THERMODYNAMICS COURSE: SOLVED PROBLEMS

PROBLEMUNIT4: VOLUMETRIC PROPERTIES OF FLUIDS

The vapor pressure of liquid bromine at 9.3°C is 100 Torr. If the heat of vaporization is 30910
J/mol, calculate the normal boiling point of bromine.
DATA:
9.3°C

ΔHˆ V 30910 J/mol

SOLUTION:

Considering that the ΔHˆ V it is constant, that is, it does not depend on Ty and the equation is applicable
Clausius-Clapeyron, we have:

ˆ
ΔH ˆ R
ΔH
lnP* = − V + C = − V +C
RT T
where:
ˆV
ΔH 30910moleJ
= =3717.82535K
R 8.314mel KJ
Additionally, the constant Cla can be calculated from the known vapor pressure value P* at a
given temperature T, as indicated below:
ˆ VR
ΔH
C=lnP*+ =ln (100 +) 3717.82535K
T 282.45K
17.76794
Therefore, in the case of liquid bromine, the Clausius-Clapeyron equation that will allow us to calculate the
vapor pressure at a given temperature is:

ΔHˆ VR
lnP* = - +C
T

( ) − 3717.82535 +17.76794
lnP*Torr=
T ( K)

The normal boiling point bT 0 It is the temperature at which bromine boils at a pressure of 760 Torr.
(1 atm), this is, P* = P = 760 Torr, then, solving for T from the Clausius Clapeyron equation,
0

we obtain:

ˆ VR
ΔH ΔHˆ VR
lnP* = - +C =C−lnP*
T T
ˆ VR
ΔH
C−lnP*

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THERMODYNAMICS COURSE: SOLVED PROBLEMS

T ( K= 3717.82535
)
(
17.76794−lnP*Torr )
Substituting data:

T( K=T 3717.82535K
) 0bK=
( ) =333.8978K
(
17.76794−ln 760 )
T ( K=T
)( )0b60.75°C

2. The vapor pressure of diethyl ether is 100 Torr at -115°C and 400 Torr at 17.9°C. Calculate:
a) The heat of vaporization;
b) The boiling point in a city where the barometric pressure is 620 Torr;
c) The enthalpy of vaporization at the normal boiling point;
d) ΔG0from vaporization at 25°C.

DATA:

T1= -115°C = 158.15 K P1* = 100 Torr

T2= 17.9°C = 291.05 K P2* = 400 Torr
SOLUTION:
a) Considering that the Clausius Clapeyron equation is applicable in this case, we would have:

ΔHˆ ˆ R
ΔH
lnP* = − V + C = − V + C
RT T
Therefore, for the initial conditions:

ˆV
ΔH ˆ R
ΔH
lnP1* = − +C= − V +C
RT1 T1
So:
ˆ VR
ΔH
C=lnP 1+ (1)
T1
While for the final conditions:

ˆV
ΔH ˆ R
∆H
lnP2* = − +C= − V +C
RT2 T2
y
ˆ VR
ΔH
C=lnP 2+ (2)
T2
By equating equations (1) and (2), it results in:

M. C. LUISNIETOLEMUS FIQ-UMSNH Page2of43

THERMODYNAMICS COURSE: SOLVED PROBLEMS

ˆ VR
ΔH ˆ VR
ΔH
lnP1 + =lnP2 +
T1 T2
ˆ VRΔHVRˆ
ΔH
lnP1 -lnP =2 −
T2 T1
P1 ΔHV ˆ 1−1
ln  =
P2 R T2 T1

ˆ
P1 ΔHVT−T
ln = 1 2

P2 R T1 T2

ˆV
ΔH
= T1 T2 ln P1


R T−T P
1 2 2

ˆ V= RTT
ΔH

1 P2 1 =
(8.314 )(158.15K291.05K
J
molK
)( ) 100Torr
ln ln
T−T
1 2
P 2
158.15K−291.05K 400 Torr
ˆ V3991.87833mol
ΔH J

In addition:
ˆ V3991.87833mol
ΔH J
= 480.13932K
R 8.314mel JK

ˆ VR
ΔH ˆ VR
ΔH
C=lnP 1+ =lnP2 +
T1 T2
Therefore, the value of C can be calculated based on the known values of P* and T corresponding to
the initial or final conditions:
ˆ VR
ΔH
C=lnP 1+ =ln (100 +) 480.13932K 7.64114
T1 158.15K
Finally:

ΔHˆ VR
lnP* = - +C
T

480.13932 +7.64114
( )−
lnP*Torr=
T ( K)

b) To calculate the boiling point at P = P* = 620 Torr, we will base ourselves on the Clausius equation.
Clapeyron:

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THERMODYNAMICS COURSE: SOLVED PROBLEMS

ĤVR
T=
C−lnP*
When P* = 620 Torr then Tb:

ΔHˆ VR
Tb= = 480.13932K 396.34K
C−lnP 7.64114 - ln 620 ( )
c) The normal boiling point is the one that corresponds to P* = P0= 760 Torr:

ΔHˆ VR 480.13932K
Tb0= = 476.41K
C−lnP0 7.64114−ln 760 ( )
The vaporization entropy at the normal boiling point is given by the equation

ˆ 0V 3991.87833molJ
ΔH
ˆ 0V=
ΔS = =8.37908 J
Tbo
476.41K mol K
ˆ V At 25°C (298.15 K) it is calculated from the equation:
d) TheΔG

ˆ 0V= ΔHˆV0 -TΔSˆ0V

ΔG
J
mol
( )
ˆ 0V=3991.87833−298.15K8.37908
ΔG ( J
molK ) 1493.655628 J
mol

3. The heat of vaporization of water is 40,670 J/mol at the normal boiling point, 100°C. The pressure
Barometric pressure in a city is around 620 Torr.
a) What is the boiling point of water in that city?
b) What is the boiling point at a pressure of 3 atm?
DATA:

ΔHˆ 0V 40670 J/mol T=Tb0 = 100°C = 373.15 K

P = 620 Torr
SOLUTION:
Considering that the Clausius Clapeyron equation is applicable in this case, we would have:

ΔHˆ ˆ R
ΔH
lnP* = − V + C = − V + C
RT T
Therefore:
ˆV
ΔH 40670molJ
= 4891.74886K
R 8.314molJK
So:
ˆ VR
ΔH
C=lnP + ) 4891.74886K 19.74265
=ln (760 +
T 373.15K

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THERMODYNAMICS COURSE: SOLVED PROBLEMS

Therefore, the equation that relates the vapor pressure of water to the temperature would be:

( =) - 4891.74886 +19.74265
lnP*Torr
T( K)
a) The boiling point in that city corresponds to the temperature at which P* = P = 620 Torr, from the equation of
From Clausius Clapeyron we obtain:

ˆ R
ΔH ΔHˆ VR
lnP* = − V + C =C−lnP*
T T
ˆ VR
ΔH
T=
C−lnP*

T ( K= 4891.74886
)
(
19.74265−lnP*Torr )
Substituting data:

T ( K= 4891.74886K
) ≈367.44K
(
19.74265−ln 620 )
T= Tb94.29 C
b) When the P = P* = 3 atm = 2280 Torr, the boiling temperature of water would be:

T( K=
) 4891.74886 = 4891.74886K 407.28192K ≈ 407.28K
19.74265 - ln P *( Torr)19.74265 - ln 2280
( )
T=T=134.13°C
b

4. The vapor pressures of liquid sodium are:

T (°C) 439 549 701

P* (Torr) 1 10 100

Determine the normal boiling point, the heat of vaporization, and the entropy of vaporization at the
normal boiling point of liquid sodium.
SOLUTION:
Based on the Clausius Clapeyron equation, we have that a representation of nP* vs 1/T (K) gives us
it should give a straight line, in case this equation is applicable for liquid sodium:

ˆ R
ΔH ˆ 1
ΔH
lnP* = − V + C lnP* = C - V
T R T
Therefore, an adjustment of the experimental data will be made according to the indicated representation:

T (K) 712.15 822.15 974.15

P (Torr) 1 10 100

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THERMODYNAMICS COURSE: SOLVED PROBLEMS

The results obtained are as follows:

17.12637875
ˆV
ΔH
=12193.76996K
R
r=0.99999573
Therefore, the Clausius Clapeyron equation for liquid sodium would be as follows:

( ) − 1219.76996 +17.12637875
lnP*Torr=
T ( K)
The resulting graph that includes the fitting of the experimental data is shown below:

5.0
4.5
4.0
-12194/T + 17.126
R² = 1
3.5
3.0
2.5
2.0
1.5
1.0
0.5
0.0
0.001 0.0011 0.0012 0.0013 0.0014 0.0015
1/T (K)

Therefore, the normal boiling point of liquid sodium would be:

ΔHˆ VR 12193.76996K
Tb0= = ≈1162.08K
C−lnP017.12637875 - ln 760 ( )
While the molar latent heat of vaporization is:

ΔHˆ V ˆV (
ΔH=12193.76996K R)
12193.76996K
R
ˆV ( )
ΔH=12193.76996K8.314×10 ( -3 kJ
molK ) 101.37900 kJ
mol

and the molar vaporization entropy at the normal boiling point of liquid sodium is:

M. C. LUISNIETOLEMUS FIQ-UMSNH Page 6 of 43

THERMODYNAMICS COURSE: SOLVED PROBLEMS

ˆ 0V
ΔH 101379.00molJ J
ˆ 0V=
ΔS = 87.23930
Tb 1162.079469K
0
molK

5. Naphthalene, C10H8, melts at 80°C. If the vapor pressure of the liquid is 10 Torr at 85.8°C and 40 Torr at
119.3°C, and that of the solid is 1 Torr at 52.6 °C, calculate

the ˆ vap of the liquid, the normal boiling point and ΔSvaporˆa Tb.
ΔH
b) The vapor pressure at the melting point;

ˆ sub del
c) Assuming that the melting temperatures and the triple point are the same, calculate.ΔH
ˆ fus .
solid and ΔH

d) What should the temperature be if the vapor pressure of the solid must be less than 10?-5Torr?
DATA:

M (C10H8128.17050 g/mol Tf0 80°C = 353.15 K

T185.8°C = 358.95 K P1* = 10 Torr

T2= 119.3°C = 392.45 K P2* = 40 Torr
T = 52.6°C = 325.75 K 1 Torr
SOLUTION:

Firstly, the ˆ vaporWe will calculate the liquid based on the Clausius Clapeyron equation:
ΔH

ˆV
ΔH
= T1 T2 ln P1 T=
1T2P
 
2
T−T P T−T P2  ln
R 1 2 2 1 1

ˆ V= RTT
ΔH 1 P

1 =
(8.314 ) ( 358.95K)(
J
molK
) 10Torr
2
ln ln
T−T
1 2
P 2
358.95K−392.45K 40 Torr
ˆ V=48466.198973molJ
ΔH
In addition:
ΔHˆ V ˆ R
ΔH
lnP* = - +C= − V +C
RT T
Therefore:
ˆV
ΔH 48466.198973mole
J
= =5829.46824K
R 8.314molJK
So:
ˆ VR
ΔH ˆ VR
ΔH
C=lnP 1+ =lnP2 +
T1 T2

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THERMODYNAMICS COURSE: SOLVED PROBLEMS

ˆ VR
ΔH
C=lnP 1+ =ln (10 )+ 5829.46824K 18.542920
T1 358.95K
Thus, the equation that relates naphthalene pressure to temperature would be:

( ) − 5829.46824 +18.54292
lnP*Torr=
T ( K)
So, the normal boiling temperature is:

ΔHˆ VR 5829.46824K
Tb0= = ≈489.48 K
C−lnP018.54292−ln 760( )
and the molar entropy of vaporization at the normal boiling point of naphthalene is:

ˆ 0V
ΔH 48466.198973mol J J
ˆ 0V=
ΔS = 99.01643
Tb0 489.47634K molK

b) The vapor pressure of the liquid at the melting point, that is,Tf 0for80°C
a =T=
353.15 K

5829.46824 - 5829.46824K +18.54292

( )−
lnP*Torr=
T ( K) 353.15K
P* 7.65884 Torr
c) The Clausius Clapeyron equation is also applicable to naphthalene in solid state in
equilibrium with its vapor, therefore, in this case:

ˆ
ΔH ˆ R
ΔH
lnP* = − s +C= − s +C
RT T
To evaluate ΔHˆ S yC, we have the following data:

T1= 52.6°C = 325.75 K P1* 1 Torr

T2= 80.0°C = 353.15 K P2* 7.65884 Torr
So:

ˆ
ΔH T1 T2 P1
= ln
R T1−T 2P  2

ˆ s = RTT
ΔH 1 P

1 =
(8.314 ) (325.75K)(
J
molK
) 1 Torr
2
ln ln
T−T
1 2
P 2
325.75K to 353.15K 7.65884 Torr
ˆ s=71064.24008moleJ
ΔH
Therefore:

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THERMODYNAMICS COURSE: SOLVED PROBLEMS

ˆ s71064.24008mol
ΔH J
= =8547.53910K
R 8.314melJK
So:

ˆ sR
ΔH ˆ sR
ΔH
C=lnP 1+ =lnP2 +
T1 T2
ˆ sR
ΔH
C=lnP 1+ =ln (1 )+ 8547.53910K 26.239567
T1 325.75K
Therefore:

( ) − 8547.5391 +26.239567
lnP*Torr=
T( K)
On the other hand:

ΔHˆ S= ΔHf+
ˆ ΔHv ˆ

ΔHˆ fΔHS− ΔH
ˆ v=71064.24008
ˆ mol
-48466.19897
J
mole
=22598.04111moleJ J

d) The temperature necessary for the vapor pressure of solid naphthalene to be 10-5Torr, it will be
so:

ˆ SR
ΔH 8547.5391K
T= = =226.40993K ≈ 226.41 K
C−lnP* 26.239567 - ln (10−5 )

T=226.41K=-46.74°C

6. The vapor pressure of ethanol is 135.33 mmHg at 40°C, and 542.50 mmHg at 70°C. Calculate the molar heat.
of vaporization and the vapor pressure of ethanol at 50°C.

R. ΔHˆ V = 9 880 cal/mol; P* = 221.0 mmHg at 50°C

DATA:

T1= 40°C = 313.15 K P1* = 135.33 mmHg

T270°C = 343.15 K P2* 542.50 mmHg
SOLUTION:

Firstly, the ΔHˆ v We will calculate the liquid based on the Clausius Clapeyron equation:

ˆ V= RTT
ΔH 1 P

1 =
(8.314 ) ( 313.15K343.15K
J
molK
)( ) 135.33 mmHg
2
ln ln
T−T
1 2
P 2
313.15K - 343.15K 542.50 mmHg

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THERMODYNAMICS COURSE: SOLVED PROBLEMS

ΔHˆ V=41348.73833moleJ
In addition:

ΔHˆ V ˆ R
ΔH
lnP* = - +C= − V +C
RT T
Therefore:
ˆ V41348.73833mol
ΔH J
= =4973.38686K
R 8.314melJK
So:

ˆ VR
ΔH ˆ VR
ΔH
C=lnP 1+ =lnP2 +
T1 T2
ˆ VR
ΔH
C=lnP 1+ =ln (135.33 +) 4973.38686K 20.78952
T1 313.15K
Thus, the equation relating ethanol pressure to temperature is:

4973.38686 +20.78952
(
lnP*mmHg=)−
T ( K)
For T = 50°C = 323.15 K, the vapor pressure of ethanol is:

4973.38686K +20.78952
( )
P*mmHg=exp−
323.15K
P*=221.226mmHg

7. The heat of vaporization of ethyl ether, C4H10O (M = 74.12 g/mol) is 83.9 cal/g, while its pressure
The vapor pressure at 30°C is 647.3 mmHg. What will be the vapor pressure at 0°C?

DATA:
ΔHV83.9 cal/g M = 74.12 g/mol

P1 647.3 mmHg T1303.15 K

SOLUTION:
The molar latent heat of vaporization of ethyl ether is:

cal
ˆ V cal =M g ΔHV
ΔH
mol mol g

g cal
ˆ V74.12
ΔH 83.9 =6218.668 cal
mol g mol

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THERMODYNAMICS COURSE: SOLVED PROBLEMS

ˆ V 6218.668 mol cal

ΔH
= =3129.6769K
R 1.987molcalK
In addition, based on the Clausius-Clapeyron equation, we have:

ˆ V= RTT
ΔH 1 P

RT T P 
2
ln 1 =  1 2
ln 2
T−T
1 2
P T−T2 1P2 1

So, forT2= 0°C = 273.15 K, the vapor pressure P2 of ethyl ether is:

P2 ΔHVTˆ2-T 1
ln =
P1 R T1T2

P2 =exp ΔHˆ VT2-T 1 ˆ VT−T

ΔH
P2 =P exp
1
2 1

P1 R T1 T2 R T1 T2
-30
( ) 3129.6769K
P2 =647.3mmHgexp ( )
( 303.15K273.15K
)( )
P2 208.2925mmHg

8. The vapor pressure of chloromethane, CH3Cl (M = 50.49 g/mol), between -47 and -10°C can be represented
by the equation:
1149 +7.481
( )
T
What will be the heat of vaporization of this liquid in calories per gram?
R.104.1 cal/g
DATA:
M = 119.38 g/mol
SOLUTION:
The equation indicated:

(
logP*mmHg=
10
-) +7.481
T
it is similar to the Clausius Clapeyron equation, the difference is the type of logarithm used, as
indicate below:

ΔHˆ V ΔHˆ R
lnP* = - +C= − V +C
RT T
On the other hand, we have to:

log lnb
lna
So, based on the above, we can write the proposed equation as follows:

M. C. LUISNIETOLEMUS FIQ-UMSNH Page11of43

THERMODYNAMICS COURSE: SOLVED PROBLEMS

log10P  = lnP = − 1149 +7.481



ln10 T
Therefore:
1149 +7.481
(
lnP mmHg =) ln10
( - )
T

(
lnP mmHg =) - +17.22564
T
From the previous equation, it follows that:

ˆV
ΔH
=2645.67027K
R
ˆV (
ΔH=2645.67027K ) ( )
R=2645.67027K1.987 ( cal
mol K )
ˆ V5256.94683mol cal
ΔH
Therefore:
ˆ V( mole
ΔH cal )
5256.94683molcal 104.1186cal
ΔHV= =
M ( mol )
g
g
50.49molg

9. It is observed that a liquid boils at 120°C under a pressure of 725 mmHg. Its molar heat of
Vaporization is 8,200 cal/mol. Calculate the normal boiling point of the liquid.
data

T1= 120°C = 393.15 K P1 725 mmHg

ΔHˆ V = 8200 cal/mol

P2 = 760 mmHg

SOLUTION:
To calculate the normal boiling point of the liquid (T2We will use the Clausius equation.
Clapeyron:

ˆ V= RTT1 P RT T P 

ΔH 2
ln 1 =  1 2
ln 2
T−T
1 2
P T−T2 1P2 1

Or well:
ˆV
ΔH  T−T 
= T1TP
2
ln 1 1 2 = R ln P1
R T−T
1 2
P 2 TT
12
ˆ VP 2
ΔH

1 − 1 = R P1
ln
T2 T1 ΔHˆ VP  2

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 THERMODYNAMICS COURSE: SOLVED PROBLEMS

1 = 1 + R P1 = 1 1.987 mol K 725mmHg cal

ln + ln
T2 T1 ΔHˆ VP 393.15K8200
2 mol760mmHg
cal

T2121.77°C

10. The normal boiling point of C6H6Br is 156.15°C. Using Trouton's rule, determine the
vapor pressure at 100°C and compare it with the observed value of 141.1 mmHg.
DATA:

Tb0 = 156.15°C = 429.3 K ΔSˆ 0v = 21 cal/mol K

SOLUTION:
Based on Trouton's rule, we have that:

ˆ 0V
ΔH
ˆ0V=
ΔS =21melcalK
Tb0
Therefore, we would have that the molar latent heat of vaporization is:

ˆ V0
ΔH=21 ( cal
molK )T =21(
b
0 cal
molK )(429.3K=9015.3
) cal
mol

Therefore:
ˆ 0V 9015.3mole
ΔH cal
= =4537.14142K
R 1.987melcalK
On the other hand, based on the Clausius Clapeyron equation, we have that:

ΔHˆ V
lnP* = - +C= − +C
RT T
For T = Tb0 At 429.3 K we have that P* = P0= 760 mmHg, therefore:
ˆV R
ΔH
C=lnP*+ =ln (760+) 4537.14142K 17.202015
T 429.3K
Therefore, the equation that relates the vapor pressure P* with T for the C6H6BR would be:

(
lnP*mmHg=) − 4537.14142 +17.202015
T ( K)
From the previous equation, we can evaluate the vapor pressure at any T, in the case where T
= 100°C = 373.15 K, results:

P*=exp− 4537.14142K +17.202015=154.93205mmHg

373.15K

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 THERMODYNAMICS COURSE: SOLVED PROBLEMS

11. The CCl4it has the following vapor pressures at the indicated temperatures:

T(°C) 30 50 70 100
P*(mmHg) 142.3 314.4 621.1 1463.0

Establish the equation that expresses log10P as a function of temperature.

SOLUTION:
Assuming that the Clausius Clapeyron equation is applicable for CCl4, the experimental data
would adjust to the equation:

log10P*=A+ =BA+B 1
T T
Where T is the temperature in K and P* is the vapor pressure. Fitting the experimental data to this.
equation applying the least squares method, results in:

T(K) 303.15 323.15 343.15 373.15

P*(mmHg) 142.3 314.4 621.1 1463.0

3.4

3.2

log P* = -1635/T + 7.5521

3.0
R² = 0.9998
2.8

2.6

2.4

2.2

2.0
0.0026 0.0027 0.0028 0.0029 0.003 0.0031 0.0032 0.0033 0.0034
1/T(K)

A= 7.5520527 B= -1634.99016 K r= 0.9998962

Then, the equation would look like this:

1634.99016
( )
logP*mmHg=7.5520527−
T ( K)
10

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 THERMODYNAMICS COURSE: SOLVED PROBLEMS

2. Beattie and Marple [J. Am. Chem. Soc., 72, 1450 (1950)] provided the following equation for the pressure of
vapor of 1-butene as a function of temperature between -75 and 125 °C:
1343.516 -167.515×10−5T
( )
logP*atm=5.475462−
10
T
ˆ V, as a function of temperature; b)
Halle: a) the expression ofΔH ΔHˆ V a 300 K; c) the boiling point
normal of the liquid.
R.c) 267 K
SOLUTION:
a) In this case, the Clausius Clapeyron equation is not applicable, which results when considering that
ˆ V it is not a function of T, therefore, one must start from the equation:
theΔH

dlnPΔHV ˆ
=
dT RT2
For what ΔHˆ V would be given by the following equation:

dlnP
b̂HV=RT2 (1)
dT
Therefore, the derivative will first need to be [Link] dTand then substitute into the equation
(1) to obtain the equation that allows us to calculate the ˆ V based on T, as shown at
ΔH
continuation:
lnP =5.475462− 1343.516 -167.515×10−5T
(
logP*atm=
10
)
ln10 T
1343.516 -167.515 × 10−5T
( 5.475462
lnP=ln10 ) −
T

lnP=12.607717− 3093.559914 -385.7175×10−5T

T
dlnP = d 12.607717− 3093.559914 -385.7175×10−5T
dT dT T

dlnP -3093.559914 d1 - 3 8 5 . 7 1 7 5 × 1 0 dT
−5

dT dT T dT

dlnP -3093.559914- 1 -385.7175×10−5

( 1)
dT T2

dlnP3093.559914
= -385.7175×10−5 (2)
dT T2
Substituting equation (2) into equation (1), it results in:

ˆ V=RT 2dlnP =RT2 3093.559914 -385.7175×10−5

ΔH
dT T2

M. C. LUISNIETOLEMUS FIQ-UMSNH Page 15 of 43

THERMODYNAMICS COURSE: SOLVED PROBLEMS

ˆV
ΔH
=3093.559914−385.7175×10−5 T 2
R
Or, in SI units, the equation would read as follows:
ΔH (
ˆ V= R3093.559914 -5 2
− 385.7175 × 10^T )
ˆV (
ΔH=8.314×10 -3 kJ
molK ) (3093.559914-385.7175×10
−5
T2 ) ( K)
ˆ V( mol
ΔH )
kJ 25.719857 - 3.206856 x 10−5 T 2 ,
T ( K)

b) For T = 300 K, the molar latent heat of vaporization would then be:
ˆ V=25.719857−3.206856×10^T-5
ΔH 2
( molkJ )
ˆ V-1.482848−5
ΔH kJ
mol ( kJ
molK2
)(300K) 2

ˆ V22.833687mol
ΔH kJ

c) The normal boiling point of the liquid will be calculated from the equation:
1343.516 -167.515×10−5T
( )
logP*atm=5.475462−
10
T
In this case, the liquid will begin to boil when it reaches the temperature Ta which P* =P0= 1 atm,
substituting into the equation:

1343.516 -167.515×10−5T
( )
log101atm=5.475462−
T

5.475462− 1343.516 -167.515×10−5T=0

T
Multiplying the equation by T results in:

T5.475462− 1343.516 -167.515 × 10−5T=T0 ( )

T
5.475462T−1343.516−167.515×10−5T 2=0

)(
( -1 5.475462T-1343.516-167.515×10 T -1
−5 2
0 ) ( )( )
167.515 × 10−5T 2-5.475462T + 1343.516 = 0
By solving the quadratic equation we obtain:
T=Tb0 267.2156K ≈ 267.22K

M. C. LUISNIETOLEMUS FIQ-UMSNH Page 16 of 43

 THERMODYNAMICS COURSE: SOLVED PROBLEMS

13. The vapor pressure of CO2Solid is 76.7 mmHg at -103°C, and 1 atm at -78.5°C. Calculate the heat of
sublimation of CO2.
R.6160 cal/mol
DATA:

T1= -103°C = 170.15 K P1* 76.7 mmHg

T2= -78.5°C = 194.65 K P2* = 1 atm = 760 mmHg
SOLUTION:
Assuming that the molar latent heat of sublimation does not depend on temperature, we can apply the
Clausius-Clapeyron equation indicated below:
ˆs
ΔH
= T1 T2 ln P1 T=T 1 P2

