iuollceJ slql

JoJ

J"gzte *s'v pue *11'v

tL\\ 'uo!$ano Jo sonlu^ otll oJ ]

']uelellp ',H'V 'Coge st le^emoq [1iq611s {uo 'rNf l,{l/{OC le onle4 slt utorJ luoralltp fuen sl il lnq eOuer ernleredLrel stq] Je^o ]uelsuoc Illerluesse sl .S'V

side. hence a increases. This can also be seen from the results EN.510.312 Thermodynamics 25 to 50"C, implying tlrat a increasecl.

P6.4

Drarw up the follor'ving equiliblium table and recognize that. since rx << corrpal'ecl to I within rnclle flactior.r factors.

(d)

Le Chatelier"s principle provides the answers, As plessure increases, a decreases. since the more c:olxpitct state (less moles of gas) is favourecl at hi-ch pressures. As tentper.ature increases the sicle ol the reaction that can absorb heat is favourecl. Since A,11" is pc'lsitive, that is the right-hand

COr(g)

/t.:+rron)'': =l_.--l =ll.8xlo-rl f4x({).010) ) '

=: CO(g; + J Or(g)

Problem Set 9 (10 pts)

'

ol parts (a)

l, a rray

ancl

(b), Kincreased frorn Fall 2011

be neglected when

T.0t

LVt

z0l gst
08'z 09'z

z0t
8SI

r-loru r-) f/esrv f>l/"9'v

r-loru
s

tz'L
I

0LlX

p
a

L'V

z7'l W'I
96t I

v-0lln

86VL

Eivl

\IJ

(ttt) pue '(lt) '(t) snotlunbe Sutsn pelulnclec ere

.y *5'y pu '"r'V

(rl)
( t->rgevt )

\rt)

s6ir )

('t

t__-l

Ftorultoor-l= ( * zz't ) lulx 1,_your r_) f S?lt'8) \o-UlxtCt/

I "-or

=#=,H'V f'yl |. luty

Ux,,
:,77'y
ro3 3un1og

lr rl

'J )

rrz

rl

[+ +)ir-'vur-'vur
'polulncleo eq,{uru
pu N Jo senlul petrlnolc

,J

pue

3o

slud

orrrl ,{uu

ruolc .,roloq elql orll

ur ue,rr3 ele (rt)

"g',V

.8,'y oql

lvt'slx ulJu- = "g'v

,,,('o1)=

(r)

,,,(oi)"

I d=ll-= L+ 'i'!rorr'
[rt
t

to)x"

x = t tll r,,( p "d

tE

{*!zil^ ""^

[sosua 1mi.red

rsl ,:rff = ,

nzI

"1* t --;TI

o|*t

nl

^#^-V,tq=
,1*t
u(n

suorlce{ oloru elerurxo.tddy

suorloB{ 0lolAI

un!I

n un

n-L - 1\
toJ

slunotuv

,o
t/\nrEEllInol

lvcll lHc

INSTRUCTOR'S SOLUTTONS MANUAL: pHyStCAL CHEMtSTRY

In this reaction the rrunrber ol electrons transferrecl. rr, is not irrmeiliately apparent, as in part (a) To fincl v rve break the cell leaction c'lorvn into hall'-reactions as ftrllow,s:
R : {O,1g; + 26 e + 26 H-(aq) -+ l3 II,O(t) L: 4 CO,(g) + 26 e- + 26 H-(aq) + Ciot{,,,(g) + 8 H"O(l) R- L; Co[{,,,(s) + f o,19; -+ 4 CO,(g) + 5 FLO(l)

Hence.

r,

= 26.

Therelore.
P6.16

F--LG" vF

+2746.06 kJ nrol j (26) x (96.485 kC rrol--r)

Hg,CI,(s) + Zn(s) -+ 2 Hg(l) +

ZnCl,(aq)

(a)

tr.il= Lr.rr

25.(r9-1 rrrV ----.

lup[6.27.25"C1

Q = u(z|2*)u.(Cl ) = \T,b(Zn|'lllr'Ixy?lh(Cl-)/6';:. rvhere Lt1Zn\,)=6,1r(Cl-)=2b,ancl y_y\=yi

Therefore. Q =

yl x

4h3

Ib

D/6" hcre ancl belowl Ei.,r

All(l Lccr = t..rr

Eilrr

- --,-lrtt-l/rry.'t=
-

25.69-1 rrrV

(38.54 mV) x ln(4rlrb)- (38.54 rrV) ln(y*)

Zn,1

(b)
(c)

E[rr = E"(Hg]./t1g) _ E" (2n2,I

A,G = -vFE"rr=

-(2)x

(9.648-5

- -r'tri|,,= *(2) x (9.6485 x l0rC nrol-r; x (1.0304 V) = -198.84 kJ nrol-l A, Go *'" I .9884 x I 05 J nrol-l 1,- r.ln A- = RT (8.3115 J K-r nrol r) x (ZqS. t S rc - 80.21 I so ,\ Ftr4 " l{Fl
A,G"
__

