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Instructor's Soltutions

JlLlluJu,,'lion to

CHElV1lCAL ENGINEERING THERrvl0DYN AMICS

Sixth Edition

p

J. ~'L Snlith • H. C. Voln Nt'5S • 1\1.1\<1. Abbott

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--."'-.;

Chapter 1 - Section A - Mathcad Solutions

1.4 The equation that relates deg F to deg Cis: t(F) = 1.8 t(C) + 32. Solve this equation by setting t(F) ;;;; t(C).

Guess solution: t := 0

Given

t = 1.8t + 32

1.5 By definition:

F P= - A

F = mass·g Note: Pressures are in gauge pressure.

F:= P·A

m g = 9.807- 2 s

A := ~. 02 A = 12.566mm2 4

mass i= F :·w~r¥'·:~'~~.,*:~~, . .- ADs. g

P:;;:::3000bar

1.6 By definition:

F P= - A

F = massg

F:= P·A

ft g = 32.174- 2 sec

A := 2.D2 A = O.023in2 4

mass := F;~~-"E:~Ppq~~lgP1 ADs. g

P ,:= ,3000atm

D:;;::: O.17in

1.7 Pabs = p-g-h + Patm

, ""gm

P':;;:::,13.535·-', ,-, , ,3 ·em

m g:= 9.832·- 2 s

h := 56.38cm

Patm:= 101.78kPa

Pabs := p-g-h + Patm

1.8

, ',gtn

P := 13.535·-,'-, 3 em

'ft g:= 32243·-- 2 s

h:= 25.62in

Patnl:~;29.86in_ Hg

Pabs := p-g-h + Patm

1

1.10

.•... gm Assume the following: p" .:= 135-.-' . '3 -em

. ··.m

g':= 9.8- . '. 2

s

P :;;;;; 400bar

p h:=p.g

Ans.

1.11 The force on a spring is described by: F = K x where K is the spring constant. First calculate K based on the earth measurement then gl\1ars based on spring measurement on Mars.

On Earth:

F = mass-g = K-x

mass :=O.40kg

.' .... m

g r= 9.81'---' . '., .... 2

s

x:= 1.08cll1

F := mass-g On Mars:

F = 3.924N

K'= F x

K = 363.333 N m

x r= OAOem FMars gMars:= -mass

FMars = 1.453N

Ans.

1.12 Given:

d

-p:::;: -p.g

dz

and:

M·P p=R·T

Substituting:

d M·P

-p = -_.g

dz R·T

Separating variables and integrating:

fPDenver 1 Jzoenver (M.g)

-dP= - - dz

P R·T

Psea 0

After integrating:

(PDenver) _ -M·g

In - --'ZDenver

Psea R·T

Taking the exponential of both sides and rearranging:

(-M-g )

_ ~'ZDenver

PDenver - psea·e

Psea:= latm

M:=29gm mol

2

1.15

- .3

.' .. cm-arm

R:= 82;06 .

. . mol- K

'r:={IO + 273.15)K

M.g

--'ZDenver = 0.194 R-T

(-M.g )

R- T - ZOenver

PDenver := psea·e

ZI>enver.:= ··1, mi

1.13 The same proportionality applies as in Pb. 1.11.

....... ... .. ..ft

·gearth :=32.186,~ . 2

·s

.... . .. :ft

gmoon .;= 5.32~2 s .

gearth ~learth := ~lmoon'-gmoon

Ll1earth = 113.498

Wmoon := M'gmoon

1.14

5.00dollars hr

costbulb := ·10-

1000hr day

O.ldollars hr

costelec := ·IO-·70W

kW·hr day

dollars costbulb = 18.262-yr

Altnooh :=18.76

Ans.

ADS.

dollars costeJec = 25.567-yr

:illlij~I~~~Ans.

costtotal := costbulb + costelec

D := 125ft

mass :=. 2501bm

Patm :::::30.12in_Bg

n 2 A :=-·D

4

3

. __ ._-----

. ft

g .::;= 32.169 ~ 2 s

A = 1.227ft2

(a) F:= Patm·A + mass·g

ADS.

F (b) Pabs:=A

ADS.

(c) L\.l:= L 7ft

Work := F·6.1

ADs.

ADs.

1.16

D:~ 0.47m

mass:= 150kg

m

g :=·9.&13;."..; '2 s

Patm.:= 101.57kPa

11: 2 A :=-·D 4

~~·:;~.~:'i:~p~~~:~t~Q!:;~

2 A = 0.173m

(a) F:= Patm·A + mass-g

ADS.

F (b) Pabs:=A

ADS.

(c) 6.1 :=O.&3rn

Work : .... F·L\.I

.~gt~·~·~t::t~'~~:~~~l~ ADS. '~g~:'E!'tt.:~%1·~ ADS.

1.18

mass:» 1250kg

ill u :=40-

s

1 2

EK := +rnass-u

2

Work:= EK

g~,[~~':il."R;"!~~E:W ADS. W~rk·~·i:·~.,io~J(J ADS.

1.19 Wdot = mass·g·bh .0.91.0.92

time

Wdot:=200W

m

g :"" 9.&'_;" .' 2

s

L\.h:=5Om

Wdot mdot := ----g·b,h·0.91·0.92

ADS.

4

Chapter 2 - Section A - Mathcad Solutions

2.1 (a)

Mwt:= 35·kg

m g:= 9.8·- 2 s

Az:= 5'm

(b)

AUtotal := Work

Ans.

(c) By Eqs. (2.14) and (2.21):

dU + d(PV) = Cp·dT

Since P is constant, this can be written:

MH20·Cp·dT = MH20·dU + MH20·P·dV

Take Cp and V constant and i~tegrate: MH20·CP·(t2 - t1) = AUtotal kJ

t1 :=20·degC Cp := 4.18· .- MH20 :=25·kg

kg·degC

AUtotal t2 := t1 + ~--MH20'Cp

(d) For the restoration process, the change in internal energy is equal but of opposite sign to that of the initial process. Thus

Q := -AUtotal

(e) In all cases the total internal energy change of the universe is zero.

2.2 Similar to Pb. 2.1 with mass of water == 30 kg.

Answers are:

(a) W = 3.43 kJ

(b) Internal energy change of the water = 2.86 kJ

(c) Final temp. = 20.027 deg C

(d) Q = -2.86 kJ

5

2.4 The electric power supplied to the motor must equal the work done by the motor plus the heat generated by the motor.

i .= 9.7amp

E:= HOV

Wdotmech:= L25hp

Wdotelect .= j·E

3 Wdotelect = 1.067 x 10 W

Qdot := W dote1ect ~ W dotmech

2.5

t

Eq. (2.3): L1U = Q + W

Step 1 to 2: AUt12. := ..,..2001

Q12 := L\Ut12 ~ W 12

W12 ::=-6000J

'~!~a.·~"~~~{*j:t~~~J\

Ans.

L1Ut34 := Q34 + W34

W34:= 3001

'~~!~~J;j;~~~~~g.J,~,j

Ans.

Step 3 to 4: Q34:;;:;: -8001

Step 1 to 2 to 3 to 4 to 1: Since L\Ut is a state function, L\Ut for a series of steps that leads back to the initial state must be zero. Therefore, the sum of t

the AU values for all of the steps must sum to zero.

Step 2 to 3:

3 L1Ut23 = -4 x 10 J

Q23:= -38001

il'1~?::~·§t~igI~;·.

Ans.

For a series of steps, the total work done is the sum of the work done for each step.

6

Ans.

Step 4 to 1: LlUt41:= 47QOJ

3 W41 = 4.5x 10 J

Q41 := L\Ut41 - W41

Note: Q12341 = -W12341

Ans.

2.11 The enthalpy change of the water = work done.

M:= 20;kg

, '" ,'. kJ

Cp.i= 4.18·_;__.;..-

, 'kg·degC

. . ' . . -

At::::: .1 O·degC

Wdot :=0.25·kW

M·Cp·Llt L\'t:= ---

Wdot

2.12

Q :=7.5·kJ

AU :=-J2·kJ

W:== AU """'-' Q

':W:;~tts:i~i$kJ Ans,

'~~~':fgt2@ ADs.

AU := -12·kJ

Q := liU

2.l3 Subscripts: c, casting; w, water; t, tank. Then

IDe·liUe + mw·t\..Uw + mt·t\..Ut = 0 Let C represent specific heat,

C = Cp = Cv

Then by Eq. (2.18)

me:= 2·kg

mw:= 40·kg

kJ Cc := 0.50· "', ,', ,,'

" kg-degC

kJ

Ci := 0.5: ",' ", ... ,,',

,kg·degC

',,', 'kJ

Cw:=4.18· """"

" ' '"kg·degC

tc := 500· degC

tl := 2s·degC

(guess)

Ans.

7

2.15 mass:» J-kg
(a) AT :=lK
m
(b) g:= 9.8-
2
s
AEp
Az:=
mass-g
(c) AEK:= AUt 2.17

Ai:::::. SOm

D:=2m

mdot := pu-A

. kJ

Cy:= 4.18-~

. kg·K

fo,Ut := mass.Cv·AT~y~::\~c'4fJ$~ ADS.

AEp:= AUt

~~]>~:~~'§t§J)l~ ADS.

u:~ j ~~::"

Ans.

.kg p :=1000- ..

m3

m u:=5~ S

IT 2 A :=-D 4

2 A = 3.142m

4 kg mdot = 1.571 x 10 -

S

2.18 (a)

.... . kJ U 1 :=762.0· kg

(b)

.' kJ

U2 := 2784.4·-.' .'

, .. k

. g

PI :"" lQ02.7~kPa

.' '. ->. 3

: .r- em' VI := 1,128·-: ··gm

ADS.

P2:= 1500·kPa

. 3

, ·em

V2:= 169.7·-'

. gm

AH := H2 - HI

ADS.

ADS.

8

- .. ~''''--

2.22

D1 :=2.5cm

·····.m uj :=2.....: s

. Di· ~= 5cm

(a) For an incompressible fluid, p=constant. Bya mass balance, mdot = constant = UtAtP = uZA2p.

mdotj-Hj - (mdotl·Hl + mdot2-H2) = Qdot mdotj - mdot 1 - mdot; = 0

mdotl·(H3 - HI) + mdot2·(H3 - H2) = Qdot mdot.Cp.(T3 - r.) + mdot2·Cp.(T3 - T2) = Qdot T3·Cp.(mdotl +mdot2) = Qdot+ mdotj-Cp-Tj +rndotj-Cp-Tj

(b)

2.23 Energy balance:

Mass balance:

Therefore:

or

kg rridotj t= 1.0- '.

. s

kJ Qdott> ....:.30_:_

s

Ans.

II := 25degC

.. . kg mdot2 := 0.8-.

. . s

T:2.:=·75degC

kJ Cp:= 4.18-·.-kg·K

2.25 By Eq. (2.32a):

By continuity, incompressibility

Mf = Cp·AT

kJ Cp:= 4.18· ...........••. .. .. kg·degC

9

SI units:

Dl.::=.2,S·cm

D2 :=3.8·cm

Ans.

D2 :=7.5cm

L1T := ~.[ 1 _ (01)4J

2·Cp D2

Ans.

Maximum T change occurrs for infinite D2:

L1T := ~.[ 1 _ (DI)4]

2·Cp D2

Ans,

2.26 T 1:= 300K Tz:= 520K

... m

uI:= lO~ s

m li2 := 3.5-

. s

. k

molwt:= 29~ krnol

Wsdoti= 98.8kW

kinoI ndot .= 50 -.-

. .. hr

7 Cp :=-·R 2

L1H := Cp.(Tz - TI) By Eq. (2.30):

Qdot :~ [ ill I + [ u~ 2 - un molwt J ndot - W sdotC,llt~t,;cfj:9 ;<)</4k WAn s.

3 kJ Llli = 6.402 x 10 --

kmol

2.27 By Eq. (2.32b):

2 L1U L1H =-- 2·ge

also

VI T1 P2

By continunity, constant area

V2 Uz = li1'VI

2 2 2

L1U = li2 - ul

10

P}:=lQO·psi

II :=,579_67;ral1kine

fl·lbf

R = 3.407 -"",--. -'---~ mol-rankine

T2 := 578·rankine

" ... gm

molwt.r= 28- .. - r: . . mol

(guess)

7 Ul2 ~(T2 PIJ2 ]

-.R.(T2 - r.) = -_. -._ -] -molwt

2 2 T] P2

T2 .= Find(T2) ii!~··~1$Y~1'filirtRih~

,'-.':. - .,-;:,',.--.>-.-.", ;"~:: ."_ .

Given

'. m 2.28 Ul:::::: 3---s

By Eq. (2.32a):

. ill 2.29 lil := 30·--s

m ti2 := 500·s

Ans.

(119.1S·degF)

.' '. m U2::::;:; 200;-s

-, .... . ..•...... 'kJ Hj ;=334.9·-.· ..

. kg

.... , .kJ

H1:== 2726.5--. ' .•. kg

2 2 u2 - ul

Q:= H2-HI +--- 2

Ans.

.'. . .... kJ

H .. '1 := 311205'-

. kg

.: .: .. kJ

H2 .= 2945.7· _.' • kg

(guess)

By Eq. (2.32a): Given

Continuity:

3 em V 1 :,;" 388.61·-'. - gm

3

. .. em

V2 :=667.75-- •.. _'. gm

Ans.

11

2.30 (a) tt :,,;,'30.degC

12 := 250· degC

, J "

Cv:= 20.8· ,',

, mol-degC

By Eq. (2.19): Q := n.Cy.(t2 - tI)

n:~ 3·mol

Take into account the heat capacity of the vessel; then

my:= 100-kg

, kJ c,,:= O.s.~,.;._' - kg·degC

(b) tl :=200~degC

tz .= 40· degC

'Cp:=29.1. Joule

, mol-degf:

By Eq. (2.23):

2.31 (a) t1:= 70·degF

t2 := 350·degF

BTU CV:=5·.','" """ ' mol-degf

By Eq. (2.19):

Take account of the heat capacity of the vessel:

my := 200· Ibm

BTU Cy := 0.12·-~___;,

, Ibm·degF

ri i= 4·mol

Ans.