2
T−T P T−T P ln
R 1 2 2 2 1 1

Substituting data:

ˆ s=
ΔH RT T P ( cal (
1.987 molK ) )(
170.15K194.65K ) 76.7mmHg
1 2
ln =
1
ln
T−T
1 2
P 2 170.15K−194.65K 760mmHg
ΔHˆ s=6160.2895molcal

14. The sublimation pressure of N2Oh la la the relationship

1294 +1.405log T−0.0051T+4.800
10
( −)
logP*atm= 10
T
Determine the expression for the heat of sublimation of N2 Or as a function of temperature.
SOLUTION:
In this case, the Clausius-Clapeyron equation is not applicable, which results when considering that the
ΔHˆ S it is not a function of T, therefore, we must start from the equation:
dlnPΔHS ˆ
=
dT RT2
For what ΔHˆ S would be given by the following equation:

ˆ S=RT 2dlnP
ΔH (1)
dT
Therefore, the derivative will have to be evaluated first. dlnP dT and subsequently substitute in the equation
(1) to obtain the equation that allows us to calculate the ΔHˆ S based on T, as shown at
continuation:
1294 +1.405log T−0.0051T+4.800
10
( −)
logP*atm= 10
T

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 THERMODYNAMICS COURSE: SOLVED PROBLEMS

lnP = − 1294 +1.405 lnT -0.0051T+4.800

ln10 T ln10

1294 +1.405 lnT -0.0051T + 4.800

(
lnP =ln10− )
T ln10

lnP = − 2979.54511 +1.405lnT−117.4318×10−4T+11.052408

T
dlnP = d − 2979.54511 +1.405lnT−117.4318×10−4T+11.052408
dT dT T

dlnP -2979.54511 d1 +1.405 dlnT -117.4318×10−4 dT +0

dT dT T dT dT

dlnP -2979.54511- 1 +1.405 1 -117.4318×10−4

( 1)
dT T2 T

dlnP 2979.54511
= 1.405
+ -117.4318 × 10−4 (2)
dT T2 T
By substituting equation (2) into equation (1) we obtain:

ΔHˆ S=RT 2dlnP =RT2 2979.54511 +1.405 -117.4318×10
−4
2
dT T T
ˆS
ΔH
=2979.54511+1.405T−117.4318×10−4T 2
R
In SI units, the equation would be:
ΔH (
ˆ S = R2979.54511 -4
+ 1.405T - 117.4318 × 10T 2
)
ˆS
ΔH=8.314 ( J
molK ) (2979.54511+1.405T-117.4318×10 T 2K
−4
)( )

ˆ S( molJ ) =24771.938044+11.68117T−976.32799×10−4T 2T K (
ΔH )

15. The vapor pressure of liquid arsenic is given by the equation

2460 +6.69
(
logP*mmHg=
10
−)
T
and that of solid arsenic by
6947 +10.8
(
logP*mmHg=
10
−)
T
Find the temperature at which the two forms of As have the same vapor pressure. What is the value?
this pressure?
SOLUTION:
If the two forms of A have the same vapor pressure, to find the T we will proceed to
equal both equations:

M. C. LUISNIETOLEMUS FIQ-UMSNH Page 18 of 43

 THERMODYNAMICS COURSE: SOLVED PROBLEMS

As (liquid): As (solid):

( = ) − 2460 +6.69
logP*mm
10
( −)
logP*mm=
10
6947 +10.8
T T
Equalizing:

− 2460 +6.69= − 6947 +10.8

T T
Now, multiplying both terms of the equation by T results in:

T− 2460 +6.69=T− 6947 +10.8

T T
-2460 + 6.69T = -6947 + 10.8T
4487 = 4.11T
4487=4.11T
4487K 1091.72749K
T=
4.11
T ≈ 1091.73 K = 818.58 °C

Then, the vapor pressure of the liquid or solid at this temperature will be:
2460 +6.69 6947 +10.8
− −
P * (m m =) 1 0 T
=10 T

2460 +6.69 6947 +10.8

− −
P * (m m =) 1 0 1091.73 =10 1091.73
=27333.5230mmHg=35.9652atm

16. The flow time of water through an Ostwald viscometer is 1.52 min. For the same
volume of an organic liquid with a density of 0.800 g/cm3The time is 2.25 minutes. Determine
the viscosity of the liquid in relation to that of water and its absolute value in millipoises. The temperature is
at 20°C. The density of water at that temperature is 0.99829 g/cm3.
DATA:
t11.52 min 10.99829 g/cm3
t22.25 min 20.800 g/cm3
20°C 11.002 cP = 0.01002 Poise
SOLUTION:
In the case of the Ostwald viscometer, the following equation is applicable:

1 t
1 1 2 t2
= =2
2 2 2t 1 t
1 1

If we assign liquid (1) to water and liquid (2) to the organic liquid, therefore:

M. C. LUISNIETOLEMUS FIQ-UMSNH Page 19 of 43

 THERMODYNAMICS COURSE: SOLVED PROBLEMS

2 t2
2 = 1
1 t1
Substituting data, it results in:

g
0.800 2.25 minutes
(
η=0.01002
2
Poise ) cm3
g
0.99829 cm3
1.52 min

20.01188611 Poise = 11.88611 mP

17. A steel ball with a density of 7.90 g/cm3and 4 mm in diameter takes 55 s to travel a
distance of 1 m falling through a liquid with a density of 1.10 g/cm3Calculate the viscosity
of the liquid in poise.
DATA:
Density = 7.90 g/cm³3 4 mm = 0.4 cm
1 m = 100 cm t = 55 s
m= 1.10 g/cm3
SOLUTION:
Considering the applicability of Stokes' Law in the case of the steel ball descending in the liquid,
we have:

2r2 ( − m )g
=
9v

where:
d
v=
t
Therefore:
2r2 ( − m )g
=
d
9
t

=
2 r 2ρ( - ρg tm )
=
2 ( 0.2 cm7.90
) 2
( g
cm3
-1.10 g
cm3
)(980.66 cm
2 ) (55 seconds
)
9d 9 (100cm )

g
η=32.601497 cms
32.601497 Poise

18. A sphere with a radius of 5×10-2cm and a density of 1.10 g/cm3falls at a constant speed
through a liquid whose density is 1.00 g/cm3and its viscosity of 1.00 poise. At what speed
Does the sphere descend?
DATA:
r = 5 × 10-2cm ρ = 1.10 g/cm3

M. C. LUISNIETOLEMUS FIQ-UMSNH Page 20 of 43

 THERMODYNAMICS COURSE: SOLVED PROBLEMS

m1.00 g/cm3 η = 1.00 poise (g/cm s)

SOLUTION:
Assuming that Stokes' Law is applicable, we have:

2r2 ( − m )g
=
9v
Therefore, the speed of descent of the sphere in the liquid will be:

v=
2r 2 ( − m )g (
25 times 10
−2
)(
2
cm1.10 g
cm3
-1.00 g
cm3
)(980.66 )cm
2
=
9h (
9 1.00 g
cms )
v=0.054481cm
s

19. Suppose the same conditions as in problem 18, except that the density of the sphere is
now of 0.90 g/cm3What will the speed be in this case? Explain the significance of the result.
SOLUTION:
Since in this case the density of the sphere is less than that of the liquid, the sphere will float in the liquid and
It will not descend through this, therefore, Stokes' law would not be applicable.

20. Using the viscosity coefficient data of C2H5OH based on the given temperature
In the table, find the constants A and B of the equation for this substance:

log10 η=A+ B
T
T(°C) 0 20 40 60 80
(ctp) 0.284 0.233 0.197 0.140 0.118

Additionally, determine the value of the viscosity coefficient of alcohol at 70°C.

SOLUTION:
To calculate the constants A and B of the proposed equation, a data fitting will be performed.
using the least squares method, considering that a representation of the values of 1/T(K)
vs log10Could you give us a straight line, as indicated below:

T(K) 273.15 293.15 313.15 333.15 353.15

(ctp) 0.284 0.233 0.197 0.140 0.118

The results obtained are as follows:

A= -2.25098 B= 471.3414K r= 0.986478

Therefore, the equation that relates viscosity η with temperature T would be:

log10ₕ(c)( = 471.3414 -2.25098

)
T ( K)

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THERMODYNAMICS COURSE: SOLVED PROBLEMS

The graph corresponding to the representation of the experimental data in the previously mentioned form
indicated, as well as, the trend line is shown in the following graph:

0.0027 0.0029 0.0031 0.0033 0.0035 0.0037 0.0039

-0.50

-0.55

-0.60 log = 471.34/T - 2.251

R² = 0.9731
-0.65

-0.70

-0.75

-0.80

-0.85

-0.90

-0.95
1/T(K)

For a temperature T = 70°C = 343.15 K, we obtain:

471.3414K -2.25098
343.15K
η=10 0.13261ctp

M. C. LUISNIETOLEMUS FIQ-UMSNH Page 22 of 43