EXAMEN FINAL DE FISICO-QUIMICA I

CURSO
ALUMNO
PROFESOR
CODIGO DEL CURSO
CODIGO DEL ALUMNO

FISICO-QUIMICA I
Castillo L. Marco A.
Amador Paulino
PQ 211 A
20154119B

PROBLEMAS

Cap 2,3,4 y 5 Problemas 1-5

Captulo 2
P2.1 Una muestra que contiene de 1 mol de tomos de gas ideal (par el

3
CV ,m = R ) se lleva a travs del ciclo que se observa en la figura
2

cual

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.

SOLUCION
The temperatures are readily obtained from the perfect gas equation,

T=

pV
nR

T1=

( 1.00 atm ) (22.4 dm3 )

=273 K =T 3 [ isotherm ] .
(1.00 mol)(0.0821 dm 3 atmmol1 K 1 )

Similarly, T2 =

546 K .

In the solutions that follow all steps in the cycle are considered to be
reversible.

1 2

Step

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
=n CV ,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
H=q p =+5.67 103 J
If this step is not reversible. Then w, q, and

would be indeterminate.

2 3

Step

w=0

[Constant volume].

3
qv= U=n C V , m T =(1.00 mol) ( 8.214 J K 1 mol1 ) (273 K )
2
H=U + pV

From

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
and

are

zero

for an isothermal process in a perfect

gas; hence for the reversible compression

q=w=nRTln

V1
22.4 dm 3
=(1.00 mol)(8.314 J K 1 mol1 ) (273 K ) . ln (
)
V3
44.8 dm 3
+1.57 10 3 J ,

q=1.57 103 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
1
2
3

V/dm3
22.44
44.8
44.8

p/atm
1.00
1.00
.50

T/K
273
546
273

Thermodynamic quantities calculated for reversible steps

Step

1 2

Process

q/kJ

w/kJ

U / kJ

H /kJ

+5.67

-2.27

+3.40

+5.67

constant =p ex
2 3

V constant

-3.40

-3.40

-5.67

3 1

Isothermal,
reversible

-1.57

+1.57

+0.70

-0.70

Cycle

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.

P2.2 Una muestra consiste en 1.0 mol de CaCO 3 (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?
SOLUCION

w=p ex V [ 2.8]

Hence

w (pex )

Vf=

nRT
V i;
pex

so

V Vf

nRT
=nRT =(1.0 mol)( 8.314 J K 1 mol1)(1073 K )
pex

( )

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 .

P2.3 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 CO 2 se comporta

segn la ecuacin de van der Waals, y calcule w,

U, Y

H.

SOLUCION
Since the volume is fixed w=0 .

U =q

Since

at constant volume V =+ 2.35 kJ .

H= U + ( pV )= U +V p[ V =0]
From the van der Waals equation

p=

RT
a
2
V mb V m

p=

So

RT
V m b

V m =0 at constant volume .
H= U +

Therefore

RT
V mb .

From the data,

3

V m=

15.0 dm
=7.5 dm3 mol1 ,
2.0 mol

T =( 341300 ) K =41 K .

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 .

P2.4 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
calcular w, q y

B=28.7 cm 3 mol1

para

para este cambio de estado.

SOLUCION

The virial expression for pressure up to the second coefficient is

p=

RT
B
1+
Vm
Vm

( )(

w= pdV =n
i

V m. f
RT
B
1
1
1+
d V m=nRTln
+nBRT

Vm
Vm
V m .i
V m .f V m . i

( )(

( )

From the data,

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

V m .i =

5.25 cm3
3
1
=75.0 cm mol
70 103 mol

V m. f=

6.29 cm 3
3
1
=89.9 cm mol
3
70 10 mol
And so

( V1

m .f

1
1
1
=(28.7 cm3 mol1 )

=6.34 102
3
1
3
1
V m. i
89.9 cm mol
75.0 cm mol

Therefore,

w=(217 J ) ln

+ ( 217 J ) ( 6.34 10
( 6.29
5.25 )

U =q+ w

Since

)= (39.2 J )+ ( 13.8 J )=25 J .

U =+83.5 J

and

q= U w=( 83.5 J ) + ( 25 J )=+109 J

H= U + (pV )

( pV )=nRTB

1
1
1
=nRTB

Vm
V m . f V m .i

( )

pV =nRT 1+

With

B
Vm

as

)
T =0

( 217 J ) ( 6.34 102) =13.8 J

Therefore

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

P2.5 Una muestra de1.00 mol de molculas de un gas ideal con

7
C p . m= R
2

se somete al siguiente ciclo (a) calentamiento a 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,

para cada paso y para la relacin total.