(b) tl:= 400·degF

" BTU

Cp:= 7·" ",

, .mol-degf

Q := n.Cp.(t2 - t1)

By Eq. (2.23):

(9~;~;.:~ZR9~~11~

12

n:::::o 4·mol

Ans.

Ans.

Ans.

Ans.

2.33

2.34

. . BTU

HI :=1322.6·___.;.Ibm

.' . . .... ft3 V 1:::.::3.058·-··.·_.

Ibm

rc 2 _·Dl ,uI

4

mdot:=---

VI V2

U2 := mdot·-rc 2 _·D2

4

'. . . BTU

H2 :=1148.6·-.- ... c:

.' ' .. 'lbnl

·.it ul:==10·~ s

.. " • ft3

V2:= 78.14·-··Ibm

4 Ib mdot = 3.463 x 10 - sec

ft uz = 22.997- sec

2 2

u2 - ul

Eq. (2.32a): Ws:= H2 - HI + --- 2

Wdot .= -Ws·mdot

BTU Ht:= 307·- .. :-.' :

. . '" Ibm

ft?

VI := 9.25·Ibm

rc 2 _·DI 'UI 4

mdot:=---

VI V2

U2 := mdot·-rc 2 -·D2 4

BTU Ws = -173.99-Ib

ADs.

.. '<. I1TU H2 :== 330"-"'-, .. lb

m

DI := 4·in

Ib mdot = 679.263- hr

ft U2 = 9.686- sec

BTU Ws:=5360,-' . _-_ ..

. Ibrnol

2 2

il2 -UI Ws BTU

Eq. (2.32a): Q:= H2 - HI + - -- Q = -98.82--

2 molwt Ibm

Qdot r= mdot-Q c~ili~'llli~ Ans.

13

._-- -----

2.36 T I := 300· K

P := I-bar

n:=

I·kg

n = 34.602mol

gm 28.9·mol

bar·cm3 r,

VI := 83.14· .-

mol-K P

3 em

VI = 24942- mol

Whence

W := -n·P·2· V 1

Ans.

Given:

Whence

. joule

Cpt= 29." .

·moi'K

Q:= n·~H

n

Ans.

zu := _Q_+_W_

2.37 Work exactly like Ex. 2.10: 2 steps, (a) & (b). A value is required for PVff, namely R.

J

R = 8.314-rnol-K

TI:= 293.1S·l( PI ::;: lOOO·kPa 7 .

Cp := ~~R 2

T2 ::;:::333.15·K P2 ::;::: lOO·kPa 5 .

Cy:=--R . 2

(a) Cool at const VI to P2 (b) Heat at const P2 to T2

Ta2 = 29.315K

14

3 J ~Hb = 8.841 x 10 -

mol

3 J ~Ua = -5.484 x 10 - mol

R·TI VI:= -PI

3 -3 m VI = 2.437 x 10 - mol

3 m

V2 = 0.028- mol

3 J ~Ha = -7.677 x 10 -.mol

3 J ~Ub = 6.315 x 10 -. mol

Ans.

Ans,

15

Chapter 3 - Section A - Mathcad Solutions

3.1 ~ = ~tT p) p

At constant T, the 2nd equation can be written:

dp

- = K·dP

P

~ := _1n_(_1._01_)

~p = 225.2bar

K

Since

-_ 3 _ em

c.:= 0.125·-- - gm

fV2

Work = - PdY

VI

3.4 b :=2700·bar

-- -r- 6 -_ 1

.1( := 44.1S.IO -bar P2 = 1.01· P 1

PI := I-bar

P2 := 500·bar

a bit of algebra leads to

fP2

Work:= c- _P- dP

P +b

PI

Alternatively, formal integration leads to

3.5 K = a + b-P

- - - -~6- -1

a:= 3;9·10·atm -

P2 := 3000'atm

Combine Eqs. (1.3) and (3.3) for const. T:

fP2

Work .= y. (a + b·P}P dP

PI

16

Ans.

b := -O.I.1O-9~atm~2 3

V := l-ft (assume const.)

ADS.

----------

1 . m3 VI := -_ .. - .. _ ... _.

1590 kg

. kJ

Cp:=O:84·· .

. . kg-degt:

M:,..5·kg

P:= l-bar

tl := O·degC

t2 := 20· degC

With beta independent of T and with P=constant,

dV

- = l3·dT V

Li Vtotal := M·LiV

Ans.

Work := -P·Li Vtotal (Con st. P)

3.8 PI:= 8.bar

Q := M.Cp.(t2 - tl)tfs'J1:)q Ans.

Lllitotal := Q tlil~:~,~~,~!~ ADS •

P2 := l-bar

Tl .= 600·K

7 Cp:="..·R 2

. ·5 .. Cy:=_·R

2

(a) Constant V:

P2 T2:= Tl·_

PI

LiU := Cy-LiT

Llli := Cp·LiT

(b) Constant T:

Work := RTlm(:~J

(c) Adiabatic:

W = 0 and

LiU = Q = Cy·LiT

LiT = -525K

Q and

Ans,

Ans.

LiU = LiH = 0

and

Q=W

Q and

ADS.

Q=O

and

L\.U = W = CV·L\.T

17

Cp y.=Cv

Wand

3.9 P 4:== 2bar

PI:= lObar

T2 = 331.227K

.6.U := Cv·.6. T

~~i~;~~~f~ii! ADS,

•.....•... 7

Cp :=-R 2

5 Cv:= -R 2

Tt:== 600K

R·Tl VI :=-PI

R

T4:~ Tl{;:t

Step 41: Adiabatic

.6.U41 := CY·(TI - T 4) i1H41 := Cp.(TI - T4) J

Q4I:= 0-

mol

T2:=600K

Step 12: Isothermal

J .6.U12 := 0-

mol

18

L'lH := Cp- L'l T

ADs.

3 -3 m VI = 4.988)( 10 -

mol

T4 = 378.831K

3 J i1U41 = 4.597 x 10 -

mol

3 J i1H4l = 6.436 x 10 -

mol

J Q4I = 0- mol

3 J W4I = 4.597 x 10 - mol

3 m V2 = 0.017- mol

J i1U12 = 0- mol

J ilH12:= 0·mol

Step 23: Isochoric

J W23:= 0- mol

J ':\H12 = 0- mol

3 J Q12 = 6.006 x 10 -

mol

3 J W12 = -6.006 x 10 -

mol

T3 =400K

3 J .:\U23 == -4.157x]0 -

mol

3 J .:\H23 = -5.82 x 10 -

mol

3 J Q23 = -4.157 x 10 -

mol

J '

W23 = 0-

mol

T4 = 378.831 K

R·T4 ,m3

V4:= -- V4 = 0.016-

P4 mol

Step 34: Isobaric

J ,:\U34 = -439.997- mol

J ilH34 = -615.996- mol

J Q34 = -615.996- mol

J W34 = 175.999- mol

3.10 For all parts of this problem: T2 = T] and

6.U = ilH = 0 Also Q = -Work and all that remains is

to calculate Work. Symbol V is used for total volume in this problem.

19

Pjr=vl-bar

P2:= 12·bar

(a)

(b) Step 1: adiabatic compression to P2

P2'Yi-PI'YI Wl:=----y - 1

Step 2: cool at const P2 to V2

(c) Step 1: adiabatic compression to V2

Work:~ hVlm(:~)

.W()tK~/:g~.?~<~~ ADs.

(intermediate V)

3 Vi = 2.702m

(intermediate P)

Pj·V2-PI,VI WI :=----y - 1

Step 2: No work.

(d) Step 1: heat at const VI to P2 WI = 0

Step 2: cool at const P2 to V2

20

Work:= WI

Work:= W2

WI zz: 3063kJ

W2 = 2042kJ

Pi = 62.898 bar

WI = 7635kJ

(e) Step 1: cool at const PI to V2

WI = ] IOOkJ

Step 2; heat at const V 2 to P2

Work:= Wi

'waHz:i':'j,f6hkJ

.- .-'- .- c' ' •• _.' • - .:.-(. __ ":~':_:., : ••

Ans.

3.17 (a) No work is done; no heat is transferred.

t

6.U = .6.T= 0

T2 = r. = IOO-degC

Not reversible

(b) The gas is returned to its initial state by isothermal compression.

Work = nRTln(~~J

but

, 3 VI := 4·m

4 3 V2:= -·m 3

3.18 (a) Pj := lOO·kPa 7

Cp ::='..;.·R

2

P2;= 50Q·kPa

T1,:= 303.15·K Cp y:=-

Cv

,5 Cv:=-·R 2

Adiabatic compression from point 1 to point 2:

kJ Q12:= 0-mol

6.U12 := Cy-(Tz - Tl)

,~~})i~,i~\~~~~~;

6.H12 := Cp'(T2 - r.)

;~,l1,.·".".:,},~.~.i~,.";,,,·.,·· .• ·,~~i~;~

.- .- c_ .- • r' _-.- -0- "-"-" '~, .-.-

Ans .

21

Cool at Pz from point 2 to point 3:

kJ L1H23 = -5.15- mol

Ans.

kJ Q23 = -5.15- mol

Ans.

Isothermal expansion from point 3 to point 1:

"'U31 = "'H3I = 0 P3 r= P2 W31 :~ R.T3.ln(~:J

Q31 := -W31

Ans.

FOR THE CYCLE: L1U = 1I.H = 0

Q := Q12 + Q23 + Q31 Work:= W12 + W23 + W31

i~I~!~!~i~~h~~i~~j~;I~

(b) If each step that is 80% efficient accomplishes the same change of state, all property values are unchanged, and the delta H and delta U values are the same as in part (a). However, the Q and W values change.

Step 12:

W12 W12:= -- 0.8

Q12 := 1I.U12 - W12

Step 23:

W23 W23:= -- 0.8

22

--- ~----.----

Step 31: W31:= W31,O,8

FOR THE CYCLE:

Q := Q12 + Q23 + Q31

Work:= W12 + W23 + W31

IIlll£!lt

3.19 Here, V represents total volume.

Pf:~lOOO.kPa

V ····3

.. i:= I-rn

... joule Cp:=21·-mol·K

Cy:= Cp - R

Cp y:=Cv

Work ~ nRT,ln( ~~)

(a) Isothermal:

T2 := Tl

ADs.

(b) Adiabatic:

P2'Y2-Pl'Yl Work := ----y - I

23

3.20

(c) Restrained adiabatic:

Pext :"" 100·kPa

PI,VI

n:=--

KTI

Work T2:= --+T] n·Cy

VI T2 P2:= P1'-'V2 TI

Tl:= 423.15·K

. 7 Cp :=-·R 2

Step 12:

If

VI V]

r=-=-

V2 V3

kJ W12 = -2.502- mol

Step 23:

kJ Q23 = -2.079- mol

Process:

Work = L1U = -PexrL1 V

AU = n·Cv·AT

Ans.

Ans.

P3 := 3·bar

5 Cv r= -·R 2

. kJ

L~llt2 .= 0·- .. - ".

. . mol

T3 := 323.15·K

·kJ AU 12 :=0'-· - .,

.. mol

Then

TI P3

r:=-·-

T3 PI

kJ Q12 = 2.502- mol

kJ W.2··3.· t= 0·-. - . .... .. mol

kJ AU23 = -2.079- mol

kJ Mi23 = -2.91- mol

Work:= W12 + W23

ADS.

Q ;= Ql2 + Q:n

24

LllI := i1H 12 + i1H23

Ans.

Ans.

3.21 By Eq. (2.32a), unit-mass basis:

molwt := 2Sgm

. mol

1 2

i1H + -·Au = 0 2

But

i1H = Cp·AT

Whence

.7 R Cp :='2' rnolwt

· ..... ····m

til:= 2.5--'s

2 2 u2 - li1

tz > t1---- 2·Cp

3.22

7 Cp:;:::: ~~R

2

... 5

Cv:=-'R 2

Tl := 303.15·K

PI := l-bar

P3 := lO·bar

i1U := Cy.(T3 - Tl) .····.······•··· •• "f··'.·····' •• ·· C·i:'.·, (:.1tJi

. ·i\U-==2~n79~

, . ·'·'·-mol

Ans .

i1H := Cp.(T3 - r.)

~)~!~i":

ADs.

Each part consists of two steps, 12 & 23. T2 P2:= PI'-

Tl

Work:= W23

'$~~~~~i Ans,

25

Q := llU - Work

~s~~t~~~~i Ans,

Q12 :"'" M112

kJ W12 = -0.831- mol

kJ W23 = 7.718- mol

Q := llU - Work

.: ---; .-:'- - kJ'

W!~k- :,' 6:.~8~.~~I

~.~~t~i~

ADS.

Work:= W12 + W23

ADS.

(c)

WI2:= RT"~{~~J

Q23 := ~H23

Work:= W12 + W23

11'~1i~i Ans.

", kJ

Q = -2.894.-'-' Ans.

. mol

Q := llU - Work

For the second set of heat-capacity values, answers are (k.J/mol):

ilU = 1.247

llU = 2.079

(a)

Work = 6.762

Q = -5.515

26

(b) (c)

3.23

PI := l-bar

For the process:

Step 12:

kJ W12 "" 5.608- mol

Step 23:

For the process:

Q := Q12 + Q23

Work = 6.886

Q = -5.639 Q = -3.725

Work = 4.972

T3 := 393.l5·K 7

Cp;= ..;;;.,R

, 2

5 Cv:='":"·R 2,

~u := CV·(T3 - Tl)

~WJ~'rf;~~\(:~r

~H := Cp.(T3 - Tt)

',.') 'i;-:-"id

Llli = '2.619 _- - Ans.