(d)

From part (a):

1'2212v = 1.0304 v

- (38.54'rv) x rn(4r, x 0.0050) - (38.54'rV)

. lny (e)

--'

(1.2271

V)-r9.1864 V; .. ^.^F -- -' V)- (1.{).1{)l : ---- ---:---I:j--t_i_t_=*0.2699 so l- _lir.ZC-rl

i

logTr = -1.-,* I AI1tz 15.75)

I = i2-irn rr" )[5.76]

where b(Znr*) = b = 0.0050 nrol

kg-r and

r-lotu

[I

90'9VLT'- =

152

ancl

v=2
tr6.18
Pr

-I

x (25.69.1 rrrV) y ln(,1r,,/,1,_)

= +0.267

6V

_ (_0.7628 V) =

I.0304t]

x l0rC mol-r) x (l.22j2y)= -236.81 k.l mol-r

x rny*

1r(Cl-) =

21,

= 0.010 mol kg-r

[se1qe1qep]

= x (E) + (si'let-) x r-loru f{ [(to'rt-) - Gt'ttz ) + (8''O'J)*r'V V = *9t V (3.0' HoJ),r'V - (l'O?H) "ttVg (r)o'u s +(3)'olt e(3)'oi+(8)o'H'o (q)

[a1qu1u1up] r-lollt

(z) r-loru J)t s8t'96) x

I loLu n t t'lrz+ "J V f{ tl'LtZ-=(t'OtH)*r'V

(t)OeU <- (B)rO

=Vtz.gl 1'l=

sI uollc eJ lleo

tl'9d

eql
(e)

\)086

( t
(f)

E
$
t;

Ft"t

86's-

-t.l= frl 8'

l+L

Ig)o

x (u) x

) 086 x t1[08'z =

(ioi'z)-

(l)]

(oJ)*H'v

_= ".js

+ (a)zH =

*9'V

(tJou)

"11,r

F
-.

Thi'

Jti

lt

lJ r.

Hence. pl

Usin-u in:,

fli" =.

Tlris valrrr. ploblenr. (

ctnc/.

Plt.t.tr,

We then d:

0/.c
E*t1/v

RHence.

L; Co[{,,,(s) +
r,

o,19; -+

CO,(g) + 5 FLO(l)

= 26.

Therelore.
P6.16

F--LG" vF

+2746.06 kJ nrol j (26) x (96.485 kC rrol--r)

Hg,CI,(s) + Zn(s) -+ 2 Hg(l) +

ZnCl,(aq)

ancl

v=2
tr6.18

(a)

tr.il= Lr.rr

25.(r9-1 rrrV ----.

lup[6.27.25"C1

Q=

u(z|2*)u.(Cl ) = \T,b(Zn|'lllr'Ixy?lh(Cl-)/6';:. rvhere Lt1Zn\,)=6,1r(Cl-)=2b,ancl y_y\=yi

Therefore. Q =

yl x

4h3

Ib

D/6" hcre ancl belowl Ei.,r

All(l Lccr = t..rr

Eilrr

- --,-lrtt-l/rry.'t=
-

25.69-1 rrrV

-I

x (25.69.1 rrrV) y ln(,1r,,/,1,_)

(38.54 mV) x ln(4rlrb)- (38.54 rrV) ln(y*)

Zn,1

(b)
(c)

E[rr = E"(Hg]./t1g) _ E" (2n2,I

A,G = -vFE"rr=

= +0.267

6V

_ (_0.7628 V) =

I.0304t]

-(2)x

(9.648-5

x l0rC mol-r) x (l.22j2y)= -236.81 k.l mol-r

- -r'tri|,,= *(2) x (9.6485 x l0rC nrol-r; x (1.0304 V) = -198.84 kJ nrol-l A, Go *'" I .9884 x I 05 J nrol-l 1,- r.ln A- = RT (8.3115 J K-r nrol r) x (ZqS. t S rc - 80.21 I so ,\ Ftr4 " l{Fl
A,G"
__

(d) .

From part (a):

1'2212v = 1.0304 v

- (38.54'rv) x rn(4r, x 0.0050) - (38.54'rV)

x rny*

$
t;

lny

--'

(1.2271

V)-r9.1864 V; .. ^.^F -- -' V)- (1.{).1{)l : ---- ---:---I:j--t_i_t_=*0.2699 so l- _lir.ZC-rl

i

(e)

logTr = -1.-,* I AI1tz 15.75)

I = i2-irn rr" )[5.76]

where b(Znr*) = b = 0.0050 nrol

kg-r and

1r(Cl-) =

21,

= 0.010 mol kg-r

l-lrus. 1 =

jlt+t

x (0.00-50) + (0.010)l = 0.01 5

_s)r/2

nnluslllnol lvclv\f

11ffio"r u

.(p) ped ur lep lulueruuedxe

( Holq+l r

(s)Byl(s)13Syl(, 341ourSZll0'0'be)lJeN'(r-EIlotuggglg'6'be)gge51l("d.E)'Ulla

(r-)

