PROBLEMAS DEL CAPTULO IV

Lupis, C. H. P.: Chemical Thermodynamics of Materials

Solucin:

eug 5

4. Co{..r\. ul eo .4","^L
d.r.rra^I :

h)

Vt--t,o I

: ta
1o

o.rr) =- -,i^,|^?
e Jo

\o 4pt6vn dr--',v.tA ^ l*
4t't *tk*cro

dac-aaaJ-

B ?orq r4^^ Upo)fi .o

r )q

*"'*- ,) lrrtLr
..^r_rrl*rco.

^ *r-o

*LKl,.*

S*-r.

par^

<{(r)

,tn*a^

\z-.*.*os +4-

{s'r?-{
'

ll_
i"
l)lt

; _Io,LTrr
b,

."d1

!AL

r)

v? eir

-, I

f*

oo

= Aloaorr

3rq
.{,,\

31,

=AloEY

ft
,JZ z

L
3

qro,tt,

0
\r'.

-o/yr

- ,
( ?'r1
( + 4{rI t.;{;i

J*/

=[eqTt;"cl r
J-

G"

ruo

l _Jr.rr^L vtrrr.l

BL

go

". d^ *g*rou

r {.4

a(el problema:
Otra forma de resolver

Su,

(d- o)

* , .uJ**,*ro
d- AboJ*,tto
$L

Solucin:

6ot

14B 'h

3-88

c,$,.,oJ. r,r,,*\ bo. ,r. 273'k Z

&
P"trtdoal
P: looo "*tt^.
Otra\"'
forma
de resolver ela.problema:

Q*t,

ok

Z \.r

.ro.torro Curt;tLo

&lgov
L73"V
1 18 ol.

d^ t

:)

B*= (o.B) ( r*)t

Br: p

cs

",

t)( b.baAyAJ.
g2

Br=

U9

-Al 6"73 A'r No

At

A'cetAqclnh U,-r,ol pr, T:_ ?-73-kd"*.^ A),, ."a A rn,-..o",, l)

tl^ vo.A^Jrro

Itroo"k

T:

kt

'tr fr

t?oo "L

*"

\,'tvo.t-r-c*[

d^

\5.15
\\g "'1.
\* 1,rr.Q.* cr.. t- {,b. L

I
tQ-r--rrt.o>
q-*

0.
No ( r*)*

l^--)

o.b

B.= (o'r ) (a'86\3'\)o

0*

= 4rr,?g t .xJo
bL

q.

2.34

AA51a k-

eo"8t

0I a*a"

tf o o

0"1,.^,rr- C.\.4a. ) o\

'T-z-

\oo':r.

cr",r.r-Gndg cr.

*L* $.*j*

fioo* t,rn'*-

f.;O,'ac +^-^-

NL

to*".d* Iu:
a; i

nq-r,

&/v:

t**n

re

l*rp,r* d^" C,z Q

c,p : -hp
t""r

Af'-

f\tc*
T;* S 13* 3r' f : l$0o ,t[*
.

qrd;wtrw

f3 (lrso) p
$.a

(tao*\A,

(&t'osr

(r{isd###i#}*sJHd:?
)Ltntlr"
(sL

IG
a-2gf4\
TG (tclc".r)

.dA

q.

0 q. ??3*k ) lwJ***.

T--- lFOo "V*. b & [*e]e o$-^-.

| 7

t;

looc &

cffi::lMen*ut_-*__
--*'t?.")

(taocr\( /.uoqq )

Fo'6,u*.Jq#

'ttoo r?^)

C,AT

[.o^d* t*

t#lr) ;

')

A
L3 Y +ilo-

44, #g 6r l&orh H lrnpo*[,^"'

"

I o^^^ \^^-o,t

,T
I
I

Chapter

IV.

Chemical Potentials, Fugacities, and Activities

-0.8
i
i

icn

,*
:\
:\/
:

:<
:Q

1.5

.o
t

-3.0

-4.5

kru.