- r - '-' - -. - niol

• < .' -~?'."

Q12 := -W12

kJ Q12 = -5.608-'-, mol

kJ W23 := 0·-- 'mol

Q23 := ~u

Work:= W12 + W23

ADS.

T3 = Tj So ...

W= R.h1n(;J

But

Also

In(_P ) = _T_2_-_T_1

PI r,

Therefore

r, := 800·K

27

ADS.

3.25

3 VA:= 256·cm

r:= -0.0639

Define:

Assume ideal gas; let V represent total volume:

-VA"Cr+ 1) VB:=----

-----

r

Ans.

Cp y:=· .. CV

P(final) = P2

The process occurring in section B is a reversible, adiabatic compression. Let

TB(fmaI) = TB

Since the total volume is constant,

2·nA·R·Tl nA·R-(TA + TB)

=------

PI

or

--=---

(a)P2:= 125'atm

y-I

(P2J Y

TB:=TI' Pt

Q = nA{1..U A + ~UB)

q := CY·(TA + TB - 2.TI)

Define

- Q q--

nA

28

(1)

(2)

(3)

Ans.

(b)

Combine Eqs. (1) & (2) to eliminate the ratio of pressures:

TA :=42S·K

(guess) TB := 300·K

y~l

Given

(1)

(e)

By Eg. (2),

TB:= 325·K

(1)

TB := Find(TB)

:~t~{~~~l:~~9~i{ ADs. c~Z~0.J~~~~@

Ans.

Ans.

c_pi;¥,"':1'&23'~im ADs .

• c ._. • ••• ~ ;,-~ _;-':'~'-._ .,~_ c:.

:fX-;~f16~j(

~ ~-~:' ; 0-.:,2 ._ .. ~

ADS.

Ans.

(d)

Eliminate

TA + TB from Eqs. (1) & (3):

kJ q:=3·mol

(2)

(1)

29

'T~ .. ::in$19:66E.: Ans.

. ,," -. . ... ~,' . - ~ , ..... -,; ", ..

3

..... em

3.30 B:=~242.5·-··-·

mol

. 6 .... ···..cm

C :=25200·_····_·

. '; 2

mol"

T:= 373.lS·J(

P2 r= 55·bar

B

B':=-

R·T

-3 1 B' = -7.817 x 10 - bar

c- 82

C':=---

C' = -3.492 x 10- 5 _1_ bar2

(a) Solve vi rial eqn. for initial V.

Guess:

R·T Vl:=p]

Given

B C = 1+-+-

Vl V/

Vl := Find(VI)

3 em VI = 30780- mol

Solve virial eqn. for final V.

Guess:

Given

PZ'Y2

---

R·T

B C 1+-+-

V2 vl

3 em V2:-:: 241.33- mol

Eliminate P from Eq. (1.3) by tbe virial equation:

Ans.

(b) Eliminate dV from Eq. (1.3) by the vlrial equation in P:

30

ADS.

Note: The answers to (a) & (b) differ because the relations between the two sets of parameters are exact only for infinite series.

3.32 T c .= 282.3' K

T := 298.15·K

Tr = 1.056

P;=12·bar

p Pr;= - Pc

Pr = 0.238

01:=0.087

(guess)

(a)

3 . em.

B := -140--·· _ ...

mol

6

. .. em

c:= 7200·_· ._.

mor

R·T V:=P

3 em V = 2066- mol

Given

p.y B C

-=1+-+R.T Y y2

<~·,g'·tj§'I~S~~

. ·····mol

Y := Find(V)

(b)

0,422 BO .= 0.083 - _T 1.6

r

BO = -0.304

0.172 Bj := 0.139 ---

T 4.2 r

-3 B, = 2.262 x 10

Z·R·T V:=--

p

(c) For Redlich/Kwong EOS:

o.r= 1

E := 0

Q ::::: 0.08664

'¥ := 0,42748

Table 3.1

-05 a(Tr) ;= Tr .

Table 3.1

Eq. (3.51)

31

Eq. (3.50)

Calculate Z

Guess:

Z:= 0.9

Z := Find(Z) Z = 0.928

Z·R·T Y:=-p

ADs.

(d) For SRK EOS:

0: :.=;:1

E:= 0

o := 0.08664

'l' :== 0.42748 Table 3.1

Table 3.1

q(Tr) '. __ 'l"CX (r, , ill)

Eq. (3.51)

or,

Eq. (3.50)

Calculate Z

Guess:

Z:= 0.9

Given Eq. (3.49)

Z := Find(Z) Z = 0.928

Z·R·T V:=--

ADs.

p

(e) For Peng/Robinson EOS:

a:= 1 +[2

E:= 1 - [2 n := 0.07779

'P := 0.45724 Table 3.1

a (r-, (0) := [ 1 + (0.37464 + 1.54226", - 0.26992,}). [1 - T) ) J 32

Table 3.1

q{Tr);= tp.a{Tr,co) Q·Tr

Calculate Z

Eq. (3.51)

Eq. (3.50)

Guess:

Z:= 0.9

Given Eq. (3.49)

Z := Find(Z)

Z = 0.92

v:= _Z_'R_'_T P

ADS.

3.33 Tc :=305.3;K

T:=323.l5·K

T, ;;;;; 1.058

Pc := ,48.72·bar

P :~ I5·bar

p

Pr:= - Pc

P, = 0.308

co :=0.100

(guess)

(a)

3

, ,em

B := "-156.7·-' -,' mol

,6 , ,em

G:= 9650·-' -" 2 mol

R·T Y'=p

3 em V = 1791-,,,-

mol

Given

p.y B C

-=1+-+R·T V y2

:~~~J,t1t~

p.y Z:=R·T

y := Find(V)

(b)

0.422 Bo := 0.083 - -~

T, 1.6

BO = -0.302

0.172 Bl := 0.139--T 4.2

r

-3 Bl = 3.517x 10

33

ADs.

(e) For Redlich/Kwong EOS:

rr:= 1

E: := 0

!1 := 0.08664

'Y:= 0,42748

Table 3.1

-0.5 a(Tr) := T,

Table 3.1

q (r.) '. __ \}I. a ( T r)

Eq. (3.51)

Q·Tr

Eq. (3.50)

Calculate Z

Guess:

Z:= 0.9

v:= _Z_.R_·T_ P

ADs.

Z := Find(Z) Z = 0.906

(d) For SRK EOS;

o := 1

8: := 0

Q:::: 0.08664

P:= 0.42748 Table 3.1

Table 3.1

q(Tr) '.= tp.a(Tr,co)

Eq. (3.51)

Q·Tr

Eq. (3.50)

Calculate Z

Guess:

Z:= 0.9

Given Eq. (3.49)

34

Z := Find(Z) Z =: 0,907

y:= _Z_'R_'_T p

(e) For Peng/Robinson EOS:

IT := 1 +{2

8:= 1 '-[2 n :=0,07779

ADS.

'l'. := 0,45724 Table 3.1

Table 3.1

Eq. (3.51)

Eq. (3.50)

Calculate Z

GuesS:

z .- 0.9

Given Eq. (3.49)

Z := Find(Z)

y:= _Z_,R_'T_ P

z = 0.896

3.34 Te:= 318.7·K

T T, :=-

Te

T := 348.l5·K

n, r= 37.6·bar

P ;= IS·bar

p Pr := - Pe

()) := 0.286

(a)

3 ··cm B:= -194---·

mol

.. 6 ... ·cm C:= 15300·-- 2 mol

Given

p.y B C

-=1+-+R.T Y y2

35

ADs.

Tf = 1.092

Pr = 0.399

(guess)

R·T

V:=-

p

3 Y = 1930 em mol

V := Find(V)

rv

Z:;;= -

R·T

(b)

0.422 BO := 0.083 - -T 1.6 r

BO = -0.283

0.172 Bj := 0.139 ---

Tr4.2

BI = 0.02

Z·R·T V:=-p

(e) For Redlich/Kwong EOS:

(J :=1

n := 0.08664

'P := 0.42748

Table 3.1

-0.5 c.(Tr) := T,

Table 3.1

Eq. (3.51)

Eq. (3.50)

Calculate Z

Guess:

Z:= 0.9

Z := Find(Z) Z = 0.888

Z·R·T V:=-p

Ans.

(d) For SRK EOS;

cr:= 1

E :=Q

Q:== 0.08664

T:=0.42748 Table 3.1

36

Table 3.1

Eq. (3.50)

Calculate Z

Guess:

Z:= 0.9

Given Eq. (3.49)

Z := Find(Z) Z = 0.895

V:= _Z_·R_._T P

(e) For PenglRobinson EOS:

o :=::: 1 +/2

E .= 1- f2 Q .= 0.07779

T ::::: 0.45724 Table 3.1

Table 3.1

Eq. (3.51)

Eq. (3.50)

Calculate Z

Guess:

Z:= 0.9

Given Eq. (3.49)

Z := Find(Z) Z = 0.882

Z·R·T V:=-p

Ans.

37

3.35 T:=523.l5·K

(a)

3 em B::::= ~152.5·-··- .. . mol

Given

p.y z·=. R·T

(b) Tc:= 647.1·K

T Tr:= -

Tc

Tr :;::: 0.808

P:= 1800·kPa

. 6

..... em

C ;= -5800·_· -

. ·mof

p.y B C

-=1+-+R·T V y2

Bj := 0.139 ~ 0.172 Tr4.2

Z·R·T Y:=-p

(c) Table F.2:

. 3 3.37 B:~ ..;.53A·cm ... mol

Pc := 220.55·bar

P

Pr:= -

Pc

Pr = 0.082

Bl = ~0.281

Z:;::: 0.939

molwt :« 18.015. gm mol

or

6 C:= 262(). qn .. 12 mo

38

R·T

V '= - (guess) . p

Y .= Find(Y)

Ans.

co := 0.345

BO :;::: ~0.51

Ans.

3 cm

Y := 124.99·_·molwt

gm

Ans.

9

..... .cm

D :==5000· _ ... ~...... n := mol

01013

T := 273.15·K

Given

p.y

RT

BCD 1 +-+-+Y y2 y3

i :"" 0 .. 10

( ~ 10 )

Pi:"" 10 + 20·j -bar

B,Pi zi. .- 1 +--

1 R.T

110 ·10
20
40
60
80
100
120
140
160
180
200 Eq. (3.12)

Eq. (3.37)

bar

1
0.953
0.906
f--
0.861
f--
0.819
f--
0.784
0.757
0.74
0.733
0.735
0.743 f(P ,Y) := Find(Y)

(guess)

Eq. (3.38)

1
0.951
0.895
0.83
0.749
0.622
0.5+0.179i
0.5+0.281i
0.5+0.355i
0.5+0.416i
0.5+0.469i Note that values of Z from Eq. (3.38) are not physically meaningful for pressures above 100 bar.

39

Zl j =

1
0.953
0.906
0.859
0.812
0.765
0.718
0.671
0.624
0.577
0.53 T .= 273. 15·K

Given

p.y

R-T

BCD 1+-+-+Y y2 y3

i := 0 .. 10

( - 10 )

Pj i= 10 + 20·j -bar

B,Pi Z1·::= 1 +-

1 R.T

1.10 ·10
20
40
60
80
100
120
140
160
180
200 Eq. (3.12)

Eq. (3.37)

bar

1
0.953
0.906
0.861
0.819
0.784
0.757
0.74
f---
0.733
f---
0.735
0.743 f(P , V) := Find(V)

R·T Yj:=--

Pi

(guess)

Eq. (3.38)

1
0.951
0.895
0.83
0.749
0.622
O.5+0.179j
0.5+0.281i
O.5+0.355i
0.5+0.416i
05+0.469j 0.906 0859 0.812 0.765 0.718 0.671 0.624 0.577

0.53

Note that values of Z from Eq. (3.38) are not physically meaningful for pressures above 100 bar.

39

0.9

0.8

Z2i

0.7

0.6

0.5 0

50

100

150

~1 Pi' bar

3.38 (a) Propane:

r, .= 369.8·K

Pc .= 42.48· bar

T := 313.15·K

P := B.7l·bar p

Pr :=-

Pc

T Tr :=Tc

Tr = 0.847

For RedlichlKwong EOS:

o := 1

.Q := 0.08664

q; := 0.42748

s := 0

-05 a(Tr) := Tr .

Table 3.1

Eq. (3.50)

Calculate Z for liquid by Eq. (3.53) Guess:

Z := 0.01

40

-. <,

200

0);= .OJ52

P, == 0.323

Table 3.1

Eq. (3.51)

Given

Z := Find(Z) Z = 0.057

Ans,

p

Calculate Z for vapor by Eq. (3.49) Guess:

Z:= 0.9

Given

Z := Find(Z)

Z = 0.789

v:= _Z_·R_·_T P

Ans.

Rackett equation for saturated liquid:

T Tr:= -

Tc

T, = 0.847

.' .· ... ·.3

. ' ... " .em·

Vc .::;:: 20Q.O·~ Ze ::;:;0.276

. . '.' mol

For saturated vapor, use Pitzer correlation:

BO := 0.083 _ 0.422 T 1.6

r

BO = -0.468

Bl := 0.l39 _ 0.172 Tr4.2

Bl = -0.207

R·T ( ) r,

V :=-+R- BO+ffi·Bl·-

P Pc

Ans.

