semester One 2008 Examination Period

Faculty Of Engineering

EXAM CODES: CHE 3161

TITLE OF PAPER: Chemistry and Chemical Thermodynamics - PAPER 1

EXAM DURATION: 3 hours writing time

READING TIME: 10 minutes

THIS PAPER IS FOR STUDENTS STUDYING AT:( tick where applicable)

 Berwick  Clayton  Malaysia  Off Campus Learning  Open Learning
 Caulfield  Gippsland  Peninsula  Enhancement Studies  Sth Africa
 Pharmacy  Other (specify)

During an exam, you must not have in your possession, a book, notes, paper, calculator, pencil case, mobile
phone or other material/item which has not been authorised for the exam or specifically permitted as noted
below. Any material or item on your desk, chair or person will be deemed to be in your possession. You are
reminded that possession of unauthorised materials in an exam is a discipline offence under Monash Statute 4.1.

No examination papers are to be removed from the room.

AUTHORISED MATERIALS

CALCULATORS  YES  NO

OPEN BOOK  YES  NO

SPECIFICALLY PERMITTED ITEMS  YES  NO

if yes, items permitted are:

DETAILED ANSWERING INSTRUCTIONS are listed on page 2

Candidates must complete this section if required to write answers within this paper

STUDENT ID __ __ __ __ __ __ __ __ DESK NUMBER __ __ __ __

1
 CHE 3161 (JUN 08)

Answering Instructions for Candidates

1. Attempt all questions

2. Marks for each question are indicated

3. A list of formulae used in the course is appended at the end

4. The data below should be used wherever relevant

R = 8.3143 J mol-1 K-1 = 83.143 cm3 bar mol-1 K-1

2
 CHE 3161 (JUN 08)

Question 1. (20 Marks)

Storage is required for 35,000 kg of propane, received as a gas at 10°C and 1 atm. Two modes of
storage are proposed:

I: Store it as a gas at 10°C and 1 atm

II: Store it as a liquid in equilibrium with its vapour at 10°C and 6.294 atm. For this mode of
storage, 90% of the tank volume is occupied by liquid.

(a) For proposal I, estimate the volume of gas using the two-term virial expansion form of the
Lee/Kesler generalized correlation.

(b) For proposal II, estimate the molar volume of the liquid using the Rackett equation, and the
molar volume of the gas using the two-term virial expansion form of the Lee/Kesler
generalized correlation. Estimate the total volume of the storage tank necessary under this
proposal.

(c) Based on your calculations, briefly discuss the pros and cons of the two proposals.

Data for propane:

Mw = 44.097 g/mol, ω = 0.152, Tc = 369.8 K,

Pc = 42.48 bar, Zc = 0.276, Vc = 200.0 cm3 mol-1,
Tn = 231.1 K

3
 CHE 3161 (JUN 08)

Question 2. (20 Marks)

A reversible cycle executed by 1 mol of an ideal gas for which CP = (5/2) R and CV = (3/2) R
consists of the following:

• Starting at T1 = 700 K and P1 = 1.5 bar, the gas is cooled at constant pressure to T2 = 350 K.

• From 350 K and 1.5 bar, the gas is compressed isothermally to pressure P3.

• The gas returns to its initial state along a path for which P T = constant.

(a) Calculate the amount of work and heat transferred in each path.

(b) Calculate the thermal efficiency of the cycle. Note that the thermal efficiency is defined as
the ratio of the net work to the heat input into the cycle.

4
 CHE 3161 (JUN 08)

Question 3. (20 Marks)

Estimate the bubble temperature of a binary liquid mixture of n-pentane (1) and n-heptane (2) at
760 Torr if the liquid composition is given by x1 = 0.4 and x2 = 0.6. Also determine the composition
of the vapour which is in equilibrium with the liquid. The vapour pressures of n-pentane (1) and n-
heptane (2) are given by the Antoine equation,
B
log10 P sat [Torr] = A " o
t [ C] + C
where the parameters values for the two components are listed in the Table below.
A B C
!
n-Pentane (1) 6.87632 1075.780 233.205
n-Heptane (2) 6.89386 1264.370 216.640

Assume the mixture obeys Raoult’s law.

