Beruflich Dokumente
Kultur Dokumente
16
D SOLUTIONS
which they determined the structure of cesium iodide crystals at a pressure of 302 gigapascals
(GPa), How many atmospheres and bars is this pressure?
2.98
I 06
atm, 3.02
106
bar
and to atmsspheres.
value of the pressure (in atm) exerted by a 33.9-foot column of water. Take the
density of water to be 1.00 g.mL-1.
16-4. At which
19.33 m. Now
dm.s-2)(103.3 dm)
-40"
16-5. A travel guide says that
481
482
Clrapter 15
as tsmperature
This will provide a rough estimate of the temperature, decreasing in accuracy
At room
degrees.)
zero
below
increases. (of course, it is not valid for celsius temperatures
temperatures, it is accurate enough for ordinary purposes'
Actual 7
("C)
Actual 7
("F)
Travel 7 ('F)
30
10
50
50
zv
68
'70
30
86
90
40
ta4
110
G-6. Research in surface science is carried out using ultra-high vacuum chambers that can sustain
pressures as low as 10-r2 torr. How many molecules are there in a 1.00-cm3 volume inside such an
apparatus at2g8K? What is the corresponding molar volume 7 at this pressure and temperature?
We
will
PV
(16.1a)
RT
(10-'2 torr)(1.00 cm3)
(82.058 cm3 . atm. mol-' . K-' ) (760 torr' atm-' ) 1298 K)
5.38
so there arc 3.24
10-20
mol
: r
tl
16-7.
=17
v
n
1.00 cm3
5.38
10-
mol
1.86
l0re cm3'mol-l
Use the following data for an unknown gas at 300 K to determine the molecular mass of the gas.
The line of best fit of a plot of P/p versus p will have an intercept of RT I M . Plotting, we flnd that
the intercept of this plot is 0.56558 bar'g-''dm3, and so M : 44.10 g'mol-r.
general chemistry that Dalton's law of partial pressures says that each gas in a
mixture of ideal gases acts as if the other gases were not present. Use this fact to show that the
partial pressure exerted by each gas is given by
P,
-r
/rt\
IJ-
I P,^..,
toral
tota': /ry,P.^,^,
\Inr/
where P, is the partial pressure of the
jth
gas and
),
486
Chapter 16
1.2
i.0
0.8
0.6
0,4
K
K
^,,
6*1
volur:
of CO at20A K and 1000 bar. Compare your result to the result you would get using the ideal-s-.
equation. The experimental value is 0.04009
L.mol-r.
We can use the Newton-Raphson method (MathChapter G) to solve these cubic equations of s::
We can express f (T) for the van der Waals equation as (Example 16-2)
r(v)
and
s:
f '{V)
as
f' (v)
3v'
z (r,
3:i
&.,3
T),
",
co, a:1.4734
;r:':
(Equation 16.9)
fr.*
i.,+
'j'r
r(v)/-':T' - Yv'
p
:,..;
' .{i:
and
Bf;r
v- (\"'n' + p - -4-)
iEF)'*Tvzp
AB
/'(V) as
A\
f'(V)=3V'-tIV-(n'+BRr
'
P'
P fiTF)
\"
17.208 dm6.bar.mol*z.Kt/2 and B : 0.02i394 dm3.mol-r (Table r6.4). App;..
the Newton-Raphson method, we find that the Redlich-Kwong equation gives a result r-:
7: 0.03866 dm3.mol-r. Finally, the ideal gas equation gives (Equation 16.1)
For
co, A =
nftr
--
(0.083145 dms.bar.mol-t.K-1)(200
1000 bar
K)
0.01663 dmj.mol_l
The experimental value of 0.04009 dm3 .mol-r is closest to the result given by the Redlich-K
equation (the two values differ by about3To).
pressures given by (a) the ideal-gas equation, (b) the van der Waals equa:.
(c) the Redlich-Kwong equation, and (d) the Peng-Robinson equarion for propane at 40C i
and p - 10.62 mol'dm-3. The experimental value is 400 bar. Take cu 9.6938 L2.mol-r :=
f = 0.0563? L.mol-r for the Peng-Robinson equation.
Tlre Properties of
:.
487
b,
Cases
: yV
(0'083145 dm3
bar'mol-r'Kr)(400 K)
3s3.2bar
s!--2
'= v -b
v"
For propane, a
^
-r=
:
c.
8008 bar
RT
'D_
- v-B
For propane, A
16.4).
Then
(0.083145dm3.bar,mol-r.-';i+OOf;
0.09416 dm3.mol-r - A.06ziZ3 dm3.mol-r
'^
:
d.