,,.,

Figure 2. Reduced second virial coefficient, B2lNe(r*)r as a function of the

perature, kTlu*. Curve C is calculated from equations (19) and (20). The
points on C are a mixture of data for Ar. Ne. N2, and CH. Curves A and
quantum ef[ects for I{e and H. respectivel'. (.Ajier Hli lll.',

Solucin:

\r5

\l

(-

>-.=,

il* Li

z-:

-l lo

p trs

!1

\hs#/

\_
ab

,fu\

H
b

r\t

c-

'_)

s-d

.rD

Lr*
yt
F)t
\

1_

,"-t

1-,-

01"l

<
f$
|

rl<_\

-llA
L---C

F \>s

1l

-O

rJ

*\k

\_

\q-

\------,
o

11"

- )-.s

--

<_

?*f \<

ll

L*c{

\'q'

1-P

\--c

ale
o

lN)

qq

rl

q\

t'

-9

-t

1-

nl<
-\

-T5

$*

L;-t

-\'i"|s

%l

,^\
<l

1!

e"1)

.-^)

1 J)

1l

-O

1-

tl'

='-

+r-

s-^

y'

Irs

l
b

g.

?
r

.-l

{-A

"{

\*-/
+=
7
e_

t.

8I

{s^n

eh

L\\

?
l.

'F
r\
p3

tr*
F

F\

9=.

FrA

oFi
x1l

f:
x.,-

f3

iF

9"
T

flI
:-

V<''--rfl
o,e
-1.,
ch f

T
30

q.,J
-f

c)-tE-*

t-J-

dh
oJ 2
i

e -F"

i's,

Otra forma de resolver el problema:

*yu

E !.'h n.

#'H*.:f#iff-t) r
aSrAJ t

't

:.

A}q*"#} z,[
{. l$-'p*t'$
\,

(*9,,

tbh'l>) (Et 'lrust'rtJ

i***'*.-*'@

(st'r)T

-s

ob

tl *

(q,ca
| ',

'"+

) (sr'?',8$ o'l

?blr{rq'o

r,"'r'ryrufsrl,r71*o

o*

7h

lrlr

*1*

q'.,l

I ? bhh s'

lb-ut

{,,

ql0o "l

+r

G,qt f

*l$,f,

(:r

) CIecr

t? tf ^ o,

lv

1r'T wU,$f
I

q \/\t'!' $${s\

l-

l.

,1-ol

'

*(il*t

tl *fl tt ?

T*

-**o'*h

*r ,*
',vap 4'r l)u 'i*fl
"I

Y'vwfl **L

{p)r"

ar"rrtpl"rt

*l*n

**'

":

$tl

"ra'''a^'nr,l*r\

"""\'?

*{ )

51d -tNd

a r\

It,b:qr+ *tN ' 7 Sa'c) *,A

'lbhftg"o t'A

'[**/

*tt *3t x "!\ 't i-q l

t"Yr".^tr oltt t'\ avl
:il1 l*

In Fs/*1, or* *rtl?&$"

tl o
'i,-r\.f rr

o^luJffi?ft.--.

r.r'rant"ltl*rrr

(:

+rnd)(q*n) (':

J?Jr.ft :' (u

$'?P

t
^ l{:ra',rr

.)

(,:

t.uu{\

n #f

(-* +d)to-

J,^#:

**ru $} "J;a

d q *"*f

"

'i4 *p rrnrulf

}r

e{ryry

*u"r?

lf "*?O

rfi + ffi{rffi]ru''fldY
**,
,d

$ og-*, J

q* A

s)'r")*v.,"'rv?

Ar-a

*_.--.- +

'l

l-/, T,(E*
AP L'uW;f-J I*AtL;;*
*.y?
;

"#*.-h)

d-

ili-

6A

'*l

1tu

btiJ

'l

(-'

,J 'dlt-{

^d\

"L-*,
F
'btr
I

T*A

zA

dp
a

\l!fi\ tdttp rnrro

'61

J7)

i'a

r'ilD '

lt

"\

dP

of tltnxzp

*L',u

tio-l,qp y

t,

,l

I
J

'\
bt)

tt/

*Y

,r*p y^w-t Jp

?3 or

\)

Solucin:

4, Lr' -o0"," !,, &

Vq, v/.o|.
l[rt^L[t) y b (e^^ Lts/,-.r)
^(..^
fturq "l wtl-rr orA-o N. sor,r q = l. t l O b t:o"o51 l, P*o J\^^[.r,rr.gtll
e"It^ .lo \* vato-'- e,: 2,2Sg
b: o,o{g. 1,* \o, $u*.,4qdro d^
)
eolo>
3cl% C Ll.l 10 7.4J" dt l*\, a*n*lrro. d,.^^br^V
A^"> erv r-u-ror rr,r-Lt"L
,

(rr^a
d- \OoO,,nL
e-r.t.n
b Otra forma
de resolver el problema:
.

