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Chapter 2:
2.1) Una muestra que contiene de 1 mol de tomos de gas ideal
3
(par el cual CV ,m = R ) se lleva a travs del ciclo que se observa en
2
la figura 2.34. (a). Determine la temperatura en los puntos 1,2 y 3.
(b) Calcule q, w, U , y H para cada paso y para el ciclo global. Si
de la informacin dada no puede obtener una respuesta numrica,
consigne +, -, 0, o? segn corresponda.
Solution:
The temperature are readily obtained from the perfect gas
pV
equation, T=
nR
( 1.00 atm ) (22.4 dm3 )
T1= =273 K =T 3 [ isotherm ] .
(1.00 mol)(0.0821 dm 3 atmmol1 K 1 )
Similarly, T2 = 546 K .
In the solution that follow all steps in the cycle are considered to be
reversible.
Step 1 2
3 1 1 3
q=n C V , m T = (1.00 mol ) ( 8.214 J K mol ) ( 273 K )=+3.40 10 J .
2
3
H=q p =+5.67 10 J
Step 2 3
3 1 1
qv= U=n C V , m T =(1.00 mol) ( 8.214 J K mol ) (273 K )
2
From H=U + pV
H= U + ( pV )= U + ( nRT )= U + nR T
Step 3 1
V1 22.4 dm 3
q=w=nRTln =(1.00 mol)(8.314 J K 1 mol1 ) (273 K ) . ln ( 3
)
V3 44.8 dm
3 3
+1.57 10 J , q=1.57 10 J
constant=
1-->2 5.67 -2.27 3.4 5.67
Pext
2-->3 V constant -3.4 0 -3.4 -5.67
Isothermal
3-->1 , -1.57 1.57 0 0
reversible
Cycle 0.7 -0.7 0 0
nRT
w=P ex V [2.8] Vf= V i; So V Vf
pex
nRT
Hence w (Pex ) ( )
P ex
=nRT =(1.0 mol) ( 8.314 J K 1 mol1)(1073 K )
W 8.9 kJ .
Solution:
H= U + ( pV )= U +V p[ V =0]
V m =0 at constant volume .
RT
Therefore
H= U +
V mb .
1 1 3
RV T (8.314 J K mol )(15.0 dm ) (41 K )
= =0.68 kJ .
V m b 7.46 dm 3 mol1
Therefore H= ( 2.35 kJ ) + ( 0.68 kJ )=+3.03 kJ .
Solution:
RT B
p= ( )(Vm
1+
Vm )
f f
V
w= pdV =n
i i
RT
( )(
Vm
1+
B
Vm )
d V m=nRTln m . f +nBRT
V m .i
1
( )
1
V m .f V m . i ( )
From the data,
5.25 cm3 3 1
V m .i = 3
=75.0 cm mol
70 10 mol
6.29 cm 3 3 1
V m. f= 3
=89.9 cm mol
70 10 mol
And so
1 1 1 1
B (V m .f
)
V m. i
=(28.7 cm3 mol1 ) ( 3
89.9 cm mol
1
3
75.0 cm mol
1
=6.34 102)
Therefore,
w=(217 J ) ln ( 6.29
5.25 )
+ ( 217 J ) ( 6.34 102
)= (39.2 J )+ ( 13.8 J )=25 J .
Solution:
This cycle is represented in Figure 2.2 assume that the initial temperature is
298K.
7 5
U =n CV . m T ; CV .m=C p . mR= RR= R ,
2 2
V1
q=w [First with U =0 ]; w=nR T 1 ln
V3
c
T1
c
V 2 T =V 3 T
2
c
3 , hence V 3=V 2
( )
T3 where
CV .m 5
c= =
R 2
( 2 ) ( 298 K ) 52
So V 3=( 24.45 dm )
3
( 298 K ) 3
=138.3dm .
22.45 dm 3
w=(1.00 mol ) ( 8.314 J K 1 mol1 ) ( 298 K ) ln ( 138.3 dm 3 )
3
4.29 10 J =+ 4.29 kJ .
q=4.29 kJ .
Chapter 3:
H 1 + H s =C p ,m ( 1 ) ( T f T ) + C p , m ( s ) ( T f T ) = C p ( T f T )
fus H (T )=fus H ( T f ) C p ( T f T )
T
( f ) ( T T )
fus H + Cp f
T T
H (T )
Thus , S sur = fus =
T
1
6.01 kJ mol 268273
S sur =
268 K
+(37.3 J K 1 mol 1 )
268 ( )
+21.7 J K1 mo l1
STotal = S sur + S= ( 21.721.3 ) J K1 mo l1=+0.4 J K1 mol1
Since STotal >0, the transition1 s is sponta neous at5 C
(b)A similar cycle and analysis can be set up for the transition
liquid vapor at 95 C , However since the
transformation here is to the high temperature state (vapor)
from the low temperature state (liquid), which is the opposite
of part (a), we can expect that the analogous equations will
occur with a change of sign.