SOLUCION

This cycle is represented in Figure 2.2 assume that the initial temperature is
298K.
(a)First, note that
SINCE

w=0

(constant volume). Then calculate

is known ( T =398 K

and then calculate q from

the First Law.

7
5
CV .m=C p . mR= RR= R ,
2
2

U =n CV . m T ;
U =( 1.00 mol )

( 52 ) (8.314 J K

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
Likewise

w= U =6.19 kJ

since

T ( b )= T ( a)

H ( b)= H ( a)=8.67 kJ
[First Law with

q=0

,
].

(c) U = H=0

q=w

V 2=V 1=

[Isothermal process in perfect gas].

U =0

[First with

w=nR T 1 ln

];

V1
V3

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

=
=24.45 dm 3 .
p1
1.00 atm
c
2

V 2 T =V 3 T

c
3

V 3=V 2

, hence

c=

So

T1
T3

( )

where

CV .m 5
=
R
2

V 3=( 24.45 dm 3 )

( 2 ) ( 298 K ) 52
=138.3dm 3 .
298 K

w=(1.00 mol ) ( 8.314 J K 1 mol1 ) ( 298 K ) ln

22.45 dm 3
138.3 dm 3

4.29 10 J =+ 4.29 kJ .
q=4.29 kJ .

Captulo 3
P3.1 Calcule la diferencia en la entropa molar (a) entre agua lquida y hielo a -

5 C , (b) entre agua liquida y vapor a

95 C

1,00 atm . Las diferencias

entre las capacidades calorficas de fusin y evaporacin son

y

37,3 J K mol

41,91 J K 1 mol 1 , 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.
SOLUCION
(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 ,

Where

S1=C p , m ( 1 ) ln

s S=C p ,m ( s ) ln

And

S1 + S s= C p ln

Tf
[ 3.19; f =0 C ,=5 C ]
T
Tf
T

Tf
with C p=C p ,m ( 1 )C p ,m ( s )=+37.3 J K1 mol1
T

trs S ( 1 s , T f ) =
Thus , trs S ( 1 s , T ) =
trs S ( 1 s , 5 C )=

fus H
[ 3.16 ]
Tf

fus H
T
C p ln
Tf
Tf

6.01 10 3 J mol 1
268
( 37.3 J K 1 mol1) ln
273 K
273
1

21.3 J K mol
S sur =

fus H (T )
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

( T T )
( f )
+ Cp f
T
T
fus H (T )
Thus , S sur =
=
T
fus H

S sur =

6.01 kJ mol
268273
+(37.3 J K 1 mol 1 )
268 K
268

+21.7 J K1 mo l1
1

STotal = S sur + S= ( 21.721.3 ) J K mo l =+0.4 J K mol

Since STotal >0, the transition1 s is spontaaneous 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.

trs S ( 1 g , T )= S ( 1 g , T b ) + C p ln

T
Tb

vap H
T
+ C p ln . C p=41.9 J K 1 mol 1 .
Tb
Tb

trs S ( 1 g , T )=

40.7 kJ mol1
368
(41.9 J K 1 mol1) ln
373 K
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 .
P3.2 La capacidad calorfica del cloroformo (tricolorometano,

CHC l 3 ) en el

intervalo de temperaturas de 240 a 330 K est dada por

1

J K mo l
2
()=91,47+ 7,5 10 ( 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.
SOLUCION
T2

T2

C dT
T
a+bT
Sm = p ,m
[ 3.18 ] =
dT =a ln 2 +b(T 2T 1)
T
T
T1
T
T

( )

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

K
+ ( 0.075 J K
( 300
273 K )

1
1
10. 7 K mol

mo l1) (27 K )

P3.3 Un bloque de cobre con una masa de

0C

temperatura de

se introduce dentro de un contenedor aislado en el

H 2 O(g)

cual hay 1 mol de

2 Kg ( C p ,m =24,44 J K1 mo l1 ) y una

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.)
SOLUCION
(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

(1.00 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)

 S ( H 2O )=

n vap H
T
[ 3.16 ] +n C p ,m ln f [ 3.19 ]
Tb
Ti

( )

( 1.00 mol ) ( 40.656 1 03 J mol1 )

330.2 K

+ ( 1.00 mol ) ( 75.3 J K 1 mol 1 ) ln

373.2 K
373.2 K

108. 9 J K 9.22 J K =118. 1 J K

1

S ( Cu )=mC s ln

Tf
330.2 K
3
1 1
=(2.00 10 g) ( 0.385 J C g ) ln
Ti
373.2 K

( )

145. 9 J K

1
1
1
S ( Total )=118. 1 J K + 145. 9 J K =28 J K

This process is spontaneous since

S ( surroundings )

is zero and, hence,

S ( universe ) = S ( Total ) >0

V=
At

3
1
1
nRT (1.00 mol )(0.08206 d m atm K mol )(373.2 K )
=
=30.6 d m3
p
1.00 atm

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
)(30.6 d m3)
pV
760 Torr
n=
=
=0.193 mol
RT (0.08206 d m3 K 1 mol 1 )(330.2 K )
(130 Torr) (

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,
while the remainder

n1 , of the vapor condenses in to a liquid

( 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=1.00 mol

n1
pv
,
RT

depends of the equilibrium temperature through

where p is the vapor pressure of water, we will 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

C p , m ( H 2 O , g )=33.6 J mo l1 K1 [ Table 27 ] , =47.2 C .