5
 CHE 3161 (JUN 08)

Question 4. (20 Marks)

The van Laar constants for the system methanol (1) – benzene (2) are given by A = 2.2643 and B =
1.7023. Predict t-x-y data for the system at 730 Torr and compare with the following set of
experimental VLE data:

t (°C) x1 y1
59.72 0.1240 0.4945
56.39 0.5290 0.6070

Note that the van Laar equations are:

A B
ln "1 = 2
; ln " 2 =
# A x1 & # B x 2 &2
%1+ ( %1+ (
$ B x2 ' $ A x1 '

The vapour pressures of methanol (1) and benzene (2) are given by the Antoine equation,
! B
log10 P sat [Torr] = A " o
t [ C] + C
where the parameters values for the two components are listed in the Table below.
A B C
!
Methanol (1) 8.08097 1582.271 239.726
Benzene (2) 6.87987 1196.760 219.161

6
 CHE 3161 (JUN 08)

Question 5. (20 Marks)

For the catalytic dehydrogenation of 1-butene to 1,3 butadiene,

C4 H 8 (g) " H 2 (g) + C4 H 6 (g)

carried out at 900 K and 1 bar and with a ratio of 10 mol of steam per mole of 1-butene, determine
!
the extent of reaction at equilibrium. Also determine the extent of reaction in the absence of steam.
Ideal gas behaviour can be assumed for the gas mixture, and the heat of reaction can be assumed to
be independent of temperature.

Thermochemical Data on Enthalpies and Free energies of Formation:

C4H8 C4H6 H2
!G of 298 [kJ/mol] 72.503 149.02 0

!H of 298 [kJ/mol] -0.1992 110.1 0

7
 CHE 3161 (JUN 08)

CHEMISTRY & CHEMICAL THERMODYNAMICS

CHE3161

AIDE-MÉMOIRE

dW = −P dV t

Z V2t
W =− P dV t
V1t

∆U = Q + W

dU = dQ + dW

F = 2−π+N

H =U +P V

 
∂U
CV ≡
∂T V

 
∂H
CP ≡
∂T P

  
d(mU)cv 1 2
+∆ H + u + zg ṁ = Q̇ + Ẇ
dt 2 fs

 
1 ∂V
β≡
V ∂T P

8
 CHE 3161 (JUN 08)

 
1 ∂V
κ≡−
V ∂P T

P V = RT

CP = CV + R

PV
Z≡
RT

RT a
P = − 2
V −b V

RT a(T )
P = −
V − b (V + ǫb)(V + σb)

α(Tr ) R2 Tc2
a(T ) = Ψ
Pc

RTc
b=Ω
Pc

EOS α(Tr ) σ ǫ Ω Ψ Zc
vdW 1 0 0 1/8 27/64 3/8
−1/2
RK Tr 1 0 0.08664 0.42748 1/3
SRK αSRK (Tr , ω) 1√ 0√ 0.08664 0.42748 1/3
PR αP R (Tr , ω) 1 + 2 1 − 2 0.07779 0.45724 0.30740

2
αSRK (Tr , ω) = 1 + (0.480 + 1.574ω − 0.176ω 2) 1 − Tr−1/2


2
αP R (Tr , ω) = 1 + (0.37464 + 1.54226ω − 0.26992ω 2) 1 − Tr−1/2


9
 CHE 3161 (JUN 08)

RT a(T ) V −b
V = +b−
P P (V + ǫb)(V + σb)

Z −β
Z = 1 + β − qβ
(Z + ǫβ)(Z + σβ)

Pr
β=Ω
Tr

Ψ α(Tr )
q=
Ω Tr

Z = Z 0 (Tr , Pr ) + ω Z 1 (Tr , Pr )