41

Parts (b) through (t) are worked exactly the same way. All results are
summarized as follows. Volume units are cu.cm./mole.
RiK, Liq. RiK, Vap. Rackett Pitzer
(a) 108.1 1499.2 94.2 1537.8
(b) 114.5 1174.7 98.1 1228.7
(c) 122.7 920.3 102.8 990.4
(d) 133.6 717.0 109.0 805.0
(e) 148.9 1516.2 125.4 1577.0
(0 158.3 1216.1 130.7 1296.8
(g) 170.4 971.1 137.4 1074.0
(h) 187.1 768.8 146.4 896.0
(i) 153.2 1330.3 133.9 1405.7
(j) 164.2 1057.9 140.3 1154.3
(k) 179.1 835.3 148.6 955.4
(I) 201.4 645.8 160.6 795.8
(m) 61.7 1252.5 53.5 1276.9
(n) 64.1 1006.9 55.1 1038.5
(0) 66.9 814.5 57.0 853.4
(p) 70.3 661.2 59.1 707.8
(q) 64.4 1318.7 54.6 1319.0
(r) 67.4 1046.6 56.3 1057.2
(s) 70.8 835.6 58.3 856.4
(t) 74.8 669.5 60.6 700.5
42 3.39 (a) Propane Tc;;:;:369.S·k

T:=(40 + 273.15)·K

T ~ 313.1SK

P := 13.71· bar

T

Tr:=Tc

Tr = 0.847

P, = 0.323

From Table 3.1 for SRI(:

o := 1

E := 0

n := 0.08664

\{' := 0.42748

Eq. (3.51)

Eq. (3.50)

Calculate Z for liquid by Eq. (3.53) Guess:

Z := 0.01

Given

Z := Find(Z)

Z = 0.055

v:= _Z_·R_·_T P

Ans.

Calculate Z for vapor by Eq. (3.49) Guess:

Z:= 0.9

Given

Z := Find(Z) Z = 0.78

v:= _Z_·R_·T_ P

Ans.

43

Parts (b) through (t) are worked exactly the same way. All results are
summarized as follows. Volume units are cu.cm.!mole.
SRK, Liq. SRK, Vap. Rackett Pitzer
(a) 104.7 1480.7 94.2 1537.8
(b) 110.6 1157.8 98.1 1228.7
(c) 118.2 904.9 102.8 990.4
(d) 128.5 703.3 109.0 805.0
(e) 142.1 1487.1 125.4 1577.0
(I) 150.7 1189.9 130.7 1296.8
(g) 161.8 947.8 137.4 1074.0
(h) 177.1 747.8 146.4 896.0
(i) 146.7 1305.3 133.9 1405.7
(j) 156.9 1035.2 140.3 1154.3
(k) 170.7 815.1 148.6 955.4
(I) 191.3 628.5 160.6 795.8
(m) 61.2 1248.9 53.5 1276.9
(n) 63.5 1003.2 55.1 1038.5
(0) 66.3 810.7 57.0 853.4
(p) 69.5 657.4 59.1 707.8
(q) 61.4 1296.8 54.6 1319.0
(r) 63.9 1026.3 56.3 1057.2
(s) 66.9 817.0 58.3 856.4
(t) 70.5 652.5 60.6 700.5
44 3.40 (a) Propane

r, .= 369.8·K

P~ := 42.48·bar

0):=0.152

T :=(40+273.15)-K

T = 313.l5K

P :::: n.7l-bar

T Tr:=Te

T, = 0.847

P Pr:= - Pe

Pr = 0.323

From Table 3.1 for PR:

a(T"",) .= [ I + (0.37464 + 1.54226m - 0.269920,2).(1- T}) J

CJ := 1 + {2 E := I - fi n:= 0.07779 \}J:= 0.45724

Eq. (3.51)

Eq. (3.50)

Calculate Z for liquid by Eq. (3.53) Guess:

Z:=0.01

Given

Z := Find(Z)

Z = 0.049

V := _Z·_R._T P

ADs.

Calculate Z for vapor by Eq. (3.49) Guess:

Z:= 0.6

Given

Z := Find(Z) Z = 0.766

v:= _Z._R_·T P

ADS.

45

Parts (b) through (t) are worked exactly the same way. All results are
summarized as follows. Volume units are cu.cm.zmole.
PR, Liq. PR, Vap. Rackett Pitzer
(a) 92.2 1454.5 94.2 1537.8
(b) 97.6 1131.8 98.1 1228.7
(e) 104.4 879.2 102.8 990.4
(d) 113.7 678.1 109.0 805.0
(e) 125.2 1453.5 125.4 1577.0
(f) 132.9 1156.3 130.7 1296.8
(g) 143.0 915.0 137.4 1074.0
(h) 157.1 715.8 146.4 896.0
(i) 129.4 1271.9 133.9 1405.7
U) 138.6 1002.3 140.3 1154.3
(k) 151.2 782.8 148.6 955.4
(I) 170.2 597.3 160.6 795.8
(m) 54.0 1233.0 53.5 1276.9
(n) 56.0 987.3 55.1 1038.5
(0) 58.4 794.8 57.0 853.4
(p) 61.4 641.6 59.1 707.8
(q) 54.1 1280.2 54.6 1319.0
(r) 56.3 1009.7 56.3 1057.2
(s) 58.9 800.5 58.3 856.4
(t) 62.2 636.1 60.6 700.5
46 3.41 (a) For ethylene,

'. ,,,.... . . .: gin .' .' ":.' .

'molwt:= 28.054......,_1'.· .r, :=282.JK mo

Pc:;::: SOAO·bar

T

Tr:=-

Tc

co := 0.087 P

Pr:= -

Pc

T := 328.15·K

P·;=3S·bar

T, = 1.162

P, = 0.694

From Tables E.1 & E.2:

Zo:= 0.838

ZI:=0.033

Z := Zo + roZj

Z = 0.841

n'-

• -r- molwt

18~kg

Z·n·R·T Vtotal := --p

(b) T:= 323.15·K

P:= 11S:bar

3 Vtotal := O.25·m

T

T '-_

r .-

Te

T, = 1.145

p Pr:=Pe

Pr= 2.282

From Tables E.3 & E.4: Zo := 0.482

Z1 := 0.126

Z = 0.493

p. Vtotal

n = 2171 mol

n:=---

mass t= n-rnolwt

Z·R·T

_m~~i'~~,~2,~2'§*~:,:' Ans.

3.42 Assume validity of Eq. (3.37).

...

PI := .Ibar

Tr :=300K

3 em VI::::: 23000-' _ ..

. . mol

3 B = -I.942 x 103 em mol

With this B, recalculate at P2

47

B,P2

Z2:= 1 +-- Z2 = 0.611 R·T1

R·Tl,Z2 V2 :=--P2

3.43 T:= 753.15·K

Te:=' 513.9·K

P := 6000~kPa

P c := 61.48· bar

ro :=" 0.645

0.422 Bo :== 0.083 - --

T 1.6 r

0.172 B1:=0.139---

Tr4.2

For an ideal gas:

R·T V'=P

3.44 T := 320· K

P :=' l S-bar

ro::;= 0.152

3 em

V e:== 20Q--· .-. mol

T, = 0.865

..... 3 Vtank :== 0.35·m

0.8· Vtank

mliq:=--Vjjq

molwt

0.422

BO := 0.083 - -- Bo = -0.449

T/6

48

Ans.

T

T . __

r .-

Te

Tr = 1.466

P

Pr :=-

Pc

P, == 0.976

Bo = -0.146

Bl = 0.104

ADs.

Te:= 369.8·K

Pe:= 42.48·bar

Zc:= 0.276

gm molwt:» 44.097-.···

. . mol

Pr == 0.377

3 em

Vliq == 96.769- mol

Ans.

0.172 Bl:=0.139--- Bl=-0.177

Tr4.2

R.T r,

Vvap:= - + (BO + (O.Bl)·R.-

P Pc

3.45 T :::=, 298.15·K

P := 2.43· bar

0.422 BO := 0.083 - --

Tr 1.6

0.172 Bl := 0.139 ---

Tr4.2

0.2· V tank

mvap :=

Vvap molwt

Te:= 425J·K

Pc :::::37.96·bar

3 Vvap:= 16'm

BO = -0.661

Bl ::;: -0.624

R·T ( r,

V := - + Bo + (O.Bl)-R--

P Pc

Vvap

v

mvap :=

molwt

3.46 (a) T:= 333.15·K

P::: 14QOQ·kPa

0), :,=O.lDO

3 3cm Vvap = 1.318 x 10 -, -

mol

T Tr:= -

Tc

p Pr:= - Pc

molwtr= 58.123· gm

, mol

3 V = 9.469 x 103 cm mol

Tc := 305,3·K

Pc :== 48,.72·bar

V',' "'0' J "" total := " •. 15;m

49

Ans.

T Tr :=Tc

p Pr:= - Pc

Ans.

T, = 0.701

P, = 0.064

T, = 1.091

Pr = 2.874

, ' gm molwt.;= 30.07-'-,'

',' 'nio}

From tables E.3 & E.4: Zo:= 0.463

Z := Zo + (r}·ZI

methane :=

Ytotal V

rnolwt

(b)

V:= Vtotal 40~kg

or

U Tr= - Z

Whence

z, :=-'-0.037

Z = 0.459

Z·R·T Y:=--

3 V = 90.87 em mol

p

Ans.

P r= 20000·kPa

where

p·v

U'=--

R·Tc

mol U = 29.548- kg

0.889 Tr= -- at Z

P Pr:= -

Pc

Pr = 4.105

This equation giving T r as a function of Z and Eq. (3.54) in conjunction with Tables E.3 & E.4 are two relations in the same variables which must be satisfied at the given reduced pressu reo The intersection of these two relations can be found by one means or another to occur at about:

Tr := 1.283

Whence

T = 391.7K

3.47 VtotaI;= O.15.m3

r, := 282.3· K

Vtatal V := .-"'(-40~'k-g--:-.) . molwt

or

Pr = fl·Z

and

Z ;= 0.693

T := 298.15·K

Pc := SOAO·bar

.... gm molwt := 28.054 _ .. -. . mol

co := 0.087

where

R·T

(1'=--

pc·Y

o: = 4.675

50

Whence

P, = 4.675·Z at

T Tr :=Tc

r, = 1.056

This equation giving P r as a function of Z and Eq. (3.54) in conjunction with Tables E.3 & E.4 are two relations in the same variables which must be satisfied at the given reduced temperature. The intersection of these two relations can be found by one means or another to occur at about:

r, := 1.582

and Z:= 0.338

Ans.

mwater

3 em V = 26.667- gm

3.48 mwafer;= 15 -kg

VtotaI:= OA·m3

Vtotal V:=---

Interpolate in Table F.2 at 400 degC to find:g~j;':~2;g~i~~ ADS.

3.49 Tl:= 298.l5·K

r, := 305.3· K

Trl = 0.977

PI := 2200·kPa

Pc := 48.72· bar

Prl==0,452

3 Vtotal := O.35·m

rn r= 0.100

From Tables E.l & E.2: ZO:= .8105

ZI := ~0.0479

Z = 0.806

Z·R·TI VI:= --PI

3 em VI = 908- mol

T2:= 493.15·K

Tr2 ::: ] .615

Assume Eq. (3.37) applies at the final state.

0.422 BO := 0.083 - -T 1.6 r2

BO = -0.113

0.172 BI := 0.139 ---

. T 4.2

r2

BI=0.116

51

3.50 T:= 303.15· K

Tc;= 304.2·K

' ... ' . .3

V total':= 0.5- ill

P c;=·· 73;83' bar

BO = -0.341

0.172 B1 :"" 0.139 ---

Tr4.2

BI = -0.036

Vtotal V .= -(-lO-'k-g~J

molwt

3 3em V = 2.2x 10 - mol

R-T

P := --------

V - (Bo + ro.BI)-R. Tc Pc

T Tr:=-

Tc

ro:= 0.224

3.51 Basis: 1 mole of LIQUID nitrogen

Tn:= 77.J·K

Pc. :=34.d·bar

" '>. grn

m .. olwt::::;:28.014·-· .-,',

, , .. mol

0.422 BO := 0.083 - --

T, 1.6

Bo = -0.842

52

Tn Tr :=Tc

P

Pr:= - Pc

Ans.

Tr = 0.997

.' .' ..... gill .molwt.:« 44.01 '-. '-. . . . mol

Ans.

T, = 0.613

Pr == 0.03

V ', "'3'4 '7' .... 3

· ... I··:=·cm

lq, .... ' .... '.

B 1 :=: -1.209

Z :=: 0.957

p. Vliq

n '=---

vapor· Z.R. r,

-3 nvapor = 5.718 x 10 mol

Final conditions:

ntotal := I -rnol + nvapor

2· Vliq V:=-ntotal

3 em V = 69.005- mol

T:=298J5·K

T Tr:=-

Tc

T; :=: 2.363

R·T Pig:= - V

Pig = 359.2bar

Use RedlichlKwong at so high a P.

Q := 0.08664 q.t := 0.42748

- 5 ex (Tr) := Tr .

q'.a(lr)-R2'T!

a := (3.42)

Pc

3 a = 0.901 m3 bar·em

moll

Q·R·Tc b:=---

(3.43)

3 b = 26.737 em mol

Ans.

3.52 For isobutane: Tc := 408.1·K Pc := 36.48,bar

3 .cm VI .= ~ .824·_·· ._ ..

gm

Tl := 300·K PI := 4·bar T2 := 415·K

P2 := 75·bar

53

Tj Pj T2 P2
Trl :=- Prj :=- Tr2:"" - Pr2:= -
Te Pc Te Pc
Trl "" 0.735 Prj = O. I I Tr2 = 1.017 Pr2 = 2.056 From Fig. (3.17):

Prl .= 2.45

The final T > Tc, and Fig. 3.17 probably should not be used. One can easily show that

p·Ve Pr = Z·R·T

with Z from Eq. (3.54) and Tables E.3 and E.4. Thus

.. 3 .. em Yc<=262.7·-· .. :_.