(v+) (p *
h): *t

5"<^

:-)

(V-b) (P V"+ar) =

p\"* ov -

Pb{

t-

.,.

Va- dr-r Waob

2rV"
L

\o .".,o".*i"' aL

rT

r,

v==o

o\1 (tb+a-t)vt*av- 'f =-<>

Sn frne ?*1- tI '
(Zes,'lv, .^"(o \t.,
"cc>qcufu
\oe.,

\3-

Lt

toooXo,os'tt) +

,-^*

'

V (r'qo\(o'o:ar) = o
lo. oaaos)telu) tJt* \'31? -

'\a. (-t*,,o *t, '"^L =s'c )

V T; 118
=> log)o\*- 63.,t-Vt+t,31oV- o.oS43 =o
\, =' o' os6o5 \\t ?
J d'Ft.,ro !^'a-- o. oeob -^

r{-o.^"

p-

o.

ogos

\}s - oI'-' f *.-l

---"-'ogoqi.

;) II ur-- o' .
o3ot t
t" r
\

"L

i o

ra-nc'

-oo

Q*ol v'*t,lo

l*

e.r)o-ca.l'

faJta d

.tlq

looc,us-f Crooo)[o.o'{?-s) + Lo.oaeos)tzq$] N"*

tooo

t'-

61.l3vt+ l.2s3V

o' o46\ = o

-- o -ou13 \ls )
.
o. o^rolz i. ( ooo qo.Vr=
'L
J
l v,

l u.= o,otto?1 L )

l.2s3V - (l..ztr[oo{1*8):6

CH'

*rre {ou^= o' o5?3o

Jf

C-^ I, .ra.

4'

----ta
v."\{'

P*, o{-o lodo

cl,-\

oha.c.,

eJo a, to-

'e&p.n*n.J*^

J.#n-

'(or:a

e'."bL"*ot-

lr*orc*'f ( t)

.,i

l^{ $r
a*s

r'

p**rl&
I

"J

(t,)

s3q I

0'.0f 6o,f -_ ggq I

1,"

(r\ = - !-^U.ensz) +^

Cf*

2.ozrud

+ 2.3oB: o. (41?

o .c.l17

S*=

= 0ooo )U, QD 55)

,h,,n-t A*{,r${ flu,o

J Cf*.f
| u se

,r-,^( o\ ? s ^[

tqo

e)-r ot-^

p*;ro.

(n -Off?3

A"oqef

{o. oszcrs*}L e*f

2 Le- as*})
J

(o *taoSl{,Zqt)(o .os?8}

" ${{f;f
0- os?-)- - o-ot{? F

l*(+/r) : -!^(o.r1so) -B.216a+ a*,rf,r+: o.7s8r

r= ?n : (rood[1.e9*q1)
. ?C8l

{=

x,f,*

ct"o-*

-1,* fJ

.*

*^t{^" f. :

't

6r

L,:
4',o

P'lo)Lllcrr.r)
legg.

b*n

.frO**l .o J *,Lr.'**o
"tq l* ."*rrp*(a-

"

&.uot 388 '72*"#^

Solucin:

Otra forma de resolver el problema:

?Jtr.fr U sotu \^^(rr. J r qcrs ,

Doo.e.re$Jo

*[ H*b[-^^^ .{

\* cr*..-.l^

d^*

efi"r^" ' "(l

t^*--\^,,t

.,) &*

oL* /^-'f
fu,2 2. ?.3 Llst
b -- o .o4 qB Ll, /*--; t

ee

aatt^^Jr qt*

- d^

, ,.l ^

\. = 3tr )

vL
o,a*

L.;\,r ?6,c
4A,- Vo, t+^ W"Ls

f4;ra.

