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ChemS 360: Advanced Physical Chemistry I

Exercise 1
Problem 1
Oxidation of glucose is the principle source of energy for animal cells. Assume glucose
(C6H12O6(s)) reacts with oxygen (O2(g)) to produce carbon dioxide (CO2(g)) and liquid water (H2O(l)).

C6H12O6(s) CO2(g) H2O(l)

Δ H f ° [kJ /mol] ‒1274.4 ‒393.509 ‒285.830

(a) Write a balanced chemical reaction and determine the standard heat of reaction.
(b) Assuming a person needs 150 kJ of energy per kg of body mass per day, and this energy
comes solely from glucose, how much glucose is needed to sustain a 60 kg person?
(c) There are about 7 billion people in the world. How much CO2 do they produce a day only
through respiration?
Solution
(a)
C 6 H 12 O6 ( s ) +6 O2 ( g ) →6 C O2 ( g ) +6 H 2 O ( l )

Δ H rxn °=6 Δ H f ° ( C O2 ( g ) ) +6 Δ H f ° ( H 2 O ( l ) )−6 Δ H f ° ( O2 ( g ) ) −Δ H f ° ( C 6 H 12 O6 ( s ) )

(
Δ H rxn °=6 −393.509
kJ
mol ) (
+6 −285.830
kJ
mol
− −1274.4
kJ
mol)(
°=−2801.6
kJ
mol )
(b)

(150 daykJ∙ kg ) ( 60 kg) =3.212 mol =0.5787 kg

( mol )
2801.6
kJ day day

(Molar mass of C6H12O6 is 180.16)

(c) 1 mole of glucose produces 6 moles of carbon dioxide:

(
6 3.212
mol
day )
( 7 ×109 ) =1.35× 1011 mol =5.94 × 106 tonnes
day day
Problem 2

From the following data, determine Δ H f ° for diborane, B2 H 6 (g) , at 298 K:

(1) B2 H 6 ( g ) +3 O2 ( g ) → B 2 O3 ( s ) +3 H 2 O(g) Δ H r °=−1941 kJ mo l

−1

()
−1
3 Δ H r °=−2368 kJ mo l
(2) 2 B ( s ) + O ( g ) → B2 O 3 (s )
2 2

(3) H ( g )+ ( ) O ( g ) → H O(g)
−1
1 Δ H r °=−241.8 kJ mo l
2 2 2
2
Solution

We want to add the above reactions in a way that eliminates H 2 O(g) and B2 O3 (s), which is:
( Reaction1 )−( Reaction2 )−3 × ( Reaction 3 )
We get the following reaction:
B2 H 6 (g) → 2 B( s)+3 H 2 ( g )

Δ H r °=−1941 kJ mo l−1−(−2368 kJ mol −1) −3 (−241.8 kJ mol−1 ) =1152kJ mo l−1

Since B(s) and H 2 (g) both have Δ H f °=0, the Δ H f ° of B2 H 6 ( g ) is −1152kJ mol −1
Problem 3
A gas at 250 K and 15 atm has a molar volume 12% smaller than that calculated from the
perfect gas law.
(a) Calculate the compression factor under these conditions.
(b) Calculate the molar volume of the gas.
(c) Which are dominating in the sample: the attractive or the repulsive forces?
Solution
(a)
PV R P(0.88 V ideal )
z= = =0.88
RT P V ideal

(b)

V R=
zRT
=
(
( 0.88 ) 0.082057
L ∙atm
K ∙ mol)(250 K)
=1.2
L
P 15 atm mol
(c) Attractive forces
Problem 4
Two kmol of nitrogen gas are compressed isothermally (T=298 K) and reversibly from an initial
pressure Pi of 1 MPa to a final pressure Pf of 5 MPa. Derive an expression for and calculate the
work done on the gas during the compression if it follows:
(a) The ideal gas law.
(b) The van der Waals (vdW) equation of state.

vdW coefficients a [atm dm6 mol-2] b [dm3 mol-1]

N2 1.352 0.0387

Solution
(a)

( ) ( )
Vf Vf

w=−∫ PdV =−∫

Vi Vi
( ) nRT
V
V P
dV =−nRT ln f =−nRT ln i
Vi Pf

(
w=−( 2 kmol ) 8.3145
J
mol ∙ K )
( 298 K ) ln (
1 MPa
5 MPa )
=7980 kJ

(b) We need to calculate the initial volume:

( )
2
an
2 ( i
Pi + V −nb )=nRT
Vi

There is only one real root, V i=4.923 m3

Approximated the Vi in an2/Vi2 by nRT/Pi and in the equation put the values of R=0.082
lit.atm/(mol.K), T=298 K, P=1MPa = 9.86923 atm
The final volume can be calculated using the following equation:

( ) ( )
2 2
an an
2 ( i
Pi + V −nb )= P f + 2 ( V f −nb )
Vi Vf

There is only one real root, V f =0.9639 m3

( ) ( ( ) ( ))
Vf Vf
nRT an
2
V −nb 2 1 1
w=−∫ PdV =−∫ − 2 dV =− nRT ln f +an −
Vi Vi
V −nb V V i −nb V f Vi

w=7960 kJ
Problem 5
A process stream is being cooled from 25 ℃ to 0 ℃ using chilled brine. The rate of heat
removal is 50 kW .
(a) What is the theoretical coefficient of performance (CoP)?
(b) What is the theoretical power requirement for the refrigeration system?
(c) If the actual CoP is 2.5, what is the power requirement to run the refrigeration system?
Solution
(a)

|Qcold| |Qcold| T cold 273.15 K

CoP= = = = =10.9
|w| |Qhot|−|Qcold| hot cold
T −T 25 K

(b)

|Q cold| 50 kW
|w|= = =4.58 kW
CoP 10.9
(c)

|Q cold| 50 kW
|w|= = =20 kW
CoP 2.5
Problem 6
A sample consisting of 2.00 mol of diatomic perfect gas molecules at 250 K is compressed
reversibly and adiabatically until its temperature reaches 300 K.

Given that C v =27.5 J K−1 mol−1, calculate:

(a) q
(b) w
(c) ΔU
(d) ΔH
(e) ΔS

Solution
(a) Since the process is adiabatic, q=0 .
(b)
From the 1st Law of Thermodynamics: Δ U =q +w
The process is adiabatic, so w=Δ U
For an ideal gas:
Tf

Δ U =n ∫ C v dT =( 2.00 mol ) ( 27.5 J K −1 mol−1 ) ( 300 K−250 K )=2750 J

Ti

Thus, w=2750 J .
(c) Δ U =w=2750 J
(d)
From the definition of enthalpy:
Δ H =Δ ( U + PV ) =Δ U + Δ( PV )

For an ideal gas, PV =nRT

(
Δ H =Δ U + nR Δ T =( 2750 J ) + ( 2.00 mol ) 8.3145
J
mol ∙ K)( 50 K ) =3580 J

(e)
qrev
Δ S= =0
T
Problem 7

Calculate Δ H tot and Δ S tot when two iron blocks, each of mass 1.00 kg, one at 200 ℃ and the
other at 25 ℃ , are placed in contact in an isolated container. The specific heat capacity of iron
is 0.449 J K−1 g−1 and may be assumed constant over the temperature range involved.

Solution
We need to calculate the equilibrium temperature. For an isolated container:
m1 C 1 ( T eq −T 1) + m2 C 2 ( T eq −T 2 ) =0

Note that m1=m2=m and C 1=C2 =C :

T 1+T 2 473.15 K +298.15 K
T eq= = =385.65 K
2 2
To evaluate Δ H tot:
Δ H tot =Δ H 1 + Δ H 2 =m1 C 1 ( T eq −T 1 ) +m2 C2 ( T eq−T 2 )=0

To evaluate Δ S tot:
q rev mC
dS= = dT
T T

Δ S=mC ln
( )
Tf
Ti

Thus:

Δ S tot =Δ S1 + Δ S 2=mC ln
( ( ) ( ))
T eq
T1
T
+ ln eq
T2

Δ S tot =( 1,000 g ) ( 0.449 J K g ) ln

−1 −1
( 473.15 298.15 ) K
( 385.65
) +ln (
385.65
) =23.7
J
Problem 8
Nitric acid hydrates have received much attention as possible catalysts for heterogeneous
reactions that bring about the Antarctic ozone hole. Worsnop et al. investigated the
thermodynamic stability of these hydrates under conditions typical of the polar winter
stratosphere. They report thermodynamic data for the sublimation of mono-, di-, and
trihydrates to nitric acid and water vapors:
HN O3 ∙ n H 2 O ( s ) → HN O3 ( g ) +n H 2 O( g)

for n = 1, 2, and 3. Given Δ G r ° and Δ H r ° for these reactions at 220 K, use the Gibbs-Helmholtz
equation to compute Δ G r ° at 190 K.

n 1 2 3
Δ G r ° [kJ/mol] 46.2 69.4 93.2
Δ H r ° [kJ/mol] 127 188 237

Solution
Gibbs-Helmholtz equation:

( )
∂ ΔG − Δ H
∂T T
= 2
T
Integrating from T 1 to T 2 and assuming Δ H does not vary with temperature:
T2 T2

T 1
∂ ΔG
( )
T
−Δ H
∫ ∂ T T dT =∫ T 2 dT
1

Δ G2 Δ G1 Δ H Δ H
− = −
T2 T1 T2 T1

∴ Δ G 2= Δ G 1
( ) ( )
T2
T1
+ Δ H 1−
T2
T1

For n=1:

Δ G r (190 K ) =( 46.2 kJ mol −1 ) ( 190

220 )+ ( 127 kJ mol ) (1−
−1
220 )
190
=57.2 kJ mol −1

For n=2:

Δ G r (190 K ) =( 69.4 kJ mol −1) ( 190

220 ) + ( 188 kJ mol ) (1−
−1
220 )
190
=85.6 kJ mo l −1

For n=3:
Δ G r (190 K ) =( 93.2 kJ mo l−1 ) ( 190
220 )
+ ( 237 kJ mo l ) (1−
−1
220 )
190 −1
=112.8 kJ mo l
Problem 9
A gaseous sample consisting of 1.00 mol molecules is described by the equation of state:
P V m=RT (1+BP)

Initially at 373 K, it undergoes Joule-Thomson expansion from 100 atm to 1.00 atm. Given that
5
C p= R , μ=0.21 K at m−1, B=−0.525
2
K
T ( )
at m−1, and that these are constant over the

temperature range involved, calculate Δ T and Δ S for the gas.

Solution
Let the temperature be a function of the pressure and the enthalpy:

dT = ( ∂∂ TP ) dP+( ∂∂ HT ) dH
H P

For a Joule-Thomson process, dH =0.

From the definition of the Joule-Thomson coefficient: μ= ( ∂∂ TP ) =0.21 K at m

H
−1

We can find Δ T by integrating:

P2

Δ T =∫
P1
( ∂∂ TP ) dP=μ ( P −P )=(0.21 K at m
H
2 1
−1
) ( 1 atm−100 atm )=−20.8 K

Let the entropy be a function of the pressure and the temperature:

dS= ( ∂∂ PS ) dP+( ∂∂TS ) dT

T P

From Maxwell relations and (dG=−SdT +VdP ):

( )
∂V Cp
dS=− dP+ dT
∂T P T

Plugging in the equation of state:

−R ( 1+BP ) Cp
dS= dP+ dT
P T

(( ) ) ( )
P2 T2

Δ S=−R∫
P1
( 1
P )T
C
T 1
P
+ B dP+∫ p dP=−R ln 2 + B ( P2−P1 ) +
P1
5R
2
T
ln 2
T1

(
Δ S=− 8.3145
J
K )(ln ( 1001 )−0.525( 362.6K K ) ( 1−100 )− 52 ln ( 352.2
373 )) =35.9
J
K
Problem 10
Pure substances are described by a “fundamental equation” that relates their energy and
entropy to extensive variables. The fundamental equation for a particular substance is given as:
3
aUV b n
S= −
n UV
where S is the entropy, U is the internal energy, V is the total volume and n is the number of
moles. The variables a and b are constants. An equation of state can be derived for this
substance using the equation:
1 P μ
dS= dU + dV − dn
T T T
from which we find the following:

P
T
=( )
∂S
∂V U,n

=(
∂U )
1 ∂S
T V ,n

P 1
(a) Derive expressions for and as functions of n, V, and U.
T T
(b) Eliminate U from the above expressions to find an expression for P in terms of V and T.
Solution
(a)

( )
3
P ∂S aU b n
= = +
T ∂V U,n n U V2

=(
∂U )
3
1 ∂S aV b n
= +
T V ,n n U2 V

(b) Dividing the above expressions:

3 2 2 4
aU b n aU V +bn
+
n U V2 nU V
2
U
P= 3
= 2 2 4
=
aV b n aV U +bn V
+ 2
n U V 2
nU V
⇒ U =PV
3
1 aV b n
∴ = +
T n P2 V 3
 ∴ P=
√ bT n 4
3
nV −aT V
4

Problem 11
The ideal gas is defined as:
(a) P-V-T behavior is described by the equation of state PV=RT.
(b) Internal energy is only a function of temperature.
Denbigh suggests an alternative definition: a single-component ideal gas is a substance whose
chemical potential is given by:
G=RT ln ( P )+ λ(T )

Prove that properties (a) and (b) follow from Denbigh’s definition.
Solution
(a) Starting from the differential:
dG=−SdT +VdP
Thus,

V= ( ∂∂ GP ) = ∂∂P ( RT ln ( P )+ λ ( T ) ) = RTP
T
T

(b) Similarly,

S=− ( ∂∂TG ) = −∂
P ∂T
( RT ln ( P )+ λ ( T )) =−R ln ( P )−λ ' (T )
P

Using the definition of Gibbs energy:

G=H −TS=U + PV −TS=RT ln ( P ) + λ (T )

Thus,
'
U + PV + RT ln ( P ) +T λ ( T )=RT ln ( P ) + λ (T )
Solving for the internal energy:

U =λ ( T )−T λ ' ( T )−PV =λ ( T )−T λ' ( T )−RT

The above relation shows that internal energy is only a function of temperature.