WEEK 4

PHYSICAL CHEMISTRY
 D. Second Law of Thermodynamics

• One statement formulated by Kelvin:

No process is possible in which the
sole result is the absorption of heat
from a reservoir and its complete
conversion into work.
D. Second Law of Thermodynamics
1. The dispersal of energy
• We can begin to understand the role of the
distribution of energy by thinking about a ball
(the system) bouncing on a floor (the
surroundings). The ball does not rise as high
after each bounce because there are inelastic
losses in the materials of the ball and floor. The
kinetic energy of the ball’s overall motion is
spread out into the energy of thermal motion
of its particles and those of the floor that it
hits. The direction of spontaneous change is
towards a state in which the ball is at rest with
all its energy dispersed into random thermal
motion of molecules in the air and of the
atoms of the virtually infinite floor.
D. Second Law of Thermodynamics
1. The dispersal of energy
• We appear to have found the signpost of
spontaneous change: we look for the direction
of change that leads to dispersal of the total
energy of the isolated system. This principle
accounts for the direction of change of the
bouncing ball, because its energy is spread out as
thermal motion of the atoms of the floor. The
reverse process is not spontaneous because it is
highly improbable that energy will become
localized, leading to uniform motion of the ball’s
atoms.
 2. Entropy
• The Second Law of thermodynamics is used to identify the signpost of spontaneous
change. It can also be expressed in terms of entropy (S) which is a state function
• Entropy (S) - is a measure of the energy dispersed in a process.
• The First Law uses the internal energy to identify permissible changes; the Second Law
uses the entropy to identify the spontaneous changes among those permissible changes.
• The Second Law of thermodynamics can be expressed in terms of the entropy where Stot
is the total entropy of the system and its surroundings:
The entropy of an isolated system increases in the course of a spontaneous change:
ΔStot > 0
2. Entropy
a. The thermodynamic definition of entropy
• The thermodynamic definition of entropy concentrates on the change in entropy (dS) that occurs as
a result of a physical or chemical change (in general, as a result of a ‘process’). The definition is
motivated by the idea that a change in the extent to which energy is dispersed depends on how much
energy is transferred as heat.
• The thermodynamic definition of entropy is based on the expression

𝒅𝒒𝒓𝒆𝒗
dS =
𝑻

• For a measurable change between two states initial (i) and final (f) this expression integrates to the
equation below. That is, to calculate the difference in entropy between any two states of a system, we
find a reversible path between them, and integrate the energy supplied as heat at each stage of the
path divided by the temperature at which heating occurs.

𝒇
𝒅𝒒𝒓𝒆𝒗
∆𝑺 = න
𝒊 𝑻
2. Entropy Given: Step 1:
a. The thermodynamic definition of entropy ∆𝑺 = Change in Entropy ∆𝑼 = q + w
𝒏 = Number of molecules ∆𝑼 = 0
R = Gas constant 0=q+w
𝐓 = Temperature -w = q
qrev = heat reversible qrev = -wrev
dqrev = delta or differential of
heat reversible Step 2:
Vi = Initial Volume 𝑓
𝑑𝑞𝑟𝑒𝑣
Vf = Final Volume ∆𝑆 = න
∆𝑼 = Change in Internal Energy 𝑖 𝑇
1 𝑓 𝑞𝑟𝑒𝑣
q = heat ∆𝑆 = ‫𝑣𝑒𝑟𝑞𝑑 ׬‬ =
𝑇 𝑖 𝑇
w = work
Step 3:
Formula: qrev = -wrev
∆𝑼 = q + w 𝑉
w = -nRT ln 𝑉𝑓
𝑓
𝑑𝑞𝑟𝑒𝑣 𝑖
𝑉
∆𝑆 = න qrev = - −nRT ln 𝑉𝑓
𝑖 𝑇 𝑖
𝑉
w=
𝑉 𝑑𝑉
-nRT‫𝑉 𝑓 𝑉׬‬ = -nRT
𝑉
ln 𝑉𝑓 qrev = nRT ln 𝑉𝑓
𝑖
𝑖 𝑖
2. Entropy
Step 4:
a. The thermodynamic definition of entropy 𝑞
∆𝑆 = 𝑇𝑟𝑒𝑣
𝑉
qrev = nRT ln 𝑉𝑓
𝑖

