You are on page 1of 29

Examen final de Fisicoqumica 1:

Cristobal Guerreros, Carlos Enrique


Cdigo: 20141387C
Captulos 2, 3,4 y 5 / Problemas del 1 al 5
Docente: Amador Paulino
NOMBR CAPITUL
PROBLEMAS
E OS
Cristob 2, 3, 4 Desde el 1 hasta
al y5 el 5

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

w=p ex V =p V =nR T [ ( pV )= ( nRT ) ] .

w=( 1.00 mol ) ( 8.314 J K 1 mol1 ) ( 546273 ) K =2.27 103 J

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

q= U w=+3.40 103 J (2.27 103 J ) =+5.67 103 J

3
H=q p =+5.67 10 J

If this step is not reversible. Then w, q, and H would be


indeterminate.

Step 2 3

w=0 [Constant volume].

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

(3.40 103 J )+ ( 1.00 mol ) ( 8.314 J K 1 mol1 ) (273 K )=5.67 103 J .

Step 3 1

U And H are zero for an isothermal process in a


perfect gas; hence for the reversible compression

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

If this step is not reversible, then q and w would have different


values which would be determined by the details of the process.
Total cycle

state p/atm V/dm3 T/K


1 1 22.44 273
2 1 44.8 546
3 0.5 44.8 273

Thermodynamic quantities calculated for reversible steps

Step Process q/kJ w/kJ U ( kJ ) H (kJ )

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

COMMENT. All values can be determined unambiguously for the


reversible cycle. The net result of the overall process is that 700J of
heat has been converted to work.

2.2) Una muestra consiste en 1.0 mol de CaCO3 (s) se descompuso


al ser calentada 800C. El calentamiento se llev a cabo en un
contenedor con un mbolo que estaba inicialmente descansando
sobre el slido. Calcule el trabajo efectuado durante la
descomposicin completa a 1.0 atm. Qu trabajo se efectuara si
en vez de tener un mbolo el contendor estuviese abierto a la
atmosfera?
Solution:

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 .

Even if there is no physical piston, the gas drives back the


atmosphere, so the work is also
W 8.9 kJ .

2.3) Una muestra consistente en 2,0 moles de CO2 ocupa un


volumen fijo de 15,0 dm3a 300K. Cuando a ste se suministran
2,35Kj de energa como calor, su temperatura se incrementa a
341K. Asuma que el CO2 se comporta segn la ecuacin de van der
Waals, y calcule w, U, Y H.

Solution:

Since the volume is fixed w=0 .

Since U =q at constant volume V =+ 2.35 kJ .

H= U + ( pV )= U +V p[ V =0]

From the van der Waals equation


RT a RT
p= 2 p=
V mb V m So V m b [

V m =0 at constant volume .

RT
Therefore
H= U +
V mb .

From the data,


3
15.0 dm
V m= =7.5 dm3 mol1 , T =( 341300 ) K =41 K .
2.0 mol

V mb=( 7.54.3 102 ) dm3 mol1 =7.46C .

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 .

2.4) Una muestra de 70 mmol de Kr (g) se expande reversible e


isotrmicamente a 373K desde 5,25 cm3 hasta 6.29 cm3, y se sabe
que la energa interna de la muestra se incrementa en 83.5J. Utilice
la ecuacin de estado del virial hasta el segundo coeficiente
B=28.7 cm 3 mol1 para calcular w, q y H para este cambio de
estado.

Solution:

The virial expression for pressure up to the second coefficient is

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,

nRT =( 70 103 mol ) ( 8.314 J K1 mol1) ( 373 K )=217 J

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 .

Since U =q+ w and U =+83.5 J


q= U w=( 83.5 J ) + ( 25 J )=+109 J
B
H= U + (pV ) With pV =nRT 1+( Vm )
( pV )=nRTB ( V1 )=nRTB ( V1
m m. f

1
V m .i ) , as T =0

( 217 J ) ( 6.34 102) =13.8 J

Therefore H= ( 83.5 J )+ ( 13.8 J )=+ 97 J .