2 .Rt /2
1 83.02 dm6. bar. mo]
/'z(0.094
(400 K)'
1 6 dm3. mol-r ; 10.094 I 6 dm3. mol-r
438.4 bar
p'r
D
._;-__
^'l
-
Forpropane,
-._
Then
(0.083l45dm3.bar.mol-r.-'){+Oof;
0,09416 dm3.mol-r
0.05632dm3.moI-r
9.6938 dm6'bar'mol-2
:284.2bar
(0.05632)(0.09416
0.05632) dm6.mol-2
The Redlich-Kwong equation of state gives a pressure closest to the experimentally observed
pressure (the two values differ by about 107o).
. Use the van der Waals equation and the Redlich-Kwong equation to calculate the value of the
pressure of one mole of ethane at 400.0 K confined to a volume of 83.26 cm3. The experimental
value is 400 bar.
16-17
CHAPTER
19
H
p
fl
ll
D SOLUTIONS
19-1.
Suppose that a 10-kg mass of iron at 20"C is dropped from a height of 100 meters. What is the
kinetic energy of the mass just before it hits the ground? What is its speed? What would be the final
temperature of the mass if all its kinetic energy at impact is transformed into internal energy? Take
the molar heat capacity of iron to be d" :25.1 J.mol-r.K-r and the gravitational acceleration
constant to be 9.80 m.s-t.
ii
Just before the mass hits the ground, all of the potential energy that the mass originally had
converted into kinetic energy. So
PE
: msh:
9.8 kJ
will
be
KE
Since kinetic energy can be expressed as ,nuz f 2, the speed of the mass just before hitting the ground
is
/zKE\tlz
I zo.B kD l'/2
:44ms-r
=L+ffi1
',:\;)
eu
and
A,lJ
ue
,LT
f;
li
il
LT:
9.8 kJ
--2.2K
isothermally at a constant external pressure, P.^,, so that the final volume is 0.500 dm3, calculate
the smallest value {*, can have. Calculate the work involved using this value of P"*,.
Since the gas is ideal, we can write
p"
P,!,
. = v, -
{*,
15.0 bar
*=) :
3ooo
r
585
585
Chapter 19
19-3. A one-mole
can have is P' where { is the final pressure of the gas. We can use the van
(Equation
16.5) and the constants given in Table 16.3 to find P,:
der Waals equation
{*,
RT"
a
z
- - vt-b _- V;
_ (0.083145 dm3.bar.mol-'.K-')(300 K) _ 3.6551 dm6.bar.mol-2
0.750 dm3.mol-r - 0.042816 drn3.mol-r (0.750 dm3.mol-r)2
= 28.8 bar
The work involved is (Equation 19.1)
'ur
3.60kJ
19-4. Calculate the work involved when one mole of an ideal gas is compressed reversibly from
1.00 bar to 5.00 bar at a constant temDerature of 300 K.
$
r"
ll
nRT
V,: -{
$i
;i
4
-{
{
5
5
{
P,
tty^:- nRT
and
zp
'2
1'):-lo*,ov--lt#r,
:
-nRT
- (-1
ln
(f) * -rtRT
ln
rn)
\P,)
4.01 kJ
19*5. Caiculatetheworkinvolvedwhenonemoleofanidealgasisexpandedreversiblyfrom20.0dmr
to 40.0 dm3 at a constant temperature of 300 K.
w:
_rtRT tn (/ v^\
#I
: (-1
\ "t/
: - I .73 kJ
19-6. Calculate the mlnlmum amount of work required to compress 5.00 moles of an ideal gas
isothermallv at 300 K from a volume of 100 dm3 to 40.0 dm3.
594
Chapter 19
and, finally,
T. / P.\RIT,
-:-l--!l
Tt \P'l
19-18.
Show that
,lo rrtTr,+nllc,
rl
o rrGr+n\lc
-- ,2rz
for an adiabatic expansion of an ideai gas. Show that this formula reduces to Equation 19.23 for
monatomic gas.
PtVt
P,v'
Tl
Tz
We can substitute this expression into the equation from Problem 19-15 to write
(\\^'''
PrV"- \Vr)
PrV,
Taking the reciprocal gtves
P,v,
(L\o'',
PrV,- \%/
and rearranging yields
* _.(r+n72,,)
..(r+nZ")
%t '' = -PzVz'
P,
] R, so
P,Vllt = PrVltt
(19.23,
19-1 9. Calculate the work involved when one mole of a monatomic ideal gas at298
reversibly and adiabatically finm a pressure of 10.00 bar to a pressure of 5.00 bar.
expands
6w: dU = re ,dT
where eu is temperature-independent (since the gas is ideal). We can use the equation from
Problem 19-17 to write
/ P \RlI
rr:rrl*l
\r'l
For an ideal gas,
p:5R12,
so
r,:
(2e8r
(#H)'''
:226K
19-24, Liquid sodium is being considered as an engine coolant. How many grams of sodium are
needed to absorb 1.0 MJ of heat if the temperature of the sodium is not to increase by more than
lO'C. Take do : 30.8 J.K*r.mol-r for Na(l) and75.2J'K-r ,mol-r for HrO(l).