nRT ln𝑉𝑉 𝑓

∆𝑆 = 𝑖
𝑇
𝑽𝒇
∆𝑺 = nR ln
𝑽𝒊

Step 5:
𝑉
∆𝑆 = nR ln 𝑉𝑓
𝑖
𝑉𝑓
=2
𝑉𝑖
𝐽
∆𝑆 = (1 mol) x 8.31447 x ln2
𝐾mol
𝑱
∆𝑺 = 5.76 𝑲
2. Entropy Formula: Step 3:
a. The thermodynamic definition of entropy ∆𝑼 = q + w qrev = -wrev
𝑓 𝑃
𝑑𝑞𝑟𝑒𝑣 w = -nRT ln 𝑃𝑓
∆𝑆 = න 𝑖
𝑇 𝑃
𝑖
𝑃 𝑑𝑃 𝑃
qrev = - −nRT ln 𝑃𝑓
w = -nRT‫𝑓 𝑃׬‬ = -nRT ln 𝑃𝑓 𝑃
𝑖
𝑖 𝑃 𝑖 qrev = nRT ln 𝑃𝑓
𝑖

Step 1:
Given: ∆𝑼 = q + w Step 4:
𝑞
∆𝑺 = Change in Entropy ∆𝑼 = 0 ∆𝑆 = 𝑇𝑟𝑒𝑣
𝒏 = Number of molecules 0=q+w 𝑃
qrev = nRT ln 𝑃𝑓
R = Gas constant -w = q 𝑖

𝐓 = Temperature qrev = -wrev

qrev = heat reversible nRT ln𝑃𝑃 𝑓

dqrev = delta or differential of heat reversible ∆𝑆 = 𝑖

Step 2: 𝑇
Pi = Initial Pressure 𝑷𝒇
Pf = Final Pressure ∆𝑆 = න
𝑓
𝑑𝑞𝑟𝑒𝑣 ∆𝑺 = nR ln
𝑷𝒊
𝑇
∆𝑼 = Change in Internal Energy 𝑖
1 𝑓 𝑞𝑟𝑒𝑣
q = heat ∆𝑆 = 𝑇 ‫= 𝑣𝑒𝑟𝑞𝑑 𝑖׬‬ 𝑇
w = work
2. Entropy
a. The thermodynamic definition of entropy
𝑑𝑞
• We can use the definition in the equation dS = 𝑇𝑟𝑒𝑣 to formulate an expression for the change in entropy
of the surroundings (ΔSsur). Consider an infinitesimal transfer of heat (dqsur) to the surroundings. The
surroundings consist of a reservoir of constant volume, so the energy supplied to them by heating can be
identified with the change in their internal energy (dUsur). Alternatively, the surroundings can be regarded as
being at constant pressure, in which case we could equate dqsur to dHsur.

dq dq
dSsur = Tsur, rev = T sur
sur sur
• Furthermore, because the temperature of the surroundings is constant whatever the change, for a
measurable change.
dqsur
∆𝑺𝒔𝒖𝒓 =
Tsur
• The prior equations makes it very simple to calculate the changes in entropy of the surroundings that
accompany any process. For instance, for any adiabatic change, qsur = 0, so

For an adiabatic change: ΔSsur = 0

2. Entropy
a. The thermodynamic definition of entropy Given:
∆𝑺𝒔𝒖𝒓 = Change in Entropy
dqsur = delta or differential of
heat reversible
Tsur = Temperature Step 2:
dqsur
∆𝑆𝑠𝑢𝑟 =
Tsur
Formula:
dqsur 2.86 x 105 J
∆𝑆𝑠𝑢𝑟 = ∆𝑆𝑠𝑢𝑟 =
Tsur 298 K
𝑱
∆𝑺𝒔𝒖𝒓 = 959.73 or 960 𝑲
Step 1:
qsur = 286 kJ
1𝐽
qsur = 286 kJ x 0.001kJ
qsur = 286,000 or 2.86 x 105 J
2. Entropy Step 1:
a. The thermodynamic definition of entropy 2NO2(g) → N2O4(g)
∆𝐻∅ = ∆𝐻∅𝑓 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∆𝐻∅𝑓 (𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)
∅
𝑘𝐽 𝑘𝐽
∆𝐻 = (1𝑚𝑜𝑙 𝑥 9.16 ) − (2𝑚𝑜𝑙 𝑥 33.18 )
𝑚𝑜𝑙 𝑚𝑜𝑙
∆𝐻∅ = 9.16 𝑘𝐽 − 66.36 𝑘𝐽
∆𝐻∅ = −57.2 𝑘𝐽 Step 3:
dqsur
∆𝑆𝑠𝑢𝑟 =
Given: Step 2: Tsur
∆𝑺𝒔𝒖𝒓 = Change in Entropy dqsur = dHsur
dqsur = delta or differential of heat reversible qsur = −57.2 𝑘𝐽 −5.72 x 104 J
∆𝑆𝑠𝑢𝑟 =
Tsur = Temperature 1𝐽
qsur = −57.2kJ x 0.001kJ 298 K