2.5) Una muestra de1.00 mol de molculas de un gas ideal con


7
C p . m= R se somete al siguiente ciclo (a) calentamiento a
2
volumen constante hasta el doble de volumen inicial, (b) expresin
reversible, adiabtica nuevamente hasta su temperatura inicial, (c)
comprensin reversible isotrmica retornando hasta 1,00 atm.
Calcule q, w, U Y H para cada paso y para la relacin total.

Solution:

This cycle is represented in Figure 2.2 assume that the initial temperature is
298K.

(a)First, note that w=0 (constant volume). Then calculate U

SINCE T is known ( T =398 K and then calculate q from the


First Law.

7 5
U =n CV . m T ; CV .m=C p . mR= RR= R ,
2 2

U =( 1.00 mol ) ( 52 ) (8.314 J K 1


mol1 ) ( 298 K )=6.19 103 J =+6.19 kJ .

q=qV = Uw=6.19 kJ 0=+ 6.19 kJ


H= U + ( pV ) + ( nRT )=U + nR T

( +6.19 kJ ) +(1.00 mol)V 1 =+ 9.67 kJ .

(b) q=0 (Adiabatic).

Because the energy and enthalpy of a perfect gas depend on


temperature alone,

U (b)= U (a )=6.19 kJ , since T (b )= T ( a) .

Likewise H ( b)= H ( a)=8.67 kJ ,

w= U =6.19 kJ [First Law with q=0 ].

(c) U = H=0 [Isothermal process in perfect gas].

V1
q=w [First with U =0 ]; w=nR T 1 ln
V3

nR T 1 (1.00 mol) ( 0.08206 dm 3 atm K 1 mol1 ) ( 298 K )


V 2=V 1= = =24.45 dm3 .
p1 1.00 atm

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:

3.1) Calcule la diferencia en la entropa molar (a) entre agua lquida y


hielo a - 5 C , (b) entre agua lquida y vapor a 95 C y 1,00 atm .
Las diferencias entre las capacidades calorficas de fusin y
1 1 1 1
evaporacin son 37,3 J K mol y 41,91 J K mol ,
respectivamente. Distinga entre los cambios de entropa de la
muestra, del entorno y del sistema total y analice la espontaneidad
de la transicin a las dos temperaturas.
SOLUTION

(a)Because entropy is a state function trs S ( 1 s ,5 C ) may be


determined indirectly from the following cycle

Thus trs S ( 1 s ,5 C )= S1 + trs S (1 s ,0 C ) + S s ,


Tf
Where S1=C p , m ( 1 ) ln
T
[ 3.19; f =0 C ,=5 C ]
Tf
And s S=C p ,m ( s ) ln
T
Tf
S1 + S s= C p ln with C p=C p ,m ( 1 )C p ,m ( s )=+37.3 J K1 mol1
T
fus H
trs S ( 1 s , T f ) = [ 3.16 ]
Tf
fus H T
Thus , trs S ( 1 s , T ) = C p ln
Tf Tf

6.01 10 3 J mol 1 268


trs S ( 1 s , 5 C )= ( 37.3 J K 1 mol1) ln
273 K 273
21.3 J K 1 mol 1
fus H (T )
S sur =
T
fus H (T )= H 1 + fus H ( T f ) H s

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

40.7 kJ mol1 368


trs S 1 g , T =
( )
373 K
(41.9 J K 1 mol1) ln
373 ( )
+109.7 J K1 mo l1
1 1 1 1
STotal =( 109.7111.2 ) J K mol =1.5 J K mo l

Since STotal <0, the reverse transition, g 1, is spontaneous at


95 C .

3.2) La capacidad calorfica del cloroformo (tricolorometano, CHC l 3 )


en el intervalo de temperaturas de 240 a 330 K est dada por
J K 1 mo l1
()=91,47+ 7,5 102 ( T / K ) . En un experimento particular, 1 mol de
C p ,m /

