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Chan

Quiz 3 for CHM 520

Print out these questions and answer ALL questions.

Plot the needed figures with your own graph papers if applicable.

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Matric No:
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Question 1
Calculate the change in entropy (∆S) when 25 kJ of energy (q) is transferred reversibly and
isothermally as heat to a large block of iron at (a) 0°C, (b) 100°C.

Hints and answers


qrev
a) ∆S = ; ∆S = 92 J K -1
T
b) ∆S = 67 J K -1
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Question 2

Calculate the molar entropy of a constant-volume sample of neon at 500 K (S500K) given that
it is 146.22 J K–1 mol–1 at 298 K.

Given that molar heat capacity at constant pressure (Cp,m) = 20.786 J K-1 mol-1

Hint and answer


T C dT
∆S = ∫ v ; S 500 K = 152.67 J K -1 mol-1
f

Ti T
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Question 3

Calculate ΔSsys (for the system) when the state of 3.00 mol of perfect gas atoms, for which
molar heat capacity at constant pressure, Cp,m = 5/2R, is changed from 25 °C and 1.00 atm to
125 °C and 5.00 atm. How do you rationalize the sign of ΔSsys?

Hints and answers


V T  −1 −1
∆S = nR ln f ∆S = nC p,m ln f  ; ∆S total = −22.1 J K mol , not a spontaneously
Vi ,  i
T
process.
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Question 4

Calculate the change of entropy of the system (∆Ssys) when 2 mol of perfect diatomic gas
molecules, are changed from 25 oC and 1.50 atm to 135 oC and 7.00 atm.

Given that: molar heat capacity at constant pressure (Cp,m) = 7/2 R.

Hints and answers


P1 T  −1
∆S1 = nR ln ∆S = nC p,m ln f  ; ∆S sys = −7.3 J K
P2 ,  Ti 
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Solution:

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Question 5

A sample consisting of 3.00 mol of diatomic perfect gas molecules at 200 K is compressed
reversibly and adiabatically until its temperature reaches 250 K. Given that heat capacity at
constant volume (Cv,m) at 27.5 J K–1 mol–1.

a) How much heat (q) (in unit J) is supplied to the system?


b) What is the increase in internal energy (ΔU) (in unit J)?
c) How much work (w) (in unit J) is done on the system?
d) Calculate the capacity at constant pressure (Cp,m).
e) What is the increase in enthalpy (ΔH) (in unit J)?
f) What is the change of entropy of the system (ΔS) (in unit J K-1)?

Hints and answers


a) qrev = 0
b) ∆U = nC v,m ∆T ; ∆U = 4.1 ⋅ 10 3 J
c) wad = nCv,m ∆T ; wad = 4.1 ⋅ 10 3 J
d) Cp,m = Cv,m + R; Cp,m = 35.8 J K-1 mol-1
e) ∆H = nCp,m ∆T ; ∆H = 5.4 ⋅ 10 3 J
dqrev
f
f) ∆S = ∫ =0
i T
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Solution:

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Question 6

When two 1.00-kg iron blocks, one at 200 oC and the other at 25 oC, are placed in contact in
an isolated container, calculate

a) the final temperature (Tf) (in unit oC) of the two blocks,
b) the change in enthalpy (ΔH) (in unit J) from the iron blocks to the container,
c) the enthalpy change (ΔH) (in unit J) of individual iron blocks and
d) total entropy change (ΔStot) (in unit J K-1)

The specific heat capacity of iron is 0.449 J K-1 g-1 and is constant over the temperature range
involved.