Formula: qsur = -57,200 or -5.72 x 104 J ∆𝑺𝒔𝒖𝒓 = -191.94 or -192 𝑲

𝑱

dqsur
∆𝑆𝑠𝑢𝑟 =
Tsur

∆𝐻∅ = ∆𝐻∅𝑓 𝑃𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∆𝐻∅𝑓 (𝑅𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

2. Entropy
b. The entropy as state function

• Entropy is a state function. To prove this assertion, we need to

show that the integral of dS is independent of path. To do so,
it is sufficient to prove that the integral of the equation dS =
𝑑𝑞𝑟𝑒𝑣
𝑇
around an arbitrary cycle is zero, for that guarantees that
the entropy is the same at the initial and final states of the
system regardless of the path taken between them (Fig. 3.5).
That is, we need to show that
dq
‫ ׯ‬Trev = 0
• where the symbol (‫ )ׯ‬denotes integration around a closed
path.
• There are three steps in the argument:
1. First, to show that the equation above is true for a special
cycle (a ‘Carnot cycle’) involving a perfect gas.
2. Then to show that the result is true whatever the working
substance.
3. Finally, to show that the result is true for any cycle.
2. Entropy
b. The entropy as state function
• A Carnot cycle, which is named after the French engineer Sadi
Carnot, consists of four reversible stages (Fig. 3.6):
1. Reversible isothermal expansion from A to B at Th; the entropy
change is qh/Th, where qh is the energy supplied to the system as
heat from the hot source.
2. Reversible adiabatic expansion from B to C. No energy leaves the
system as heat, so the change in entropy is zero. In the course of
this expansion, the temperature falls from Th to Tc, the temperature
of the cold sink.
3. Reversible isothermal compression from C to D at Tc. Energy is
released as heat to the cold sink; the change in entropy of the
system is qc /Tc; in this expression qc is negative.
4. Reversible adiabatic compression from D to A. No energy enters
the system as heat, so the change in entropy is zero. The
temperature rises from Tc to Th.
2. Entropy
b. The entropy as state function
• The total change in entropy around the cycle is

qh qc
‫= 𝑺𝒅 ׯ‬ +
𝑻𝒉 𝑻𝒄

• However, we show in Justification 3.1 that, for a

perfect gas:

qh qc
=-
𝑻𝒉 𝑻𝒄
 Given: Step 2:
2. Entropy h = hot source ViTic = VfTfc
b. The entropy as state function c = cold sink
qh qc
= - VAThc = VDTcc
𝑻 𝒉
𝑻𝒄
Formula:
qh qc VCTcc = VBThc
= -𝑇
𝑇ℎ 𝑐

𝑉 VAVCThcTcc = VDVBThc Tcc

qrev = nRT ln 𝑉𝑓
𝑖
VAVCThcTcc = VDVBThc Tcc
ViTic = VfTfc
where c = CV,m/R ThcTcc
Step 1: VAVC = VDVB
𝑉
qrev = nRT ln 𝑉𝑓
𝑖
VAVC VDVB
𝑽 VBVC = VBVC
qh = nRTh ln𝑽𝑩
𝑨

𝑽 VA VD
qc = nRT ln𝑽𝑫
𝑪 VB = VC
2. Entropy Step 3: Step 4:
b. The entropy as state function VA VD 𝑞ℎ
= −
𝑇ℎ
x qcTc
qh qc VB = VC 𝑞 𝑇
= - 𝑐 𝑐
𝑻 𝒉
𝑻𝒄

qh = nRTh ln𝑉𝐵
𝑉 𝑞ℎqcTc 𝑇ℎqcTc
= −
𝐴
𝑞𝑐 𝑇𝑐
𝑉
qc = nRTc ln𝑉𝐷
𝐶
𝑞ℎTc = - 𝑇ℎqc
𝑉 𝑉 𝑉
qc = nRTc ln𝑉𝐷 = nRTc ln𝑉𝐴 =- nRTc ln𝑉𝐵
𝐶 𝐵 𝐴
𝑞ℎTc 𝑇ℎqc
= −
𝑞ℎ nRTh ln𝑉𝑉 𝑇ℎ𝐵 ThTc 𝑇ℎTc
= 𝐴 = −
- nRTc ln𝑉𝑉
𝑞𝑐 𝑇𝑐𝐵
qh qc
=-
𝐴