(noting that

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 .

converge to yield a value of

The successive approximations eventually

=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 )

S ( H 2O )=

n vap H
T
+ nC p , m ln f =119. 8 J K 1
Tb
Ti

( )

S ( Cu )=mC s ln

Tf
1
=129. 2 J K
Ti

( )

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

P3.4 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
(b)

AA

AB

(c) G A

GB

1,00 d m
(d)

. Calcule (a) S A

SB ,

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 .
SOLUCION

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

pB , f =2 p B ,i .

halved at constant temperature, so the pressure was doubled,

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

3

T A , f p A , f V A , f ( 2 p A ,i)(3.00 d m )
=
=
=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

S
=n
C
ln
[
3.19
]
+
nR
ln
[ 3.13 ]
A
V
,m
(a)
T A ,i
V A, i

( )

( )

3.00 d m3
S A =(2.00 mol)(20 J K mo l ) ln ( 3.00 )+(2.00 mol)(8.314 K mol )ln
2.00 d m3
1

50.7 J K

V B, f
1.00 d m3
1
1
=(2.00 mol) (8.314 K mol )ln
V B ,i
2.00 d m3
S B =nR ln

( )

11.5 J K 1
(b) The Helmhotz free energy is defined as
B is isothermal,

U =0

and

A=U TS .

( TS )=T S ,

Because section

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

U , A

( TS ) ,

so we cannot compute

is indeterminate in both magnitude and sing. We know that in a

perfect gas,

depends only on temperature; moreover,

increasing function of T, for

T >0. U >0

as well. But

U
T

U (T )

is and

(heat capacity) , which is positive since

( 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.

S ( Total system) = S A + S B =( 50.711.5 ) J K 1=+39.2 J K1

(d)

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

P3.5 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

q , w , U , H ,

valores de

respuesta en forma de cuadro de valores

obtenidos.
SOLUCION

Step 1
+11.5 kJ
-11.5 kJ
0

Step 2
0
-3.74 kJ
-3.74 kJ

Step 3
-5.74 kJ
+5.74 kJ
0

Step 4
0
+3.74 kJ
+3.74 kJ

Cycle
-5.8 kJ
-5.8 kJ
0

-6.23 kJ

+6.23 kJ

+19.1 J

q
W

Stot

-11.5 kJ

+11.5 kJ

Step 1

U = H=0 [ isothermal ]
w=nRT ln

Vf
pf
=nRT ln
[ 2.11,Boyl e ' s law ]
Vi
pi

( )

( )

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

atm
=11.5 kJ
( 1.00
10.0 atm )

q=w=11.5 kJ

S=nR ln

Vf
[ 3.15 ]=nR ln 1.00 atm =+19.1 J K 1
Vi
10.0 atm

( )

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

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 mol 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
knownm so

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
[ 3.10 ] =1 300 K =0.500=1+ c [ 3.9 ]
Th
600 K
qh

rev =1

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

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

3
q rev
[ 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

and

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
But

G= ( HTS )= H S T [ no changeentropy ]
is not known, so

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

CAPITULO 4
P4.1 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.
SOLUCION
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
(T /K )

10,5916 (T /K ) = 8, 3186

1871,2

10,5916 - 8, 3186 = (T /K )

445.5
(T /K )

2.273 =

445.5
(2.273)

1425, 7
(T /K )

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,

196 K

y P = 11,1 Torr

P4.2 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.
SOLUCION
Use the definite integral form of the Clausius-Clapeyron equation:

Ln ( P

vap H
R

)=

1
T

1
T

At normal boiling point

= -29,2 + 273 K

Calculating for

= 40 + 273 K

313 K and

(20,25 .10 3 J /mol)

J
(8.314
.)
mol . K

1
244 K

P
Ln ( 1 atm

)=

Ln( 1 atm

P =(
P

244 K and

= 1 atm

P =?
1
313 K

) = 2.206

1 atm

e 2.206

= 9.07 atm.