We must have a coolant which can absorb 1.0 x 106 J without changing its temperature by more
than l0 K. The smallest amount of sodium required will allow the temperature to change by
exactly 10 K. We can consider this a constant-pressure process, because liquids are relatively
incompressible. Then, substituting LT :10 K into Equation 19.40, we flnd
LH
:e ,l,r:
308 J.mol-r
(r o x 10'D
fg)
f?ry) :746ks
\308J/ \ I mol /
gg
63.5 46 oo. mo 1- t
rto.tr'mol-r .K-l)(363 K - x)
(9.628
1.224
10s J
'19-26. A 10.0-kg sample of liquid water is used to cool an engine. Calculate the heat removed (in
joules) from the engine when the temperature of the water is raised from 293 K to 373 K. Take
e p :'75.2J'K-r .mol-r for Hro(l).
We can use Equation 19.40. where
L.H
nC
rLT =
LT :373
l0 .0 x g
9.'m
18 .0 l) 2 D
- 293K:
-l
"1
rrt
rr
80 K. This eives
mot-r
'K-')(80 K) =
3340 kJ
597
602
Chapter
19-34. Given the following data for sodium, plot ff 1fl - fltO) against I for sodium: melting point,361 K; boiling point, 1156 K; A,u.Ho:2.60 kJ.mol-l; A,ooHo =9'1.4 kJ.mol-r;
C" {r) : 28.2 1' mo|-t. x-' ; 2"(t) : 32.i J. mol-t t<-' ; Zr(g) : z}.BJ. mol*' K-'
.
Err>
J r,,,,
,tt)ar + AH
\'ap
7T
+lr
l,n
r(gdr
Notice the very lalge jump between the liquid and gaseous phases.
140
t
r00
F-
l*
20
T/K
19-35. The A,H'
2Fe(s)
+ lor(e) -+ Fero,(s)
3 Fe(s)
+ 2 Or(e)
--+
A,H":
-206kJ'mol*'
-136 kJ.mol-l
Fe.,Oo(s) L,H"
4 FerO.,(s)
Set up the problem so that the summation of two reactions will give the desired reaction:
4[FerOr(s)
3[3 Fe(s)
+ 2 Oz(g)
4 FerOr(s)
19-36.
2 Fe(s)
+ jOr(S)J
--+ FerOo(s)1
L,H :4(206) kJ
L,H :3(-136) kJ
a.Fl
Fe(s)---+3 FerOu(s)
416 kJ
; or(e) -+
A,H for
Hro(l)
A,Ho
-285.8 kJ.mol-'
2 F"(g)
Thermodynamics 603
L,H :4(*273.3)kJ
jo](c)l
L,H
2(285.8) kJ
L,H = -521.6 ki
->
p-xylene
Because m-xylene and p-xylene are isomers, their combustion equations are stoichiometrically
equivalent. We can therefore write
p-xylene
L,H = -4553.9kJ
L,"H
rn-xylene----+p-xylene L.H :
19-38. Given that A,H"
+2.9kJ
and the
+4556.8 kJ
Or(e)
->
6 CO'(B)
+ 6 HrO(l)
We ate given A,F/' for the combustion of fructose in the statement of the problem. We use the
values given in Table 19.2 for COr(S), HrO(l), and Or(g):
arH'[Co2(g)]
A,H"[or(g)l
: -393.509 kJ.mol-r
:0
arH'[H2O(I)]
-285.83 kJ.mol-'
L,H"
-2826.7 kJ.mol-i
:f
nrA"lproductsl
-I
o,"'freaoanrs]
A.H"[fructose]
9-39.
a.
b.
19
Compare the heat of combustion per gram of the fuels CH.OH(l) and N,Hn(1).
604
Chapter 19
We
will
A,H"[CO,(B)]
Af 11.[N2H4(l)]
+50.6
ArH"[Nr(g)J:
a.
kJ.mol-r
Af H"[CH1OH(I)]
-239.1kJ'mol-'
L,Ho
- | n,A"lproductsl - I ort"lreactants]
: 2(*28s.83 kJ) + (-393'5 kJ) - (-239.1 kJ)
: (\mol-126.:kI
,) f +g\ = _zz.tkJ s_,
methanol / \32.OaZ /
g
b.