CHC l 3 se calienta desde 273 hasta 300 K. Calcule el cambio de la


entropa molar de la muestra.
SOLUTION

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

Sm =(91.47 J K 1 mol 1 ) ln ( 300 K


273 K )
+ ( 0.075 J K 2
mo l1) (27 K )

10. 7 K 1 mol 1

3.3) Un bloque de cobre con una masa de 2 Kg ( C p ,m =24,44 J K1 mo l1 ) y

una temperatura de 0C se introduce dentro de un contenedor

aislado en el cual hay 1 mol de H 2 O(g) a 100 C y | atm. (a)


Asumiendo que todo el vapor esta condensado como agua, Cul ser
la temperatura final del sistema, el calor transferido del agua al cobre
y el cambio entropa del agua, del cobre y del sistema total? (b) De
hecho, hay presente algo de vapor de agua en el equilibrio. A partir
de la presin del vapor del agua a la temperatura calculada en (a) y
asumiendo que las capacidades calorficas del agua gaseosa y liquida
son constantes, y tomando sus valores a esa temperatura, obtenga un
valor mejorado de la temperatura final, del calor transferido y de las
diversas entropas. (Sugerencia, usted necesitara realizar
aproximaciones factibles.)
SOLUTION

(a) q ( Total )=q ( H 2 O ) +q ( Cu ) =0 ; henceq ( H 2 O )=q(Cu)


q ( H 2 O )=n ( vap H ) +n C p ,m (H 2 O, l)(100 C)

Where is the final temperature of the water and copper?


q ( Cu )=m C s ( 0 ) =mC s ,C s=0.385 J K 1 g1

Setting q ( H 2 O ) =q ( Cu ) allows us to solve for .

n ( vap H )n C p ,m ( H 2 O, l ) ( 100 C )=mC s

Solving for yields:

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 ( Cu )=( 2.00 10 3 g ) ( 0.385 J C1 g1 ) ( 57.0 K )=4.39 1 04 J =43.9 kJ

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

( 1.00 mol ) ( 40.656 1 03 J mol1 ) 330.2 K

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

This process is spontaneous since S ( surroundings ) is zero and,


hence,

S ( universe ) = S ( Total ) >0

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

At 57 C the vapor pressure of water is 130 Torr (Handbook of


Chemistry and Physics). The amount of water vapor present at
equilibrium is then
1 atm 3
(130 Torr) ( )(30.6 d m )
pV 760 Torr
n= = =0.193 mol
RT (0.08206 d m3 K 1 mol 1 )(330.2 K )

This is a substantial fraction of the original amount of water and


cannot be ignored. Consequently the calculation needs to be
redone taking into account the fact only a part, n1 , of the vapor

condenses in to a liquid while the remainder ( 1.00 moln1 ) remains


gaseous. The heat flow involving water, then, becomes

q ( H 2 O )=n1 vap H + n1 C p ,m ( H 2 O , l ) T ( H 2 O ) + ( 1.00 moln1 ) C p , m ( H 2 O , g ) T ( H 2 O )

Because n1 depends of the equilibrium temperature through


pv
n1=1.00 mol , where p is the vapor pressure of water, we will
RT

have two unknowns (p and T) in the equation q ( H 2 O ) =q (Cu) .


