S. Elliott Lira - HWP 2

Chapter 2 Practice Problems
(P2.1) Energy Balance: …………………………………………………………Eqn. 2.33

d   gz  
in out
v2  v2 gz  in  v2 gz  . . .
m U       H    m    H    m out  Q  W EC  W S
dt   2 gC gC   inlets  2 gC gC  outlets  2 gC gC 

closed system, no mass flow  m in  m out  0 ,
valve stuck preventing any steam from going out  m out  0 , no change in volume
.
occurs (no expansion or contraction)  W EC  0 , no work has been added
.
or removed, and there is no pump nor turbine  W S  0 .
Ignore K.E. and P.E.
d
mU   Q
.
 the final energy balance becomes.

dt
(P2.2) Before the valve is stuck,  there is steam escaping and therefore,
there is an enthalpy for the vapor leaving, no expansion / contraction
work, no shaft work, no kinetic or potential energy occurred.

 
d .
 energy balance will be mU   
m out
H out
 Q , note m  m out
dt
(P2.3) (Solution for gas furnace). Assume the house is air-tight. Furnace has been heating the
home steadily,  the system (furnace) is a steady-state open system, 
d   v2 gz  
 
m U      0  m  m ,
in out
dt   2 gC gC  
Furnace is fixed size, no expansion/contraction work occurs. Consider just the hot side of
the heat exchanger. Q loss
Fuel
and air
.
Q
 m out H out  m in H in  Q Furnace House
(Chap 3 will consider reactions such as Combustion gases
combustion, but the E-balance doesn’t need to be

written differently!)
Note: if the small shaft work from blower is included, then the boundary includes the
house air in and out of the furnace, and the boundary includes both sides of the heat
To accompany Introductory Chemical Engineering Thermodynamics
© J.R. Elliott, C.T. Lira, 2001-2014, all rights reserved. (12/4/2014) 1 of 11
exchanger. For this boundary, all heat transfer is within the furnace, and there is no Q
term, but there are four mass flow terms (fuel/air in, combustion gas out, house air in,
house air return) and a small (negligible compared to other terms) Ws term.
(P2.4) (Solution for gas furnace.) Assume house is air-tight, m in  m out  0 .

System: the house and all contents, consider just the house side of heat exchanger 
closed, unsteady-state system.
 there is heat gain and heat lost in the house.
No expansion / contraction work nor kinetic, potential energy change.
The internal energy of the system could change with respect to time depending on heat
gain and heat loss, or could be zero if they are balanced. If the furnace is properly sized,
there will be a net gain in temperature of the house!
Q loss
Fuel
and air
Q
Furnace House
Combustion gases
d
mU   Q gain  Q loss , where Q. is negative.
. .
dt loss
Note: if blower is included within system, then you also should be clear whether the
boundary includes the entire heat exchanger (in which case the Qgain term is replaced with
enthalpy flow terms), or just the house side of the heat exchanger. In either event, the Ws
term will be small relative to other terms since there is so much heat coming from
furnace.
(P2.5) System is child:

no mass flow across boundary of child. ignore heat transfer from cold snow. impact
of snow is a surface work that is interpreted as shaft work.
in out
d  mv 2 mgz   v2 gz  in  u2 gz 

dt 
mU 
2 gC
    
gC  child inlet 
H  
2 gC gC 
 m   
outlet 
H    mout  Q  W EC  W S
2 gC gC 
we might now think of the snow as a system. Again ignoring heat transfer from melting, and
ignoring potential energy change of snow and any melting or T change of snow,
 mv 2 mgz 
  mU     Q  W EC  W S , snow ,
 2 g C g C  snow
The work terms are equal and opposite

 mv2   mv2 
  mU     
 2 g C  c h ild  2 g C  sn o w

(P2.6) System: the bulb and its contents.

System is closed steady state system, 
d
  0 ….  is left side of equation.
dt
There is no work acting on the bulb and no mass flow in or out.
 U  0
Photons
Q loss
Consider photons as heat transfer by radiation Q photons and heat loss from bulb, Q bulb ,
Q net  0
m out Q photons
(P2.7) System: the sunbather at 12:00 noon (open system).
No work has been done, no kinetic or potential energies.
No mass flow in, but perspiration loss, m body   m out
Unsteady state, still getting hot.
Consider photons to be heat transfer by radiation.
 by using the equation 2.64 (text book) and drop out all the zero values,
d
 energy balance will be: ( mbodyU body )  m body H V  Q
dt
(steam tables could be used to estimate the enthalpy of the evaporating perspiration if the
T is known or estimated).
(P2.8) System: the balloon and its contents.

Unsteady state system, open system. gas
No heat gain or loss.
No shaft work.
Mass changing with respect to time, as it gets flat, m  m out
Volume of the balloon is changing the work of expansion / contraction occurs.
Kinetic energy effected by changing the velocity of the balloon.
No potential energy change.
out
d  2
mvballoon   v2  dm 
 energy balance is:  mU      H    W EC
dt  2 gC   2 gC  dt
(P2.9) (a) Potential energy (P.E),  P = m*g*h, ( 1J  1Nm )
where m = mass,
g = gravity,
h = height or distance that the body moved by.
P.E 1000 Nm
 P.E  mgh / g c ,  h  
mg / g c 1kg * 9.8066 N / kg
 h  101.97m
This is why potential energy is often ignored when thermal changes are present– the
height change must be very large to be significant.
(b) Kinetic energy = potential energy
1 1/ 2
 2 g K .E  2   2*1(kgm / Ns ) *1000 Nm 
  2
1
 K .E  mv 2 ,  u   c    
2 gC  m   1kg 
 v  44.72m / s
This is why kinetic energy is often ignored when thermal changes are present– the
velocity change must be very large to be significant.
(P2.10)Closed system, unsteady-state, 1 block, 2 water, 3 tank.
Energy balance U=0
m1*U1+ m2*U2 + m3*U2 = 0
1 Q0
2
T2
W EC  0
U = T1
CvdT ), U  CvT 3
(T – 400)*200*0.380 + 4.184*4000*(T-300)+500*0.380*(T-300) = 0
Solve for T,  T = 300.447K
UBLOCK = 200*0.38*(400-300.447) = -7566J
UWATER = 4000*4.184*(300.447-300) = 7480.9J
(P2.11) Unsteady-state, closed system, Energy balance with block at 50m deep in the water.
m1*U1+ m2*U2 + m3*U2 +m4(kg)*z(m)*g/gc(N/kg) = 0 (1J=1kgm2/s2)
200*.38*(T-400)-0.2*50*9.81+4000*4.184*(T-300)+500*.38*(T-300) = 0 
T = 300.453  UBLOCK = -7566
(P2.12) a. Unsteady-state closed system WEC  0(rigid ) U  Q

Ugas = nCvT=5mole*200*5cal/mol-K =5000cal.;
with gas AND vessel
U  n gas Cv gas T  mvessel Cv vessel T 
5000  mvessel CvT  5000  80(0.125)200  7000 cal
b. U  Q  W EC  U  W EC  Q   H  Q  mCpT
5mole*200*7cal/mol-K = 7000cal
(P2.13) Unsteady state, closed system.

Assume Ideal Gas.  Cp = Cv + R, and Cp = 7R/2 (diatomic)
7R/2 – R = Cv;  Cv = 5R/2 = 5*8.314/2 = 20.785J/g-k
Q = U + W ( no work )
 Q = U = 20.785* (400 – 300)
 Q = 2079J/mol
(P2.14) Steady state, open system.

660oF = 348.88oC T(oC) = (T(oF) – 32)*5/9
Through the valve  0  m in H in  m out H out  H in  H out
From steam tables (back of the book).
Interpolate for 348.88oC to find Hin
350  348.88 2563.64  H
 =  Hin = 2570.64 J/g
350  345 2563.64  2594.9
Outlet at 1 atm. Use sat T table to find P=1.014 MPa (close enough to 1 atm). Hout is less
than HsatV= 2676 J/g, so the outlet is two-phase.
Hvap = 2256 J/g and find HsatL = 419.2 J/g
H  qH vap  H SatL
 2570.64 = q*(2256) + 419.2
 q = 0.954
(P2.15) as in example 2.6 about transformation of kinetic energy.
 the simplified energy balance is:
v 2
H 
2 gC
v 2   D 4 
 H  1   1   1
2 gC   D2  
 
 if : D2    H  18 J / kg
D1

 Cp 
   4.041  Cp  4184 J / kg  moleK
 R  water
 Cp 
&   3.5  Cp  3623.9 J / kg  moleK
 R  nitrogen
H 18 J / kg  mole
 H  Cp (T )  Tnitrogen    0.00496 K
Cp 3623.9 J / kgmoleK
 0.00496 K  0.004 K  Trise
 Trise  max  0.001K
(P2.16) Steady state, open system.

 0  m in H in  m out H out  Q
a) P1 = 15 MPa , T1 = 600oC  H1 = 3583.1 kJ/kg (Steam Table)

P2 = 10MPa , T2 = 700oC  H2 = 3870 kJ/kg (Steam Table)
H = Heat = Q = H2 – H1 = -287 kJ/kg
b) for H ig take lowest P at 600oC and 0.01MPa
Hig = 3706 J/g ( at 600oC and 0.1MPa)
H in  H ig (3583.1J / g  3706 J / g ) * 18 g / mole
= = - 0.305
R *T in
8.314 J / mole  K * (600  273.15) K
(P2.17) There are several ways to look at this problem, and some choices of system boundries
are more difficult than others. One method is presented.
(a). System: piston, donote with subscript p
closed system, 0.1m 2 area
no Q (neglect)
no flow (rigid body)
0.1m3
no change of internal energy (piston doesn’t change T)
P i  10bar
g v 2
mp z  m p  W S,p
gC 2 gC
surface forces cause movement; treat this as Ws.
Now we need to determine Ws. The work done by the gas (subscript g) and the
atmosphere (subscript a) will be equal to the work done on the piston. The gas and
atmosphere are closed systems that change size.
System: gas

W EC , g    Pg dV g ..............................................................................(2)
System: atmosphere.
Note : dV g  dV a
W EC ,a    Pa dV a   Pa dV g ............................................................(3)
Combining work interaction at boundary
W s , p  W EC , g  W EC , a
Which results in the working equation.
g v 2
mp z  m p  W S , p   Pg dV g   Pa dV g ...........................(4)
gC 2 gC
W S , p  n g  ( RT / V )dV   Pa d V
V2 0.25
WS,p = (ngRT1* ln - 0.1*(0.25 - 0.1)) = (P1V1* ln - (0.1*.015)).....(5)
V1 0.1
WS,p = (1.0*0.1*ln2.5-.015)*1E6cm3/m3 = 76629J
From E. Bal.
mv2/2gc = WS,p - mgz/gc = 76629J - 700*9.81*(2.5m-1m) = 66328.6J....(6)
v = 13.76m/s
(b) Free flight, system: Piston, closed system, constant T.
Equation (1) applies where WS,p = 0 (no surface forces acting on piston, because we will
ignore air resistance). The kinetic energy will go to zero at the top of flight. The initial
kinetic energy from part (a).
g v 2
mp z  m p  700(9.81)z  66328.6 J  0.....................................(7)
gC 2 gC
z  9 . 6 m
(not counting 2.5 meters of tube).
(c) PgVg = constant, since isothermal, P2 = P1V1/V2 = 4 bar

V2
(d)  5.88,  V 2  0.588
V1
plugging into (5)
WS,p = (1.0*0.1*ln5.88-0.1*(0.588-0.1))*1E6 cm3/m3
WS,P = 128350 J
Using (6)
mv2/2gc = 128350 – 700*9.81(5.88 –1) = 94840 J

plugging into (7)
 700 * 9.81 * z  94840 J ,
 z  13.8m, free, flight
(e) the piston will accelerate when the upword force (Fup) > down ward force (Fdown). The
piston will decelerate when Fup< Fdown. The maximum exit velocity will be obtained if the
piston leaves the cylinder at the condition Fup = Fdown.
Fup  P2 A
mg
Fdown  Pa A 
gC
mg
P2 A  Pa A  .....................................................................................(8)
gC
P2 can be related to V2 since gas is isothermal, PVg = constant,
P1V1
P2  ...............................................................................................(9)
V2
Substituting (9) into (8) , and inserting the values.
(1E 6 Pa)V1 V2 (0.1m 2 )  (0.1E 6 Pa)(0.1m 2 )  700 * 9.81
V2
 5.93,  V 2  0.593m 3
V1
Answer will be almost the same as (d)
Plugging into (5)
WS,p = (1.0*0.1*ln5.93-0.1*(0.593-0.1))*1E6 cm3/m3
WS,p = 128700 J
Using (6),
mu2/2gc = 128700 – 700*9.81(5.93 –1) = 94846 J
sub. Into (7)
 700 * 9.81 * z  94846 J ,
 z  13.8m, free, flight
(P2.18)
1m
V1
Initial and final conditions , P1 = 50 psig = 64.7 psia = 0.4462MPa.