T
trs S ( 1 g , T )= S ( 1 g , T b ) + C p ln
Tb
vap H T
+ C p ln . C p=41.9 J K 1 mol 1 .
Tb Tb
T2 T2
C dT T
Sm = p ,m [ 3.18 ] =
T
T 1 T
a+bT
T 1
( T1 )
dT =a ln 2 +b(T 2T 1) ( )
a=91.47 J K 1 mo l1 , b=7,5 102 J K1 mo l1
10. 7 K 1 mol 1
n ( vap H +C p ,m ( H 2 O , l ) 100 C )
=
mC s +n C p ,m ( H 2 O, l )
3 1 1 1
(1.00 mol)(40.656 1 0 J mo l +75.3 J C mol 100 C)
2.00 1 03 g 0.385 J C1 g1+1.00 mol 75.3 J C1 mo l1
57.0 C=330.2 K
q ( H 2 O )=43.9 kJ
STotal = S ( H 2 O ) + S(Cu)
n vap H T
S ( H 2O )=
Tb ( )
[ 3.16 ] +n C p ,m ln f [ 3.19 ]
Ti
373.2 K
+ ( 1.00 mol ) ( 75.3 J K 1 mol 1 ) ln (
373.2 K )
108. 9 J K19.22 J K 1=118. 1 J K1
Tf
S ( Cu )=mC s ln ( )
Ti
3
=(2.00 10 g) ( 0.385 J C g ) ln
1 1 330.2 K
373.2 K ( )
145. 9 J K1
S ( Total )=118. 1 J K + 145. 9 J K =28 J K
1 1 1
3 1 1
nRT (1.00 mol )(0.08206 d m atm K mol )(373.2 K )
V= = =30.6 d m3
p 1.00 atm
With
n vap H Tf
S ( H 2O )=
Tb ( )
+ nC p , m ln
Ti
=119. 8 J K
1
Tf
S ( Cu )=mC s ln ( )
Ti
=129. 2 J K
1
SOLUTION
T A , f p A , f V A , f ( 2 p A ,i)(3.00 d m3 )
= = =3.00 so T A , f =900 K
T A , i p A ,i V A , i ( p A ,i )(2.00 d m3 )
T A, f V A ,f
(a) S A =n C V ,m ln T ( )
A ,i
[ 3.19 ] + nR ln
V A, i ( )
[ 3.13 ]
3.00 d m3
S A =(2.00 mol)(20 J K 1 mo l1) ln ( 3.00 )+(2.00 mol)(8.314 K1 mol1)ln ( 2.00 d m3 )
50.7 J K 1
V B, f 3
( )
V B ,i
=(2.00 mol) (8.314 K1 mol1)ln
1.00 d m
2.00 d m
3 ( )
S B =nR ln
1
11.5 J K
Step 1
U = H=0 [ isothermal ]
Vf p
w=nRT ln ( )
Vi pi ( )
=nRT ln f [ 2.11,Boyl e ' s law ]
Vf
S=nR ln ( )
Vi
[ 3.15 ]=nR ln 1.00 atm =+19.1 J K 1
(
10.0 atm )
1
S ( sur )= S ( system ) [ reversible process ] =19.1 J K
Step 2
q=0 [ adiabatic ]
U =n CV ,m T [ 2.16 b ]
w= U =3.74 kJ
H= U + ( pV )= U +nR T
6.23 kJ
STotal =0
G= ( HTS )= H S T [ no changeentropy ]
Step 3
These quanties may be calculated in the same manner as fot Step 1
or more easily as follows.
U = H=0 [ isothermal ]
Tc q
rev =1 [ 3.10 ] =1 300 K =0.500=1+ c [ 3.9 ]
Th 600 K qh
q rev 3
S= [ isothermal ] = 5.74 1 0 J =19.1 J K 1
T 300 K
STot =0
Step 4
U And H are the negative of their values in Step 2. (Initial
and final temperatures reversed.)
w= U =+3.74 kJ
STot =0
Cycle
STot =0
Solution:
At the triple point, T1, the vapor pressure of liquid and solid are
equal; hence
For the Liquid sulfur dioxide: log (P (Torr)) =8, 3186 1425, 7/
(T/K).
1871,2 1425, 7
10,5916 (T /K ) = 8, 3186 (T /K )
1871,2 1425, 7
10,5916 - 8, 3186 = (T /K ) - (T /K )
445.5
2.273 = (T /K )
445.5
T = K
(2.273)
T = 196 K
1871,2
Log (P (Torr)) = 10,5916 (196 K ) = 1,0447
P = 101,0447 Torr
P = 11,1 Torr
P vap H 1 1
Ln ( P )= R ( T - T )
P
Ln ( 1 atm ) = 2.206
2.206
P =( 1 atm ) e
P = 9.07 atm.
