10/6/2010

Suggested Problems
● 3.1a
Calculate the change in entropy when 25 kJ of energy is
transferred reversibly and isothermally as heat to a large
block of iron at (a) 0°C, (b) 100°C.
● 3.2a
Calculate the molar entropy of a constant-volume sample
of neon at 500 K given that it is 146.22 J K−1 mol−1 at 298
Entropy TUT K.
● 3.3a
Chemistry 251: Calculate ∆S (for the system) when the state of 3.00 mol of
Phys Chem. for Chem. Eng. perfect gas atoms, for which 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 ∆S?
● 3.5a
Calculate ∆H and ∆Stot when two copper blocks, each of
mass 10.0 kg, one at 100°C and the other at 0°C, are
placed in contact in an isolated container. The specific heat
capacity of copper is 0.385 J K−1 g−1 and may be assumed
constant over the temperature range involved.

We can calculate the entropy change going from 298 K to 500 K using the Cv,m & entropy relationship; the
reason we can use this expression is because the question specifies it is a constant volume process:
(a) Simple application of the definition for entropy (dispersal of energy, as heat, at a particular
temperature): dqrev CV,m dT Tƒ
∆S = ƒ = ƒ = CV,mln
T T Ti
dq rev q
∆S = ƒ = 500
T T ∆S = (20.786J K—1mol—1 —8.3145 J K—1mol—1)ln
298
20.786 J K‐1 mol‐1 is CP, m for neon (data table in back of the book), and recall CP,m – CV,m = R
25 000 J ∆S = 6.454183483J K—1mol—1
∆S = = 91.5750 …
273 K
However the question asks what is the molar entropy of Neon at 500k, since we are given the entropy at
Answer = 91.6 JK‐1
298 K:
(b) Similar to (a) (i) we know by definition molar entropy of a substance is from 0K to a particular temperature
(ii) we know entropy is a state function so doesn’t matter about the path taken
25 000 J
∆S = = = 67.024128 … (iii) So the entropy change we calculated going from298K to 500K, we can simply add to the
373 K entropy given at 298 K, to get the molar entropy of neon at 500 K
Answer = 67.0 JK‐1 Thus,
∆S = 6.454183483J K—1mol—1 + 146.22

Answer = 152.67 J K—1mol—1

3.1(a) Calculate the change in entropy when 25 kJ of 3.2(a) Calculate the molar entropy of a constant-volume
energy is transferred reversibly and isothermally as sample of neon at 500 K given that it is 146.22 J K−1 mol−1 at
heat to a large block of iron at (a) 0°C, (b) 100°C 298 K.

3.3(a) Calculate ∆S (for the system) when the state of 3.00 mol of 3.5(a) Calculate ∆H and ∆Stot when two copper blocks, each of mass 10.0 kg, one at
perfect gas atoms, for which Cp,m = 5/2R,is changed from 25°C and 100°C and the other at 0°C, are placed in contact in an isolated container. The specific
1.00 atm to 125°C and 5.00 atm. How do you rationalize the sign of heat capacity of copper is 0.385 J K −1 g −1 and may be assumed constant over the
∆S? temperature range involved.
Since the heat capacity doesn’t change over the temperature range, and the blocks are in an isolated
Recall S, is a state function, & because it is path independent, we can separate the whole process into system then the final temperature is an average of the two initial temperatures:
separate steps. One of the steps (i) is heating the gas from 25°C to 125°C at 1 atm (i.e. constant pressure
Tf = (100 + 0)/2 = 50 C
process, thus qrev = nCp,mT)
The enthalpy will be given by (since we dealing with a solid (so Cv,m = Cp,m), and it’s an isolated constant
dq rev CP,m dT Tƒ pressure system):
∆S i = ƒ = ƒ = C P,m
ln
T T Ti
∆H = mC∆T
398.15
∆S i= 3.00(20.78618038) ln = 18.036092 J K—1 ∆H = 10000 g × 0.385 J K—1g—150 K = 192500 J
298.15
(isolated system) Since one block cools and the other heats up, then the enthalpy lost by one block is
The next step (Sn) is the entropy change, when the pressure of the gas changes from 1.00 atm to 5.00 gained by the other thus the total enthalpy change = 0
atm at 125°C (U = 0; thus qrev = ‐w).
Entropy Change for each block is given by:
dq rev rev q
∆Sn = ƒ = Tƒ
T T ∆S = mC ln
Ti
Vƒ Pi
qrev = —w= ƒ pdV = nRT ln = nRT ln Block initially at 100C
Vi Pƒ
323.15
∆S = 10000 g 0.385 ln = —553.8759067
i iP Vƒ Pƒ V 373.15
recall ƒo r an ideal gas =
Ti Tƒ
Block initially at 0C
Pi 1.00
∆S n= nR ln = 3.0 mol × / R ln5 =2 —40.1448801 ∆S = 10000 g 0.385 ln
323.15
= 647.1677399
Pƒ 5.00 373.15

Thus overall entropy change Stot = 18.036092 + ‐40.1448801 = − 22.1 J K‐1 Thus S = ‐553.8759067 + 647.1677399 = 93.29 J K‐1

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● 3.7a (a)
The enthalpy of vaporization of chloroform ∆
Vap H 29400 J mol—1
(CHCl3) is 29.4 kJ mol−1 at its normal boiling ∆vap S = = = 87.79264214
point of 334.88 K. Calculate (a) the entropy T 334.88 K
of vaporization of chloroform at this Answer = 87.792 J K‐1
temperature and (b) the entropy change of
the surroundings. (b) Ssyt + Ssur = 0; thus Ssur = – 87.792 J K‐1
● 3.14a
Calculate the maximum non-expansion work
per mole that may be obtained from a fuel
cell in which the chemical reaction is the
combustion of methane at 298 K.
3.7(a) The enthalpy of vaporization of chloroform (CHCl3) is 29.4 kJ
mol−1 at its normal boiling point of 334.88 K. Calculate (a) the
entropy of vaporization of chloroform at this temperature and (b) the

More Problems… entropy change of the surroundings .

To answer this question you do not really need to know how a fuel cell works. But you do need to know the
balanced equation for the combustion of methane:

CH4(g) + 202(g) ‹ C02(g) + 2H20(l)

To find the max non – expansion work we use the Gibbs expression. In addition, this is occurring at
atmospheric pressure (it is ‘open’ to atmosphere), and at a ~ constant temperature i.e. it’s a constant
pressure‐temperature process, thus use Gibbs (dGP,T ≤ 0):

∆r G = Σ v ∆ ƒG8 — Σ v ∆ ƒ G8
products reactants

∆ r G = (—394.36 + (—237.13x2)) — (—50.72 + 0) = —817.9kJ mol—1

Note: Still need the balanced chemical equation to get the right answer!!!

3.14 (a) Calculate the maximum non-expansion work per

mole that may be obtained from a fuel cell in which the
chemical reaction is the combustion of methane at 298 K.