ball: 3in*2.54cm/in=7.62 cm dia
cylinder volume: V2=100cm*3.14*(7.62/2)2 = 4558.1cm3
ball mass: 0.125lbm*.454kg/lbm=.057kg ;
exit velocity: 40mi/hr *5280ft/mi*0.3048m/ft*1hr/3600sec = 17.88 m/s
Energy Balance:
see E. Bal. From (P2.17), except potential energy is not included since piston is
horizontal, ball replaces the piston of (P2.17).
adapting (4), (5) from (P.2.17)
WS,ball = 0.057/2*(17.88)2 = 9.11 J
mv2/2gc =WS,ball = 0.4462*V1*ln(V2/V1) - 0.1*(4558.1-V1) = 9.11J
Using solver V1 = 387cm3 not counting Vball.
(P2.19)
0.1 m2
0.1 m3 0.15 m3
0.8 MPa 0.1 MPa
Description: Forces are imbalanced. The piston will accelerate to the right until forces are
balanced, then decelerate to right (accel to left) until velocity is zero. Forces will then be
imbalanced and the piston will move back to left until original location is reached. In absence of
friction or viscous dissipation, motion will be perpetual. We are asked to assume isothermal.
Actual process is probably closer to adiabatic because it is so fast heat transfer is unlikely.
Nevertheless, let us assume isothermal. Heat must be added to the left side and removed from the
right side to keep isothermal.
PV = nRT for each side and will be constant for each side if isothermal because each side is
closed.
Overall E-bal around both sides:

Δ Δ Δ (1)
(a) Δ 0 and Δ 0. When piston stops the first time, Δ 0, because v =0 at

the beginning and end of motion. Therefore by the energy balance, 0 from
(1).
ln / for each side (2)

, ,
Δ Δ (3)
ln ,
ln ,
0
nLRTL = PLVL = 0.8 MPa(105cm3) = 8E4 J

nRRTR = PRVR = 0.1 MPa(1.5E5cm3) = 1.5E4 J
Eqn (3) becomes
0.1 Δ 0.15 Δ
8 ln 1.5 ln 0
0.1 0.15
Solving by trial and error Δ 0.1488 m3.
VL = 0.1 + 0.1488 = 0.2488 m3= 248,800 cm3.
VR = 0.15 - 0.1488 = 0.0012 m3= 1200 cm3.
PR = 1.5E4 J / 1200cm3 = 12.5 MPa; PL = 8E4 J / 248,800 cm3 = 0.32 MPa
(b) Δ 0 and Δ 0 still applies. Eqn (1) becomes
Δ (4)
Eqn (2) still applies. Force balance:
, Δ , Δ
cross multiply
8 4 0.15 Δ 1.5 4 0.1 Δ Jm3
8 0.15 1.5 0.1 1.5 8 Δ
1.05 9.5Δ
Δ 0.1105 m3
Eqn (1) becomes
0.1 Δ 0.15 Δ (5)
Δ 8 ln 1.5 ln
0.1 0.15
(Note: another way to find the same Δ is to maximize Δ by trial and error or by
differentiating to look for the maximum.)
Inserting Δ 0.1105
Δ 1.717 4 1/2 (note vi = 0 )
2 1.717 4
7 /
700

We can show that the pressures are balanced:
VL = 0.1 + 0.1105 = 0.2105 m3= 210,500 cm3.
VR = 0.15 - 0.1105 = 0.0395 m3= 39,500 cm3.
PR = 1.5E4 J / 39,500 cm3 = 0.38 MPa; PL = 8E4 J / 210,500 cm3 = 0.38 MPa

(P3.1)
(a) the number of microstates is 2 N (pg 91, typo in given answer, printings 1-3)
(b) 3 particles total
3!
⇒ p{2 H ,1T } = = 3 number microstates of specific arrangement (macrostate)
2!*1!
probability = (# microstates of specific arrangement)/(total # of microstates)
3 3
prob = =
23 8
(c ) # microstates.
4!
p{2 H , 2T } = =6
2!*2!
5!
p{3 H , 2T } = = 10
3!*2!
6!
p{4 H , 2T } = = 15
4!*2!
6!
p{3 H ,3T } = = 20
3!*3!
(d)
macrostate # of microstates*
H T
0 8 1
1 7 8
2 6 28
3 5 56
4 4 70
5 3 56
6 2 28
7 1 8
8 0 1
8!
* number of microstates =
m!(8 − m)!
total number of microstates is 28 = 256, which is the same as the sum from the table.
portion of microstates (probability) for requested configurations:
{5:3} = 56/256 = 0.219 = 22%
{4:4} = 70/256 = 0.273 = 27%
{3:5) = 22% like {5:3}
probability of any one of the three most evenly distributed states = 22% + 27% + 22% =
71%
(e) for 8 particle system, Stirling’s approx will not apply
ΔS/k = ln(p{4:4}/p{5:3}) = ln (70/56) = 0.223

© J.R. Elliott, C.T. Lira, 2001, all rights reserved. (2/3/2009) 1 of 7
(P3.3) 15 molecules in 3 boxes, molecules are identical
N!
pj = ………………………………………....Eqn. 3.4
∏m !
i =1
ij
15!
p1 = = 75075
9!4!2!
15!
p2 = = 756756
(5!) 3
ΔS ⎡p ⎤
= ln ⎢ 2 ⎥ = 2.31
−
k ⎣ p1 ⎦
(P3.4) two dice.

ΔS
= ?? for going from double sixes to a four and three.
k
⇒ for double sixes, we have probability of 1/6 for each dice.
2!
⇒ p1 =
(16 )!*(16 )!
for one four and one three ⇒ probability applied for 1/6 for each one in each dice,
2!
⇒ p2 =
(16 )!*(16 )! * 2
ΔS ⎛p ⎞
= ln⎜⎜ 2 ⎟⎟ = ln 2 = 0.693
k ⎝ p1 ⎠
(P3.5) ΔS = ??
Assume Nitrogen is an Ideal gas ⇒ PV = RT ……………. Eqn. 1.15
8.314(cm 3 * MPa / mole − K )* 300 K
⇒ P1 = = 0.108MPa
23(L / mole ) * (1000cm 3 / 1L)
Similarly ⇒ P2 = 0.00723MPa
T P
ΔS = Cp ln 2 − R ln 2 ……………………………………… Eqn. 3.23
T1 P1
7R
Cp = …..(ig)
2
7R 400 0.00723
ΔS = * ln − 8.314 * ln = 30.88 J / mole − K = 1.07 kJ / kg − K
2 300 0.108
(P3.6) (a) m-balance: dnin = -dnout

S-balance:
d (nS ) in dn out
= − S out ⇒ n in dS in + S in dn in = − S out dn out
dt dt
But physically, we know that the leaking fluid is at the same state as the fluid in the tank;
therefore, the S-balance becomes:
(ndS + Sdn) inside = −( Sdn) out , and dn inside = −dn out so ΔS = 0
from the steam table .
At 1 bar = 0.1 MPa
O T S
State P(Mpa) T C H(kJ/kg) S(kJ/kg*K)
100 7.361
1(in) 1 400 3264.5 7.4669
2 (out) 0.1 120.8 2717.86 7.4669 120.8 7.4669
150 7.6148
By interpolation, implies T = 120.8 C O
(P3.7) (a) Steady-state flow, ΔH = Ws
Start 1 mole basis:

x1 = 0.333, x 2 = 0.667, adiabatic, Cp = x1Cp1 + x 2 Cp 2 , Cp for each is the same anyway.
MW = x1 MW1 + x 2 MW2 = 0.333(12 + 16) + 0.667 * 2 = 10.66( g / mole)
R = 1.987BTU/lbmol-R.
T2
7
ΔH = WS = ∫ CpdT = * R * (1100 − 100 )° R
T1
2
⇒ ΔH = 6954.5 BTU / lbmol
& m = 1ton / h = 2000lb / h.
& MW = 10.66lb / lbmol
2000lb lbmol 6954.5 BTU
⇒ ΔH = * *
h 10.66lb lbmol
⇒ ΔH = WS = 1,305,000 = 1.3 * 10 6 BTU / h
(b) η = ?? of the compressor.
To find the efficiency of the compressor, ⇒ S1 = S2
But the enthalpy and the internal energy will change which gives a change in the
'
W
Work. ⇒ η = S = ??
WS

T2′ P
ΔS = 0 = Cp ln − R ln 2
T1 P1
T2′ P
⇒ Cp ln = R ln 2
T1 P1
Cp R
⎛T′ ⎞ ⎛P ⎞
⇒ ⎜⎜ 2 ⎟⎟ = ⎜⎜ 2 ⎟⎟
⎝ T1 ⎠ ⎝ P1 ⎠
R
⎛P ⎞ Cp
⇒ T2′ = ⎜⎜ 2 ⎟⎟ * T1
⎝ P1 ⎠
2
⎛ 100 ⎞ 7
⇒ T2′ = ⎜ ⎟ * 559 R
⎝ 5 ⎠
T2′ = 1315 R
& ΔH ′ = Cp (T2′ − T1 ) = 6.95(1315 − 559) ΔH ′ 5258
⇒η = = = 0.76
⇒ ΔH ′ = 5258 BTU / lbmol ΔH 6955
(P3.8) Adiabatic, steady-state open system ⇒ Q = 0, &(Cp/R = 7/2)………………………… ig

625
7R 1kmole
W = ∫ CpdT = * (625 − 300) = 9457.175kJ / kmole * = 337.76kJ / kg
300
2 28kg
η = ??
R
T ′ ⎛ P ⎞ Cp
ΔS = 0 ⇒ 2 = ⎜⎜ 2 ⎟⎟
T1 ⎝ P1 ⎠
⇒ T2′ = 533.5K
⎛ 7 * 8.314 ⎞
⇒ ΔH ′ = Cp (T2′ − T1 ) = ⎜ ⎟ * (533.5 − 300 )
⎝ 2 ⎠
⇒ ΔH ′ = 6794.77kJ / mol
ΔH ′ 6794.77kJ / kmol
⇒η = = = 0.718
ΔH 337.76kJ / kg * 28kg / kmol
⇒ η = 71.8%
(P3.9) work required per kg of steam through this compressor?