There are two ways out of this dilemma; (1) p may be expressed as
a function of T by use of the Clapeyron equation (Chapter 4), or (2)
by use of successive approximations. Redoing the calculation
yields:

n1 vap H + n1 ( H 2 O ,l ) 100 C+ ( 1.00n1 ) C p ,m ( H 2 O , g ) 100 C


=
m Cs + nC p ,m ( H 2 O ,l ) + ( 1n1 ) C p , m ( H 2 O , g )

With

n1=( 1.00 mol )( 0.193 mol )=0.80 7 mol


1 1
(Noting that C p , m ( H 2 O , g )=33.6 J mo l K [ Table 27 ] , =47.2 C . at this
temperature, the vapor pressure of water is 84.41 Torr,
corresponding to

n1=( 1.00 mol )( 0.123 mol )=0.87 7 mol

This leads to =50.8 C . the successive approximations eventually

converge to yield a value of =49.9 C=323.1 K for the final


temperature. (At this temperature, the vapor pressure is 0.123 bar)
Using this value of the final temperature, the heat transferred and
the various entropies are calculated as in part (a).

q ( Cu )=( 2.00 10 3 g ) ( 0.385 J C1 g1 ) ( 49.9 K ) =38.4 kJ =q ( H 2 O )

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

S ( Total )=119. 8 J K 1 +129. 2 J K1=9 J K1

3.4) Considere un gas ideal contenido en un cilindro y separado por


un pistn adiabtico sin friccin en dos secciones A y B. Todos los
cambios en B son isotrmicos, es decir, un termostato rodea a B para
mantener su temperatura constante. Hay 2 moles de un gas en cada
una de las secciones. Inicialmente T A =T B =300 K , V A =V B =2,00 d m3 . Se
suministra energa como calor a la Seccin A y el pistn se mueve
hacia la derecha en forma reversible hasta que el volumen final de la
Seccin B es de 1,00 d m3 . Calcule (a) S A y S B , (b) AA y
AB (c) G A y GB (d) S del sistema total y de su entorno.
Si no pueden obtener valores numricos, indique si los valores serian
positivos, negativos, cero o indeterminados para la informacin que
posee. (Se asumen CV ,m =20 J K 1 mol 1 .

SOLUTION

First, determine the final state in each section. In section B, the


volume was halved at constant temperature, so the pressure was
doubled, pB , f =2 p B ,i . The piston ensures that the pressure are
equal in both chambers, so p A , f =2 p B ,i=2 p A ,i . from the perfect gas
law

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

(b)The Helmholtz free energy is defined as A=U TS . Because

section B is isothermal, U =0 and ( TS )=T S , so


A B=T B SB =( 300 K ) (11.5 J K1 )=3.46 1 03 J =+3.46 kJ

In section A, we cannot compute ( TS ) , so we cannot compute


U , A is indeterminate in both magnitude and sing. We know

that in a perfect gas, U depends only on temperature; moreover,


U
U (T ) is and increasing function of T, for (heat capacity),
T

which is positive since T >0. U >0 as well. But ( TS )> 0 too,


since both the temperature and the entropy increase.
(c) Likewise, under constant-temperature conditions
G= HT S

In section B, H B =0 (constant temperature, perfect gas),


so
GB =T B S B =( 300 K ) (11.5 J K1 )=3.46 103 J
GA Is indeterminate in both magnitude and sign.
1 1
(d) S ( Total system ) = S A + S B =( 50.711.5 ) J K =+39.2 J K

If the process has been carried out reversibly as assumed in the


statement of the problem we can say

S ( system ) + S ( surroundings )=0

Hence , S ( surroundings )=39.2 J K 1

3.5) Un ciclo de Carnot utiliza 1 mol de un gas ideal monoatmico


como la sustancia de trabajo a partir de un estado inicial de 10,0 atm
y 600 K. Se expande de manera isotrmica a una presin de 1,00 atm
(Paso 1) y luego de manera adiabtica a una temperatura de 300 K
(Paso 2). Esta expansin esta seguida de una compresin isotrmica
(Paso 3) y luego una compresin adiabtica (Paso 4) para llegar
nuevamente al estado inicial. Determine los valores de q , w , U , H ,
respuesta en forma de cuadro de valores obtenidos.
SOLUTION