𝑞ℎ
=
𝑇
− 𝑇ℎ 𝑻𝒉 𝑻𝒄
𝑞𝑐 𝑐
2. Entropy
b. The entropy as state function
• We begin this step of the argument by introducing the efficiency, ε (epsilon),
of a heat engine:

𝒘𝒐𝒓𝒌 𝒑𝒆𝒓𝒇𝒐𝒓𝒎𝒆𝒅 𝒘
𝜺= =
𝒉𝒆𝒂𝒕 𝒂𝒃𝒔𝒐𝒓𝒃𝒆𝒅 𝒒𝒉

• The definition implies that, the greater the work output for a given supply of
heat from the hot reservoir, the greater is the efficiency of the engine. We can
express the definition in terms of the heat transactions alone, because (as
shown in Fig. 3.7) the energy supplied as work by the engine is the difference
between the energy supplied as heat by the hot reservoir and returned to the
cold reservoir:
𝒒 +𝒒 𝒒
𝜺= 𝒉 𝒄=1+ 𝒄
𝒒𝒉 𝒒𝒉
q q
• (Remember that qc < 0.) It then follows from the equation h = - c that
𝑇ℎ 𝑇𝑐

Tc
𝜺𝒓𝒆𝒗 = 𝟏 −
Th

• The Second Law of thermodynamics implies that all reversible engines

have the same efficiency regardless of their construction.
2. Entropy
b. The entropy as state function

• Suppose engine A is more efficient than engine B and that we

choose a setting of the controls that causes engine B to acquire
energy as heat qc from the cold reservoir and to release a certain
quantity of energy as heat into the hot reservoir. However,
because engine A is more efficient than engine B, not all the
work that A produces is needed for this process, and the
difference can be used to do work. The net result is that the cold
reservoir is unchanged, work has been done, and the hot
reservoir has lost a certain amount of energy. This outcome is
contrary to the Kelvin statement of the Second Law, because
some heat has been converted directly into work. In molecular
terms, the random thermal motion of the hot reservoir has been
converted into ordered motion characteristic of work. Because
the conclusion is contrary to experience, the initial assumption
that engines A and B can have different efficiencies must be
false.
2. Entropy
b. The entropy as state function

• Any reversible cycle can be approximated as a collection of

Carnot cycles and the cyclic integral around an arbitrary path
is the sum of the integrals around each of the Carnot cycles
(Fig. 3.9). This approximation becomes exact as the individual
cycles are allowed to become infinitesimal. The entropy
change around each individual cycle is zero (as demonstrated
above), so the sum of entropy changes for all the cycles is
zero. However, in the sum, the entropy change along any
individual path is cancelled by the entropy change along the
path it shares with the neighboring cycle. Therefore, all the
entropy changes cancel except for those along the perimeter
of the overall cycle.

qrev qrev
෍ = ෍ =𝟎
𝑻 𝑻
𝑨𝒍𝒍 𝒑𝒆𝒓𝒊𝒎𝒆𝒕𝒆𝒓
2. Entropy
c. The thermodynamic temperature

• Suppose we have an engine that is working reversibly between a hot Trace:

Tc
source at a temperature Th and a cold sink at a temperature T; then 𝜀𝑟𝑒𝑣 = 1 −
Tc Th
we know from the equation 𝜀𝑟𝑒𝑣 = 1 − that
Th Tc
Th = 1 - 𝜀𝑟𝑒𝑣
T = (1 − ε)Th

• This expression enabled Kelvin to define the thermodynamic T

Th x T c = 1 - 𝜀𝑟𝑒𝑣 x Th
temperature scale in terms of the efficiency of a heat engine. The h
zero of the scale occurs for a Carnot efficiency of 1. The size of the
unit is entirely arbitrary, but on the Kelvin scale is defined by setting T = (1 − ε)Th
the temperature of the triple point of water as 273.16 K exactly.
Then, if the heat engine has a hot source at the triple point of water,
the temperature of the cold sink (the object we want to measure) is
found by measuring the efficiency of the engine. This result is
independent of the working substance.
3. Impact on engineering: Refrigeration