By looking at the steam table in the back of the book
P(MPa) T(OC) H(kJ/kg) S(kJ/kg-K)

0.8 200 2839.7 6.8176
4 500 3446 7.0922
W = ΔH = 3446 − 2839.7 = 606.3kJ / kg

now find W’ = ??
ΔS = 0 (reversible), ⇒ look in the steam table (@P = 4.0MPa) to find a similar
value for S = 6.8176kJ/kg-K, if this value is not available so find it by interpolation.
H(kJ/kg) S(kJ/kg-K)
3214.5 6.7714
H' = ?? S' = 6.8176
3331.2 6.9386
3331.5 − H ' 6.9386 − 6.8176
⇒ = , ⇒ H ' = 3246.7
3331.2 − 3214.5 6.9386 − 6.7714
⇒ ΔH ' = W ' = 3246.7 − 2839.7 = 407kJ / kg
407
⇒η = = 0.67, ⇒ η = 67%
606.3
(P3.10)@ P = 2.0 MPa & T = 600OC, ⇒ H = 3690.7 kJ/kg, S = 7.7043kJ/kg-K (Steam table)
TOC HL(kJ/kg) ΔHvap(kJ/kg)

steam table 20 83.91 2453.52
Interpolation 24 100.646 2444.098
steam table 24 104.83 2441.68
H = H L + q(ΔH Vap ) = 1006.46 + 0.98 * (2441.68) = 2493k .49 J / kg

⇒ WS = ΔH = 3690.7 − 2493.49 = 1197.21kJ / kg
ΔH W
η = ?? , η = = ,
ΔH ' W '
⇒ ΔS = 0 ( reversible), ⇒look for S in the sat’d temp. steam table and find H
by interpolation, ⇒ W ' = 1408.0kJ / kg
1197.2
⇒η= = 0.8503, ⇒ η = 85%
1408.0
(P3.11)
P1 = 0.1MPa, Sat ' d vap
P2 = 10 MPa
T2 = 1100 O C
State P(MPa) T(OC) H(kJ/kg) S(kJ/kg-K)

1 0.1 99.61 2674.95 7.3589
2' 10 4062.53 7.3589
2 10 1100 4870.3 8.0288
interpolation for above table:

H'2 = 4062.53 (interpolation)
H(kJ/kg) S(kJ/kg-K)
3992 7.2916
4062.53 7.3589
4114.5 7.4085
⇒ ΔH = WS = 4870.3 − 2674.95 = 2195.35kJ / kg

mass flow rate = 1 kg/s
⇒ W S = 2195.35kJ / s = 2195350 watt
& 1watt = 0.001341022hp
⇒ W = 2944.01hp
S
& ΔH ′ = 4062.53 − 2674.95 = 1387.58kJ / kg
ΔH ′ 1387.58
⇒η = = = 0.63
ΔH 2195.35
⇒ η = 63.2%
(P3.12) Ethylene gas is to be continuously compressed from an initial state of 1 bar and 20° C to
a final pressure of 18 bar in an adiabatic compressor. If compression is 70% efficient compared
with an isentropic process, what will be the work requirement and what will be the final
temperature of the ethylene? Assume the ethylene behaves as an ideal gas with CP = 44 J/mol-K
(ANS. 13.4 kJ/mol, 596K)
Ebal: ΔH = W.
⎛ R ⎞
⎜ ⎟
⎛ T rev ⎞ ⎛ P ⎞⎝ Cp ⎠
Sbal: ΔSrev = 0 => ⎜ 2 ⎟ = ⎜ 2 ⎟ => T2rev = (20+273)*18^(8.314/44) = 506K.
⎝ T1 ⎠ ⎝ P1 ⎠
rev rev
W = Cp(T2 -T1) = 44*(506-293) = 9372J/mol => Wact = 9372/0.85 = 13.4kJ/mol
Wact = Cp(T2act -T1) = 13400 => T2act = (13400/44)+293 = 597K
(P3.13) Through the valve ⇒ H in = H out
P in = 3MPa P out = 0.1MPa Tout = 110O C = 383.15K

out
(By interpolation) Find H from steam table.
150 − 110 2776.6 − H out

=
150 − 100 2776.6 − 2675.8
out
⇒ H = 2695.96 kJ/kg
At 3MPa table use same value for Hin to find Sin
2856.5 − 2695.96 6.2893 − S in

⇒ By interpolation =
2856.5 − 2803.2 6.2893 − 6.1856
⇒ Sin = 5.976kJ/kg-K

The process should be irreversible. To find Sout, interpolate using temperature at 0.1 MPa:
150 − 110 7.6148 − S out

=
150 − 100 7.6148 − 7.3610
Sout = 7.4118 kJ/kg-K, since Sout>Sin entropy has been generated. The entropy balance is:
0 = S in m in − S out m out + S
gen

(P4.1)
(a) the number of microstates is 2 N
(b) 3 particles total
3!
 p{2 H ,1T }   3 number microstates of specific arrangement (macrostate)
2!*1!
probability = (# microstates of specific arrangement)/(total # of microstates)
3 3
prob  
23 8
(c ) # microstates.
4!
p{2 H , 2T }  6
2!*2!
5!
p{3 H , 2T }   10
3!*2!
6!
p{4 H , 2T }   15
4!*2!
6!
p{3 H ,3T }   20
3!*3!
(d)
macrostate # of microstates*
H T
0 8 1
1 7 8
2 6 28
3 5 56
4 4 70
5 3 56
6 2 28
7 1 8
8 0 1
8!
* number of microstates =
m!(8  m)!
total number of microstates is 28 = 256, which is the same as the sum from the table.
portion of microstates (probability) for requested configurations:
{5:3} = 56/256 = 0.219 = 22%
{4:4} = 70/256 = 0.273 = 27%
{3:5) = 22% like {5:3}
probability of any one of the three most evenly distributed states = 22% + 27% + 22% =
71%
(e) for 8 particle system, Stirling’s approx will not apply
S/k = ln(p{4:4}/p{5:3}) = ln (70/56) = 0.223

(P4.2) Initial ( each x represents 5 molecule)
xxxx
Final
x x
x x
Create a space with a three empty boxes for the initial state. The number of molecules is
too small to use Stirling’s approximation.
p1 = 20!/(20!0!0!0!) = 1
p2 = 20!/(5!5!5!5!) = 20*19*18*17*16*15*14*13*12*11*10*9*8*7*6/(5*4*3*2)^3 =
11732745024
S/k = ln(p2/p1) = ln(11732745024) = 23.18
(P4.3) 15 molecules in 3 boxes, molecules are identical

N!
pj  ………………………………………....Eqn. 4.4
m !
i 1
ij
15!
p1   75075
9!4!2!
15!
p2   756756
(5!) 3
S p 

 ln  2   2.31
k  p1 
(P4.4) two dice.

S
 ?? for going from double sixes to a four and three.
k
 for double sixes, we have probability of 1/6 for each dice.
2!
 p1 
16 !*16 !
for one four and one three  probability applied for 1/6 for each one in each dice,
2!
 p2 
16 !*16 ! * 2
S p 
 ln 2   ln 2  0.693
k  p1 
(P4.5) S = ??
Assume Nitrogen is an Ideal gas  PV  RT ……………. Eqn. 1.12
8.314cm 3 * MPa / mole  K * 300 K
 P1   0.108MPa
23L / mole  * (1000cm 3 / 1L)
Similarly  P2  0.00723MPa
T P
S  Cp ln 2  R ln 2 ……………………………………… Eqn. 4.29
T1 P1
7R
Cp  …..(ig)
2
7R 400 0.00723
S  * ln  8.314 * ln  30.88 J / mole  K  1.07 kJ / kg  K
2 300 0.108
(P4.6) (a) m-balance: dnin = -dnout

S-balance:
d (nS ) in dn out
  S out  n in dS in  S in dn in   S out dn out
dt dt
But physically, we know that the leaking fluid is at the same state as the fluid in the tank;
therefore, the S-balance becomes:
(ndS  Sdn) inside  ( Sdn) out , and dn inside  dn out so S  0
from the steam table . At 1 bar = 0.1 MPa
T S
State P(Mpa) TOC H(kJ/kg) S(kJ/kg*K)
100 7.361
1(in) 1 400 3264.5 7.4669
2 (out) 0.1 120.8 2717.86 7.4669
120.8 7.4669
150 7.6148
By interpolation, implies T = 120.8OC
(P4.7) (a) Steady-state flow, H = Ws
Start 1 mole basis:

x1  0.333, x 2  0.667, adiabatic, Cp  x1Cp1  x 2 Cp 2 , Cp for each is the same anyway.
MW  x1 MW1  x 2 MW2  0.333(12  16)  0.667 * 2  10.66( g / mole)
R = 1.987BTU/lbmol-R.
T2
7
H  WS   CpdT  * R * 1100  100  R
T1
2
 H  6954.5 BTU / lbmol
& m  1ton / h  2000lb / h.
& MW  10.66lb / lbmol
2000lb lbmol 6954.5 BTU
 H  * *
h 10.66lb lbmol
 H  WS  1,305,000  1.3 * 10 6 BTU / h
(b)   ?? of the compressor.

To find the efficiency of the compressor,  S1 = S2
But the enthalpy and the internal energy will change which gives a change in the
'
WS
Work.     ??
WS
T P
S  0  Cp ln 2  R ln 2
T1 P1
T P
 Cp ln 2  R ln 2
T1 P1
Cp R
T  P 
  2    2 
 T1   P1 
R
P  Cp
 T2   2  * T1
 P1 
2
 100  7
 T2    * 559 R
 5 
T2  1315 R
& H   Cp (T2  T1 )  6.95(1315  559) H  5258
    0.76
 H   5258 BTU / lbmol H 6955
(P4.8) Adiabatic, steady-state open system  Q = 0, &(Cp/R = 7/2)………………………… ig

625
7R 1kmole
W   CpdT  * (625  300)  9457.175kJ / kmole *  337.76kJ / kg
300
2 28kg
  ??
R
T   P  Cp
S  0  2   2 
T1  P1 
 T2  533.5K
 7 * 8.314 
 H   Cp T2  T1     * 533.5  300 
 2 

 H  6794.77kJ / mol
H  6794.77kJ / kmol
    0.718
H 337.76kJ / kg * 28kg / kmol
   71.8%
(P4.9) work required per kg of steam through this compressor?

By looking at the steam table in the back of the book
P(MPa) T(OC) H(kJ/kg) S(kJ/kg-K)

0.8 200 2839.7 6.8176
4 500 3446 7.0922
W  H  3446  2839.7  606.3kJ / kg

now find W’ = ??
S = 0 (reversible),  look in the steam table (@P = 4.0MPa) to find a similar
value for S = 6.8176kJ/kg-K, if this value is not available so find it by interpolation.
H(kJ/kg) S(kJ/kg-K)
3214.5 6.7714
H' = ?? S' = 6.8176
3331.2 6.9386
3331.5  H ' 6.9386  6.8176
  ,  H '  3246.7
3331.2  3214.5 6.9386  6.7714
 H '  W '  3246.7  2839.7  407 kJ / kg
407
   0.67,    67%
606.3
(P4.10)@ P = 2.0 MPa & T = 600OC,  H = 3690.7 kJ/kg, S = 7.7043kJ/kg-K (Steam table)
TOC HL(kJ/kg) Hvap(kJ/kg)

steam table 20 83.91 2453.52
Interpolation 24 100.646 2444.098
steam table 24 104.83 2441.68
H  H L  q(H Vap )  1006.46  0.98 * (2441.68)  2493k .49 J / kg

 WS  H  3690.7  2493.49  1197.21kJ / kg
H W
  ?? ,    ,
H ' W '
 S = 0 ( reversible), look for S in the sat’d temp. steam table and find H
by interpolation,  W '  1408.0kJ / kg
1197.2
  0.8503,    85%
1408.0
(P4.11)
P1  0.1MPa, Sat ' d vap
P2  10 MPa
T2  1100 O C
State P(MPa) T(OC) H(kJ/kg) S(kJ/kg-K)

1 0.1 99.61 2674.95 7.3589
2' 10 4062.53 7.3589
2 10 1100 4870.3 8.0288
interpolation for above table:
H'2 = 4062.53 (interpolation)
H(kJ/kg) S(kJ/kg-K)
3992 7.2916
4062.53 7.3589
4114.5 7.4085
 H  WS  4870.3  2674.95  2195.35kJ / kg

mass flow rate = 1 kg/s
 W S  2195.35kJ / s  2195350 watt
& 1watt  0.001341022hp
 W  2944.01hp
S
& H   4062.53  2674.95  1387.58kJ / kg
H  1387.58
    0.63
H 2195.35
   63.2%
(P4.12)
Ebal: ΔH = W.
 R 
 
 T rev   P  Cp 
Sbal: ΔSrev = 0 =>  2    2  => T2rev = (20+273)*18^(8.314/44) = 506K.
 1   1
T P
rev rev
W = Cp(T2 -T1) = 44*(506-293) = 9372J/mol => Wact = 9372/0.85 = 13.4kJ/mol
Wact = Cp(T2act -T1) = 13400 => T2act = (13400/44)+293 = 597K
(P4.15) Through the valve  H in  H out
P in  3MPa P out  0.1MPa Tout  110O C  383.15K

out
(By interpolation) Find H from steam table.
150  110 2776.6  H out


150  100 2776.6  2675.8
 H
out
= 2695.96 kJ/kg
At 3MPa table use same value for Hin to find Sin
2856.5  2695.96 6.2893  S in

 By interpolation 
2856.5  2803.2 6.2893  6.1856
 Sin = 5.976kJ/kg-K
The process should be irreversible. To find Sout, interpolate using temperature at 0.1 MPa:
150  110 7.6148  S out


150  100 7.6148  7.3610
Sout = 7.4118 kJ/kg-K, since Sout>Sin entropy has been generated. The entropy balance is:
0  S in m in  S out m out  S
gen
(P4.18) An insulated cylinder is fitted with a freely floating piston, ...