BP
Z =1+
RT

BPc
= B0 + ω B1
RTc

Pr
Z 0 = 1 + B0
Tr

Pr
Z 1 = B1
Tr

0.422
B 0 = 0.083 −
Tr1.6

0.172
B 1 = 0.139 −
Tr4.2

0.2857
V sat = Vc Zc(1−Tr )

10
 CHE 3161 (JUN 08)

CPig
= A + B T + C T 2 + D T −2
R

Z T2
∆H = CPig dT
T1

∆H B C 1 1
= A (T2 − T1 ) + (T22 − T12 ) + (T23 − T13 ) − D ( − )
R 2 3 T2 T1

CPig mixture = yA CPig A + yB CPig B + yC CPig C + · · ·

dP sat
∆H = T ∆V
dT

|QC |
η =1−
|QH |

TC
η =1−
TH

dQrev
dS =
T

T  
dT P
Z
∆S = CPig − R ln
T0 T P0

   
∆S T C D P
= A ln + B (T − T0 ) + (T 2 − T02 ) − (T −2 − T0−2 ) − ln
R T0 2 2 P0

d (m S)cv X Q̇j
∆ (S ṁ)fs + − = ṠG > 0
dt j
Tσ,j

   
1 2
Ẇideal = ∆ H + u + zg ṁ − Tσ ∆ (S ṁ)fs
2 fs

11
 CHE 3161 (JUN 08)

Ẇlost = Tσ ṠG

A=U −T S

G= H −T S

dU = T dS − P dV

dH = T dS + V dP

dA = −P dV − S dT

dG = V dP − S dT

   
∂T ∂P
=−
∂V S ∂S V

   
∂T ∂V
=
∂P S ∂S P

   
∂P ∂S
=−
∂T V ∂V T

   
∂V ∂S
=−
∂T P ∂P T

   
∂V
dH = CP dT + V − T dP
∂T P

 
dT ∂V
dS = CP − dP
T ∂T P

   
∂P
dU = CV dT + T − P dV
∂T V

12
 CHE 3161 (JUN 08)

 
dT ∂P
dS = CV + dV
T ∂T V

     
G V H
d = dP − dT
RT RT RT 2

P
GR dP ′
Z
= (Z − 1) (constant T )
RT 0 P′

P
HR
 
∂Z dP ′
Z
= −T (constant T )
RT 0 ∂T P P′

P P
SR

∂Z dP ′ dP ′
Z Z
= −T − (Z − 1) (constant T )
R 0 ∂T P P′ 0 P′

ρ
GR dρ
Z
= (Z − 1) + Z − 1 − ln Z
RT 0 ρ

ρ
HR
 
∂Z dρ
Z
= −T +Z −1
RT 0 ∂T ρ ρ

ρ ρ
SR
 
∂Z dρ dρ
Z Z
= ln Z − T − (Z − 1)
R 0 ∂T ρ ρ 0 ρ

 
1 Z + σβ
I= ln
σ−ǫ Z + ǫβ

GR
= (Z − 1) − ln(Z − β) − q I
RT

HR
 
d ln α(Tr )
= Z −1+ − 1 qI
RT d ln Tr

SR d ln α(Tr )
= ln(Z − β) + qI
R d ln Tr

13
 CHE 3161 (JUN 08)

B
ln P sat = A −
T +C

HR (H R )0 (H R )1
= +ω
RTc RTc RTc

SR (S R )0 (S R )1
= +ω
R R R

HR dB 0 dB 1
  
0 1
= Pr B − Tr + ω B − Tr
RTc dTr dTr

SR dB 0 dB 1
 
= −Pr +ω
R dTr dTr

dB 0 0.675
= 2.6
dTr Tr

dB 1 0.722
= 5.2
dTr Tr

Z T2
∆H = CPig dT + H2R − H1R
T1

T2
dT P2
Z
∆S = CPig − R ln + S2R − S1R
T1 T P1

yi P = xi Pisat (i = 1, 2, . . . , N)

yi P = xi Hi

yi P = xi γi Pisat (i = 1, 2, . . . , N)

14
 CHE 3161 (JUN 08)

y1 /x1
α12 ≡
y2 /x2

yi
Ki =
xi

L+V =1

zi = xi L + yi V (i = 1, 2, . . . , N)

zi Ki
yi = (i = 1, 2, . . . , N)
1 + V (Ki − 1)

N
X zi Ki
=1
i
1 + V (Ki − 1)

 
∂(nG)
µi ≡
∂ni P,T,nj

X
d(n G) = (n V ) dP − (n S) dT + µi dni
i

µαi = µβi (i = 1, 2, 3, . . . , N)

 
∂(nM)
M̄i ≡
∂ni P,T,nj

X
M= xi M̄i
i

   
∂M ∂M X
dP + dT − xi dM̄i = 0
∂P T,x ∂T P,x i

15
 CHE 3161 (JUN 08)

X
xi dM̄i = 0 (constant T , P )
i

dM
M̄1 = M + x2
dx1

dM
M̄2 = M − x1
dx1

H̄i = Ūi + P V̄i

dḠi = V̄i dP − S̄i dT

 
∂ Ḡi
S̄i = −
∂T P,x

 
∂ Ḡi
V̄i =
∂P T,x

X
H ig = yi Hiig
i

X X
S ig = yi Siig − R yi ln yi
i i

Gig
i = Γi (T ) + RT ln P

µig
i = Γi (T ) + RT ln yi P

X X
Gig = yiΓi (T ) + RT yi ln yi P
i i

16
 CHE 3161 (JUN 08)

Gi = Γi (T ) + RT ln fi

fi
φi =
P

GR
i = RT ln φi

P
dP
Z
ln φi = (Zi − 1) (const. T )
0 P

 
BP
ln φi =
RT

ω
φi = φ0i φ1i

 
Pr
φi = exp (B 0 + ωB 1 )
Tr

Vil (P − Pisat )
 