Solution:
3
(14.4 10 J /mol)
dp
dT = m3 m3
(180 K)(14.5 . 103 1,15104 )
mol mol
dp
dT = +5.56 KPa/K
dlnp vap H dp
= (with d (lnp) = )
dT RT p
3
(14.4 10 J /mol)
dp
dT = J = +5.42 KPa/K
(8.314 .)(180 K )
mol . K
%percentage error =
(5.56 KPa
K )
(5.42
KPa
K
)
= 2,5 %
5.56 KPa /K
(liq) ( sol)
(a)( T )p - ( T )p = -Sm(liq) ( - Sm(sol) )
( liq ) ( sol )
( )p - ( )p = -Sm (liq) + Sm (sol) = - S
T T
fus
H fus
= T ( fus)
kj
( liq ) ( sol ) (6,01 )
( )p - ( )p = mol = - 22, 0 J/mol.K
T T ( )
(273,15 K )
( gas) ( liq)
(b)( T )p - ( T )p = -Sm(gas) ( - Sm(liq) )
H fus
T ( fus)
kj
( gas) ( liq) (40,6 )
( )p - ( )p = mol = -109 J/mol.K
T T ( )
( 373,15 K )
(c) = = ( T ) T => = ( - Sm)
T T
T
( liq ) ( liq ) M
(a) ( p )T - ( p )T = Vm(liq) - Vm(sol) . [Vm =
; where M is the molar mass]
( liq ) ( SOL ) g 1
( p )T - ( p ) T = (18,02 mol ) ( 1,000 g/ cm -
1
0,917 g /cm )
( liq ) ( SOL )
( p )T - ( p ) T = - 1,63 cm/mol
( gas ) ( liq )
(b) ( p )T - ( p )T = Vm (gas) - Vm (liq)
( gas ) ( liq ) g 1
( p )T - ( p ) T = (18,02 mol ) ( 0,598 g /dm -
1
0,958 g /dm )
( gas ) ( liq )
( )T - ( ) T = +30,1 dm /mol
p p
(d) At 1,0 atm and 100C (liq )= ( gas )
Chapter 5:
Solution
pA
KA = XA = 15.58 KPa from the point at xA = 0.0898
pB
KB = XB = 47.03 KPa from the point at xB = 0.0898
Solucin
3
= (16.62 + 2 x 1.77 x b1/2 + 2 x 0.12b) cm3 mol-1
V
Vsalt = ( ) mol-1 (problema 5.2)
b H2O
Solution
Let m (CuSO4), which is the mass of CuSO4 dissolved in 100g of
solution, be represented by
100 mB
w= mA +mB = mass percent of CuSO4
mA +mB mA
P= V nA = MA
V V
VA = ( ) = ( ) MA
nA nB mA B
mA +mB
= ( ) x MA
mA p
MA 1
= p + (mA + mB) MA mA p
1 w 1 w 1
= ( ) =
mA p mA w p mA +mB w p
Therefore,
MA 1
VA = wMA ( )
p w p
And hence
1 VA d 1
= +w ( )
p MA dw p
Therefore, plot 1/p against w and extrapolate the tanget to w = 100
to obtain VB/MB. Fort he actual procedure, draw up the following
table
Four tangets are drawn to the curve at the four values of w. As the
curve is a straight line to within the precisin of the data, all
tangents are coincident and all four intercepts are equal at 0.075 g -
1
cm3. Thus
V (CuSO4) = 0.075 g-1 cm3 x 159.6 g mol-1 = 12.0 cm3 mol-1
Solution
nE M E
NEME = nwMw, or nw = Mw
n E M EVw
Hence, V = nEVE + Mw
V
MEV
Which solves to nE = M EVw , nw =
VE+ VEMw + MEVw
Mw
1
nE
Furthermore, xE = nE+nW = ME
1+
Mw
ME
Since ME = 46.07 g mol-1 and Mw = 18.02 g mol-1. Mw = 2.557.
Therefore
xE = 0.2811, xW = 1 xE = 0.7189
At this composition
VE = 56.0 cm3 mol-1, Vw = 17.5 cm3 mol-1 (Fig. 5.1 of the text)
100
Therefore, mE = 56+ 2.557+17.5 = 0.993 mol,
mw 45.7
Vw = = = 45.8 cm3 of wter
Pw 0.997
V = dV = VEdnE = VEnE
Where we have assumed that both VE and Vw are constant over this
small range of mE. Hence
1.00 cm x 0.789 g cm
V = (56.0 cm3 mol-1) x 46.07 g mol = +0.96 cm3