Steam 0.5kg, Pi= 9 bars, q=0.9, goes to satd vapor at 30 bars, Wair = -360 kJ.
The volume change of the air is equal and opposite the volume change of the steam. The
volume change of the steam is (using sat properties at 0.9 MPa)
Visteam = 0.5kg (VsatL + q (VsatV – VsatL))m3/kg = 0.5(0.001121 + 0.9(0.2149-.001121)) =
0.09676m3
Vfsteam = 0.5*VsatV= 0.5kg*.0667m3/kg = 0.03335 m3;
Vsteam = 0.03335 – 0.09876 = - 0.06541 m3.
Vfair = Viair + Vair = 0.05 + 0.06541 = 0.1154 m3
Because we are not told the mass and area of the piston, let us consider it massless, so
that the initial pressure of the air is 9 bar and the final pressure is 30bar. The air will be
treated like an ideal gas.
d(nU)=Hindn + dWair; integrate term-by-term
nfUf – niUi = Hin(nf – ni) -360
for the air, let HR = 0 for 50 bar and 300K, the inlet condition.
ni = PV/RT = 0.9MPa (0.05m3)(106cm3/m3)/8.31447 (cm3-MPa)/300 = 18.041 moles
nf = PV/RT = 3MPa(0.1154m3)(106cm3/m3)/8.31447 (cm3-MPa)/Tfair = 41638/Tfair moles
Let HR =0 at 50 bar and 300K  UR = HR-(PV)=0-RTR = -2494.3 J/mol
Because U is independent of P, then Ui= UR = -2494.3 J/mol.
For air, use Cv = 2.5R = 20.786 J/mol-K
The energy balance becomes
41638/Tfair [20.786(Tfair -300) -2494.3] J= -360000 J
Trial&Error  Tf = 297 K; the temperature change is very small for this case.

QC
(P5.1) COP = coef. of performance =
WS ,net
Using state numbers of Fig 5.8-5.9. P-H plot will look like Fig 5.9. Use P-H chart and
table from Appendix E. Saturated values are from the table:
state 2 is satV at –40C  H2 = 372 kJ/kg (chart)
state 3, outlet of the reversible compressor is found by following the isentropic
line to 40C, where H3’ = 438 kJ/kg.
state 4 is satL at H4 = 256 kJ/kg (table)
state 1, H1 = H4
QC  H 2  H 1   372  256  116kJ / kg

WS = (H3 – H2) = 438 – 372 = 66 kJ/kg
Q 116
 COP  C   1.76
W  66
S
QC = COP (WS) = 1.76 (9000 J/day) = 16 kJ/day
(P5.2) Methane,. See Fig 5.8-5.9. Methane chart Appendix E.

Tevap  280 O F , P  0.032 MPa
 H 2satV  339 Btu / lbm
S 2satV  2.35 Btu / lb.O F
Pressure of 3’ isn’t given, however, it will be the same as the condenser outlet (P4) since
the condenser will be considered to be isobaric. State 4 will be satL at 40F, so P4 = P3’ =
2 MPa. Follow isentropic line from the compressor inlet state to 2MPa. At P3’=2MPa,
and S3’ = 2.35 Btu/lbmF, H3’ = 485 Btu/lbm, and T3’ = 40F. At the outlet of the
condenser, the fluid will be saturated liquid at 2 MPa,
T4  160 O F , P4  2 MPa
 H 4satL  218 Btu / lbm
satliq
S4 1.54 Btu / lb.O F
State T(OF) P(MPa) H(Btu/lb) S(Btu/lb*OF)

1 -280 0.032 218
2 Sat'd vap -280 0.032 339 2.35
3' 40 2 485 2.35
4 -160 2 218 1.54
H 2  H1 Q H  H 4 339  218
COP   C  2 
H 3  H 2 WS ,net H 3  H 2 485  339
 COP  0.83
(P5.3) Rankine Cycle, Fig 5.2
temperatures 200 O C & 99.6 O C , Sat vapor from Turbine outlet can be found in the Sat
Pressure table Appendix E.

The turbine is assumed to be adiabatic and reversible since no other specifications are
given. The inlet state will then have the same entropy as the outlet. Since the
boiler/superheater outlet is to operate at T3 = 200 C, and S3 = 7.3592, we must hunt in the
superheated tables to find this combination. This will occur between 0.2 and 0.3 MPa.
Interpolating, the value of H can be found. Values are tabulated below:
State TOC P(MPa) H(kJ/kg) S(kJ/kg*K) V(m3/kg)

4’ sat vap 99.6 0.098 2675 7.359
5 sat liq. 99.6 0.098 417 1.3028 0.001043
3 200 0.271 2867 7.3592
6 417.18
WS,turbine  H 4  H 3   2675  2867  192kJ / kg

H pump  WS , pump   VdP  VP
1043cm 3 * 0.271  0.098 1J kJ
 H pump  * 3 * 3
kg cm * MPa 10 J
 H pump  0.180kJ / kg.
 WS,net  192  0.180  191.82kJ / kg
 WS,net   191.82   191.82
&   
Qboiler H 3  H 6  (2867  H 6 )
 H 6  417  0.18  417.18kJ / kg
  191.82 
   0.0783
2867  417.18
   7.83%
(P5.6) Inlet: 300 psia/14.504 = 20.68 bar; (550 oF + 460)/1.8-273.15 = 288 oC = 561.15K
Steam.xls => H1=2993.9; S1 = 6.7004
Outlet: S2 = 1.3072 + 0.95(7.3541 - 1.3072) = 7.053; H2 =419.17+0.95*2256.4=2562.8
W = 2562.8-2993.9 = -431.1
S2' = S1 => q' = (6.7004-1.3072)/(7.3541-1.3072) = 0.8919
H2' =419.17+0.8919*2256.4=2431.7 => W' = 2431.7-2993.9 = -562.2
=> ηE = 431.1/562.2 = 76.7%
(b) Base Rankine cycle on actual turbine => Wp = 1.9J/g; QH = 2993.9-(419.17+1.9) = 2572.8
ηθ = (431.1-1.9)/2572.8 = 16.7%

(P6.1)
(a)
Expansion Rule:

chain rule
1
(b)
Expansion rule:
(c)
chain using T since it is measureable
/
Use expansion rule:
thus:
To accompany Introductory Chemical Engineering Thermodynamics, 2nd edition

(P6.2) Pr = 30, T r = 15
(a) Use virial equation of state.
Z = 1 + ( B 0 + ω B 1 ) Pr / T r …………………………………………..Eqn. 6.6
0 0.422
B = 0.083 − 1.6
T r
Where, ………………………………. Eqns. 6.8 & 6.9
1 0.172
B = 0.139 − 4.2
T r
⇒ B 0 = 0.077459277
& B 1 = 0.138998
& ω = −0.041(book )
30
⇒ Z = 1 + (0.077459277 − 0.041 * 0.138998) * = 1.14
15
(b) ρ = ??
T = T r * T C = 15 * 44.4 = 666 K
P = Pr * PC = 2.653 * 30 = 79.59 MPa
PV Z * R * T 1.14 * 8.314 * 666

Z = , ⇒ V = = = 3.93cm 3 / g
RT P * MW 79.59 * 20.179
1 1
⇒ ρ = = = 0.254 g / cm 3
V 3.93
(P6.4)
T 1 = 111K
P1 = 1atm ≈ 0.1 MPa
T 2 77 O F = 25 O C = 298.15K
=
Use PREOS.XLS,
⇒
Stable Root
has a lower
Current State Roots fugacity
T (K) 111 Z V fugacity
3
P (MPa) 0.1 cm /gmol MPa
answers for three 0.9670679 8924.6249 0.096803
root region 0.0263855 243.49944
0.0036451 33.639114 0.093707
Use Solver, and set target cell on the volume and make it equal to
33.639114*2 = 67.278228,
Then by changing the cell of pressure, making sure that T 2 = 298.15K
Current State Roots

T (K) 298.15 Z V
3
P (MPa) 33.839895 cm /gmol

(P7.2) Pr  30, Tr  15
(a) Use virial equation of state.
Z  1  ( B 0  B 1 ) Pr / Tr …………………………………………..Eqn. 7.6
0.422
B 0  0.083  1.6
Tr
Where, ………………………………. Eqns. 7.8 & 7.9
0.172
B  0.139  4.2
1
Tr
 B 0  0.077459277
& B 1  0.138998
&   0.041(book )
30
 Z  1  (0.077459277  0.041 * 0.138998) *  1.14
15
(b)   ??
T  Tr * TC  15 * 44.4  666 K
P  Pr * PC  2.653 * 30  79.59MPa
PV Z * R * T 1.14 * 8.314 * 666

Z , V    3.93cm 3 / g
RT P * MW 79.59 * 20.179
1 1
   0.254 g / cm 3
V 3.93
(P7.4)
T1  111K
P1  1atm  0.1MPa
T2  77 O F  25 O C  298.15K
Use PREOS.XLS,

Stable Root
has a lower
Current State Roots fugacity
T (K) 111 Z V fugacity
P (MPa) 0.1 cm3/gmol MPa
answers for three 0.9670679 8924.6249 0.096803
root region 0.0263855 243.49944
0.0036451 33.639114 0.093707
Use Solver, and set target cell on the volume and make it equal to
33.639114*2 = 67.278228,
Then by changing the cell of pressure, making sure that T2 = 298.15K
Current State Roots

T (K) 298.15 Z V
3
P (MPa) 33.839895 cm /gmol

answers for three #NUM! #NUM!
root region #NUM! #NUM!
#NUM! #NUM!
& for 1 root region 0.9184568 67.278228
 P2  33.84 MPa
(P7.5) if the pressure change, implies the volume will change, but we have to keep in
mind that the number of moles stay the same.
So, by using PREOS.XLS for 20 O C & 1bar  V  24302.829cm 3 / gmol
Current State Roots

T (K) 293.15 Z V
3
P (MPa) 0.1 cm /gmol
#NUM! #NUM!
& for 1 root region 0.9976523 24302.829
 V  0.0243m 3 / 1mole
4m 3
 V  4m 3  n   164.61moles
0.0243m 3 / mole
For T = 293.15 K and P = 200 bars  V  9.68E  5m 3 / mole
Current State Roots

T (K) 293.15 Z V
3
P (MPa) 20 cm /gmol

#NUM! #NUM!
& for 1 root region 0.7948306 96.860006
 V  n * V  164.61moles * 9.68E  5m 3 / mole  0.01593m 3

 V  15.93L
(P7.6)
Current State Roots

T (K) 311.15 Z V fugacity
3
P (MPa) 10 cm /gmol MPa
answers for three #NUM! #NUM! #NUM!
#NUM! #NUM! #NUM!
& for 1 root region 0.282507981 73.08617 5.546459
V  73.1E  6m 3 / mole
0.15m 3
n  2051.98moles
73.1E  6m 3 / mole
The molar volume will stay constant as the gas is cooled. Some checking shows that at 273.15
the saturated liquid volume is 48.2 cm3/mol, thus the system is 2 phase. The shortcut equation
can be used to estimate the vapor pressure, but the EOS needs to be used to calculate the molar
volumes. Using goal seek…
Current State Roots
T (K) 273.15 Z V
P
(MPa) 3.465769 cm3/gmol
answers for three 0.69011426 452.2278
root region 0.195655461 128.2119
0.073553994 48.1995
The container must be filled with compressed liquid at this temperature to reach 10 MPa.
Current State Roots
T (K) 273.15 Z V
3
P (MPa) 10 cm /gmol
& for 1 root region 0.196286053 44.57849
Now, the molar volume stays constant when the vessel is heated. Use solver to find the pressure
that gives the same molar volume.
Current State Roots
T (K) 311.15 Z V fugacity
3
P (MPa) 34.02393 cm /gmol MPa
& for 1 root region 0.599451881 45.58 9.053131

(P8.1) G  H  TS
G  G ig H  H ig S  S ig
   …………………………………Eqn. 8.21
RT RT R
 
H  H ig  Z  d  3 a  d
  T   Z 1    T    Z 1
 T     2 RT 1  b   
5/ 2
RT 0 0
dx 1
note:   log e (ax  b)
ax  b a