?.--

n/*V )

T.=

o. 1rs'l

L'l/.^^.\

J-

\*

\*r^go*^l*^,

cor-r,rgo-.ri|"^,"^,

P.:41

6'6 ^\*

T*

( f+q)
"L \rr.-.'.Io^-* C

o,oa-clr

r.? lo " otlzE)z

\e8.q *t/'^^-r\

T.z

(c^J1o^

2.2'r

o=4

\a

*lc..,L

o.r

d,* \o

so/r+Vo (9t rs e.r I)

*r?

\o

Vo^r, dLr fn/*n-b

Solucin:

),

'1*"7

t"oo\

Jd-

= ':*

eF"\*4 :',*',t "l

v"{a

xT|d a
w

tr(Jbft

"v-{rt

' 'i,' ,it

*va
t*A

( -9-* se,.t -!, r ) (

$l ) =,h

qtf-,

s tr 9j

1c/ \rL

J
.'t

**h

,w'\

***\

=-a

hl s lix
o r tf1'tr

tobo

:d":

,:d'

]fut

\r3

rwra f f1

tW

Tdiil

?
-d

tw

( ut

(:

'o/'* stY :

","*@

\ ef2

?
ryyr'tlg6}w-*rril
I

=-2y

wr:'o*

I"f

l\^/a*)-J*T

'|.lcrr..lou

o\

Erolkf.tr\v^r-co

T-|"'tfl

= \v
^/'O
---'+

""'o1"arrr

i^ofartcypo^y\ ?,F"-\ot-anb V
":-:-:J:-'

-\ *

*1"i

' Tt.6/\ g ,oFlas or?

Otra forma de resolver el problema:

,a.coJr.-,o

?9 S -*,lc crwral,nr

' b rorcrr. .^-"t \r\rns5^

".Sp

t\"'o $
11YTf* "un oppe lrr ro& 1p ioreal"t '\ 1-\"0 ' vnt'cs)rxs'tr
u 1'onl1 rro&r. .,'P Ypr-r,ltw.?rr"\ S otro or".h,1
f 'bFht!ols.A/,'?t(|Fh
w v ' ?roozr --r \o ob'o :b trarssrvf fr" v-v bprloE D*-lxo wyn v\a)

Answers to Problems

Solucin:

ies

7.

ap"rlaxz

02 p.zl

EXT

0;

dln^yz__ I
8.

aXl> 0. These conditions yield

I
aX3 X7'

o2ln"!z_

Xz'

LXz

a3 p'rl

a: plP: jX and pllpr:

From

,,
rAg
'-

d3ln^yz=_2
aX32 Xl

YtlY2, we deduce

\t'gXs(P e'glPsu
^Ycuxcu

* 16gXae(PelPc")

Using L'Hospital's rule,

(ffi)

.,rg+o

(ft),^"-o

:' "' ffi

13

Similarly,

_ (d(t - Y1.1J\ _ (dYc"\

\x*- xg-r - \tt - xo)/ *Ae+r \dx..,,/r."-o
/ dYo,

:et'to9i"Jo-l
9. AtP:1atm,

ln^y"

:0.075

- -1.8, "ye:0.165, aB:0.041.InPs -

(A.FI,,"'/R) x

(llTb- llT) and Pe : 6.1 x l0-8 atm. Consequently, at P: I

Ps: asPs:0.41 x 6.1 x 10-E :2.5 x l0-e atm.
At p : g000 atm, ( ln a"lap)r: (vn - vi)/R? and

x 7999 x 0.0242 :
_ [t* v" _ _vi vr
dp : -2.25
(s)r",- Jt
RT
1.987 x 1000
Thus (a)sooo atm : 0.803 x 0.041 : 0.033.
(cn)sooo",-

,n
r

atm,

_0.219

With no information on the fugacity of B in the gas phase, we may assume

It follows then that ps:0.033 x 6.1

that it behaves as a perfect gas.

x l0-E - 2.0 x l0-e atm.

Chapter V

l.

2.

22.9% CHo, 77.1%

3.

2037'K.

4.

AGo

5.

The reaction taking place may be written SO2 + 2H2S

the basis of I mol SOz and 1.5 mol H2S we obtain

417"K.