(r-lour-) tT,'18)

v-ltx zy:-)x

Z=

- "z

Hc

log y* = -(2) x (0.50s) x (0.01

-0.125 so /. = l0.Z5l

t9I

a#'';fo

orotlld'(bu),g3+(be)-137+(s)By7<-(s)133y2+(s)zH

ffi"'fr:

( Ho)P -r t -.? = {(-lr)D(*H)rlu1ft - "Tt =

tuo{ peure}qo en[^ otltr 01 [le.{\ flqe4reruer se;edruoc stql

x
(,-1oru

[tqlzt's pue tz'sl.l(-tJ)r(*H

()

"xut - ^,,-

St'862)+(,-1oru

Jr0r x ssre'6) x (z)=rn, nl

j; - "z = ( ;ffi;"tft: - "t:

fI

l8'9gZ-)=S'VJ + I'V = H'V

r-lou r-) t Z'L8-

FIo- rrtrzrz-l=

tqut#-

fff)r^ '/ .zp ) = t'o

rrsS -

[#0,1-

rr'?

(r) 8!'9d

(u) 1lcd ur se ,l

ll

(-r)"9rV olelnr
uorsseldxe aql
r

eruotur.uB ue8oJlrurp oltJlru olelltu <_ IoN <_ jotrt

rHN <__ ,N

:spnpo;d

Eur.tro110.; eq1 30 ,{ue p1er.,t o1

suorlcole olroceJ ,{uru lueprxo olgltrru o.rr

ozH + uo] <-

prJu croueqtro [8uEqle lour{lo Hoof,iHJ <_ oHJiHl e HozHJrH:)

enlE^ oql ojslnrl Pue

.rouI o,r

.lu

'pes,{1o.rp,{q s}

dIV

olou

'{rezr

Jo uoq^\ suorrJuoJ lJruoqo peldnoc o^rrp 01 olqeile^u sl rJo,r\ Jo f{ gg Jo unturxulu y .cruo8rexe pue snoeuuluods drv Jo srsflo.rpfq or{1 eruu s11ec lecr8olorq ur suorlpuoc uorleJlueouoc orlr

(r0I

xs_0t)ut(X g1g) x

(,_1oru )

r_) f 9?tt.8) +r_loru

'lw

r lor.u fI gg- = f{ I t+ =

I) x

[4-to,

ll,-HFldmati
= [dJV] 'L = Hd suorlrpuoc Iroc aqr qlru .{B,eua

+ =6qJa )utJv "D'v

s_01

*"''v

e'v 1=ty pue, ,r.:

'8ur1sere1ur sl .W ae.g srs,,(1o.rprq

aiv

eqtr

x 0.1 = [.a] = [aCV] Jo uorrurnoreo oqr

'cruo8repue sr 1;
uorrerncruJ srqJ
I l+ = IE_ =

lsnoauuluods 10u sr drv Jo srs.{10rp,(q eql suo'rpuoc p-rpuls Jepun

l'qr

s,4Aoqs

(ru yru r-0t)ut (x ots) x (,_1oru r_) f 94E.8) _

[Ot'si

r_Jotu

[I

aA UIw -og,v="g,v o0 ulJu +.9'y = 69'V

'(1'9 rtudtuly r_lou f)t

r_toru

f)

tto,,r{

lnoqE Jo '(Ereue oo{ prEpuls lectSolorq eqr ue,rr8 f8reue oe4 elers prepuels eq} olelnclgc uuc

(bu).OtH + (be) rog '1 gd go (6) '(r-Lup

e1e1s

14

+ (bu)4gy <_ (t)Oztt + (be)61y

srs,{1o.rpfq

dIV

eql

louI 1 -,a)

se1e1s

pJEpul?ls 1eoo1olq oql or rsrruoJ ur oroz syunbe gd (") e1u1s prnpuzu'rqr uorlnlos ruloru 01.9 ube u1

prepuls

w I qll^r posn o.re suorlu.]luoouoc

lOt'gl A

ut

Jy + *9'V = 9,V

6uueeur6ue Fctuaqc pue 'ocuotcs pluoruuolnue,{6ogorq :suol1ecr1dd, o1

"ro,1n1og
.uolldrunssu se8 pegled eql Jo eruJ ur pegrlsnleq 1ou furu poge paunl ,{1eug srqr 1err1 lerlauoq 'ezruS0ceg 'drqsuollule;

:slcnpord Bu*ro11o3 eq1 .srseqlu.{s , ue p1er.,( feru 3o luelrnpor Ioueqlo eq1 dIV roJ popoou qle oql ozrJrln 01 e^Jone uuc rungelcuq e ,se1 '{Ereuo oo{ egl eseelel ,(11eoruo8lexe o1 rted otreiilu/lou

elnleledrual

aq1

runtJqtlrbJ/.

|
\

',1.,,4,a