L,H"
: I
lrH'[products]
:2(-285.83
kJ)
-I
o,g"lreactants]
(+50.6 kJ)
: (\ -u??
f J++) : _ re 4 kJ.g-,
=t=\_t)
molNrH,
) \32.046 g/
More energy per gram is produced by combusting methanol.
Using Table 19.2, calculate the heat required to vaporize 1.00 mol of CCln(l) at298 K
Ig-40.
CCl,(l)
We can subrracr ArH"[CCl4(1)] from
A"ooH
-+
CClr(B)
32.5 kJ
19-41. Using the ArH" data in Table 19.2, calculate the values of A,H' for the following:
a' crHoG) + HrO0l ----+ CrHtoH(l)
b.
CHo(e)
1+ Clr(S)
----+ CClo(l)
a HCl(g)
a.
L,Ho
-27'7'69 kJ
(-285.83 kJ + 52'28kJ)
-44'14kJ
135'44 kJ
(-74'81 kJ)
-429'87 kI
b.
L,H" -- 4(-92.31kJ)
1942,
rQ)
75.2
J.mol-r.K-r;
e rG) = 33-6J'mol-r'K-r.
608
Chapter 19
We can solve this polynomial using Simpson's rule or a numerical sofware package. Working in
Mathematica, we find that the final temperature will be 4040 K.
1947.
Explain why the adiabatic flame temperature defined in the previous problem is also called the
maximum flame temperature.
The adiabatic flame temperature is the temperature of the system if all the energy released as
heat stays within the system. Since we are considering an isolated system, the adiabatic flame
temperature is also the maximum temperature which the system can achieve.
?"tor{s)l/n :3.094+
(1.561
x l0-3 K-t)T -
(4.65
x l0-7
9-2172
f-:.
(2.00mol)R
[""
Jzss
:64.795 kJ.mol-r
d$
ill
g['
yrt-
#i
hdI
H;
lii..'
dl,:
1949.
When one mole of an ideal gas is compressed adiabatically to one-half of its original volume.
the temperature of the gas increases from 273 K to 433 K. Assuming that eu is independent of
temperature, calculate the value of Zu for this gas.
Equation 19.20 gives an expression for the reversible adiabatic expansion of an ideal gas:
,ar
: -ffav
Integrating both sides and substituting the temperatures given, we find that
T
J[9tar:-[!a,
JV
e
,nl=
433
Culnfr:
e
-J 19-50.
-Rh
-Rln2
1.59
Use the van der Waals equation to calculate the minimum work required to expand one mole
of COr(g) isothermally from a volume of 0.100 dm3 to a volume of 100 dm3 at n3 K. Compare
your result with that which you calculate assuming ideal behavior.
Hu tA,
l0:
ff#^rw^w=
@a
lq : l,4lq J130,41,4Y
t,s,r6
PE=
D,3lt+:
34'P:L
J1" n"l
rl .tr?*Im
KL=D
+?*0
Tncr*na*
APE -- Pr
(xo^) -
PE bk
| = - 4q0,5 hd m, s-L :
KL
--
ry'
/r)
)U
1
)Wt
bl*'-""'f'"-d
Uv
q4rr^A^e
-4gO,S
?350I
:
tA* ^K3WKlFor
^efua"L
lEec tW
(r^qgtre t"lc\*"r
C ' ot+ Coz,
-3q3
^hf,lmot"
%=
ilra"*D
@ | *.*lputrc
{
tlx,"
,L4
*lAL
nCv,,
AT t*q dw,,w.*n T
con
A,nt
,nd,,*t* &u,\rwyn
clta'r,rX<"
U har.tdrogo
o"
rCI
(carnpuausn
on
lo brr-)
', fuaPt6na*l
0"1\1t11=
Vi
k*ry*^"f.h
eb,--,tej ro:
AltL=1 pf
1r= - k)c
Firu,r\^o&ts
cur.oir=")
%urnLs {g= -
w^ attlnr-url "/Yxtav
R{V) JV
[/t
,lV
L
F'u
^a,"il
T, pUr= ng]
0.1ttrU
V'=4'1xtlu
(tat^W%51.*r)
tt
ttcrwptpe^'
Tt a*
frr = _ _^sl; dV --
/b
t
Uba'at-
is \\e
Dt\r/"e- pex
laerot'I,k2
,@
o-+
uh*,h
uu*,
i.aAAInd-
r,)c
tl)c=
440,q?
Alt. =e
(blc
bo^'l=
44,0q?