LH"

K:

5.5

}l2.

fAS" :29,900

103

ph,o

21.46T cal.

4\2(2.5

Z}IzO + 3S(l). On

- r)

Pso,Ph,s (l - fX1.5 -

2L)

which yields tr, : 0.725. The composition of the flue gases is 15.5% SOr,
2.8% HrS, and 81 .7% H2O. The production rate is 31.2 tonnes/hr and the
heat generated is 9.6 x 10 kcal/hr (exothermic reaction).
I

"L

rrr-courr.crtt< r,r.rt-:rr,rlau.cc cr* zt^ - f.oarr,bo. \o. cooot,.ror-r^ {q.r,r.uo.lrr,

rstca5 q.*- b< c*b^ *l,t$o-..o
<.-rrll"o r,\ .|e,-,r.r.,.,.,.,o d^ Lr.
A p"*lo
I
"u,
ov.,.goatcr.
d^fa^A"lrr-[
Otra forma de
resolver el problema:
d^ -gr^ yo

&***"r6frr c)- \o

trc{*? t'"{*d"'t

=)

K,rz Xt T;

&a=

y- n,

)* a d'n.J'-"u'^lto'*fo""^it
&l
acltu'd^'l
Var.,.> $^,- \.^
y-"
*\
\hc-'tt\'it^l'a.'"
lo^^)o
lt
e\'
NL U fo''r
p,logo,rraroJ
a-t'{tyt'A# d"z '
,^r'**,o^r.....n 1o -t< \\'\c'tt*^*-o\*t"t- '\^-

fl** *f*o \oJo

,!

.&t-,ra{y'

,, *"ld*#' *

s)

*)

&4*

rz

reTA*rQt
r-d,o**n-.*("*-,

r ''f-;A d z

*,r*# d retrrf,-'- htKu

ffr'*,4.-.,

^*.[.,*-r,

*^,

&t"c'q" '*{ ftr',,--'$q qJl {l**o

;
Ut
d
?f,e

-)

"{ S"u.t*{*-'\u/t.*} h

,,

Ceil &
du
{.q"'l*

&u* F*^/*

d'uu,

ffiffi:;.

*r J*,, L,fl.*(h'* v

ffi

r o,

*l 3,r*

*,ru

L *.(

't^

b'*

+-fi*'\%-q

sm

J-0* f*,

*f*

Jffim',wmrsE,wb

r\

dta

J,[*y
dY*

1du

4
Cltlh'

.al'#tts

*,

<

{tJ,r
cr \q

Vt

= tr-r*
Y,F

wrrrl?rrfo. hTF * -'b

,t

4ttf

*d;F

aac"\vriyo,,F*Ft

!'

'

-.&Tlr'r_*_-rr-"-dd

*ilr

*?.clcv*\".:i

"X"

flo

(+)'$:ft)"l'

[""i

tJ rC
af l._

^Y,

--/

(=

l'

iffiwP,a \-

-T'*l-*f
=<1

,1."-m\"*

3
('+

\"tg

l,r

;dP
r 3,lwfrt

**

P
)J"

.{%e

,&I- (Y,F
?

\"d*dt-'-'rrrdt'

7a

r;t!
JzF ra

'I

"(*{

l',

Answers to Problems

ies

7.

ap"rlaxz

02 p.zl

EXT

0;

dln^yz__ I

8.

aXl> 0. These conditions yield

I
d3ln^yz=_2
aX3 X7'
aX32 Xl

o2ln"!z_

Xz'

Solucin: LXz

a3 p'rl

a: plP: jX and pllpr:

From

,,
rAg
'-

YtlY2, we deduce

\t'gXs(P e'glPsu
^Ycuxcu

* 16gXae(PelPc")

Using L'Hospital's rule,

(ffi)

.,rg+o

(ft),^"-o

:' "' ffi

13

Similarly,

_ (d(t - Y1.1J\ _ (dYc"\

\x*- xg-r - \tt - xo)/ *Ae+r \dx..,,/r."-o
/ dYo,

:et'to9i"Jo-l
9. AtP:1atm,

ln^y"