1 a 1 
 ln 1  b   ln 1  b   Z  1
3 3a
  Z 1 
2T 3 / 2 b R 0 2 RT 3 / 2 b 
 

S  S ig d
   T Z  Z  1  ln Z ………………………..Eqn. 8.23
R  T   
0
 
3 a   b a  d
  d       ln Z
0 
2 RT 3/ 2
1  b    0 
1  b RT 3/ 2
1  b    
3 a 1 
ln 1  b   ln 1  b   ln 1  b   ln Z
a
 3/ 2 
2 RT  b  RT 3 / 2
G  G ig H  H ig S  S ig
  
RT RT R
3a  1  3 a 1  
ln 1  b   Z  1    ln 1  b   ln 1  b   ln 1  b   ln Z 
a
 3/ 2 
2 RT  b   2 RT
3/ 2
b  RT 3/ 2

G  G ig
  ln 1  b   ln 1  b   Z  1  ln Z
a

RT bRT 3 / 2
Or by using Eqn. (8.26)

G  G ig

Z  1d  Z  1  ln Z

RT 0


G  G ig  b  d
 Z  1  ln Z
a
    
RT 0
1  b RT 3/ 2
1  b   
G  G ig
  ln 1  b   ln 1  b   Z  1  ln Z
a

RT bRT 3 / 2

(P8.2) Z  1  b / Tr

 H  H ig   Z  d
Depature function       T    Z  1 …………Eqn. 8.24
 RT  0  T   

 H  H ig   b  d b  Tr b b 2b
      Tr  2     
 Tr   Tr
2
 RT  0 Tr Tr Tr
 U 
T2
(P8.3) (a)  Cvdt  U ,   T 

T1 V
 Cv

U  U ig  Z  d
 T 2 
R 0  T   
 U   dZ  2  Z 
2
d
   (2T    T  2  )
 T V  dT    T   

Cv  Cv ig  dZ  2  Z 
2
d
   (2T    T  2  )
R 0  dT    T   
(b) Z  1 
b
1  b
  exp(a )  
T
 
 dZ 

a
   2 exp(a T )
 dT   T
 
 2Z  a a2

  2   2  3 exp(a )   4 exp(a )   
 T   T T T T
     

Cv  Cv ig a a T 2a 2  d
   {2T 2 exp(a )  2T 2  3 exp(a )  exp(a ) }
R 0 T T T T T 4 T 
First two terms cancel, integral with respect to  is simple.

Cv  Cv ig a 2 
R
 2 exp(a )
T T
 
(P8.4) Helmholtz Energy,  A = ??

A  A ig U  U ig S  S ig
Departure function,    …………….Eqn.8.20
RT RT R


U  U ig  Z  d
  T  ………………………………………….Eqn. 8.22
RT 0  T   

 9.5 N Ab   9.5 N A b
 T d  
 
2
0 RT RT
 
S  S ig  Z  d d
  T    Z  1  ln Z ………………………Eqn. 8.23
R 0  T  
 0

  
 9.5 N A b   4b  d 9.5 N A b
 T d   
 
   d  ln Z
0  RT 2
 0  1  b   0
RT
 9.5 N A b 9.5 N A b
   4 ln1  b     ln Z
RT RT
A  Aig  9.5 N Ab
    4 ln 1  b   ln Z
RT RT
or by using Eqn. (8.25)

A  A ig  Z 1
    d  ln Z
RT 0
 
 
A  A ig 4b 9 .5 N A b 
  d   d  ln Z
RT 0
1  b 0
RT
A  A ig  9.5 N A b
    4 ln 1  b   ln Z
RT RT
(P8.5) 1g-mole of 1,3 butadiene

P1  25bars  2.5MPa
P2  125bars  12.5MPa
T1  400 K
T2  550 K
Use PREOS.XLS, use PROPS page
For State 2:
T (K) 550 Z V H-Hig U-Uig S-Sig
P (MPa) 12.5 cm3/gmol J/mol J/mol J/molK
& for 1 root region 0.67898224 248.3825681 -8054.423 -6586.505 -11.10052
State 1 has three real roots. Take the more stable root (lower fugacity value).
For State 1
T (K) 400 Z V fugacity H-Hig U-Uig S-Sig

P (MPa) 2.5 cm3/gmol MPa J/mol J/mol J/molK
answers for three 0.668475 889.2328 1.871218 -3460.25 -2357.73 -6.24206
root region 0.180657 240.3178
0.103098 137.145 2.008636 -14993.7 -12011 -35.6649
H  H 2  H 1  H 2  H 2ig   H 2ig  H 1ig   H 1  H 1ig 

S  S 2  S1  S 2  S 2ig   S 2ig  S1ig   S1  S1ig 
Find H 2ig  H 1ig  ??
T2 T2
 H 2ig  H 1ig   CpdT   ( A  BT  CT 2  DT 3 )dT

T1 T1
 AT2  T1  
B 2
2
 C
  D

T2  T12  T23  T13  T24  T14
3 4
 
A B C D
-1.687 3.42E-01 -2.34E-04 6.34E-08
 H 2ig  H 1ig  17173.81J / mole

T2
Cp P
Similarly for S 2ig  S1ig  
T1
T
dT  R ln 2
P1
 T   P 
C
 D
  
 S 2ig  S1ig   A ln 2   BT2  T1   T22  T12  T23  T13   R ln 2 
  T1  2 3   P1 
 S 2ig  S1ig  22.87 J / mole  K

 H  12579.63 J / mole
& S  18.01J / mole  K
T2
U   Cv(T )dT  H  RT2  T1  , Cv  Cp  R

T1
U 2ig  U 1ig  17173.81  8.314 * 550  400  15926.71J / mole

    
& U  U 2  U 1  U 2  U 2ig  U 2ig  U 1ig  U 1  U 1ig 
 U  15926.71  6586.505  2357.73
 U  11697.94 J / mole
V  V2  V1  248.4  889.2
 V  640.8cm 3 / mol
(P8.7)
T1  623.15K
P1  5MPa
Use PREOS.XLS
S1  S 2
T (K) 623.15 Z V H U S
P (MPa) 5 cm3/gmol J/mol J/mol J/molK
& for 1 root region 0.986361 1022.041 18750.12 13639.92 9.1954
 Use Solver in the spread sheet by changing pressure to 0.2MPa

and Fixing the entropy value = 9.1954J/mol-K and in this case
S1  S 2 =9.1954J/mole-K then we can find H andH
T (K) 404.71 Z V H U S
P (MPa) 0.2 cm3/gmol J/mol J/mol J/molK
& for 1 root region 0.99499 16739.56 5234.912 1887 9.1954
 T  404.71K
H   5234.912  18750.12  13515.21J / mole
H W H  H1
  0.8   0.8  s  2
H  Ws H 2  H 1
H 2  18750.12
 0.8 
5234.912  18750.12
 H 2  7937.95 J / mol
 H  H 2  H 1  7937.95  18750.12
 H  10812.166 J / mol
T (K) 452.012672 fugacity H U S

P (MPa) 0.2 MPa J/mol J/mol J/molK
answers for three #NUM! #NUM! #NUM! #NUM!
root region
#NUM! #NUM! #NUM! #NUM!
& for 1 root region 0.199324 7937.95 4192.62 15.50748631
 T2  452 K
P8.8 The outlet of the boiler will be 200C, and the outlet of the condenser will be 65 C. Ignore
the pressure drops through the boiler and condenser.
Key: Refer to Fig 5.1
4 - outlet of turbine, sat’d vapor at the operating pressure of the condenser (0.1027 MPa)
5 - outlet of condenser, sat’d liquid at 65 C
6 - outlet of pump at the pressure of the boiler (4.087 MPa)
2 - outlet of the boiler at 200 C and 4.087 MPa
3 - outlet of superheater at 4.087 MPa and currently unknown pressure.
Strategy:
The answer requires the net work through the turbine and pump and also requires the heat
transfer in the boiler/superheater. For the turbine, we need states 3 and 4, for the pump, we need
states 5 and 6, for the boiler/superheater duty, we need states 6 and 3. Therefore of the listed
states, we only need 3, 4, 5 and 6. The pump and turbine will be reversible to get maximum
efficiency.
Reference state: Choose 298K, 0.1 MPa, take liquid root since it is more stable.
Reference State For real fluid Roots
ig ig ig
T (K) 298 reference state Z V fugacity H-H U-U S-S
3
P (MPa) 0.1 identifier index cm /gmol MPa J/mol J/mol J/molK
0 for HR = 0, 1 for UR = 0 1 0.973865 24128.21 0.09745 -181.766 -117.015 -0.39515 answers for three
0 0.02256 558.9447 root region
0 for ig, 1 for real fluid ref 2 0.001922 47.61241 0.015328 -40666.4 -38193.6 -120.856
1 3 #NUM! #NUM! #NUM! #NUM! #NUM! #NUM! & for 1 root region
State 4, saturated vapor at 0.1027 MPa, and 65C

Current State Roots Stable Root has a lower fugacity
T (K) 338.15 Z V fugacity H U S
3
P (MPa) 0.1027 cm /gmol MPa J/mol J/mol J/molK
answers for three 0.9814393 26866.581 0.100826 42337.01 39577.81 126.072
root region 0.0152363 417.0899 33794.35 33751.52 83.07621
0.0018284 50.051902 0.100788 4618.871 4613.731 14.53248
& for 1 root region #NUM! #NUM! #NUM! #NUM! #NUM! #NUM!
H4= 42.337 kJ/mol
State 5, saturated liquid at 65 C from table above, H5 = 4.619 kJ/mol
State 6, outlet of reversible pump will be at 4.087 MPa and have S = 14.53248 J/mol-K as in
State 2. Use solver or goal seek to adjust T at P=4.087MPa to match S=14.53248.
3
answers for three #NUM! #NUM! #NUM! #NUM! #NUM! #NUM!
root region #NUM! #NUM! #NUM! #NUM! #NUM!
#NUM! #NUM! #NUM! #NUM! #NUM! #NUM!
& for 1 root region 0.0724201 49.935951 0.111711 4818.061 4613.972 14.53248
H6 = 4.818 kJ/mol
State 3, has P=4.087MPa, and the same entropy as State 4, S = 126.072 J/mol-K. Use solver or
goal seek to adjust T at this P until S is matched.

3
answers for three #NUM! #NUM! #NUM! #NUM! #NUM! #NUM!
root region #NUM! #NUM! #NUM! #NUM! #NUM!
#NUM! #NUM! #NUM! #NUM! #NUM! #NUM!
& for 1 root region 0.9021541 1116.9198 3.704821 55803.11 51238.26 126.072
H3 = 55.803 kJ/mol
Therefore, the total work is the sum of the turbine and pump work,
WS = (H4 - H3) + (H6-H5) = 42.337 - 55.803 + 4.818 - 4.619 = -13.267 kJ/mol
The heat transfer in the boiler/superheater is:
QH = H3 - H6 = 55.803 - 4.818 = 50.985 kJ/mol
The thermal efficiency is
 = 13.267/50.985 * 100% = 26 %

(P9.1) Carbon Dioxide,

P1  1.5MPa
P2  0.1MPa
T1  25 O C  298 K
T2  ??
(a) assume ideal gas,
for a valve, H  0
 H  0  Cp T ,
 T  0,  T2  298K
(b) by using excel PREOS.XLS, implies H2 = H1, then T2 = 268.2K

(P10.01) The stream from a gas well consists of 90 mol% methane, 5% ethane, 3% propane and
2% n-butane. This stream is flashed isothermally at 233 K and 70 bar. Use the shortcut K-ratio
method to estimate the L/F fraction and liquid vapor composisitons. (ANS. L/F = 0.181) …
Solution
By short-cut vapor pressure eqn.
LM10^ L 7 a1   fF1  1 I OOP
M N M G
H J
K P
QPQ
K N
i
yi 3 T ?, i
i
xi Pr ,i
yi  x i K i
Though not required, the table below also shows bubble T and dew T calculations at 70 bar.
For the bubble calculations, in each column, the temperature at the top of the column is used to
calculate the K-ratio. Then yi = xiKi. The temperature is adjusted until the sum of y’s is unity. This
is an iterature calculation.
For the dew T calculations, in each column, the temperature at the top of the column is used to
calculate the K-ratio. Then xi = yi/Ki. The temperature is adjusted until the sum of x’s is unity. This
is an iterative calculation.
To accompany Introductory Chemical Engineering Thermodynamics 1 of 8
© J.R. Elliott, C.T. Lira, 2004-2014, all rights reserved, (11/27/2014)
For the isothermal flash calculation, the T = 233K and the pressure is 70 bar, so the K-ratio is
fixed, as tabulated in the column under ‘233’. Equation 10.23 is programmed in the cells below the
value of L/F=0.181 below the ‘Flash’ title. Each row holds the value of the term
‘Di = zi(1-Ki)/[Ki + (L/F)(1-Ki)]’ from equation 10.23. These values are summed at the bottom of
the column. The criteria for the isothermal flash is that L/F is adjusted until the sum goes to zero, as
is shown at L/F = 0.181. Once the value of L/F is found, the xi values and yi values in the last
columns are generated separately using equations 10.15 and 10.16 respectively.
pMPa= 7.000 BUBT DEWT FLASH

z Tc Pc w 210.9 y 300.5 x 233 0.181 x y
C1 0.9 190.6 4.6 0.011 1.108 0.997 4.7949 0.188 1.767 -0.424 0.553 0.977
C2 0.05 305.4 4.88 0.099 0.049 0.002 0.6332 0.079 0.111 0.1632 0.184 0.020
C3 0.03 369.8 4.25 0.152 0.006 0.000 0.1456 0.206 0.016 0.152 0.155 0.002
nC4 0.02 425.2 3.8 0.193 8E-04 0.000 0.0379 0.527 0.003 0.1088 0.109 0.000
1.0000 0.9997 5E-07 1.000 1.000