. <>, mol

Zo ::=03356

·il:=~O.0756

Z := Zo + O)·Z]

Z = 0.322

P2,Ve Pr2 := Z.R.T2

Pr2 = 1.774

Eq. (3.65):

Prl V2:= Vj'-

Pr2

ADS.

3.53 For a-pentane:

Pc:= 33.7·bar

. ..... gm Pl:=0.63.-· _

-. ". 3

em

It:::: 291.J.5·K

Pl .• :=·l·bar

P2 : ~ 120·bar

P2 Pr2:= - Pc

Trl = 0.62

Prl = 0.03

Tr2 = 0.88

Pr2 = 3.561

From Fig. (3.17):

Prt:=2.69

Pr2 ;=2.27

By Eq. (3.65),

Pr2 P2:= Pr'-

Prl

Ans.

54

3.54 For ethanol: Tc:= 5I3~9.K

Pc :== 61.48·bar

. 1 .·cm Ve ::::.} 67·-· .- . . mol

From Fig. 3.17:

3.55 For ammonia:

Te:= 405.1'·K

Pc:=·112.8·bar

3 .cm Vc:=]25·- - _ •.. '

. mol

Pr:=2.28

P :=

T .= 4$J.15·K

P :=200·bar

T

Tr:= - Te

inolwt:=4ko69:<gIU . mol

Pr Vc molwt

T·:= 293.15·K

P:= 857·kPa

Zc:= 0.242

Eq. (3.63):

0.422 Bo := 0.083 - _-

Trl06

0.172 Bl := 0.139 - _-

Tr4.2

BO = -0.627

BI = -0.534

55

Pr P = PrPc = Vc

T Tr:=-

Tc

P

Pr:=-

Pc

(i) := 0253

3 cm

Vliquid = 27.11- mol

Tr = 0.882

Pr = 3.253

ADS.

Tr;:;; 0.723

Pr = 0.076

R·T ( ) r,

Vvapor ::0: -- + BO + ro-Bj ·R·-

P Pc

3 em

Vvapor = 2616-mol

L1Y ;= Yvapor- Vliquid

ADS.

Alternatively, use Tables E.1 & E.2 to get thevapor volume:

20;::;;; 0.929

21:== ~0.071

2 := Zo + co-Zj

Z =: 0.911

Z·R·T Yvapor:= -p

3 em

Vvapor = 2591-mol

L1 V := V vapor - Vliquid

ADS.

3.58 10 gal. of gasoline is equivalent to 1400 cu ft. of methane at 60 degF and 1 atm. Assume at these conditions that methane is an ideal gas!

ft3·atm

R = 0.7302---Ibmo I, rankine

T ':=519.67 -rankine

:3 V ':== 1400· ft

p.y

n:=--

R·T

n = 3.6891bmol

For methane at 3000 psi and 60 degF:

Tc:== IQO.6·L8·rankine

T:= 519.67·rankine

T Tr:=-

Tc

Tr = 1.515

Pe> 45.99·bar

p:~ 3000·psi

P

Pr:= -

Pc

P, == 4.498

ill := 0.012

From Tables E.3 & E.4:

20:=0.819

21:=0.234

Z := Zo + 0)·Z1

Z = 0.822

56

3.59 T := 25K P := 3213bar

Calculate the effective critical parameters for hydrogen by equations (3.55) and (3.56)

43.6 Tc:=----·K 21.8K 1+---

2.016T

T, = 30.435K

20.5

Pc := . bar

1 + 44.2K

2.016T

Pc = 1O.922bar

m:=O

T

Tr:= -

Tc

Initial guess of volume:

R·T Y'=-

P

3 V = 646.903 em mol

Use the generalized Pitzer correlation

0.422 BO := 0.083 - --

T/6

) Pr

Z := 1 + (BO +w·Bj .Tr

BO = -0.495

0.172

Bl := 0.139 - -- Bl = -0.254

Tr4.2

Ans. Experimental: Z = 0.7757

For RedlichlKwong EOS:

c := 1

~ := 0

n := 0.08664

'f' := 0.42748

Table 3.1

() - 0.5

a Tr t= r,

Table 3.1

Eq. (3.51)

57

Calculate Z

Eq. (3.50)

Guess:

Z::=c 0.9

Z :== Find (Z)

3.61 For methane: 0):= 0.012

Experimental: Z = 0.7757

Tc:= 190.6K

Pc :=45.99bar

At standard condition: T ""I(60:":l251+273:JS} Pitzer correlations:

T

Tr ::=c - Te

0.422 BO := 0.083 - --

Tr1.6

Pr ZO:= 1 +Bo'-

Tr

Z := Zo + (O·ZI

(a) At actual condition:

Pitzer correlations:

T Tr:= -

Tc

0.422 BO :== 0.083 - _-

Tr 1.6

T = 288.706K

Tr = 1.515

P

Pr:= - Pc

Pr = 0.022

BO = -0.134

0.172

Bj :== 0.139 - -~ B] = 0.109

Tr4.2

Zo = 0.998

ZI == 0.00158

Z == 0.998

Z·R·T VI :==-P

3 m VI == 0.024-mol

T :=[(50 ~ 3:2)0% '" 273.15}::

T == 283.15K

P:=300psi

It = 1.486

P Pr ::=c -

Pc

P, == 0.45

BO = -0.141

58

0.172 Bj :"" 0.139 ---

Tr4.2

Z := Zo + m·21

3

. 6 ft ql:= 150·10 .. -.-

day

(c) D := 22.624in

q2

u:=-

A

BI = 0.106

Zo = 0.957

Z "" 0.958

ZI = 0.0322

Z·R·T V2:=-p

3 m V2 = 0.00109-·mol

ADS.

1t 2 A :=-D

4

59

ADS.

2 A = 0.259m

ADS.

3.62

0.152 0.181 0.187 OJ9 OJ91

0;194 0.196

0.2 0.205 0.21 0.21 0.212 0.218 0.23

0.235 0.252 0.262 0.28 0.297 0.301

0.302 0.-303 O.3i .0.322 0.326·

0.266 0,266 0.263 0.263

0.26 0261

Use the first 29 components in Table B.1 sorted so that 0) values are in ascending order. This is required for the Mathcad slope and intercept functions.

ill:~ slope(ID,Zc) = ( -0.091} b := iri~rcept(ro;Zc) = (Q.291)

R:= corr(w,Zc) = (-0.878) R2= 0;771

0.29
Zc 0.28
000
mo-i-b 0.27
0.26
0
0.25 0 0.1 0.2 OJ 0.4 co

ili&1~lf~~! Ans,

60

Chapter 4 - Section A - Mathcad Solutions

4.1 (a) TO :;0;: 473.l5·K

T :"" 1373.15·K

n :"" IO'mol

For S02:

A = 5.699

-3

B=0.801·1O C=O.O

..... ·····5

D= -1.015·10

( ~ 3 5) 3

ICPH 473.15,1373.15,5.699,0.801·10 ,0.0,-1.015·10 = 5.654·10

1-.H := R·ICPH

Q := n·1-.H

:Q1~'~;~wi.Q£QZ4e;tq ADs.

(b) To :=523.15·K

T:"= 1473.15· K

For propane:

A = 1.213

B= 28.785.10';';3

..... : ... : . ·-6

C = ~8.824·10

( -3 -6) 4

ICPH 523.15,1473.15,1.213,28.785·10 ,-8.824·10 ,0.0 = 1.947·10

ICPH := 1.947.104.K 1-.H := R·ICPH Q := n·M{

~1~~i~~;~i~~~~1~ Ans.

4.2 (a) TO := 473.l5·K II := 10·moJQ:= 800·k]

... K

For ethylene:

A:= 1.424

14.394.10~J

B := -----"----"~

t .= 2 (guess) Given

Q = nOR{[ ATo(' - I) + ~T02(,2 -I)J + ~ oTl(,3 - I)J

t := Find(t)

t = 2.905

T := t·To

ADs.

(b) TO := 533.15·K

Q := 2500·kJ

For f-butene: A:= 1.967

. 31.630.10~ 3

B := -.~. -K--':-·· ~

. _9.873.10-6

C;= ... _. -'--,..;--..'-----

K2

61

t ;= 3 (guess) Given

Q = n.R{[ A·To·(' - I) + ~ Tl( / - 1)] + ~Tl(,3 - 1) J

't = 2.652

T ;= 't·To

Ans,

(c) TO :==500·degF

h:= 40·1bmol

. . 6

Q:==lO ·BTU

Values converted to SI units

TO := 533.l5K

4

n = 1.814 x 10 mol

For ethylene:

A::::; 1.424

't ;= 2 (guess)

Given

t .= Find( 't)

't = 2.256

T .= 't·TO

.··~~~£~i~~~~:· ]:ti;~l~;fJ~~~&~

Ans,

4.3 Assume air at the given conditions an ideal gas. Basis of calculation is 1 second.

p::= l-atm

TO ::;:: 122·degF

. . 3

V:::;: 250·ft

T;= 932·K

Convert given values to SI units

3 Y = 7.079m

T := (T - 32degF) + 273.15K T = 1187.37K

TO ::=: (To - 32degF) + 273.15K TO = 323.15K

rv

n:=--

R·TO

n = 266.985 mol

For air:

A.::J.355

'-3

8=0.575·10 .

C :==0.0

( - 3 5)

ICPH 323.15,773.15,3.355,0.575·10 ,0.0,-0.016·10 = 1648.702

62

ICPH :== 1648.702·K

L\H := R·ICPH Q:== n·L\H

~~;~~:~~':~~~~1'~~7g~~ Ans.

4.4 molwt.re 100.I.gm mol

TO :=323.15·J( T :=1153.15·K

IOOOO·kg

n:""--moIwt

4

n == 9.99 x 10 mol

For CaC03:

A := 12;572

. ··-3

B = 2.637~ 10

5 D.= -3.120-10

( - 3 5)

ICPH 323.15,1153.15,12.572,2.637·10 ,0.0,-3.120·10 = 11355.4

rCPR := 11355.4·K

Lill := R·ICPH

Q := n·L\H

,~;i~1~:~~·~~*·j:;r~~;~J Ans,

4.7 Let step 12 represent the initial reversible adiabatic expansion, and step 23 the final constant-volume heating.

Tl:=298.15·K

PI ::;:: 12L3·kPa

P2 .= IOL3·kPa

P2 T2:= T3'P3

T2 = 290.41 K

joule Cp :=30·-mo]·K

(guess)

Given

R

T2 = Tl{:~t

Cp ;= Find( c-)

4.9 72.150 469.7 33.70 309.2
86.177 507.6 30.25 341.9
78.114 gm Tc:= 562.2 ·K Pc := 48~98 . bar T ._ 353.2 ·K
M'-
.. - n'~
mol
92.141 591.8 41.06 383,8
84.161 553.6 40.73 353.9
63 --j.
Trl := (273.15 + 25)K Tn
Tc Tr2;= -
Tc
0.635 0.658
0.587 0.674
Trl = 0.53 Tr2 = 0.628
0.504 0.649
0.539 0.639 I1H is the value at 25 degC.

l1~xp is th e given value at the normal boiling point.

366.3 366.1 433.3 ·412.3. .

··392.5

357.2 336.7

J

. 4Hex.p .:-:;: ·3.93-~9 ~ -

gm

363.2

358,2

J

(a) By Eq. (4.13)

[ (1 - Tf2JO.38]

.1Hn:= .1H· --I - Trl

[ .1Hn - I1Hexp J

PCE:= ·100%

.1Hexp

(b) By Eq. (4.12):

This is the % error

I1Hn:= [R-Tn.rI.092·H~) -l~~~Jr

M 0.930 - Tr2 j

[I1Hn - .1Hexp J

PCE:= ·100%

.1Hexp

64

4.10 The In P vs. 1fT relation over a short range is very nearly linear. Our procedure is therefore to take 5 points, including the point at the temperature of interest and two points on either side, and to do a linear least-squares fit, from which the required derivative in Eq. (4.11) can be found. Temperatures are in rankines, pressures in psia, volumes in cu ft/lbrn, and enthalpies in Btu/Ibm. The molar mass M of tetrafluoroethane is 102.04. The factor 5.4039 converts energy units from (psia)(cu ft) to Btu.

(a) T;= 459.67 + 5

18.787 21.162 Data: P:= 23.767

26.617 29.726

AV:= 1.934-":0.012

i:= 1.. 5

o 5 10 15

1

Xj:=----

ti + 459.67

slope := slope(x, y) slope = -4952

(~P)3

dPdT := -_. slop, dPdT = 0.545

r

The remaining parts ofthe problem are worked in exactly the same way. All answers are as follows, with the Table 9.1 value in ():

(a) M-I = 90.078

(90.111 )

(b) AH = 85.817

(85.834)

(c) AH = 81.034

(81. 136)

(d) AH = 76.007

(75.902)

(e) AH = 69.863

(69.969)

65

~H is the value at o degC.

~Hexp is the given value at the normal boiling point.

.. ( .r : 270;9 "J" .....

'. ' ... , J

AH :=.11.8 .. 9.5 ...••. _ .217.8·.gm

." . .' ,[. 246.9 "J

AHexp:= .•... : .•. 1 ... · .. 0.9. ···.9 •. 5 •. ·.·.·.·•• . J ...

............. gm

194.2 . ' .. '.

