18.

2 Which of the following processes are spontaneous

and which are nonspontaneous? (a) dissolving table
salt (NaCI) in hot soup; (b) climbing Mt. Everest;
(c) spreading fi-agrance in a room by sellloving the
cap from a perfume bottle; (d) separating helium
and neon from a mixture of the gases

18.5 How does the entropy of a syytem change for each

of the following processes?
(a) A solid melts.
(b) A liquid freezes.
(c) A liquid boils.
(d) A vapor is conveited to a solid.
(e) A vapor condenses to a liquid.
(f) A solid sublimes.
(g) Urea dissolves in water.

el increases (el decveasc3

18.9 For each pair of substances listed here, choose the

one having the larger standard entropy value at
25°C. The same molar amount is used i n the coin-
palison. Explain the basis for your choice. (a) LI(s)
or Li(1); (b) C,H,OH(l) or CH30CH3(1) (Hint:
Which molecule can hydrogen-bond?): (c) Ar(ei or
Xe(g); (d) CO(g) or COz(g): re) 0 2 k ) Or Orc(g);
( f ) N02(g) or N204(9)

c") Li Cs) ar Lick) the h;gher e7hopj. L a

liquid H-\- is g ~ 3 e disorde-
r ttun in
a solid
) CAH5aHCe) or %SC-\ of these we \iquids
ind9 +he s m e MO\W mn5s. CAH5 OH is J,le k
hydmgw bond- I h i s wii\ deea.se +he number
m c ~ e w l e s in the liquid m d , he -kp;).
C H3 0 C H j h c ~ s Rc high- entrnpj .
Ce) ~ 9 ) or WJ Zoh
qases. Xe
4 these
h a s the g&
at^ rnonobmic
m o b - m-S,

(d) CO($ ]
\
r
o Some waning as in CC)

~ ~ o j nas, both ore gases , the one

hd3 ttve Largv

molar rn-s h a s the g& enimpy
dfi b mote &o-Cir~O-l d \ ~ i b m & o n a \ ma-h'on5.
18.11 Using the data in Appendix 3. calculate the standard

--
entropy changes for the following reactions at
25°C:
(a) S(s) + O,(g) SO,(,o)
(b) MgCOds) MgO(s) + COAg)
18.13 Without consulting Appendix 3, predict whether the
entropy change is positive or negative for each of

-- -
the following reactions. Give reasons for your pre-
dictions.
(a) 2KClO,(s) 2KClO,(s) + O,(g)
(b) HzOlg) H20(1)
(c) 2Na(s) + 2H20(1) 2NaOH(aq) + H2(g)
( 4 N,(g) --i 2N(g)

a AS is pcsi-litt. Solid -+ 9-

Q) A S is neg&ve. When s ~ n n d e n dinto a \ \ $ u i d ,

a gas i
{fs -hpy dc~tecse_s.

enlopLJ Shun the kc-tarrts.

-
18.17 Calculate AGO for the following reactions at 25°C:
(a) N2(g) + Odg) ---,
(b) H20(1) HzO(y)
2NO(g) he
is z-.
7 el-+-s
(c) 7-CIH,(g) + 502(g)+ACO,(gj + 2H,O(l)
(Hint:Look up the standard free energies of formu-
tion of the reactants and products in Appendix 3.)
18.19 From the values of AH and AS, pred~ctwhich of the
following reactions would be spontaneous at 25°C:
Reaction A: AH = 10.5 kJ. LS = 30 J/K; reactlon
B: AH = 1.8 kJ, AS = - 113 JIK. If either of the re-
actions is nonspontaneous at 3j°C,at what temper-
atwe might it become spontaneous?

Sihce AH is posiii~ md A S is +-,is

hcgAve,
will n-
ot -
be spontm-~ls pf -3 temp~bre
18.20 Find the temperature5 at which reactions with the
following A f i and AS values would become sponta-
neous: (a) AH = - 126 kJ, h S = 84 JIK; (b) AH =
-11.7 k J . A S = -105 JIK.

S l n ~A 6 is a negcdiut Q&, %is re-ban is

sp-beous 39FK. B w s e AH is h e q d ~ - and-
45 is pcmifi~e, %is -+ran be s p a n b c o d s
t -kmpcynh- .

Slnce A 6 is this ~ k is mn o n s p o n h e o d s
o-+ a q s \ < .

mis hc-kan is S ~ ~ + - W S d -
\ou) -kmp-hrcs - ,
-ha+ is, te-clpcy0,bes bc\o& dj.iK.

18.23 Calculate K, for the following reaction at 25°C:

HJg) + 12(g);---2HI(g) h G O = 2.60 kJ
18.25 Consider the following reaction at 25°C:

Calc~~lateAGO for the reaction. K,, for Fe(OH)2 is

1.6 X lo-".

18.27 (a) Calculate AGO and K p for the following equilib-

rium reaction at 25°C. The AG"fa1ues are 0 for
C12(g), -286 kJ/mol for PC13(g), and -325 kJ/mol
for PCl,(g).

(b) Calculate AG for the reaction if the partial pres-

sures of the initial mixture are Ppc15= 0.0029 atm,
PPCI,= 0.27 atm, and PC,* = 0.40 atm.
15.29 Consider the decomposition of calciuln carbonate:
CaCO3(.~)e CaO(s) + CO,(g)
Calc~~late the pressure in atm of C 0 2 in an equil~b-
r i ~ ~process
m (a) at 25°C and (b) at 800°C. Assurne
that AM" = 177.8 kJ and IS0 = 160.5 JIK for the
temperature range. kamb*
a p p e a r in
he+ solids do --
-H\e qdilibrium
no)

At- 256C:
CG) c o n s b t e x pvess~m.
 18.31 At 25°C. hGOfor the process
H20(1) sH20(gl
is 5.6 kJ. Calci~latethe vapor pressure of water at
this temperature.

As in the previous pmblern, #nd Kp +,, 660

Kp is the -u p t c - s s ~ r eo f ~ a k r .

18.33 What is a coupled reaction? What is its importance

in b~ologicalreactions?

A caupkd ka~t(wi 3 an= in which a -thvmodyhon?ico-Il

u n w o m b k t e a c h o n is II coup\rdl' wi* a +errnodYn-ico_Il 3
w a ~ b l e re-+- In o r d e r So ' 3
d r i ~ " +he ~ ~ F w o d e
pacJess Jlpuid prod~c+s.