(P10.2) An equimolar mixture of n-butane and n-hexane at pressure is isothermally

flashed at 373K. The liquid-to-feed ratio is 0.35. Use the shortcut K-ratio method to
estimate the pressure and liquid and vapor compositions. (ANS. P=0.533MPa;
xC6=0.78).
Solution
LM10^ L 7 a1   fF1  1 I OOP
M N M G
H J
K P
QPQ
K N
i
yi 3 T ?, i
i
xi Pr ,i
yi  x i K i
For the isothermal flash calculation, the T = 373K. Equation 9.63 is programmed in the cells
below the value of L/F=0.35 below the ‘Flash’ title. Each row holds the value of the term
‘Di = zi(1-Ki)/[Ki + (L/F)(1-Ki)]’ from equation 10.23. The value of Ki requires P which is to the
left of the table. These values are summed at the bottom of the column. The criteria for the
isothermal flash is that P is adjusted until the sum goes to zero, as is shown at P = 0.533. Once the
value of P is found, the xi values and yi values in the last columns are generated separately using
equations 10.15 and 10.16 respectively.

Though not required, the table below also shows the bubble T and dew T calculations for P =
0.533 MPa.

z Tc Pc w 349.2 y 383.2 x 373 0.35 x y
nC4 0.5 425.2 3.8 0.193 1.766 0.883 3.5299 0.142 2.906 -0.426 0.223 0.649
nC5 0 469.7 3.37 0.249 0.624 0.000 1.3902 0.000 1.11 0 0.000 0.000
nC6 0.5 507.4 3.01 0.305 0.236 0.118 0.5826 0.858 0.452 0.4257 0.777 0.351
nC7 0 540.3 2.74 0.349 0.097 0.000 0.2631 0.000 0.199 0 0.000 0.000
1.0010 0.9999 1E-06 1.000 1.000

(P10.3) A mixture of 25 mol% n-pentane, 45% n-hexane, and 30% n-heptane is flashed
isothermally at 365.9K and 2 bar. Use the shortcut K-ratio method to estimate the L/F
fraction and liquid and vapor compositions (ANS. L/F = 0.56) …
LM10^ L 7 a1   fF1  1 I OOP
M N M G
H J
K P
QPQ
K N
i
yi 3 T ?, i
i
xi Pr ,i
yi  x i K i
Though not required, the table below also shows bubble T and dew T calculations at 2 bar.

For the isothermal flash calculation, the T = 365.9 K and the pressure is 2 bar, so the K-ratio is
fixed, as tabulated in the column under ‘365.9’. Equation 10.23 is programmed in the cells below
the value of L/F=0.56 below the ‘Flash’ title. Each row holds the value of the term
‘Di = zi(1-Ki)/[Ki + (L/F)(1-Ki)]’ from equation 10.23. These values are summed at the bottom of
the column. The criteria for the isothermal flash is that L/F is adjusted until the sum goes to zero, as
is shown at L/F = 0.56. Once the value of L/F is found, the xi values and yi values in the last
columns are generated separately using equations 10.15 and 10.16 respectively.

z Tc Pc w 358.6 y 312.48 x 365.9 0.56 x y
nC4 0 425.2 38 0.193 57.73 0.000 18.804 0.000 67.18 0 0.000 0.000
nC5 0.25 469.7 3.37 0.249 2.107 0.527 0.5756 0.434 2.51 -0.227 0.150 0.377
nC6 0.45 507.4 3.01 0.305 0.821 0.369 0.1898 2.370 1.001 -2E-04 0.450 0.450
nC7 0.3 540.3 2.74 0.349 0.348 0.104 0.0694 4.324 0.432 0.227 0.400 0.173
1 7.129 3E-08 1.000 1.000

(P10.04) A mixture containing 15 mol% ethane, 35% propane, and 50% n-butane is
isothermally flashed at 9 bar and T. the liquid-to-feed ratio is 0.35. Use the shortcut K-
ratio method to estimate the pressure and liquid and vapor compositions.
LM10^ L 7 a1   fF1  1 I OOP
M N M G
H J
K P
QPQ
K N
i
yi 3 T ?, i
i
xi Pr ,i
yi  x i K i
For the isothermal flash calculation, the P=9 bar. Equation 10.23 is programmed in the cells
below the value of L/F=0.35 below the ‘Flash’ title. Each row holds the value of the term
‘Di = zi(1-Ki)/[Ki + (L/F)(1-Ki)]’ from equation 10.23. The value of Ki requires T which is to the
left under the ‘Flash’ title. These values of Di are summed at the bottom of the column. The criteria
for the isothermal flash is that T is adjusted until the sum goes to zero, as is shown at T = 319.4K.
Once the value of T is found, the xi values and yi values in the last columns are generated
separately using equations 10.15 and 10.16 respectively.
Though not required, the table below also shows the bubble T and dew T calculations for P = 0.9
MPa.


z Tc Pc w 290 y 326.9 x 319.4 0.35 x y
C1 0 190.6 4.6 0.011 32.92 0.000 49.257 0.000 45.74 0 0.000 0.000
C2 0.15 305.4 4.88 0.099 3.963 0.594 7.9952 0.019 7.027 -0.184 0.031 0.214
C3 0.35 369.8 4.25 0.152 0.86 0.301 2.0955 0.167 1.779 -0.181 0.232 0.413
nC4 0.5 425.2 3.8 0.193 0.213 0.106 0.614 0.814 0.505 0.3648 0.737 0.372
1.0016 1.0002 6E-08 1.000 1.000

(P11.1)
Practice 11.1 by two methods, left is shortcut Psat, right is Antoine, both use 2-Parameter Margules
Short-cut VP eqn 9.11 Antoine Coeff Method

Tc(K) Pc(MPa) w (1) DEA 7.080932 1202.191 230.5561
(1) DEA 496.5 3.71 0.291 (2)Chloroform 6.95465 1170.966 226.232
(2)Chloroform 536.4 5.37 0.218
Psat
T = 341.55 (mm) Psat(MPa)
T = 341.55 Psat (MPa) (1) 1147.194 0.152947
(1) 0.159506 (2) 955.6875 0.127415
(2) 0.128425
Calc gamma using azeotrope data Calc gamma using azeotrope data
gamma(1) = P/Psat(1) gamma(1) = P/Psat(1)
gamma(1) 0.626935 gamma(1) 0.653823
gamma(2) 0.778666 gamma(2) 0.78484
Calc Margules Param using 11.38 Calc Margules Param using 11.38
A12 -1.2787 A12 -1.22896
A21 -1.55901 A21 -1.41114
Calc gamma at x1 = 0.8 using 11.37 Calc gamma at x1 = 0.8 using 11.37
x1 0.8 x1 0.8
x2 0.2 x2 0.2
gamma1 0.933245 gamma1 0.940697

gamma2 0.396133 gamma2 0.426618

Bubble T calculations Bubble T calculations

Pcalc = x1*g1*P1sat + x2*g2*P2sat Pcalc = x1*g1*P1sat + x2*g2*P2sat
x1*g1 x2*g2 T Psat.1 Psat.2 Pcalc x1*g1 x2*g2 T Psat.1 Psat.2 Pcalc
0.746596 0.079227 333.0839 0.123446 0.098902 0.1 0.752558 0.085324 334.2785 0.12142 0.101076 0.1
(program Psats, guess T until Pcalc = 0.1) (program Psats, guess T until Pcalc = 0.1)
y1=x1*g1*Psat.1/P = 0.921643 y1=x1*g1*Psat.1/P = 0.913758

(P12.1)
Short-cut VP eqn
Tc(K) Pc(MPa) w MW
(1)
acrolein 506 5.16 0.33 56.06
(2)water 647.3 22.12 0.344 18.02
Antoine A B C
(2)water 8.07131 1730.63 233.426
T= 325.55 K
T= 52.4 C
Psat
vapor pressures (mmHg) Psat (MPa)
(1) 0.098287 shortcut
(2) 0.017595 shortcut
(2) 103.8657691 0.013848
Calc gamma using azeotrope data, Antoine for water

gamma(1) = P/Psat(1) w x
gamma(1) 1.017432 0.974 0.923323
gamma(2) 7.221452 0.026 0.076677
x gamma ln(gamma) Aij

1 0.923323 1.017432065 0.017282 1.905464
2 0.076677 7.221452158 1.977056 2.415166
x1 x2 g1 g2 Psat.1 Psat.2 P(MPa)

0.1 0.9 5.006280904 1.015812 0.098287 0.017595 0.065291
0.3 0.7 2.898407803 1.166734 0.098287 0.017595 0.099833
0.5 0.5 1.813735923 1.599573 0.098287 0.017595 0.103205
Repeat using shortcut Psat for water also:

Calc gamma using azeotrope data, shortcut Psat for water
gamma(1) = P/Psat(1) w x
gamma(1) 1.017432 0.974 0.923323
gamma(2) 5.68342 0.026 0.076677
x gamma ln(gamma) Aij

1 0.923323 1.017432 0.017282 1.51066
2 0.076677 5.68342 1.737553 2.178683
x1 x2 g1 g2 Psat.1 Psat.2 P(MPa)

0.1 0.9 3.677636 1.01121 0.098287 0.017595 0.052159
0.3 0.7 2.454185 1.121133 0.098287 0.017595 0.086173
0.5 0.5 1.693527 1.440922 0.098287 0.017595 0.095902

Chapter 14 Practice Problem Solutions
(P14.3)
The van laar is programmed below. A plot is shown on the following page. Then x1 is adjusted
in the two rows with shaded activities using an objective cells for each component given by the
ratio of the activities. The compositions are adjusted in each row to make the activity ratio for act
= 1, subject to the activity ratio for act2 = 1.
x1 x2 ideal excess Gm/RT gamma1 gamma2 act1 act2
0 1 0 0 0 4.78746 1 0 1
0.05 0.95 ‐0.19852 0.07665 ‐0.1219 4.4851 1.0017 0.2243 0.9516
0.1 0.9 ‐0.32508 0.14980 ‐0.1753 4.1910 1.0073 0.4191 0.9065
0.15 0.85 ‐0.42271 0.21910 ‐0.2036 3.9058 1.0175 0.5859 0.8649
0.2 0.8 ‐0.5004 0.28417 ‐0.2162 3.6299 1.0335 0.7260 0.8268
0.25 0.75 ‐0.56234 0.34457 ‐0.2178 3.3639 1.0566 0.8410 0.7925
0.332562 0.667438 ‐0.63598 0.43271 ‐0.2033 2.9478 1.1159 0.9803 0.7448
0.35 0.65 ‐0.64745 0.44927 ‐0.1982 2.8638 1.1327 1.0023 0.7363
0.4 0.6 ‐0.67301 0.49231 ‐0.1807 2.6308 1.1920 1.0523 0.7152
0.45 0.55 ‐0.68814 0.52815 ‐0.1600 2.4100 1.2720 1.0845 0.6996
0.5 0.5 ‐0.69315 0.55589 ‐0.1373 2.2019 1.3805 1.1009 0.6903
0.55 0.45 ‐0.68814 0.57445 ‐0.1137 2.0069 1.5298 1.1038 0.6884
0.6 0.4 ‐0.67301 0.58258 ‐0.0904 1.8258 1.7392 1.0955 0.6957
0.65 0.35 ‐0.64745 0.57876 ‐0.0687 1.6591 2.0409 1.0784 0.7143
0.7 0.3 ‐0.61086 0.56120 ‐0.0497 1.5075 2.4917 1.0552 0.7475
0.75 0.25 ‐0.56234 0.52771 ‐0.0346 1.3718 3.1977 1.0289 0.7994
0.8 0.2 ‐0.5004 0.47559 ‐0.0248 1.2532 4.3720 1.0025 0.8744
0.85 0.15 ‐0.42271 0.40152 ‐0.0212 1.1531 6.4841 0.9802 0.9726
0.9 0.1 ‐0.32508 0.30135 ‐0.0237 1.0742 10.6883 0.9668 1.0688
0.974976 0.025024 ‐0.11699 0.09025 ‐0.0267 1.0055 29.7630 0.9803 0.7448
1 0 0 0 0 1 46.20093 1 0