fi = φsat
i Pisat exp
RT

µi = Γi (T ) + RT ln fˆi

fˆiα = fˆiβ = · · · = fˆiπ (i = 1, 2, . . . , N)

fˆi
φ̂i ≡
yi P

P  
Z̄i − 1
Z
ln φ̂i = dP
0 P

17
 CHE 3161 (JUN 08)

" #
P 1 XX
ln φ̂k = Bkk + yiyj (2δik − δij )
RT 2 i j

δik ≡ 2Bik − Bii − Bkk ; δij ≡ 2Bij − Bii − Bjj ; δii = 0 ; δik = δki

RTcij
Bij = (B 0 + ωij B 1 )
Pcij

ωi + ωj p Zcij RTcij
ωij = ; Tcij = Tci Tcj (1 − kij ) ; Pcij = ;
2 Vcij

1/3 1/3
!3
Zci + Zcj Vci + Vcj
Zcij = ; Vcij =
2 2

µid ˆid
i = Γi (T ) + RT ln fi

fˆiid = xi fi

φ̂id
i = φi

fˆi
γi ≡
xi fi

∂(nGE /RT )
 
ln γi =
∂ni P,T,nj

ḠEi = RT ln γi

GE X
= xi ln γi
RT i

18
 CHE 3161 (JUN 08)

X
xi d ln γi = 0 (constant T , P )
i

GE
= x1 ln γ1 + x2 ln γ2
RT

d ln γ1 d ln γ2
x1 + x2 = 0 (constant T , P )
dx1 dx1

yi P yi P
γi = = ; (i = 1, 2, . . . , N)
xi fi xi Pisat

fˆi = xi Hi

GE
=A
x1 x2 RT

ln γ1 = A x22 ; ln γ2 = A x21

GE
= A21 x1 + A12 x2
x1 x2 RT

ln γ1 = x22 [A12 + 2(A21 − A12 )x1 ]

ln γ2 = x21 [A21 + 2(A12 − A21 )x2 ]

GE A′ A′
= ′ 21 12′
x1 x2 RT A12 x1 + A21 x2

 −2
A′12 x1
ln γ1 = A′12 1+ ′
A21 x2

 −2
A′21 x2
ln γ2 = A′21 1+ ′
A12 x1

19
 CHE 3161 (JUN 08)

P = x1 γ1 P1sat + x2 γ2 P2sat

xi γi Pisat
yi = ; i = 1, 2
x1 γ1 P1sat + x2 γ2 P2sat

     
γ1 γ1 γ1∗
δ ln = ln − ln
γ2 γ2 γ2∗

 
γ1 d ln γ1∗ d ln γ2∗
δ ln = x1 + x2
γ2 dx1 dx1

X
∆M ≡ M − xi Mi
i

X
GE = ∆G − RT xi ln xi
i

X
S E = ∆S + R xi ln xi
i

V E = ∆V

H E = ∆H

X
∆H ◦ = νi ∆Hf◦i
i

X
∆CP◦ ≡ νi CP◦i
i

T
∆CP◦
Z
◦
∆H = ∆H0◦ +R dT
T0 R

20
 CHE 3161 (JUN 08)

CP◦i
= Ai + Bi T + Ci T 2 + Di T −2
R

X X X X
∆A = νi Ai ; ∆B = νi Bi ; ∆C = νi Ci ; ∆D = νi Di
i i i i

T
∆CP◦ ∆B 2 ∆C 1 1
Z
dT = ∆A (T − T0 ) + (T − T02 ) + (T 3 − T03 ) − ∆D ( − )
T0 R 2 3 T T0

 
∆B 2 ∆C 1 1
∆H = ◦
∆H0◦ + R ∆A (T − T0 ) + (T − T02 ) + (T 3 − T03 ) − ∆D ( − )
2 3 T T0

ni = ni0 + νi ǫ (i = 1, 2, . . . , N)