Hints and answers


a) m1 ∆T1 = m2 ∆T2 ; Tf = 112.5 oC
b) ∆H = mC∆T; ∆H = ± 3.9·104 J
c) + 3.9·104 J for hotter block, - 3.9·104 J for cooler block
d) ∆S = mC v,s ln Tf  , ∆S tot = ∆S hot + ∆S cool ; ∆S tot = 24 J K −1
 Ti 
____________________________________________________________
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Solution:

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Question 7

Consider a system consisting of 2.0 mol CO2 (g), initially at 25 °C and 10 atm and confined to
a cylinder of cross-section 10.0 cm2. It is allowed to expand adiabatically against an external
pressure of 1.0 atm until the piston has moved outwards through 20 cm. Assume that carbon
dioxide may be considered a perfect gas with constant-volume molar heat capacity (Cv,m) =
28.8 J K–1 mol–1. Calculate:

a) Heat (q) (in unit J)


b) Work (w) (in unit J)
c) Change of internal energy (ΔU) (in unit J)
d) Change of temperature (ΔT) and the final temperature (Tf) (in unit K)
e) Initial volume (Vi) and final volume (Vf) (in unit dm3)
f) Change of entropy for the system (ΔSsys) (hint: constant volume cooling followed by
isothermal expansion)

Hints and answers


a) q = 0
b) w = −Pex∆V ; w = −20 J
c) ∆U = q + w; ∆U = 0 - 20 = -20 J
d) ∆U = nCV,m∆T; Tf = 297.803 K
nRT
e) Vi = ; Vf = 5.093 dm
3
Pi
T  V
f) ∆S = nC V,m ln f  , ∆S = nR ln f ; ∆Ssys = 0.60 J ⋅ K −1
 Ti  Vi
____________________________________________________________
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Solution:

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Question 8

The enthalpy of vaporization (∆Hvap) of chloroform (CHCl3) is 29.4 kJ mol–1 at its normal
boiling point (Tb) of 334.88 K. Calculate

a) The entropy of vaporization (∆Svap) (in unit J K-1 mol-1) of chloroform at this temperature
and
b) The entropy change of the surroundings (∆Ssurr). Please state the assumption made for b).

Hints and answers


∆H vap
a) ∆S vap = ; ∆S vap = 87.8 J K -1 mol-1
Tb
b) ∆Stot = ∆Ssurr + ∆Ssys; Ssurr = -87.8 J K-1 mol-1
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Solution:

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Question 9

Calculate the standard Gibbs energy (∆Gθrxn) (in unit kJ mol-1) of the following reaction at
298 K by referring to the standard entropies (∆Sθ) and enthalpies of formation (∆Hθf) given in
the Table 1. Is this reaction a spontaneous process?

4 HCl (g) + O2 (g) → 2 Cl2 (g) + 2 H2O (l)

Hints:
i) Standard entropies of reaction (∆Sθrxn) is the difference between the molar entropies of
the pure, separated products and the pure, separated reactants, all substances being in
their standard states at 298 K.

ii) Standard enthalpies of formation (∆Hθf) is the standard reaction enthalpy for the
formation of the compound from its elements in their reference state.

iii) ∆H θ rxn = ∑ n∆H


product
θ
f − ∑ n∆H
reactan
θ
f , n = stoichiometric coefficient

iv) ∆S θ rxn = ∑ nS
product
θ
− ∑ nS
reactan
θ
, n = stoichiometric coefficient

Table 1 Standard enthalpy of formation (∆Hθf) and standard entropy∆( Sθ) at 298 K for
related compounds
Compound ∆Hθf (kJ mol-1) ∆Sθ (J K-1 mol-1)
H2O (g) 241.82 188.83
H2O (l) -285.83 69.91
H2O (s) 37.99
Cl (g) 121.68 165.20
Cl2 (g) 0 223.07
O (g) 249.17 161.06
O2 (g) 0 205.138
HCl (g) -92.31 186.91
HCl (aq) -167.16 56.5

Hints and answers


∆H θ rxn = ∑ n∆H θ f − ∑ n∆H θ
f , ∆S θ rxn = ∑ nS θ
− ∑ nS θ
,
product reactan product reactan

∆G θ rxn = ∆H θ rxn − T∆S θ rxn ; ∆G θ rxn = −93.05 kJ mol-1


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