P4.3 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 ClausiusClapeyron.
SOLUCION
(a) Use the Clapeyron equation:

dp
dT

vap S
vap V

vap H
T (eb) vap V

dp
dT

(14.4 10 J /mol)
m3
m3
(180 K)(14.5 . 103
1,15104
)
mol
mol

dp
dT

= +5.56 KPa/K

(b) Use the Clausius-Clapeyron equation:

dlnp
dT
dp
dT

(with

d (lnp)

(14.4 103 J / mol)

J
(8.314
.)(180 K )
mol . K

%percentage error =

vap H
RT

KPa
(5.42
)
(5.56 KPa
)
K
K
5.56 KPa/K

dp
p

= +5.42 KPa/K

= 2,5 %

P4.4 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 superen riada a -5C excede al del hielo a esa
misma temperatura?
SOLUCION
(a) (

( liq)
T

( liq )
T

)p - (

)p - (

( sol)
T

( sol )
T

)p = -Sm(liq) ( - Sm(sol) )

)p =

-Sm(liq) + Sm(sol)

)p =

kj
)
mol
(
)
(273,15 K )

H fus
T ( fus)

( liq )
(
T

)p

( sol )
- (
T

(6,01

= - 22,0 J/mol.K

fus

(b) (

( gas)
T

( liq)
T

)p - (

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

)p = -Sm(gas) ( - Sm(liq) )

vap

H fus
T ( fus)

( gas)
(
T

(c)

)p

( liq)
- (
T

kj
)
mol
(
) = -109 J/mol.K
( 373,15 K )
(40,6

)p =

= ( T

=>

= ( - Sm)

(Liq) -

(sol) =

(liq, -5C) -

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

(liq, -5C)

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

(sol, 0C) )

(Liq) -

(sol) =

(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
freeze .

(liq, -5C) >

(sol, -5C) , there is thermodynamic tendency to

P4.5 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?
SOLUCION
(a) (

( liq )
p

)T - (

( liq )
p

)T = Vm(liq) - Vm(sol) . [Vm =

; where

M is the molar mass]

( liq )
p

( SOL )
p

)T - (

1
0,917 g /cm

( liq )
p

(b) (

( gas )
p

)T - (

( gas )
p

( liq )
p

)T - (

( SOL )
p

)T - (

( gas )
p

(d) At 1,0 atm and 100C

) T = Vm (gas) - Vm (liq)

( liq )
p

)T - (

)T = - 1,63 cm/mol

g
1
)
(
mol
0,598 g /dm

) T = (18,02

1
0,958 g /dm

g
1
)
(
mol
1,000 g/cm

)T = (18,02

( liq )
p

) T = +30,1

(liq )= ( gas )

dm /mol

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

CAPITULO 5
P5.1 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.

SOLUCION
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.
KA =

pA
XA

= 15.58 kPa from the point at xA = 0.0898

KB =

pB
XB

= 47.03 kPa from the point at xB = 0.0898

P5.2 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.
SOLUCION

= (16.62 +

3
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)
Therefore, VH2O =

1004.71.75
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.

P5.3 A 18C el volumen total V de una solucin formada por MgSO 4 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.
SOLUCION
Vsalt =

V
)
b

H2O

mol-1 (problema 5.2)

= 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.
3

V(H2O) =

1001.22 cm 0.050 mol x1.4 c m mol

55.49 mol

= 18.04 cm2 mol-1

P5.4 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

SOLUCION
Let m(CuSO4), which is the mass of CuSO4 dissolved in 100g of solution, be
represented by
w=

100 mB
mA +mB

= mass percent of CuSO4

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

mA +mB
V

nA =

mA
MA

The procedure runs as follows

VA =

V
)
nA

nB

V
)
mA

mA +mB
(
)
mA
p

x MA

MA

MA
p

1
mA p

+ (mA + mB) MA mA p

w
)
mA

1
w p

w
1
mA +mB w p

Therefore,
VA =

MA
p

wMA

1
( )
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

P5.5 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.)
SOLUCION
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
Mw

nEME = nwMw, or nw =

n E M EVw
Mw

Hence, V = nEVE +

V
M EVw
VE+
Mw

Which solves to nE =

nE
Furthermore, xE = nE+nW

, nw =

MEV
VEMw + MEVw

1
ME
1+
Mw

Since ME = 46.07 g mol-1 and Mw = 18.02 g mol-1.

xE = 0.2811,

ME
Mw

= 2.557. Therefore

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)

Therefore, mE =

100
56+ 2.557+17.5

= 0.993 mol,

mw = 2.557 x 0.993 mol = 2.54 mol

The fact that these amounts 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

VE =

mE 45.7
=
PE 0.789

= 57.9 cm3 of etanol

Vw =

mw 45.7
=
Pw 0.997

= 45.8 cm3 of wter

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
V = (56.0 cm3 mol-1) x

1.00 cm x 0.789 g cm
46.07 g mol

= +0.96 cm3