Step 1 Step 2 Step 3 Step 4 Cycle


q +11.5 kJ 0 -5.74 kJ 0 -5.8 kJ
W -11.5 kJ -3.74 kJ +5.74 kJ +3.74 kJ -5.8 kJ
U 0 -3.74 kJ 0 +3.74 kJ 0
H 0 -6.23 kJ 0 +6.23 kJ 0
S +19,1
0 0 0 0
J/K
S(TOT ) 0 0 0 0 0
G -11.5 kJ ? +11.5 kJ ? 0

Step 1

U = H=0 [ isothermal ]

Vf p
w=nRT ln ( )
Vi pi ( )
=nRT ln f [ 2.11,Boyl e ' s law ]

(1.00 mol) ( 8.314 J K 1 mol 1 ) (600 K) ln ( 1.00 atm


10.0 atm )
=11.5 kJ
q=w=11.5 kJ

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

S ( Total )= S ( system ) + S ( sur )=0

G= HT S=0( 600 K ) ( 19.1 J K 1 ) =11.5 kJ

Step 2

q=0 [ adiabatic ]

U =n CV ,m T [ 2.16 b ]

( 1.00 mol ) ( 32 ) (8.314 J K 1


mo l1 ) ( 300 K 600 K )=3.74 kJ

w= U =3.74 kJ

H= U + ( pV )= U +nR T

(3.74 kJ )+(1.00 mol)(8.314 J K 1 mo l 1 )(300 K )

6.23 kJ

S= S ( sur )=0 [ reversible adibatic process ]

STotal =0

G= ( HTS )= H S T [ no changeentropy ]

Although the change in entropy is known to be zero, the entropy


itself is not known so G is indeterminate.

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 c =0.500 qh=( 0.500 ) ( 11.5 kJ ) =5.74 kJ

q c =5.74 kJ w=q c =5.74 kJ

q rev 3
S= [ isothermal ] = 5.74 1 0 J =19.1 J K 1
T 300 K

S ( sur )= S ( system )=+19.1 J K 1

STot =0

G= HT S=0( 300 K ) (19.1 J K1 )=+11.5 kJ

Step 4
U And H are the negative of their values in Step 2. (Initial
and final temperatures reversed.)

U =+3.74 kJ . H=+ 6.23 kJ . q=0 [ adiabatic ]

w= U =+3.74 kJ

S= S ( sur )=0 [ reversible adiabatic process ]

STot =0

Again G= ( HTS )= H S T [ no changeentropy ]

But S is not known, so G is indeterminate.

Cycle

U = H= S=G=0 [ ( state function )=0 for any cycle ]

S ( sur )=0 [ all reversible processes ]

STot =0

q ( cycle )=( 11.55.74 ) kJ =5.8 kJ . w ( cycle )q ( cycle )=5.8 kJ


Chapter 4:

4.1) La dependencia de la temperatura de la presin de vapor


del dixido de azufre solido puede representarse en forma
aproximada por la relacin log (p (Torr))=10,5916 1871,2/
(T/K) y la del dixido de azufre liquido por log (p
(Torr))=8,3186 1425,7/ (T/K). Estime la temperatura y la
presin Del punto triple del dixido de azufre.

Solution:
At the triple point, T1, the vapor pressure of liquid and solid are
equal; hence

For the Solid sulfur dioxide: log (P (Torr))=10,5916 1871,2/ (T/K)

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

The vapor pressure of sulfur dioxide at the triple point:

1871,2
Log (P (Torr)) = 10,5916 (196 K ) = 1,0447

Log (P (Torr)) = 1,0447

P = 101,0447 Torr

P = 11,1 Torr

At the triple point, T = 196 K y P = 11,1 Torr


4.2) Con anterioridad al descubrimiento de que el fren-
12(CFCl) era nocivo para la capa de ozono de la Tierra, se
utilizaba frecuentemente como el agente dispersante en los
aerosoles de fijador para el cabello, etc. Su entalpa de
vaporizacin es 20,25 KJ/mol en su punto normal de ebullicin
de -29,2C. Estime la presin que tiene un envase de fijador
para el cabello que utiliza fren-12 que soporta una
temperatura de 40C, la temperatura de un envase que ha
estado expuesto a la luz solar. Asuma que vap H es
constante en el intervalo de temperatura involucrado e igual
a su valor a -29,2C.
Solution:
Use the definite integral form of the Clausius-Clapeyron equation:

P vap H 1 1
Ln ( P )= R ( T - T )

At normal boiling point T = -29,2 + 273 K 244 K and P =


1 atm

Calculating for T = 40 + 273 K 313 K and P = ?