J.R. Elliott, C.T. Lira, 2014, all rights reserved. (11/27/14) 16
(P15.5)
(a) Perform bubble P calculations 1-CO2, 2- ethylene. For kij = 0
COMPONENT IS CARBON DIOXIDE ID NO. IS 909
COMPONENT IS ETHYLENE ID NO. IS 201
T(K)= 222.00 P(MPa)= .8725 ZL= .2138E-01 ZV= .8674
ID LIQUID X VAPOR Y Yi/Xi
909 .5000 .4057 .8114
201 .5000 .5943 1.189
repeating across the composition range:
x1 y1 P(MPa)
0.0 0.0 1.02
0.1 0.0795 0.995
0.5 0.406 0.873
0.9 0.834 0.7012
1. 1. 0.642
End points were determined using bubble point pressure calculation using PRMIX for a single
component. No azeotrope exists.
Answer is 0.87MPa
(b) Output from prmix.exe:

Kij MATRIX MODIFIED
909 201
201 .1100
bp
COMPONENT IS ETHYLENE ID NO. IS 201
T(K)= 222.00 P(MPa)= 1.126 ZL= .2867E-01 ZV= .8358
909 .5000 .4237 .8475
201 .5000 .5763 1.153
For kij = 0.11

x1 y1 P(MPa)
0.0 0.0 1.02
0.1 0.139 1.09
0.5 0.424 1.126
0.9 0.691 0.882
1. 1. 0.642
at small x1, x1<y1. At large x1, x1>y1. Also, P maximum in mixture. Therefore, maximum P
(minimum T) azeotrope will exist.
Answer is 11.3 bar.

J.R. Elliott, C.T. Lira, (2001-2014), all rights reserved. (04/24/15) 1 of 4
(P15.6)
(a)
Pentane 7
Acetone 1051
THE DEFAULT Kij MATRIX IS
7 1051
1051 .0000
bp
COMPONENT IS n-PENTANE ID NO. IS 7
COMPONENT IS ACETONE ID NO. IS 1051
T(K)= 305.05 P(MPa)= .7785E-01 ZL= .3247E-02 ZV= .9697
7 .7280 .8345 1.146
1051 .2720 .1655 .6083
Answer: 0.78 bar, y1 = 0.83
(b) x=0.134 perform bubble pressure calcs adjusting kij until converge on experimental
pressure of 1 bar at 0.728.
ki
Kij = 0.11
REQUIRED NUMBER OF ITERATIONS WAS: 7
T(K)= 305.05 P(MPa)= .9927E-01 ZL= .4199E-02 ZV= .9634
7 .7280 .7167 .9845
1051 .2720 .2833 1.041
Kij = 0.117
T(K)= 305.05 P(MPa)= .1011 ZL= .4282E-02 ZV= .9629
7 .7280 .7078 .9723
1051 .2720 .2922 1.074
Intermediate Answer: kij = 0.117 to fit bubble pressure, azeotrope composition not matched
exactly.
bp
T(K)= 312.75 P(MPa)= .1120 ZL= .3881E-02 ZV= .9626
7 .1340 .5453 4.070
1051 .8660 .4547 .5250
Answer: kij = 0.117, BP = 1.12 bar

(P15.7)
a) using shortcut K-ratio equation at 298K, predict the vapor pressure of components.
# COMPOUND Psat ( MPa)

1 CO2 6.44
2 METHANE 32.6
3 PROPANE 0.956
4 ETHANE 4.21
Note: methane is supercritical so the vapor pressure is extrapolated.

yiP = xiPisat, xi = yiP/Pisat  guess P until xi = 1.
PNEW = POLD /  Xi
P(MPa) X1 X2 X3 X4  Xi
3 0.14 0.028 0.628 0.143 0.939
3.19 0.149 0.029 0.667 0.152 0.997
3.2 0.15 0.0295 0667 0.153 0.9995
(b) there isn’t a DP routing, use dt routine, guess P until DT = 298

COMPONENT IS METHANE ID NO. IS 1
COMPONENT IS PROPANE ID NO. IS 3
COMPONENT IS ETHANE ID NO. IS 2
T(K)= 286.67 P(MPa)= 3.000 ZL= .9407E-01 ZV= .7509
909 .2207 .3000 1.360
1 .0715 .3000 4.198
3 .5197 .2000 .3848
2 .1882 .2000 1.063
T(K)= 295.61 P(MPa)= 4.000 ZL= .1286 ZV= .6876

909 .2410 .3000 1.245
1 .0958 .3000 3.132
3 .4637 .2000 .4313
2 .1995 .2000 1.003

T(K)= 298.45 P(MPa)= 4.400 ZL= .1434 ZV= .6624
909 .2486 .3000 1.207
1 .1064 .3000 2.819
3 .4421 .2000 .4524
2 .2029 .2000 .9856
P = 4.4MPA, DT = 298.5 close enough.
P(MPa) x1 x2 x3 x4
4.4 0.249 0.107 0.442 0.203
PR predicts much different P and composition. PR should be improved by using non-zero kij
from binary data fits for even more accuracy.
4cb  db d 
(P15.8) Z  1  Note we can integrate more easily using  
 
,
1  b  b
( A  Aig )TV b c
 4 d (b )  4c ln(1  b ) ……………………..…...Eqn. 8.27
RT 0 (1  b )
(  i   iig )   ( A  A ig ) TV / RT 
ln ˆ i      ln Z ……………….Eqn. 15.17
RT  ni  T ,V ,n j  i
  (4nc * ln(1  b )) 
ln ˆ i      ln Z
 n i  T ,V ,n j  i
  (nc)  1   (b ) 
 4 ln(1  b )   4nc    ln Z
 ni  T ,V , n j  i 1  b  ni  T ,V , n
j i
 nc 
   2 xi cij  c ……………………………………………....Eqn. 15.29
  ni T ,V ,ni i i
  ( b )  1   ( nb)  1   nb  b
         i …………using Eqn. 15.22
 ni T ,V ,n j i V  ni T ,V ,n j i V   ni T ,V ,ni i V
4cn bi b  4cb  bi
second term in ln ̂ i becomes equal to  i  ( Z  1)
V 1  b b  1  b  b
  bj
 ln ˆ j  4 c  2 xi cij  ln(1  b )  ( Z  1)  ln Z
 i  b

(P16.1)
Consider the Methanol(1) + Water(2) + Acetone(3) system with a feed shown in Figure 16.10(b).
Rate each of the following products as impossible or possible, and explain.
D (x1, x2) B (x1, x2)
(a) (1,0) (0,.45) impossible, not in bow tie.
(b) (0.4,0) (0,1) impossible, not colinear
(c) (0.4, 0) (0.1, 0.9) possible
(d) (0.3, 0.7) (0.35,0) impossible because D and B are reversed

J.R. Elliott, C.T. Lira, 2014, all rights reserved. (12/04/14) 16
(P17.1) An equimolar mixture of H2 and CO can be obtained by the reaction of steam with coal.
Compute the equilibrium compositions at 550 C based on an equimolar feed of H2, CO, and
H2O. The reaction is H2O + CO = H2 + CO2. Gf data at 550 C are given.
GT = Gf (product) – Gf (reactant) = -8.84 kJ/mol

Ka (550OC) = exp(8840/(8.314*(550+273.15)) = 3.369
Compound In Out
H2O  
CO  
H2  
CO2  
Total 1 1
( )(0.333   ) * P 2
Ka = = 3.369
(0.333   ) *(0.333   ) * P 2
 = 0.176; Ans. y1 = 0.157, y2 = 0.157, y3 = 0.509, y4 = 0.176
(P17.2) One method for the production of hydrogen cyanide is by the gas-phase nitrogenation of
acetylene according to the reaction below. For a stoichiometric feed at 300C, calculate the
product composition at 1 and 200 bar given GT= 30.08 kJ/mole.
N2 + C2H2 = 2HCN
Solution: Two mole basis. Assume ideal gas.
# of moles (N2) = # of moles (C2H2) = 1.0
Compound In Out
N2  
C2H2  
HCN  
Total 2 2
Ka = exp(-30080/(8.314*(300+273.15)) = 0.0018
(2*  ) 2 * P 2
Ka = = 0.0018 ,  = 0.0208
(1   ) 2 * P 2
(Ans. y1 = 0.4896, y2 = 0.4896, y3 = 0.0416)

J.R. Elliott, C.T. Lira, 2001-2014, all rights reserved. (11/27/14) 16
(P.14.3) Butadiene can be prepared by the gas-phase catalytic dehydrogenation of 1-Butene:
C4H8 = C4H6 + H2. In order to suppress side reactions, the butene is diluted with steam before
it passes into the reactor.
(a) Estimate the temperature at which the reactor must be operated in order to convert 30% of
the 1-butene to 1,3-butadiene at a reactor pressure of 2 bar from a feed consisting of 12 mol
of steam per mole of 1-butene.
(b) If the initial mixture consists of 50 mol% steam and 50mol% 1-butene, how will the required
temperature be affected?
Gf 600K 700K 800K 900K
C4H6 195.73 211.71 227.94 244.35
C4H8 150.92 178.78 206.89 235.35
Solution:
Compound In Out
C4H8 1 1-
C4H6  
H2  
H2O  
Total  

P = 2 bar
2 0.001 0.0012 0.0014 0.0016 0.0018
   2
 13    * P
0
2 *P
Ka    -1

 1  13    * 1     -2
 13    P -3
  -4
Ka  0.01933
ln Ka
-5
Noting that lnKa = -Gtot/RT, we can -6
identify the temperature by fitting a -7 y = -13996x + 14.34
trendline to the given data. -8
 ln 0.01933 = -3.95, -9
substitute in the equation of straight line, -10
 x = -(-14.34 – 3.95 )/13996. 1/T
 x = 0.001306 = 1/T,
 T = 765.22 K = 492OC
Compound In Out 2 *P
Ka   0.1118
C4H8 1 1-   2    * 1    
C4H6  
Similarly , T  846.65K  573.6 C O
H2  
H2O    We need higher T.
Total  
  



