CHM222A/SE331: BASIC PHYSICAL CHEMISTRY

Homework Assignment - 2
Dr. Manabendra Chandra
Date: February 03, 2014

You don’t have to submit the solutions. Solutions will be posted in 5 days.

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 –2–

[ρice = 0.917 g/cm3 and ρwater = 1.000 g/cm3 at 0◦ Cand 1 atm.]; (b) reversible
vaporization of 39 g of C6 H6 at its normal boiling point of 80.1◦ Cand 1 atm; (c)
adiabatic expansion of 0.100 mol of a perfect gas into vacuum (Joule experiment)
with initial temperature of 300 K, initial volume of 2.00 L, and final volume of
6.00 L.

10. Express each of the following rates of change in terms of state functions. (a)
The rate of change of U with respect to temperature in a system held at constant
volume. (b) The rate of change of H with respect to temperature in a system held
at constant pressure. (c) The rate of change of S with respect to temperature in a
system held at constant pressure.

11. The relation (∂U/∂S)V = T is notable because is relates the three fundamental
thermodynamic state functions U, S, T. The reciprocal of this relation, (∂S/∂U )V =

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1/T, shows that entropy always increases when internal energy increases at con-
stant volume. Use the Gibbs equation for dU to show that (∂S/∂V )U = P/T.

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12. For a liquid with the typical values α = 10−3 K−1 , κ = 10−4 atm−1 , Vm = 50 cm3 /mol,

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CP,m = 150 J/mol–K, calculate at 25◦ Cand 1 atm (a) (∂Hm /∂T ) P ; (b) (∂Hm /∂P) T ;
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(c) (∂U/∂V ) T ; (d) (∂Sm /∂T ) P ; (e) (∂Sm /∂P) T ; (f) CV,m ; (g) (∂A/∂V ) T .
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13. Starting from dH = TdS + VdP, show that (∂H/∂V ) T = αT/κ − 1/κ.
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14. Show that µ J = ( P − αTκ −1 )/CV , where µ J is the Joule coefficient.

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15. The volume of Hg in the temperature range 0◦ Cto 100◦ Cat 1 atm is given by V =
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V0 (1 + at + bt2 ), where a = 0.18182 × 10−3 ◦ C−1 , b = 0.78 × 10−8 ◦ C−2 and where
V0 is the volume at 0◦ Cand t is the Celsius temperature. The density of mercury
at 1 atm and 0◦ C is 13.595 g/cm3 . (a) Show that (∂CP /∂P) T = − T (∂2 V/∂T 2 ) P .
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(b) Use this result to calculate (∂CP /∂P) T for Hg at 25◦ Cand 1 atm. (c) Given
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that CP,m = 6.66 cal mol−1 K−1 for Hg at 1 atm and 25◦ C, estimate CP,m of Hg at
25◦ C and 104 atm.
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16. This problem finds an approximate expression for Uintermol , the contribution of
intermolecular interactions to U. As the volume V changes at constant T, the av-
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erage distance between molecules changes and so the intermolecular interaction

energy changes. The translational, rotational, vibrational, and electronic contri-
butions to U depend on T but not on V. Infinite volume corresponds to infi-
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nite average distance between molecules and hence to Uintermol = 0. Therefore

U ( T, V ) − U ( T, ∞) = Uintermol ( T, V ).
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(a) Verify that Uintermol ( T, V 0 ) = ∞ = (∂U/∂V ) T dV, where the integration is at
constant T, and V 0 is some particular volume.
(b) Show that (∂U/∂V ) T = an2 /V 2 for van der Waals equation of state

an2
 
P+ 2 (V − nb) = nRT
V

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(c) Using the relation (∂U/∂V ) T = an2 /V 2 show that for a van der Waals gas
Uintermol,m = − a/Vm . (This is only a rough approximation since it omits the
effects of intermolecular repulsions, which become important at high densi-
ties.)
(d) For small to medium-size molecules, the van der Waals a values are typically
106 to 107 cm6 atm mol−2 . Calculate the typical range of Uintermol,m in a gas
at 25◦ C and 1 atm. Repeat for 25◦ C and 40 atm.

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 CHM222A/SE331: BASIC PHYSICAL CHEMISTRY
Homework Assignment - 3
Dr. Manabendra Chandra
Date: February 03, 2014

You don’t have to submit the solutions. Solutions will be posted in 5 days.