• When an energy |qc| is removed from a cool source at a

temperature Tc and then deposited in a warmer sink at a
temperature Th, as in a typical refrigerator, the change in
entropy is
qc qc
∆𝑺 = − + <𝟎
Tc Th
• The process is not spontaneous because not enough entropy is
generated in the warm sink to overcome the entropy loss from
the hot source. To generate more entropy, energy must be
added to the stream that enters the warm sink. Our task is to
find the minimum energy that needs to be supplied. The
outcome is expressed as the coefficient of performance (c):

𝒆𝒏𝒆𝒓𝒈𝒚 𝒕𝒓𝒂𝒏𝒔𝒇𝒆𝒓𝒓𝒆𝒅 𝒂𝒔 𝒉𝒆𝒂𝒕 qc

c = 𝒆𝒏𝒆𝒓𝒈𝒚 𝒕𝒓𝒂𝒏𝒔𝒇𝒆𝒓𝒓𝒆𝒅 𝒂𝒔 𝒘𝒐𝒓𝒌 = 𝒘
3. Impact on engineering: Refrigeration

• Because |qc| is removed from the cold source, and the

work |w| is added to the energy stream, the energy
deposited as heat in the hot sink is |qh| = |qc| + |w|.
Therefore,

𝟏 qh − q𝒄 qh
= =- -1
𝒄 qc qc

qcqh
• We can now use the equation = - to express this
𝑇ℎ 𝑇𝑐
result in terms of the temperatures alone, which is
possible if the transfer is performed reversibly. This
substitution leads to

𝑻𝒄
c=
𝑻𝒉 − 𝑻𝒄
3. Impact on engineering: Refrigeration

• The work to maintain a low temperature is also relevant to the

design of refrigerators. No thermal insulation is perfect, so
there is always a flow of energy as heat into the sample at a rate
proportional to the temperature difference. If the rate at which
energy leaks in is written A(Th − Tc), where A is a constant that
depends on the size of the sample and the details of the
insulation, then the minimum power (P) required to maintain
the original temperature difference by pumping out that energy
by heating the surroundings.

1
P = 𝑐 x A(Th − Tc)

Th − Tc
P= x A(Th − Tc)
Tc

𝟐
𝐓𝐡 − 𝐓𝐜
P=Ax 𝐓𝐜
4. Entropy changes accompanying specific processes
a. Expansion
• The value of ΔS of the system is independent of the path between the initial and
final states, so this expression applies whether the change of state occurs reversibly or
irreversibly because S is a state function. The logarithmic dependence of entropy on
volume is illustrated in Fig. 3.12. The total change in entropy, however, does depend
on how the expansion takes place. For any process dqsur = −dq, and for a reversible
𝑉
change we use the expression ∆𝑆 = nR ln 𝑓; consequently, from this equation
𝑉𝑖
dq
∆𝑆𝑠𝑢𝑟 = sur
Tsur

dqsur dq 𝑽
∆𝑺𝒔𝒖𝒓 = = - rev = -nR ln 𝒇
T T 𝑽𝒊

• This change is the negative of the change in the system, so we can conclude that ΔStot
= 0, which is what we should expect for a reversible process. If the isothermal
expansion occurs freely (w = 0) and irreversibly, then q = 0 (because ΔU = 0).
Consequently, ΔSsur = 0, and the total entropy change is given by the equation ∆𝑆 =
𝑉
nR ln 𝑓 itself:
𝑉𝑖

𝑽𝒇
∆𝑺𝒕𝒐𝒕 = nR ln
𝑽𝒊
4. Entropy changes accompanying specific processes
b. Phase transition

• Consider a system and its surroundings at the normal transition temperature, Ttrs, the temperature at which two
phases are in equilibrium at 1 atm. This temperature is 0°C (273 K) for ice in equilibrium with liquid water at 1
atm, and 100°C (373 K) for water in equilibrium with its vapor at 1 atm. At the transition temperature, any
transfer of energy as heat between the system and its surroundings is reversible because the two phases in the
system are in equilibrium. Because at constant pressure q = ΔtrsH, the change in molar entropy of the system is