(P17.4) The standard Gibbs energy change for ethylene oxide at 298K for the reaction is –79.79
kJ/mole. This large negative value of GT indicates that equilibrium is far to the right at 298K
but what about 550K? Heat capacity expressions are given as CP= a + b T.
Solution: The heat of reaction must be looked up. Referring to Apx E.6 for ethylene and the
DIPPR handbook for ethylene oxide, H298 = -52.6-52.51 = -105.1 kJ/mol. Following Eqs.
14.28 and 14.30,
-105100 = J + (6.57-15.4-26.65/2) 298 + (0.1389-0.0937-0.00845/2) 2982/2
-105100 = J – 22.155 *298 + 0.040975*2982/2  J =-100317 J/mol
-79790/(8.314*298) = -100317/(8.314*298) –
79790 100317 22.155 0.040975
  ln 298  298  I  I  6.16
8.314* 298 8.314* 298 8.314 2*8.314
G  100317 22.155 0.040975
  ln 550  550  6.16  12.6
8.314*550 8.314*550 8.314 2*8.314
 G = -57.7 kJ/mol. If T = 550 K, increasing T will give an adverse effect on equilibrium,
but the reaction is still very strongly favored and the impact will be indistinguishable.
P The “water gas” shift is to be carried out at a specified temperature and pressure
employing a feed containing only CO and H2O. Show that the maximum equilibrium mole
fraction of H2 in the product results when the feed contains CO and H2O in their stoichiometric
proportions. Assume ideal gas behavior.
Solution: CO  H 2 O  CO2  H 2
Compound In Out 2
CO Ka 
z z-  z   1   
H2O  
CO2      Ka  z   1     0
2
H2   0   2  Ka[ z  (1  z )   2 ]
Total 1 +z 1 +z
 (1-Ka) +Ka (1+z)  - Ka z = 0   = {-Ka(1+z) + [Ka2(1+z)2+4z(1-Ka)Ka]1/2 }/[2(1-Ka)]
2
yH2 = /(1+z) = {-Ka(1+z) + [Ka2(1+z)2+4z(1-Ka)Ka]1/2 }/[2(1+z)(1-Ka)]

yH2 = /(1+z) = {-Ka+ [Ka2+4z(1-Ka)Ka/(1+z)2]1/2 }/[2(1-Ka)]
To find maximum, take derivative and set equal to zero.
dy/dz = 0.5[Ka2+4z(1-Ka)Ka/(1+z)2]-1/2 [4(1-Ka)Ka/(1+z)2 – 8z(1-Ka)Ka/(1+z)3] = 0
1 = 2z/(1+z)  z = 1. QED.
(P17.6) Assuming ideal gas behavior, estimate the equilibrium composition at 400K and 1 bar of
a reactive mixture containing the three isomers of pentane. Formation data are given at 400K.
Solution: This is best solved by the Gibbs minimization method, adapting Example 17.13 and
GibbsMin from the Rxns.xls workbook, we obtain the following.
Gf(J/mole) Gf400/RT feed ni log(ni) yi ni(Gi/RT+lnyi)
nPentane 40170 12.08 0 0.111 -0.95 0.111 1.100
iPentane 34310 10.32 1 0.648 -0.19 0.648 6.408
neoPentane 37610 11.31 0 0.240 -0.62 0.240 2.376
Tot 1 1.000 9.884
Out In
C-bal 5 5
Hbal 12 12

(P17.7) One method for the manufacture of synthesis gas depends on the vapor-phase catalytic
reaction of methane with steam according to the equation below. The water-gas shift reaction
also is important. Bases on stoichiometric feed of methane and steam, compute the eq
composition at 600K, 1300K and 1, 100 bars.
CH 4  H 2O  CO  3H 2 rxn(1)
H 2 O  CO  H 2  CO2   rxn(2)
Compound In Out
CH4  
H2O  
CO  
H2  
CO2  
Total 2 2+21
 G600 K  164.68  214.01  22.97  72.3kJ / mole.........................rxn(1) 
 G600 K  395.14  214.01  164.68  16.45kJ / mole......................rxn(2) 
  72300 J / mole 
Ka 600 K ,1  exp   5.08E  7
 8.314 * 600 
 
 16450 
Ka 600 K , 2  exp   27.05
 8.314 * 600 
(1   2 )(31   2 )3 * P 4 P17.7
(2  21 ) 4
Two simultaneous reactions:
Ka1 
1  1 1  1  2  * P 2 CH4 + H2O =CO + 3H2
2 
(2  21 ) H2+CO2 = CO + H2O
(Details of equations described in text)
(1   2 )(31   2 )3 * P 2
 P(bars) 100
1  1 1  1  2  (2  21 )2 T(K) 1300
 2 (1   2 ) * P 2
Ka1 16113
4  2 (1   2 )
Ka2   Ka2
1  1 1  2  * P 2 1  1 1  2  0.5400
4 1 0.4513
Note: high pressure tends to disfavor rxn (1). 2 0.1491
Rxn 1 is negligible at 600K, and rxn (2) requires
y1 0.1891
CO to run or 1-2 will be less than zero. So
both reactions are zero. At 1300 K, the situation y2 0.1377
is quite different. y3 0.1041
G1300 K  226.94  175.81  53.30  104.73 y4 0.5178
 Ka1 = 16113 y5 0.0514
G1300 K  396.14  226.94  175.81  6.614
nTot 2.9025
 Ka2 = 0.54
Objective Functions
Solving by method of Example 14.9, 1 = 0.972
err1 0.0000
and 2 = 0.015 at 1 bar. At 100 bar, 1 = 0.451
err2 0.0000
and 2 = 0.149 at 100 bar

(P17.8) Is there any danger that solid carbon will form at 550C and 1 bar by the reaction:
2CO  C S  CO2
H 298 K kJ / mole G298 K kJ / mole IN Out
CO -110.53 -137.16 2 2-2
Cs 0 0 0 0 (gas)
CO2 -393.51 -394.38 0 
Tot 2-
G298 K ,T  394.38  2 * 137.16  120.06kJ / mole
H 298 K ,T  393.51  2 * 110.53  172.45kJ / mole
Increasing T, adverse affect on equilibrium
  G298 K   120060 
Ka 298 K  exp    exp   1.08E 21
 RT   8.314 * 298.15 
Using Shortcut Van’t Hoff Eq. 14.31
 Ka  H 298  1 1   Ka  172450  1 1 
 ln       ln     
 Ka298  R  T T298   1.08E 21  8.314  823.15 298.15 
 ln Ka  ln 1.08E 21  44.4  4.06  Ka  exp(4.06)  57.99
 
 
 Ka 
yCO2 * P
  2    57.99 
 *2  
 yCO * P    2  2   2  2 
2 2 2

  2    

0.9345
 = 0.9345  ratio of carbon solid to feed is = 0.46725.  There is danger.
2
Note: this exemplifies a very important and undesirable side reaction in many catalytic reactions
know as “coking.” The carbon tends to clog the catalyst pores and substantially reduce its
effectiveness. Because of this problem, fluidized catalytic crackers were developed (aka. Cat
crackers). The solid catalyst particles are fluidized by the upflow of gaseous reactants. As they
ultimately settle at the bottom, they are removed and recirculated through an oxidation zone that
burns off the coke then recycles the catalyst to the top of the bed. This is a good example of how
thermodynamics impacts reactor design.
(P17.9) Calculate the equilibrium percent conversion of ethylene oxide to ethylene glycol at
298K and 1 bar if the initial molar ratio of ethylene oxide to water is 3.
In Out(zi)
EtO 3 3-
Water 1 (1-)
Glycol 0 
Tot 4-
Kw = Psat/P = 0.0425; KEtO = 1.76; KGly = 8.6E-4; yi = zi Ki /[ Ki +L/F*(1- Ki)]
yGly P  7824 
Ka  2
 exp    23.52 and  yi = 1 are constraints,  and L/F are
yEtO * yW * P  298.15*8.314 
unknown. Guess,  = 0.99, L/F = 1/3 (all glycol in liquid, all EtO in vapor).

(P17.9) Sample solution of one reaction with vle:
(Details of input equations described in text by Elliott and Lira)
P(bar) T(K) Ka1
1.000 298 23.52
pSat(bar) K-ratios zFeed yi xi

EtO 1.76000 1.76000 0.66676 0.99961 0.56796
Water 0.04250 0.04250 0.00029 1.579E-05 0.00037
Glycol 0.00086 0.00086 0.33295 0.00037 0.43167
1.0000 1.0000 1.0000
1- 8.7055E-04
 0.99913 sum(yi-xi) 0.00000
L/F 0.77111 ErrKa 5.583E-07
As it turns out, the ethylene oxide is not so volatile after all and dissolves a fair amount in the
liquid. The guess about the extent of conversion being high was good though. A more clever
engineering approach would be to assume complete conversion and solve the simple flash. Then
back out the exact conversion assuming L/F does not change.
(P17.10) Acetic acid vapor dimerizes according to 2A1 = A2. Assume that no higher-order
associations occur. Supposing that a value for Ka is available, and that the monomers and
dimers behave as an ideal gas, derive an expression for yA1 in terms of P and Ka. Then develop
an expression for PV/n0RT in terms of yA1, where n0 is the superficial number of moles
neglecting dimerization. Hint: write n0/nT in terms of yA1 where nT = n1+n2.
Solution:
n0 n1  2n2
  y A1  2(1  y A1 )  2  y A1
nT nT
y A2 1  1  4 PKa
2
 Ka  1  y A1  y A21 PKa  y A1 
y A1 P 2 PKa
PV PV n 1
Ideal gas  1  T 
nT RT n0 RT n0 2  y A1
Note: as Ka  , PV/n0RT  ½ because the monomer is converted to dimer. Note also that
PV/n0RT is what we normally refer to as the compressibility factor, Z. This is an interesting
result with regard to equations of state and phase equilibria. Since Ka is simply a function of
temperature [ie. exp(-G/RT)], it says that we can compute Z given a pressure and temperature.
This is analogous to the pressure explicit virial equation (Section 7.4), but the form of the
pressure dependence is more complex. Exploring this perspective, generalizing to density-
dependent equations, and adapting to multimer-forming species and mixtures is the subject of
Chapter 19. Most of the physical insight contained in Chapter 19 is contained in this simple
practice problem.


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Chapter 2 Practice Problems

(P2.1) Energy Balance: …………………………………………………………Eqn. 2.33

 the final energy balance becomes.

(Chap 3 will consider reactions such as Combustion gases

combustion, but the E-balance doesn’t need to be

(P2.4) (Solution for gas furnace.) Assume house is air-tight, m in  m out  0 .

(P2.5) System is child:

The work terms are equal and opposite

To accompany Introductory Chemical Engineering Thermodynamics

(P2.6) System: the bulb and its contents.

(P2.8) System: the balloon and its contents.

(P2.12) a. Unsteady-state closed system WEC  0(rigid ) U  Q

(P2.13) Unsteady state, closed system.

(P2.14) Steady state, open system.

To accompany Introductory Chemical Engineering Thermodynamics

(P2.16) Steady state, open system.

a) P1 = 15 MPa , T1 = 600oC  H1 = 3583.1 kJ/kg (Steam Table)

To accompany Introductory Chemical Engineering Thermodynamics

(c) PgVg = constant, since isothermal, P2 = P1V1/V2 = 4 bar

To accompany Introductory Chemical Engineering Thermodynamics

Initial and final conditions , P1 = 50 psig = 64.7 psia = 0.4462MPa.

Overall E-bal around both sides:

(a) Δ 0 and Δ 0. When piston stops the first time, Δ 0, because v =0 at

To accompany Introductory Chemical Engineering Thermodynamics

nLRTL = PLVL = 0.8 MPa(105cm3) = 8E4 J

Eqn (2) still applies. Force balance:

To accompany Introductory Chemical Engineering Thermodynamics

To accompany Introductory Chemical Engineering Thermodynamics

To accompany Introductory Chemical Engineering Thermodynamics

(P3.4) two dice.

(P3.6) (a) m-balance: dnin = -dnout

(P3.7) (a) Steady-state flow, ΔH = Ws

Start 1 mole basis:

To accompany Introductory Chemical Engineering Thermodynamics

(P3.8) Adiabatic, steady-state open system ⇒ Q = 0, &(Cp/R = 7/2)………………………… ig

(P3.9) work required per kg of steam through this compressor?

P(MPa) T(OC) H(kJ/kg) S(kJ/kg-K)

W = ΔH = 3446 − 2839.7 = 606.3kJ / kg

⇒ ΔH ' = W ' = 3246.7 − 2839.7 = 407kJ / kg

TOC HL(kJ/kg) ΔHvap(kJ/kg)

H = H L + q(ΔH Vap ) = 1006.46 + 0.98 * (2441.68) = 2493k .49 J / kg

State P(MPa) T(OC) H(kJ/kg) S(kJ/kg-K)

To accompany Introductory Chemical Engineering Thermodynamics

⇒ ΔH = WS = 4870.3 − 2674.95 = 2195.35kJ / kg

(P3.13) Through the valve ⇒ H in = H out

P in = 3MPa P out = 0.1MPa Tout = 110O C = 383.15K

150 − 110 2776.6 − H out

2856.5 − 2695.96 6.2893 − S in

To accompany Introductory Chemical Engineering Thermodynamics

150 − 110 7.6148 − S out

To accompany Introductory Chemical Engineering Thermodynamics

To accompany Introductory Chemical Engineering Thermodynamics

(P4.3) 15 molecules in 3 boxes, molecules are identical

(P4.4) two dice.

(P4.6) (a) m-balance: dnin = -dnout

(P4.7) (a) Steady-state flow, H = Ws

Start 1 mole basis:

To accompany Introductory Chemical Engineering Thermodynamics

(P4.8) Adiabatic, steady-state open system  Q = 0, &(Cp/R = 7/2)………………………… ig