X X
n0 = ni0 ; ν= νi
i i

n = n0 + ν ǫ

ni ni + νi ǫ
yi = = 0
n n0 + ν ǫ

X
νi µi = 0
i

!ν i
Y fˆi
=K
i
fi◦

 
−∆G◦
K ≡ exp
RT

X
∆G◦ ≡ νi G◦i
i

21
 CHE 3161 (JUN 08)

d ln K ∆H ◦
=
dT RT 2

 
K ∆H ◦ 1 1
ln ′ = − − ′
K R T T

  T T
∆G◦ ∆G◦0 ∆H0◦ T0 1 ∆CP◦ ∆CP◦ dT
Z Z
= − 1− + dT −
RT RT0 RT0 T T T0 R T0 R T

T
∆CP◦ dT T ∆C ∆D 1 1
Z
= ∆A ln + ∆B (T − T0 ) + (T 2 − T02 ) − ( 2 − 2)
T0 R T T0 2 2 T T0

K = K0 K1 K2

 
∆G◦0
K0 ≡ exp −
RT0

  
∆H0◦ T0
K1 ≡ exp 1−
RT0 T

 T T 
1 ∆CP◦ ∆CP◦ dT
Z Z
K2 ≡ exp − dT +
T T0 R T0 R T

Y νi  P −ν
yi φ̂i = K
i
P◦

 −ν
Y νi P
(yi) = K
i
P◦

" #
Y (P − P ) X ◦
(xi γi )νi = K exp (νi Vi )
i
RT i

Y
(xi γi )νi = K
i

22
 CHE 3161 (JUN 08)

Y
(xi )νi = K
i

F = 2−π+N −r

X
ni = ni0 + νi,j ǫj (i = 1, 2, . . . , N)
j

X
νj ≡ νi,j
i

X
n = n0 + νj ǫj
j

P
ni ni0 + j νi,j ǫj
yi = = P
n n0 + j νj ǫj

!νi,j
Y fˆi
= Kj
i
fi◦

!νi,j
Y fˆi
= Kj
i
P◦

 −νj
Y νi,j P
(yi) = Kj
i
P◦

yi Φi P = xi γi Pisat (i = 1, 2, . . . , N)

φ̂i −Vil (P − Pisat )

Φi = exp
φsat
i RT

Bii Pisat
φsat
i = exp
RT
23
 CHE 3161 (JUN 08)

B11 (P − P1sat ) + P y22 δ12

Φ1 = exp
RT

B22 (P − P2sat ) + P y12 δ12

Φ2 = exp
RT

dU t + P dV t − T dS t 6 0

dGt T,P 6 0


∆G < 0

d2 (∆G/RT )
> 0 (constant T , P )
dx21

24
Solutions to Q1

(a) Tr = T/Tc = 283.15/369.8 = 0.7657

Pr = P/Pc = 1.01325/42.48 = 0.0239
n = 35,000×1000 / 44.097 = 793,705 mol

0.422 0.172
B o = 0.083 ! 1.6
=-0.5639 B 1 = 0.139 ! 4.2
=-0.3888
Tr Tr
Pr Pr
Z o = 1+ B0 =0.9824 Z 1 = B1 =-0.0121
Tr Tr
Z = Z o + !Z 1 =0.9806
ZRT
V = =2278 m3/mol  Vt = 2278×793,705 = 1.81×109 m3
P

l (1!Tr ) 0.2857
(b) V = Vc Z c = 85.4 cm3/mol

Tr = T/Tc = 283.15/369.8 = 0.7657

Pr = P/Pc = 6.294×1.01325/42.48 = 0.1501
Z0 = 0.8895; Z1 = -0.0762 Z = 0.8779
ZRT
Vg = =3.24×10-3 m3/mol = 3240.5 cm3/mol
P

n = nl + ng
0.9V t 0.1V t
n= +
Vl Vg
n
Vt = =75.09×106 cm3 = 75.09m3
0.9 0.1
+
Vl Vg

(c) Proposal I requires much larger volume than Proposal II, but its design does not need
to cater for high pressure. On the contrary, Proposal II, although requires a much
smaller volume, will need to operate at high pressure. Refrigeration system is also
required to liquefy the propane gas in the case of Proposal II.
Solutions to Q2

(a) W12 = (Cv – Cp) ΔT = - RΔT = 2909.9 J/mol

P1T1
From point 3 to point 1: P1T1 = P3T3  P3 = =3 bar
T3

RT RT
W23 = " ! PdV QV = " dV = ! 2 dP
P P
P3
W23 = RT2 ln =2017 J/mol
P2

K
W31 = " ! PdV Q PT = K ! T =
P
RT RK 2 RK
QV = = 2 " dV = ! 3 dP
P P P
K = constant = P1T1

Substitute dV into the equation and integrate:

&1 1#
W31 = '2 RK $ ' ! = -5819.8J/mol
% P1 P3 "

W12 + W23 + W31

(b) ! =
Qinput

It can be shown that both Q12 and Q23 are negative, thus indicating that heat is being
removed.

Q31 = ΔU31 – W31

= CvΔT – (-5819.8) = 10185 J/mol = Qinput

W12 + W23 + W31

!= = 0.0877
Qinput