(a) By Eq. (4.13)

(mn -~Hexp J

PCE:"" ·100%

~Hexp

273.15K Trl:== --Tc

[0.509J

Trl = 0.533

0.491

[ (1 - Tr2]038

mn:= ~H·

1 - Td

This is the % error

Tn := .••. (~:~::J .. K

.. 349.8

[0.623J

Tr2:;:;; 0.659

0.629

i1Hn := r R.Tn.[I.092{ m({;) - I.DI3)JJ'>-

M 0.930 - Tr2 J

(b) By Eq. (4.12):

(M-I - LiH J

PCE := n exp .100%

~Hexp

66

(1) -2,732,016 J (s) -492,640 J
(g) -105,140 J (t) 109,780 J
(h) -38,292 J (u) 235,030 J
(i) 164,647 J (v) -132,038 J
(j) -48,969 J (w) -1,807,968 J
(k) -149,728 J (x) 42,720 J
(I) -1,036,036 J (y) 117,440 J
(m) 207,436 J (z) 175,305 J 4.22 The solution to each of these problems is exactly like that shown in Example 4.6. In each case the value of 8.H0298 is calculated in

Problem 4.21. Results are given in the following table. In the first column the letter in ( ) indicates the part of problem 4.21 appropriate to

the 8.Ho298 value.

--- .. --- ---··---··----··r----·---- .- ..... - ...... .. ____ .. _'C·'· ___ ~r _____
TIK 1l.A 1031l.B 1061l.C 10-5 LlD IDCPHJJ 1l.HoT/J
(a) ----- -_--_ ... _- - .. - .... - ...... --.--~ 1--._-_ ............. -- ........ - '.
873.15 -5.871 4.181 0.000 -0.661 -17,575 -109,795
_._
(b) 773.15 1.861 -3.394 0.000 2.661 4,729 -900,739
(ti 923.15 6.048 -9.779 0.000 7.972 15,635 -2,]16,381
(i) 973.15 9.811 -9.248 2.106 -1.067 25,229 189,876
(j) 583.15 -9.523 11.355 -3.450 1.029 -10,949 -59,918-
(1) 683.15 -0.441 0.004 0.000 -0.643 . ___ ,._ ... :2-l~J!L -1,038,452
--- i--- .. ~-- .. -- ... ---- .. -
(m) 850.00 4.575 -2.323 0.000 -0.776 13,467 220,903
(n) 1350.00 -0.145 0.159 0.000 0.215 345 -180"j45 .
(0) 1073.15 -1.011 -1.149 0.000 0.916 -9,743 "--
168,578
(r) 723.15 -1.424 1.601 0.156 -0.083 __ .~~~:1, I2L ~_ ~;T~03'7'-[
(t) t-----------~-~
733.15 4.016 -4.422 0.991 0.083 . L. 7,424 117,204
(u) 750.00 7.297 -9.285 2.520 0.16'6--'- --1.-=~1_t_~1?'l_1 __ ~~~~ 7,2_91~
(v) 900.00 2.418 -3.647 0.991 0.235 3,534 -128,504
(w) 673.15 2.586 -4.189 0.000 1.586 4,184 -1,803,784
(x) 648.15 0.060 0.173 0.000 -0.191 -125 -- ----42--845--
(y) 1083.15 4.175 -4.766 1.814 0-:083 --'-'I---'-J1, 18.fr·---·-i12~~~] 76

4.23 This is a simple application of a combination of Eqs, (4.18) & (4.19) with evaluated parameters. In each case the value of ~Ho298 is calculated in Pb. 4.21. The values of LiA, LlB, LiC and LiD are given for all cases except for Parts (e), (g), (h), (k), and (z) in the preceding table. Those missing are as follows:

Part No. .1.A 103 LlB 106 de 10-5.1.D
(e) -7.425 20.778 0.000 3.737
(~) -3.629 8.816 -4.904 0.114
(h) -9.987 20.061 -9.296 1.178
(k) 1.704 -3.997 1.573 0.234
(z) -3.858 -1.042 0.180 0.919 ftJ 5

4.24 q := 150.106 -d· .. T:= (60 - 32)·-K + 273.15K T = 288.71 K J>:~hitm

ay 9

The higher heating value is the negative of the heat of combustion with water as liquid product.

Calculate methane standard heat of combustion with water as liquid product:

Standard Heats of Formation:

... .J

MIfCH4:= ~ 74520 - .... -. . mol

.,J. AHft)2 := O~· mol

J LiHfC02:= -393509-. ._

. mol

.. J

AHffi20liq:==...;285830-. _.: mol

~e .= L\HfC02 + 2'~fH201iq - L\HfCH4 - 2·L\Hf02

HigherHeatingYalue .= -L\He

5 J MIe = -S.906x 10 - mol

Assuming methane is an ideal gas at standard conditions:

p n:=q-R·T

s mol n = 1.793 x 10 - day

77

4.25 Calculate methane standard heat of combustion with water as liquid produc1 Standard Heats of Formationt Cfl., + 202 --> CO2 +2H20

". . .... J

AHfCH4 :==.-74520mo1

". .J AH:te02::= ~393509-· .• -..

. mol

'. . .......J AHf02:== 0 _'.' -.' . mol

'. . j MItH2· 0" ·1'::;;:: -;:285830--

· .. lq ..... .' mol

AHcCH4 .= AHfC02 + 2·AHfH201iq - AHfCH4 ~ 2·tl.HfD2 J

.M-IcCH4 = -890649-

mol

Calculate ethane standard heat of combustion with water as liquid product:

Standard Heats of Formation: C2M.; + 7/2°2 --> 2C02 +3H20

..... . .' J

AHfC2H6:== -83820'-" .. -'.

. . .... '. mol

7 tl.HcC2H6 := 2tl.HfC02 + 3.tl.HfH201iq - tl.HfC2H6 - -·tl.HfD2 2

, '.' ".' ..... '1

MIcC2I-I6 :;;::~1560688J1101

Calculate propane standard heat of combustion with water as liquid product Standard Heats of Formation: C3HS + 502 --> 3C02 +4H20

, '.' J

AHfC3HS:= -104680~

. . mol

tl.HcC3H8 := 3tl.HfC02 + 4.tl.HfH201iq ~ tl.HfC3H8 ~ S·tl.Hf02 kJ

tl.HcC3H8 = -2219.167-

mol

Calculate the standard heat of combustion for the mixtures

a)

b)

c)

Gas b) has the highest standard heat of com bustion. A

ns.

78

~~----- ..

4.26

2H2 + 02 = 2H20(1)

C + 02 = C02(g) bHf2:=-'":393S()9·J

N2(g)+2H20(l)+C02(g)=(NH2)2CO(s)+3/202 Llli:=63166Q~J

N2(g)+ 2H2(g)+C(s)+ 1I202(g)=(NH2)2CO(s)

!~~~l~X,,;g.,""~-:.~~g~ Ans.

4.28 On the basis of 1 mole of CI0H18

(molar mass = 162.27)

Q := -43960· 162.27·J

This value is for the constant-volume reaction:

CI0H18(l) + 14.502(g) = 10C02(g) + 9H20(l)

Assuming ideal gases and with symbols representing total properties,

Q = <3.U = LllI - ~ CPy) = ~H - R· T·ililgas

T := 298.15·K

~ngas := (1 0-14.5)·mol Llli = -7.145 x 106 J

This value is for the constant-V reaction, whereas the STANDARD reaction is at con st. P.However, for ideal gases H = f(T), and for liquids H is a very weak function of P. We therefore take the above value as the standard value, and for the specified reaction:

CI0H18(l) + 14.502(g) = lOC02(g) + 9H20(l)

<3.H

9H200) = 9H20(g)

CIOH18(1) + 14.502(g) = lOC02(g) + 9H20(g)

<3.H298 ;= ~H + Lllivap , .. ~",:.k .• ·"~'§!'~~~~%4~4$'g .• ·.;~.J.:,. Ans .

... ~ ," .. ~ - .' - - .;,.' ~',.- .. ; ",",-,

79

4.29 FURNACE: Basis is 1 mole of methane burned with 30% excess air.

CH4 + 202 = C02 + 2H20(g)

Entering:

Moles methane

Moles oxygen

nz := 2·1.3 79 "3 :=2,6'21

Moles nitrogen

Total moles of dry gases entering

At 30 degC the vapor pressure of water is 4.241 kPa. Moles of water vapor entering:

Leaving:

4.241

n := -13.381

4 101.325-4.241

C02 --1 mol H20 -- 2.585 mol

02 -- 2.6 - 2 = 0.6 mol N2 -- 9.781 mol

By an energy balance on the furnace:

Q = bH = b.H298 + MIp

For evaluation of .1.Hp we number species as above.

i := 1 .. 4

R := 8.314

A ::::: 48.692 B = 0.010897

80

"2 = 2.6

ll3 = 9.781

n = 13.381

114 = 0.585

(1) (2) (3) (4)

·· .••. ·.0.121

--0.227· .0.046

4 D ::::: -5.892 x 10

The TOTAL value for MCPH of the product stream:

( - 3 5)

MCPH 303.15,1773.15,48.692,10.897· 10 ,0.0, -0.5892·10 = 59.89511

MCPH t= 59.89511

Lllip := R·MCPH·(1773.15 - 303.15)

From Example 4.7:

~H298 .= -802625

;,~~ffi1&;~~<Q~~6'1~~;J

Ans.

HEA T EXCHANGER: Flue gases cool from 1500 degC to

50 degC. The partial pressure of the water in the flue gases leaving the furnace (in kPa) is

ll2

pp := ·101.325

II I + n2 + ll3 + I14

pp = 18.754

The vapor pressure of water at 50 degC (exit of heat exchanger) is 12.34 kl'a, and water must condense to lower its partial pressure to this value.

Moles of dry flue gases:

n :== n1 + nj + 04

n = 11.381

Moles of water vapor leaving the heat exchanger:

12.34

n2 = 1.578

n2:= 101.325 _ 12.34·n

Moles water condensing:

M:= 2585~ J.578

Latent heat of water at 50 degC in J/moJ:

AHsO := 2382.9·18.015

Sensible heat of cooling the flue gases to 50 degC with all the water as vapor (we assumed condensation at 50 degC):

MCPHb23.15, 1773.15,48.692,10.897·10- 3,0.0, -0.5892.105) = 60.01086 MCPH:= 60.01086

Q := R·MCPH·(323.15 - 1773.15) - ~n.Llli5of:i~,~,fB~~~i~~\1.'J Ans.

81

4.30 4NH3(g) + 502(g) = 4NO(g) + 6H20(g)

BASIS: 4 moles ammonia entering reactor

Moles 02 entering = (S}(1.3) = 6.S Moles N2 entering = (6.5)(79/21) = 24.45

Moles NH3 reacting = moles NO formed = (4)(0.8) = 3.2 Moles 02 reacting = (5)(0.8) = 4.0

Moles water formed = (6)(0.8) = 4.8

ENERGY BALANCE:

~H = bHR +bH298 +MIp = 0 REACTANTS: I=NH3; 2=02; 3=N2

i := 1 .. 3

A= 118.161

-. (30020J: ...

' ......•. ·-3

B:::; ••.. · .. 0.50. 6 ... :.010 0;593·

B = 0.02987

5 D = -1.242 x 10

TOTAL mean heat capacity of reactant stream:

MCPH(J48.15 ,298.15,118.161,0.02987,0.0, -1.2420105) = 126.61632

MCPH := 126.61632

bHR := R·MCPH·(298.15 - 348.15)

The result ofPb. 4.21(b) is used to get AHz98:=O.8,{,""905468)

PRODUCTSi=NH3; 2=02; 3=NO; 4=H20; 5=N2

0.8 3.578 3;020

82

-0.186 .,....0 .. 227

i .= 1 .. 5

A = 119.65

B = 0.027

4 D = 8.873 x 10

By the energy balance and Eq. (4.7), we can write:

TO := 298.15 T := 2

(guess)

Given

1: := Find( T)

T = 3.283

T:= TO·KT

4.31 C2H4(g) + H20(g) = C2H50H(l)

BASIS: 1 mole ethanol produced

Energy balance: M1 = Q = 1l.HR + 1l.H298

1l.H298:= -277690-(52510-241818)

4 fl.H298 = -8.838 x 10

Reactant stream consists of 1 mole each of C2H4 and H20.

i ;= I.. 2 n:= G)

.... ( ..... 1. .. 42.4)··. '. ( .: 1.4 .. 3 ... 94 .... ) .. -.3 ... ('"-'4 . .3.9.2) ... ··· ... 7"""6 (. 00.)' 5

A:= 3.470 B::= 1.450 .·10 .' C:= '. 0,0 '·10 D:=O.;21·10·

A :::: 4.894

B = 0.01584

C = -4.392 x 10- 6 0 = 1.21 x 104

MCPH(298.15, 593.15,4.894,0.01584,-4.392.10- 6,0.121'105) = 11.1192

83

MCPH ::0: 1 L 1192

4.32 One way to proceed is as in Example 4.8 with the alternative pair of reactions:

CH4+ H20 = CO + 3H2

M-l298a::::::205813

CH4 + 2H20 = C02 + 4H2

MI298b;:O: 164647

BASIS: 1 mole of product gases containing 0.0275 mol C02; 0.1725 mol CO; & H20 0.6275 mol H2

Entering gas, by carbon & oxygen balances:

0.0275 + 0.1725 = 0.2000 mol CH4

0.1725 + 0.1725 + 2(0.0275) = 0.4000 mol H2O

&H298 := 0.1725·&H298a + 0.0275·&H298b

4 AH298 :0: 4.003 x 10

The energy balance is written

REACTANTS: 1=CH4; 2=H20

n;=(~:}]

A;" G::~) B ;~(;::~~)l O~} C;= t~;4}10 ~6D ;=C)~;~jllO~

i ::0: 1 .. 2

D;= I nj·Dj

A = L728 B = 2.396 x 10-3 C::: -4.328 x 10-7 D = 4.84x 103

ICPH( 773.15,298.15, 1.728,2.396·10- 3 , -4.33·10- 7,4.84.103) = -1377.435

ICPH := -1377.435

&HR := R· ICPH

4 AHR = -1.145x 10

PRODUCTS: 1=C02; 2=CO; 3=H20; 4=H2

84

0.0275

n:=

i := 1 .. 4

A:=

0.422

.lO~3

.. 5 ,10

0,083 0:= Lni·Oj

A = 3.37

-4 B = 6.397x 10

3 D=3.579xlO

( -4 3)

ICPH 298.15,1123.15,3.370,6.397·]0 ,0.0,3.579'10 = 3164.293

ICPH := 3164.293

Mfp := R·ICPH

4.33 CH4 + 202 = C02 + 2H20(g)

C2H6 + 3.502 = 2e02 + 3H20(g)

4 LlHp= 2.631 x 10

Ans.