(20,25 .10 3 J /mol)


P 1 1
Ln ( 1 atm )= J ( 244 K - 313 K )
(8.314 .)
mol . K

P
Ln ( 1 atm ) = 2.206

2.206
P =( 1 atm ) e

P = 9.07 atm.

4.3) La entalpia de vaporizacin de cierto liquido es 14.4


KJ/mol a 180 K, su punto de ebullicin normal. Los volmenes
molares del lquido y del vapor en el punto de ebullicin son
115 cm/mol y 14.5 dm/mol, respectivamente (a) Estime
dp/dT a partir de la ecuacin de Clapeyron y (b) el error
porcentual en su valor si se utiliza en su lugar la ecuacin de
Clausius-Clapeyron.

Solution:

(a)Use the Clapeyron equation:


dp vap S vap H
dT = vap V = T (eb) vap V

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

(b)Use the Clausius-Clapeyron equation:

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

4.4) Calcule la diferencia en la pendiente a cada lado, del potencial


qumico en funcin de la temperatura de (a) el punto normal de
congelamiento del agua y (b) el punto normal de ebullicin del agua
(c) En qu valor el potencial qumico del agua superenfriada a -5C
excede al del hielo a esa misma temperatura?
Solution:

(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) )

=-Sm (gas) + Sm (liq) = - S vap

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) - (sol) = (liq, -5C) - (liq, 0C) ( (sol,

-5C) - (sol, 0C))

(Liq) - (sol) = (liq, -5C) (sol, -5C) [ (liq,

0C) = (sol, 0C)]

(Liq) - (sol) = (- Sm (liq) T ) (- Sm (sol) T )

(Liq) - (sol) = - (- Sfus T ) = -(5 K). (-22.0 J/K.mol) =


+ 110 J/mol

Since (liq, -5C) > (sol, -5C), there is thermodynamic


tendency to freeze.
4.5) Calcule la diferencia en pendiente, a cada lado, del potencial
qumico en funcin de la presin en el (a) el punto normal de
congelamiento del agua y (b) del punto normal de ebullicin del
agua. Las densidades del hielo y del agua a 0C son 0,917 g/cm y
1,000 g/cm y las del agua y del vapor a 100C son 0,958 g/dm y
0,598 g/dm, respectivamente. (c) En qu valor el potencial
qumico de vapor de agua excede al del agua lquida a 1,2 atm y
100C?
Solution:

( 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 )

Therefore, at 1,2 atm and 100C ( gas ) - (liq ) = Vvap


. p (as in Previous alternative)

= (30, 1 .103 m /mol). (0, 2 atm). (1,013. 105 Pa)


= +0, 6 kJ/mol

Since ( gas ) > (liq ) , the gas tends to condense into a


liquid

Chapter 5:

5.1 En el siguiente cuadro se indica la fraccin molar de


metilbenceno (A) en una mezcla liquida y en una mezcla gaseosa
como butanona en equilibrio a 303.15 K y la presin total p. Asuma
que se trata de un gas ideal y calcule las presiones parciales de los
dos componentes. Represntelos en funcin de sus fracciones
molares respectivas en la solucin liquida y halle las constantes de
la ley de Henry para ambos componentes.

Solution

PA = yAp and pB = yBp (Daltons law). Hence, draw up the following


table.
The data are plotted in Fig. 5.2.
We can asume, at the lowest concentrations of both A and B, that
Henrys law Will hold. The Henrys law constants are then given by.