Ar=o)
AlJe=Q=++rDe
(.de= -(c
cb.= -14,ffi7T
Q=
Qe=
v
[r) e =
te
r$e
t;=
'
,lr*
Jrqr*r,*;)
-ll]e
tl)e=
Fon-
(e suh.Afr
we+
hle
(.q tqq ?
- 4\;011^=- 4,4095 T
L- 0,1\997 D
*4,4 oq,tf
trtru*mrl& {nM,
--
-j1,6?4f
p=
tds=
^oJqqtL
-tJqsuouNV
h,RJ an"
Ltic=
<-erv.o\a,,t
-npr \o'
dV
tnt?L
Jqntr+r- V
wc-- - n Rr^0nV
$ "t*sr*p,
ey
Awt+t1o
l4.qwr,t[r)c = - Grn*)to,oze
r.'c-= l\1.1? L
bon-
!^/t lggjz\
\<
n867 LJ
= I r,4t?
(u, i-@ btcl-\u u ,trrtf^r.*,,\
41,t.= oI=
llflsq: + ?c
v
-lt,{8?T
$"=
bo t\u.
sorna,
cvr'v+=
A?/"
4mf
"4p*r*r*)
t" = +11,4?? f
<t
4^ t"+'o ptLoue'ry"a
runarirttpa"rra
,l,t-ror---Os
Qrc+ = OT
'(Awv =otr
&dlurtt
fo*t^"
- P' 4--rio-.
V-nb
\dcn-h-=
dy
-(v*
{u>
JV.
Tv,
r,5
t"
Hr.cry*,
rruu/L =
TDr\\,aivti{,"9 rynoant T
-ar
lto
f 'otj- dt/
)as
Lvj
trryL l( A nO(oor3i4s
VL
bL
I
l{u
m,t
rn,t
{ L-0rn
4
L-h"x)t) {c,o1a;/r}'')
lc,Aal L.nA'))
--{f,*t)h w K)
*tutK r,,,i1
$n$*4'r\
t3D
Ll b,(L--t
L
t
\lD
4t
')
,% bDS V a*f T,
\{'"lndflh nihat l"t;oUL"n
bo- rlnqo trn\ortv Tb i2p cer^ ryn Nlt,gr,,ha^*t^:+)r*
t.ll
{.,,
1ot't/
,t-
C-S gvlrXf
,t1,-)
a-.X
tr\ to'tl
a
rt
t@rlr_ilq
ldt
rfx\ bb'b'bEee
,F ro\ll
t'
i
0D'l
t\{\
(ft$'ot
"d )ot \\
"\\o
Lv 1,1:l'01tFi
0)
t\{
rJow
rl{PI\ ). J\\
I V1
u)4 t- )g
)9?
v"\
lf{\
'il
o\l\
\or
,\$
--{
t
vl
).H
,tGl
g 9V I,ru
.V,eg
t',
ott\
l..Wh
l,t
t\v
9v
^ v\\ro
,?lC
"fl
,SL
pH
(r)(
a)}tl
/,C/.t\
t(tlltD{ Ig
low
us{glY =((*' 0"H ).
, '[,
tbe
1,?,
tt' lr*,',-il
oJ
toUIItr
l(
bNr)
-^l(I t*).lhA
^ftfltul L 'e 'ge> -_(l('u|t
1
:nuNt)
:H\
,V
VT
(l
rIIll r
q$r1ou
',
Ir
.tt"i
.L{itr"
l,
t\\v
i!
iuxn
lWto
rt q0a6)
)U'rn1 - ot
1u
=\Y^.)
d
tlT'=[
qu-A
_il=.n$lrg
9u+
=d WilA
,f*
(ht)
'U
c*hqanrr? 1tfrd 'fdurQ
^(tr),- +\
=tlJ
4,fi-irrrur\ "eF
,4*
'"
-on, ryru
fll\i
((t
uz s
?od
il
a)
'r-i.,-S
lgbQ o
"pq& o\
..,ru%o\
V\'b+
,-
tg .
=rr-gqEF,';Fq't
-Iruft>t
hL!
- = (eS?J"tlrV
-,,07i :fff;'7r:atW{=d)v
},n\o?
rrVbv
11
ry
)(z -Q
il'
e5
5
(ozlH))H J\\r
c . (nor. yv(
(t:fI rtt! VE
i)+
rr3 '(e)
(*t sf{'
r)ltl
"bk
-{\ ryule
;wrl 11,fjT\t'8g
bI:
ul/ g,{Iob)((' 7
,t)01l,t
z)
) -Q'
( e/,n)rt.ssslselo' .)
'Q{nt/\e{
u/
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