AH298a:=-802625

AH298b:=-1428652

BASIS: 1 mole fuel (0.75 mol CH4; 0.25 mol C2H6) burned completely with 80% xs. air.

02 in = 1.8[(0.75)(2) + (0.25)(3.5)] = 4.275 mol N2 in = 4.275(79/21) = 16.082 mol

Product gases: C02 = 0.75 + 2(0.25) = 1.25 mol H20 = 2(0.75) + 3(0.25) = 2.25 mol 02 = (0.8/1.8)(4.275) = 1.9 mol

N2 = 16.082 mol

Energy balance: Q = LlH = Mf298 + LlHp PRODUCTS: 1=C02; 2=H20; 3=02; 4=N2

1.25 2.25

n.t=

1.9

16.082

5.457 3,470 3.639 3.280

A . ._c.

.-

B·..,;.·

.-

85

5 Q := -8·10

0.040

i := 1..4

D:= Lnj.Dj

A = 74.292

B = 0.015

4 o = ~9.62x 10

By the energy balance and Eq. (4.7), we can write:

TO:= 303.15

1 .= 2 (guess)

Q ~ 6.H298 = R·

Given

1 := Finder)

1 = 1.788

T := To·KI:

Ans.

4.34 BASIS: 1 mole of entering gases containing 0.15 mol S02; 0.20 mol 02; 0.65 mol N2

S02 + 0.502 = S03 Conversion = 86%

S02 reacted = S03 formed = (0.15)(0.86) = 0.129 mol

02 reacted = (0.5)(0.129) = 0.0645 mol

Energy balance: .:1H773 = L1HR + L1H298 + L1Hp

Since L\HR and MIp cancel for the gas that passes through the converter un reacted, we need consider only those species that react or are formed. Moreover, the reactants and products experience the same temperature change, and can therefore be considered together. We simply take the number of moles of reactants as beinz negative. The energy balance is then written: .:1H773 = .:1H298 + L1t1net

1: S02; 2: 02; 3: S03

[' "'J'" ['"

-0.129 ,'5.699

n:f . ~t_:;;~'.~r~~~J

86

i := 1 .. 3

A = 0.06985

-7 B = 2.58 x 10

4 D = -1.16x 10

( -7 4)

MCPH 298.15,773.15,0.06985,2.58·10 ,0.0,-1.16·10 = 0.019666

MCPH := 0.019666

~Hnet := R·MCPH(773.15 - 298.15)

Ans.

4.35 CO(g) + H20(g) = C02(g) + H2(g)

BASIS: 1 mole of feed consisting of 0.5 mol CO and 0.5 mol H2O.

Moles CO reacted = moles H2O reacted = moles C02 formed = moles H2 formed = (0.6)(0.5) = 0.3

Product stream:

moles CO = moles H20 = 0.2 moles C02 = moles H2 = 0.3

Energy balance:

Llih9S:= 0.3·[-393509 ~ (-110525 -214818)1 Reactants: 1: CO 2: H20

. . '.(' •. 0.5.,) .. (3 . .3.7.6 .. ) .•...

n:= .. '. A:=," ' ..

0.5' '3.470

4 ~298 = -2.045 x 10

'. .'.(" - 0.0. 3.1 )'., ···.·.·,· 5

D:= .. '. . ·10

.. 0]21 .r . '.'

i:= 1..2

A = 3.423 B = 1.004 x 10- 3 D = 4.5 x 103

MCPH(298.15 ,398.15,3.423,1.0035·10- 3 ,0.0,0.045.105) = 3.8103 MCPH := 3.8103

AHR := R·MCPH·(298.15 - 398.15)

3 AHR == -3.168x 10

Products:

1: CO 2: H2O 3: C02 4: H2

87

A'::=

0.083

0557

}.450 3

B:= '10-

1.045

·0;422

~0~031

i:"" 1..4

A = 3.981

-4 B = 8.415x 10

4 D = -3.042 x 10

MCPH(298.15 ,698.15,3.981,0.8415.10-3,0.0,-0.3042.105) = 4.25405

MCPH := 4.25405

L'.Hp := R·MCPH·(698.15 - 298.15)

Q := (MIR + L'.H298 + L'.Hp}J

4 MIp = 1.415 x 10

Ans.

4.36 BASIS: 100 lbmol DRY flue gases containing 3.00 lbmol C02 and 11.80 lbmol CO x Ibmol 02 and 100-(14.8-x)= 85.2-x lbmol N2. The oil therefore contains 14.80 Ibmol carbon;a carbon balance gives the mass of oil burned:

12.011

14.8· ·Ibm = 209.133 Ibm

0.85

The oil also contains H20: 209.133·0.01

----·lbmol = 0.1161bmol 18.015

Also H2O is formed by combustion of H2 in the oil in the amount

209.133·0.12

----·lbmol = 12.4481bmol 2.016

Find amount of air entering by N2 & 02 balances. N2 entering in oil:

209.133·0.02

----·lbmol = 0.1491bmol 28.013

Ibmol N2 entering in the air={8S.2-x)-O.149 =8S.0S1-x

88

Ibmol 02 in flue gas entering with dry air =

3.00 + 11.8/2 + x + 12.448/2 = 15.124 + x Ibmol (C02) (CO) (02) (H20 from combustion)

Total dry air = N2 in air + 02 in air = 85.051 - x + 15.124 + x = 100.1751bmol

Since air is 21 mol % 02,

15.124 + x 0.21 = ---- 100.175

x i= (0.21·}00.175 - 15.124)·lbmol x::= 5.9131bmol

02 in air = 15.124 + x = 21.037 Ibmols N2 in air = 85.051 - x = 79.138 Ibmoies

N2 in flue gas = 79.138 + 0.149 = 79.2871bmols

[CHECK: Total dry flue gas

= 3.00 + 11.80 + 5.913 + 79.287 = 100.00 Ibmol]

Humidity of entering air, sat. at 77 degF in Ibmol H20llbmol dry air, P(sat)=0.4594(psia)

0.4594 = 0.03227

14.696 - 0.4594

Ibmol H2O entering in air:

0.03227·100.175·lbmol = 3.2331bmol

If y = Ibmol H2O evaporated in the drier, then Ibmol H20 in flue gas = 0.116+ 12.448+3.233+y = 15.797 + Y

Entering the process are oil, moist air, and the wet material to be dried, all at 77 dcgF. The "products" at 400 degF consist of:

3.00 Ibmol C02 11.80 Ibmol CO 5.913 Ibmol 02 79.287 Ibmol N2

(15.797 + y) Ibmol H20(g)

Energy balance:

where Q = 30% of net heating value of the oil:

89

· ..... . BTU

Q := ~0.3. ,19000--· _··209.13·lbrn

lbpJ. .

Q == -1.192 x 106BTU

Reaction upon which net heating value is based:

OIL + (21.024)02 = (14.8)C02 + (12.448 + 0.116)H20(g) + (0.149)N2

MlZ98a:= -19000·209.13·BTU

6 ,1.HZ98a = -3.973 x 10 BTU

To get the "reaction" in the drier, we add to this the following:

(11.8)C02 = (11.8)CO + (5.9)02

Ml298b:= 1 L.f(.-:11 0525 + 393509)·QA2993·.atV

(y)H20(I) = (y)H20(g)

Guess: y:= 50

L\FI 298c(y):2 44012; 0 .42Q93·Y' 13TV

[The factor 0.42993 converts from joules on the basis of moles to Btu on the basis of Ibmol.]

Addition of these three reactions gives the "reaction" in the drier, except for some 02, N2, and H20 that pass through unchanged. Addition of the corresponding delta H values gives the standard heat of reaction at 298 K:

~H298(Y) := ~H298a + ,1.H298b + ilH298c(Y)

For the product stream we need MCPH:

1: C02 2: CO 3:02 4: N2 5: H20

TO := 298.15

R .= 1.986

T := 400 + 459.67 1.8

T == 477.594

3 11.8

1.045 0.$57 .0.~06 0.593 1,450

·1539T+y·

i := 1 .. 5 A(y):= L n(YkAj B(y):= L n(y)j-Bj D(y):= L n(y)j-Dj

T

.... ~ '.- -

TO

1 = 1.602

Cp(y) := R'[ACY) + B~Y) ·To{r + 1) + D(Y~J 1'·TO

90

4.12 (a)ro::::: 0.210

Tc:::::562.2K

Pc:;:: 48.9,8bar

Zc:::::O.271

3 Vc:= 259. em mol

Tn ;=<: 353.2K

P:= Ibar

T; = 0.628

P

Pr:= -

Pc

Pr = 0.02

Generalized Correlations to estimate volumes

Vapor Volume

0.422 Bo := 0.083 - --

r. 1.6

Bo := -·0.805

Eq. (3.61)

0.172 Bl := 0.139 - _-

Tr4.2

Bj = -1.073

Eq. (3.62)

Z = 0.967

p

3 4cm V := 2.838x 10 -

mol

Z·R-Tn V:=~--

Liquid Volume

3 em Vsat = 96.807- mol

d Combining the Clapyeron equation (4.11) ~H = T·~V·-Psat

dT

with Antoine's Equation

Psat = e

B A-T-C

gives

67

~V:"" V - Vsat

3 4cm ~V "" 2.829x 10 - mol

A i= 13.8594

B:= 2773.78

C ::=53.00

I A ~-c

(:-cr K

Answers for parts (b)-(e) kJ

(b) ~H = 36.262 - mol

kJ (e) ~H = 32.278 - mol

kJ (d) ~H = 28.948 - mol

kJ (e) ~H = 33.838 - mol

4.13 Let P represent the vapor pressure.

T :=348.I5,K

P := JOO.kPa

(guess)

ADs.

Given

( P ) 5622.7·K (T)

In kPa = 48.157543 - T - 4.70504·ln K

P .= Find(P)

dPdT := p.(5622.7.K _ 4_70504)

T2 T

P = 87.396k:Pa

.. '. . joule

Ml:=.31600·_· .'-" . . . ' .... mol

68

dPdT = 0.029 bar K

, 3

...... ····cm

VIiq.:=96A9·-. -'1

. '. 'mo

Clapeyron equation:

dPdT = L\H

T(V - YJjq)

L\H

V = vapor molar volume. V:-= Vliq + ---

T·dPdT

Eq. (3.38):

(PoY )

B :=y. --1

R·T

Ans.

4.14 (a) Methanol: Te::::: 512.6K

Pc ;=8b~97bar Tn;S: 337.9K

BL :=~51.2S·10-:3 CL:=131.13.10- 6

AV := 2.211

.. ·-3

BV := 12.216·10

-6 Cv r= ...:3.450·10

( BV Cv _2)

Cpv(T):= Av + _oT + -·r ·R

K K2

P:= 3bar

Tsat := 368.0K TI:= 300K T2:::::; SOOK

Estimate ilHv using Riedel equation (4.12) and Watson correction (4.13)

Tn Tm:=Tc

Tm = 0.659

Tsat Trsat:= - Tc

Trsat = 0.718

L092·H ~) - 1.013 J

L\Hn := ·R·Tn

0.930 - Trn

kJ L\Hn = 38.301- mol

( 1- T )0.38

rsat

L\Hy := L\Hn'

1 - T rn

kJ L\Hy = 35.645 - mol

69

fTsat fT2

,ill := CpdT) dT + L'lHv + CpV(T) dT

Tj Tsat

,6.H :::: 49.38 kJ mol

. kmol n:= 100 _ .. - .• _.

. hr

Ans.

(b) Benzene:

kJ xn, = 28.273- mol

kJ L'lH = 55.296- mol

(c) Toluene

kJ L'lHv = 30.625- mol

kJ 1lH = 65.586- mol

4.15 Benzene T c := 562 .. 2K

Pc:= 48.98bar

Tn :=353.2K

Tlsat:=ASl.7K

J

Cp::::162· ···•·.

. mol-K

Estimate L'lHv using Riedel equation (4.12) and Watson correction (4.13)

Tm = 0.628

T2sat Tr2sat:= -Te

Tr2sat = 0.638

1.092{ m( ::) - 1.013)

LV-! := -R-T

n 0.930 _ Tm n

kJ L'lHn = 30.588- mol

._ .( 1 - Tr2sat)0.38

L'lHv .- L'lHn

I -Tm

kJ L'lHv = 30.28- mol

Assume the throttling process is adiabatic and isenthalpic. Guess vapor fraction (x): x := 0.5

4.16 (a) For acetylene:

Te':= 308.3·K T;=::298.1S·K

... ~.

'(ri;~189A'K

70

T

T -nh1.1

T

T

T = () QF.7

1n(~J - 1.013

bar

ilHn:= R·Tn·1.092·------ 0.930 - Tm

( 1 - r, )0.38 LlHv := ilHn·

1 - Trn

kJ (b) For 1,3-butadiene: LlH298 = 88.5-

mol

(c) For ethylbenzene:

kJ LlH298 = -12.3·mol

(d) For n-hexane:

kJ LlH298 = -198.6·mol

(e) For styrene:

kJ LlH298 = 103.9·mol

4.17

1st law:

dQ = dU - dW = Cv-d'T + P·dV

Ideal gas;

and

p·V = R-T

Whence

V·dP = R·dT - P·dV

kJ ilHn = 16.91-mol

kJ ~Hv = 6.638- mol

(A)

P·dV + V·dP = R·dT

(B)

Since

o _

p·V - const

then

0-1 0

r-sv .av = -V ·dP

from which

V·dP = -P·o·dV

Combines with (8) to yield:

71

P.dV = R·dT 1-0

Ans.