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

5.2 Se midi el volumen de una solucin acuosa de NaCl a 25C a


una serie de molalidades b, y se encontr que el volumen se puede
expresar como v = 1003 + 16.62x + 1.77x3/2 + 0.12x2 en donde v =
V/cm3, V es el volumen de una solucin formada por 1.000 kg de
agua, y x = b/b. Calcule el volumen molar parcial de los
componentes en una solucin de molalidad 0.100 mol kg-1.

Solucin

3
= (16.62 + 2 x 1.77 x b1/2 + 2 x 0.12b) cm3 mol-1

= 17.5 cm3 mol-1 when b = 0.100


For a solution consisting of 0.100 mol NaCl and 1.000 kg of
wter, corresponding to 55.49 mol H2O, the total volumen is
given both by
V = (1003 + 16.62 + (0.100 x 1.77 x 0.1003/2) + (0.12 x
0.1002)) cm3
= 1004.7 cm3
And by
V= n (NaCl) VNaCl + n (H2O) VH2O = (0.100 mol x 17.5 cm3
mol-1) + (55.49 mol x VH2O)
1004.71.75
Therefore, VH2O = 55.49 = 18.07 cm3 mol-1

COMMENT. Within four significant figures, this result is the


same as the molar volumen of pure wter at 25C.

5.3 A 18C el volumen total V de una solucin formada por MgSO4 y


1.000 kg de agua expresa como v = 1001.21 + 34.69 (x 0.070)2,
en donde v = V/cm3 y x = b/b. Calcule los volmenes molares
parciales de la sal y del solvente en una solucin de molalidad
0.050 mol kg-1.
Solution

V
Vsalt = ( ) mol-1 (problema 5.2)
b H2O

= 69.38 (b 0.070) cm3 mol-1 with b = b/ (mol kg-1).

Therefore, at b = 0.050 mol kg-1, Vsalt = -1.4 cm3 mol-1

The total volumen at this molality is

V = 1001.21 + 34.69 x 0.022 cm3 = 1001.22 cm3

Hence, as in Problema 5.2.

1001.22 cm 0.050 mol x1.4 c m3 mol


V (H2O) = 55.49 mol = 18.04 cm2 mol-1
5.4 Se midieron las densidades de soluciones acuosas de sulfato de
cobre (II) a 20C, segn se indica a continuacin. Determine y
grafique el volumen molar parcial de CuSO4 en el rango medido

En donde m (CuSO4) es la masa de CuSO4 disuelto en 100g de


solucin

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

Where mB is the mass of CuSO4 and mA is the mass of water. Then


using

mA +mB mA
P= V nA = MA

The procedure runs as follows

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

5.5 Qu proporciones de etanol y agua se deben mezclar para


producir 100 cm3 de una solucin de 50% en masa de etanol? Qu
cambio de volumen se obtiene al agregar 1.00 cm3 de etanol a la
mezcla? (Utilice los datos de la Fig. 5.1.)

Solution

Let E denote etanol and W denote wter, then


V = nEVE + nwVw (5.3).
For a 50 percent mixture by mass, mE = mw, implying that

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 = 2.557 x 0.993 mol = 2.54 mol


The fact that these amount correspond to a mixture containing 50
percent by mass of both components is easily checked as follows:
ME = nEME = 0.993 mol x 46.07 g mol-1 = 45.7 g etanol
Mw = nwMw = 2.54 mol x 18.02 g mol-1 = 45.7 g wter,
At 20C the densities os etanol and wter are
PE = 0.789 g cm-3, pw = 0.997 g cm-3, Hence
mE 45.7
VE = = = 57.9 cm3 of etanol
PE 0.789

mw 45.7
Vw = = = 45.8 cm3 of wter
Pw 0.997

The change in volume upon adding a small amount of etanol can be


approximated by

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