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 CHM222A/SE331: BASIC PHYSICAL CHEMISTRY
Homework Assignment - 4
Dr. Manabendra Chandra
Date: February 03, 2014

You don’t have to submit the solutions. Solutions will be posted in 5 days. Look
at the thermodynamic tables in the Appendix of Physical Chemistry text books
by Levine or Atkins to solve the following problems:

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find ∆H298
◦ for

NH3 (g) + 2O2 (g) → HNO3 (l) + H2 O(l)

without using Appendix data.

5. Compute ∆ f H1000
◦ ◦ /[J/(mol–K)] ex-
f HCl( g) from Appendix data and these CP,m
pressions, which hold from 298 K to 1500 K.
H2 ( g):
◦
CP,m /[J/(mol − K)] = 27.14 + 0.009274( T/K) − 1.381(10−5 T 2 /K2 ) + 7.645(10−9 T 3 /K3 )

Cl2 ( g):
◦
CP,m /[J/(mol − K)] = 26.93 + 0.03384( T/K) − 3.896(10−5 T 2 /K2 ) + 15.47(10−9 T 3 /K3 )

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HCl( g):

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◦
CP,m /[J/(mol − K)] = 30.67 − 0.007201( T/K) − 1.246(10−5 T 2 /K2 ) − 3.898(10−9 T 3 /K3 )

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6. 5.32 Substance Y melts at 200 K and 1 atm with ∆fus Hm = 1450 J/mol. For solid
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◦
Y, CP,m = cT 3 + dT 4 for 10K≤ T ≤20K and CP,m ◦ = e + f T + gT 2 + hT 3 for 20 K≤
◦
T ≤ 200 K. For liquid Y, CP,m = i + jT + kT 2 + lT 3 for 200 K≤ T ≤ 300 K.
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◦
(a) Express Sm,300 of liquid Y in terms of the constants c, d, e, · · · , l.
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◦
(b) Express Hm,300 ◦
− Hm,0 of liquid Y in terms of these constants. Neglect the
difference between 1–atm and 1–bar properties of the solid and liquid.

7. For urea, CO(NH2 )2 (c), ∆ f H298

◦ = −333.51 kJ/mol and S◦
m,298 = 104.60 J/(mol/K).
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With the aid of Appendix data, find ∆ f G298 of urea.

◦
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◦
8. Some values of (Hm,2000 ◦
− Hm,298 )/(kJ/mol) are 52.93 for H2 ( g), 56.14 for N2 ( g),
and 98.18 for NH3 ( g). Use these data and Appendix data to find ∆H2000◦ for N2 ( g)
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+ 3H2 ( g) → 2NH3 ( g).

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9. Use bond energies listed in any Physical Chemistry textbooks to estimate ∆H298
◦

for CH3 CH2 OH( g) → CH3 OCH3 ( g). Compare with the true value 51 kJ/mol.

10. For CH3 OH(l ) at 25◦ C, the vapor pressure is 125 torr, ∆Hm of vaporization is 37.9
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kJ/mol, ∆ f H ◦ is −238.7 kJ/mol, and Sm ◦ is 126.8 J/(mol K). Making reasonable

approximations, find ∆ f H298

◦ and S◦
m,298 of CH3 OH( g ).

11. Let DCC and DCH be the C−C and C–H bond energies and bCC and bCH be the
∆ f H298
◦ bond–additivity values for these bonds.

(a) Express ∆ f H298

◦ of C H
n 2n+2 ( g ) in terms of bCC and bCH .

(b) Express ∆ f H298

◦ of Cn H2n+2 (g) in terms of DCC , DCH , ∆ f H298
◦ [H( g )] and

∆ f H298
◦ [C( g )].

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(c) Equate the expressions in (a) and (b) to each other and then set n = 1 and
◦ [C( g )] and
n = 2 to show that bCC = − DCC + 0.5∆ f H298
bCH = − DCH + ∆ f H298
◦ [H( g )]+0.25∆ H ◦ [C( g )].
f 298

Substitute these two equations for bCC and bCH into the equation found by equat-
ing the expressions in (a) and (b) and verify that this equation is satisfied.

12. The fuel value of hamburger is approximately 3.6 kcal g−1 . If a person eats 1
pound of hamburger for lunch and if none of the energy is stored in his body,
estimate the amount of water that would have to be lost in perspiration to keep
his body temperature constant. (1 lb=454 g.)

13. Consider the reaction

N2 (g) + O2 (g) → 2NO(g)

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Calculate the values of ∆r S◦ for the reaction mixture, surroundings, and the uni-

co
verse at 298 K. Why is your result reassuring to Earth’s inhabitants?

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