Combines with (A) to give:

R·dT dQ = Cv·dT + -- 1-6

R·dT

or dQ = Cp·dT-R·dT+--

1 - 6

o

which reduces to dQ = Cp-d'T + --·R·dT

1 - 6

or dQ = (CP + _6_).R.dT R 1-0

(C)

Since Cp is linear in T, the mean heat capacity is the value of

Cp at the arithmetic mean temperature. Thus Tarn:=q75

Integrate (C):

T:=AOO·K

.1 .

6.:= 1.55

Ans.

Ans.

4.18 For the combustion of methanol:

CH30H(g) + (3/2)02(g) = C02(g) + 2H20(g)

Mf298 := -393509 +2·(-241818) - (-200660) fiH298 = -676485

For 6 MeOH:

Ans.

For the combustion of 1-hexene:

C6H12(g) + 902(g) = 6C02(g) + 6H20(g)

72

~H298 :0:0 6·(-393509) + 6·(-241818) - (-41950)

~~~~~_':c~0~,~i~1~[~~gl;~tJ

Ans.

ilH298 0:0 -3770012

Comparison is on the basis of equal numbers of C atoms.

4.19 C2H4 + 302 = 2C02 + 2H20(g)

c c: c c c c,' ,""" """ " "" "' ,J"

MI298:=r2·(~241818) +2·(-'-'393509) '-"S2$10}-'

"", " ',mol

Parts (a) - (d) can be worked exactly as Example 4.7. However, with Mathcad capable of doing the iteration, it is simpler to proceed differently.

Index the product species with the numbers: 1 = oxygen

2 = carbon dioxide 3 = water (g)

4 == nitrogen

(a) For the product species, no excess air:

0 3.639 0.506
2 5.457
n:=
2 3.470
11.286 3.280 0.593
1 - 1..4 A ;= :Lni·Ai B :=:Lni·Bi A = 54.872

1 B = 0.012- K

For the products,

fT

Cp Lllip = R- R dT

To

To:=298J5K

The integral is given by Eq. (4.7). Moreover, by an energy balance,

LliI298 + i1Hp = 0

73

t .= 2

(guess)

-111129& = R[ A.TO·(' - 1) + ~ .T02(l- I) + ~O -(' ~ 1)]

Given

't := Find(r)

1: = 8.497

T := TO''t

Ans.

Parts (b), (e), and (d) are worked the same way, the only change being in the numbers of moles of products.

(b) no = 0.75 nn = 14.l07
2 2
(c) nO = l.5 nn = 16.929
2 2
(d) no = 3.0 nn = 22.571
2 2 T = 2198.6·K Ans.

T = 1950.9·K Ans.

T = 1609.2·K Ans.

(e) 50% xs air preheated to 500 degC. For this process,

L'l..Hair + L'l..H298 + L'l..Hp = 0

L'l..Hair = MCPH-(298.15 - 773.15)

For one mole of air:

MCPH(?73.15 ,298.15, 3.355 ,0.575'10~ 3,0.0,-0.016,105) = 3.65606

For 4.5/0.21 = 21.429 moles of air:

L'l..Hair = n·R·MCPH-L'l..T

L'l..Hair := 2l.429·8.314·3.65606·(298.15 - 773.15)._1_ mol

1 lI..Hair = -309399- mol

The energy balance here gives: [l.H298 + &fair + tl.Hp = 0

74

n·-

.-

A:='

3.470

3.280 .

3.639 5.457

1.5 2 2

16.929

A = 78.84

1: := 2 (guess)

0;506 1.045

. ··~1.lS?105 .K2 . 0.121.

0.040

1 B = 0.016- K

Given

t := Find(t)

1: =: 7.656

T :=: To·K1:

Ans.

4.20 n-C5H12 + 802 = 5C02 + 6H20(l)

By Eq. (4.15) with data from Table C.4:

AH298 := 5-(-393509) +6+,,2&5830) - (-'-146760)

4ff~~§~-_~~'~~':~-,~35;~i6~:~J Ans.

" ~ _. '.'~'.. ~ i, "-c_,,_,,,,··_ :~ ·,_·~L_:.::.-:

4.21 The following answers are found by application ofEq. (4.15) with data from Table C.4.

(a) -92,220 J

(b) -905,468 J

(c) -71,660 J (d) -61,980 J

(e) -367,582 J

(n) 180,500 J

(0) 178,321 J

(p) -132,439 J

(q) -44,370 J

(r) -68,910 J

75

Given

Cp(y)·(400 - 77}BTU = Q - Llli29S(Y)

y := Find(y)

y = 49.782

Whence

(lbmol H2O evaporated)

(lb H20 evap. per lb oil burned) Ans.

4.37 BASIS: One mole of product gas containing 0.242 mol HCN, and (1-0.242)/2 = 0.379 mol each ofN2 and C2H2. The energy balance is

Q = Llli = ~H298 + ~Hp

. .

.'. .. .... . .... ..... . .c: .0.242

AH298;= (2-135100 ~227480):-· .' -.-'J

. 2

Products:

[0242J

n:=' 0.379.'.

0.379

(4.736J

A:= 3280

6.132

i := 1 .. 3

R := 8.314

A = 4.7133

3 ~H298 = 5.169 x 10 J

"[1.359J' ..

B := 0.593 .\0- J

1.952

. ... ( . ..;;.0.725J.

D :=0.040.105

-1.299

B = 1.2934 x 10- 3

4 D = -6.526x 10

( -3 4)

MCPH 298.15,873.15,4.7133,1.2934·10 ,0.0,-6.526·10 = 5.22010

MCPH := 5.22010

AHp := R·MCPH·(873. 15 - 298.15)-J Q .= ~H298 + ~Hp

4 Lllip = 2.495 x 10 J

&~o:~B~.Q~'g~~~ Ans,

4.38 BASIS: 1 mole gas entering reactor, containing 0.6 mol HCI, 0.36 mol 02, and 0.04 mol N2.

Hel reacted = (0.6)(0.75) = 0.45 mol 4HCI(g) + 02(g) = 2H20(g) + 2C12(g)

For this reaction,

91

Llli298:= 2·{-241818)-4,{-92307)

Evaluate

TO:=:: 298;15

n i= .

-4

-I

i := 1.. 4

L\HS23 by Eq. (4.21) with

T:=823.15

R := 8.314

5 Llli298 = -1.144x 10

4 L\D = -8.23 x 10

( - 5 4)

1vIDCPH 298.15,823.15,-0.439,8.0'10 ,0.0,-8.23·10 = -0.72949

1vIDCPH := -0.72949

L\HS23 := Mf298 + 1vIDCPH.R.(T - To)

1: H20 2: CI2 3: HCl 4=02 2 2

L\A = -0.439

-5 Lill=8xlO

Heat transferred per mol of entering gas mixture:

4.39 C02 + C = 2CO

2C+ 02=2CO

~H823·J

Q := ·0.45

4

Mf823 = -117592

AH298a := 172459 (a)

AH298b.:;O; ...,221050 (b)

Eq. (4.21) applies to each reaction:

For (a):

i := 1.. 3

. (3376J.

A'"' .. · .. 1.17i .• • ··.5,457

92

.------~.- --- ---

1M = -0.476

-4 ,:ill = -7.02 x 10

5 Lill = 1.962 x 10

( - 4 5)

MDCPH 298.15,1148.15,-0.476,-7.02·10 ,0.0,1.962·10 = -0.410505

MDCPHa := -0.410505

. 5 ,6.H1148a := ,6.H298a + R·MDCPHa·(l 148.15 - 298. IS) AH1148a = 1.696 x 10

For (b):

.: (3.376J

A :=~:~;~

i := 1 .. 3

M = -0.429

-4 ,:ill = -9.34 x 10

5 Lill = 1.899 x 10

( - 3 5)

MDCPH 298.15,1148.15,-0.429,-0.934·10 ,0.0,1.899·10 = -0.549680

MDCPHb := -0.549680

Llli1148b:= AH298b + R·MDCPHb·(l148.15 -298.15) 5

L1H 1148b = -2.249 x 10

The combined heats of reaction must be zero:

nco ·AHl148a + no ·L1H1148b = 0

2 2

Define:

nco 2 r=--

nO

2

-Mi1148b

r:=----

AHl148a

Flue gas

Air

For 100 mol flue gas and x mol air, moles are:

Feed mix

C02 12.8

o

CO 3.7

o

12.8

3.7

93

r = 1.327

02

5.4

O.21x

5.4 + O.2lx

N2

78.1

0.79x

78.1 + 0.79x

Whence in the feed mix:

12.8

r=----

5.4+0.21·x

12.5 _ 5.4

r

x := ----·mol

X= 19.155mol

0.21

Flue gas to air ratio =

ADs.

Product composition:

nco := 3.7 + 2·(12.8 + 5.4 + 0.21·19.155)

nco > 48.145

nN := 78.1 +0.79·19.155 2

nN = 93.232 2

Mole % co=

ADs.

4.40 CH4 + 202 = C02 + 2H20(g) MI298a:::-:- -802625

CH4 + (3/2)02 = CO + 2H20(g)~298b::::: -519641 BASIS: 1 mole of fuel gas consisting of 0.94 mol CH4 and 0.06 mol N2 Air entering contains:

1.35·2·0.94 ;:;:; 2.538 mol 02

79

2.538·- = 9.548 mol N2

21

Moles C02 formed by reaction = 0.94·0.7 = 0.658

Moles CO formed by reaction = 0.94·0.3 = 0.282

llH298 := (O.658.Lill298a + O.282.llH298b}-J_ mol

5 J AHZ98 = -6.747 x 10 -

mol

94

... _-----

Moles H20 formed by reaction ;;;;

0.94· 2.0 = 1.88 3

2·0.658 + -·0.282 = 1.739 2

Moles 02 consumed by reaction =

Product gases contain the following numbers of moles:

(1) C02: 0.658 (2) CO: 0.282 (3) H20: 1.880

(4) 02: 2.538 - 1.739;;;; 0.799 (5) N2: 9.548 + 0.060 ;;;; 9.608

0.658 0.282 1.880 0.799· 9.608

i := 1 .. 5

0.040

R := 8.314._1- A = 45.4881 B = 9.6725 x 10- 3 D = -3.396 x 104

mol-K

B:=

( -3 4)

MCPH 298.15,483.15,45.4881,9.6725·10 ,0.0,-3.396·10 = 49.03091

MCPH := 49.03091

4 1 AHp = 7.541 x 10 -

mol

AHrx = -599.252 k1 mol

kg mdotH20 := 34.0·sec

AHp := R·MCPH·(483.15 - 298.15)·K

Energy balance:

From Table C.l:

.. . .. ..• kJ MIH20:=(398.0 -'- 104.8}-· .. .. .. ..kg

-AHH20' mdotH2o ndotfueI := -----AHrx

mol ndotfuel = 16.635- sec

95

Volumetric flow rate of fuel, assuming ideal gas:

ndotfue]·R·298.l5·K V:=------- 101325'Pa

Ans.

4.41 C4H8(g) = C4H6(g) + H2(g)

BASIS: 1 mole C4H8 entering, of which 33% reacts.

The unreacted C4H8 and the diluent H20 pass throught the reactor unchanged, and need not be included in the energy balance. Thus

Evaluate

1'.H798 by Eq. (4.21):

1:C4H6 2:H2 3:C4H8

' ..••. (·2.134J.

A:== •. 3.· .. 2 .. 4.9.' • -'1.967 '.

(26.786J· '.' .

. ." :3

it:~:;:t .: ·10-

"("0.0 J

D :=. 0°.8.3.'105

0.0 '.'

i:= 1.. 3

M:= L ni'A~B:= L nj·Bi i

M = 4.016 <ill = -4.422 x 10- 3 LIe = 9.91 x 10- 7 r = 8.3 x 103

MDCPH(298.15, 798.15 ,4.016, -4.422·10- 3,9.91.10-7, 0.08f·l 05) = 1.94537 MDCPH ::::: 1.94537

i'.H798 := 1'.H298 + MDCPH-R.(T - To) llH798 = 1.179 x 105_1_

mol

Q := O.33·mol·t.H798 'i

'"'\' .-

ADS.

96

Chapter 5 - Section A - Mathcad Solutions

5.2 Let the symbols Q and Work represent rates in kJ/s. Then by Eq. (5.8)

IWorkl rc

11= =1--

IQHI TH

Te :=:.323.15·K

Work:= QH{1 - ~~)

TR.:= 798.1S·K

k1 IWorkl = 148.78- s

.... . .kJ QH:==2~O·~

.. . ···s

By Eq. (5.1),

Qc := IQH] - IWorkl

Ans.

TH:= 750'K

5.3 (a) Let symbols Q and Work represent rates in kJ/s

Work := -95000· kW

By Eq. (5.8):

TC ::=: 30Q·K TC 11 :"" 1 -TH

But

(b) 11:= 0.35

Qc:= IQHI-Iworkl lWorkl

QH := -'----'-

11

QC:= IQHI - IWorkl

5.4 (a) TC:= 303.15·K TC 11 Carnot := I - - TH

TH:= 623.15·K

11 := 0.55'11 Carnot

97

11 = 0.6

IWorkl

QH : = -'-----'-

11

Ans.

Ans.

7{i;~~¥t~j~~:T9}~~ :~6\~':i~:lti~~:{i6:~~W

Ans.

Ans.

Ans.

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