:0.075

-1.8, "ye:0.165, aB:0.041.InPs

(A.FI,,"'/R) x
atm,

(llTb- llT) and Pe : 6.1 x l0-8 atm. Consequently, at P: I

Ps: asPs:0.41 x 6.1 x 10-E :2.5 x l0-e atm.
At p : g000 atm, ( ln a"lap)r: (vn - vi)/R? and

x 7999 x 0.0242 :
_ [t* v" _ _vi vr
dp : -2.25
(s)r",- Jt
RT
1.987 x 1000
Thus (a)sooo atm : 0.803 x 0.041 : 0.033.
(cn)sooo",-

,n
r

_0.219

With no information on the fugacity of B in the gas phase, we may assume

It follows then that ps:0.033 x 6.1

that it behaves as a perfect gas.

x l0-E - 2.0 x l0-e atm.

Chapter V

l.

2.

22.9% CHo, 77.1%

3.

2037'K.

4.

AGo

5.

The reaction taking place may be written SO2 + 2H2S

the basis of I mol SOz and 1.5 mol H2S we obtain

417"K.

LH"

K:

5.5

}l2.

fAS" :29,900

103

21.46T cal.

Z}IzO + 3S(l). On

- r)
Pso,Ph,s (l - fX1.5 - 2L)
ph,o

4\2(2.5

which yields tr, : 0.725. The composition of the flue gases is 15.5% SOr,
2.8% HrS, and 81 .7% H2O. The production rate is 31.2 tonnes/hr and the
heat generated is 9.6 x 10 kcal/hr (exothermic reaction).
I

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9.

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^Ycuxcu

* 16gXae(PelPc")

Using L'Hospital's rule,

Element B boils at 25)'K with a standard enthalpy of vaporization equal to 55,0(X
liquid
solution characterized
caUmol. At l0)'K and I atm it forms with component A a 13
I
:7X+
by the following
ln
and
VlXs-4XXs cm3t
'y":
irroperties:
-3.2X2^
.,rg+o
mol. The liquid solution is equilibrated with a gaseous phase containing A, B, and
Similarly,
argon.
It may be assumed that the gases behave ideally and that argon has no solubilit
in the liquid
the activity of(dYc"\
(d(t - Y1.1J\
/ dYo, solution._Determine
_ B in the solution and its partial pressurt
in the gas phase at T:
lO(X)oK,xo)/
Xs = 0.25, and
P = I atm as well as at P = 80) atm
\dx..,,/r."-o
\x*- xg-r \tt - you
*Ae+r
Soecify any other assumption
find it necessary to make.

(ffi)

(ft),^"-o

:' "' ffi

:et'to9i"Jo-l

Solucin:

9. AtP:1atm,

ln^y"

:0.075

-1.8, "ye:0.165, aB:0.041.InPs

(A.FI,,"'/R) x
atm,

(llTb- llT) and Pe : 6.1 x l0-8 atm. Consequently, at P: I

Ps: asPs:0.41 x 6.1 x 10-E :2.5 x l0-e atm.
At p : g000 atm, ( ln a"lap)r: (vn - vi)/R? and

x 7999 x 0.0242 :
_ [t* v" _ _vi vr
dp : -2.25
(s)r",- Jt
RT
1.987 x 1000
Thus (a)sooo atm : 0.803 x 0.041 : 0.033.
(cn)sooo",-

,n
r

_0.219

With no information on the fugacity of B in the gas phase, we may assume

It follows then that ps:0.033 x 6.1

that it behaves as a perfect gas.

x l0-E - 2.0 x l0-e atm.

Chapter V

l.

2.

22.9% CHo, 77.1%

3.

2037'K.

4.

AGo

5.

The reaction taking place may be written SO2 + 2H2S

the basis of I mol SOz and 1.5 mol H2S we obtain

417"K.

LH"

K:

5.5

}l2.

fAS" :29,900

103

21.46T cal.

Z}IzO + 3S(l). On

- r)
Pso,Ph,s (l - fX1.5 - 2L)
ph,o

4\2(2.5

which yields tr, : 0.725. The composition of the flue gases is 15.5% SOr,
2.8% HrS, and 81 .7% H2O. The production rate is 31.2 tonnes/hr and the
heat generated is 9.6 x 10 kcal/hr (exothermic reaction).
I