Δ H
ΔtrsS = Ttrs
trs

• If the phase transition is exothermic (ΔtrsH< 0, as in freezing or condensing), then the entropy change is
negative. This decrease in entropy is consistent with localization of matter and energy that accompanies the
formation of a solid from a liquid or a liquid from a gas. If the transition is endothermic (ΔtrsH> 0, as in
melting and vaporization), then the entropy change is positive, which is consistent with dispersal of energy
and matter in the system.
• An interesting feature of the data, given in table 3.2, is that a wide range of liquids give approximately the same
standard entropy of vaporization (about 85 J K−1 mol−1): this empirical observation is called Trouton’s rule.
4. Entropy changes accompanying specific processes
b. Phase transition Given:
ΔvapS∅ = Standard Entropy of Vaporization
ΔvapH∅ = Standard Enthalpy of Vaporization
Tb = Boiling Temperature
Step 2:
Formula:
ΔvapH∅
Δ H ∅
ΔvapS ∅ = T
ΔvapS ∅ = vap b
Tb
o
K = C + 273.15 ΔvapH∅ = Tb x ΔvapS ∅
𝐽
Step 1: ΔvapH∅ = 332.4 K x 85 𝐾 𝑚𝑜𝑙
K = Co + 273.15
K = 59.2 Co + 273.15 ΔvapH∅ = 28,254 𝑱 or 2.8 x 103 𝑱
𝒎𝒐𝒍 𝒎𝒐𝒍
K = 332.35 or 332.4
𝐽 0.001𝑘𝐽
ΔvapH∅ = 28,254 x
𝑚𝑜𝑙 1𝐽
𝒌𝑱
ΔvapH∅ = 28.254 or 28 𝒎𝒐𝒍
4. Entropy changes accompanying specific processes
b. Phase transition Given:
ΔvapS∅ = Standard Entropy of Vaporization
ΔvapH∅ = Standard Enthalpy of Vaporization
Tb = Boiling Temperature
Step 2:
Formula:
ΔvapH∅
Δ H ∅
ΔvapS ∅ = T
ΔvapS ∅ = vap b
Tb
o
K = C + 273.15 ΔvapH∅ = Tb x ΔvapS ∅
𝐽
Step 1: ΔvapH∅ = 184.55 K x 85 𝐾 𝑚𝑜𝑙
K = Co + 273.15
K = -88.6 Co + 273.15 ΔvapH∅ = 15,686.75 𝐽 or
𝑚𝑜𝑙
K = 184.55 3 𝐽
15 x 10 𝑚𝑜𝑙

𝐽 0.001𝑘𝐽
ΔvapH∅ = 15,686.75 𝑚𝑜𝑙 x 1𝐽
𝒌𝑱
ΔvapH∅ = 15.68675 or 16 𝒎𝒐𝒍
4. Entropy changes accompanying specific processes
c. Heating
𝑓 𝑑𝑞
• We can use the equation ∆𝑆 = ‫ 𝑣𝑒𝑟𝑇 𝑖׬‬to calculate the entropy of a system at a temperature Tf from a
knowledge of its entropy at a temperature Ti and the heat supplied to change its temperature from one value
to the other:

T𝒇 𝐝𝐪
𝐫𝐞𝐯
𝑺 Tf = 𝑺(Ti) න
Ti𝐓
• We shall be particularly interested in the entropy change when the system is subjected to constant pressure
(such as from the atmosphere) during the heating. Then, from the definition of constant-pressure heat
𝜕𝐻
capacity [Cp = 𝜕𝑇 p ], dqrev = CpdT provided the system is doing no non-expansion work. Consequently, at
constant pressure:

T𝒇 C dT
p
𝑺 Tf = 𝑺(Ti) න
Ti 𝐓
4. Entropy changes accompanying specific processes
c. Heating
• The same expression applies at constant volume, but with Cp
replaced by CV. When Cp is independent of temperature in the
temperature range of interest, it can be taken outside the
integral and we obtain the equation below. With a similar
expression for heating at constant volume. The logarithmic
dependence of entropy on temperature is illustrated in Fig.
3.13.

T dT T
𝑺 Tf = 𝑺 Ti + Cp ‫׬‬T 𝒇 = 𝑺 Ti + Cp 𝒍𝒏 T𝒇
i 𝐓 i
4. Entropy changes accompanying specific processes
c. Heating Given:
ΔS = Change of Entropy
Ti = Temperature Initial
Tf = Temperature Final
Vi = Volume Initial
Vf = Volume Final
Cp = Heat Capacity at constant pressure
CV = Heat Capacity at constant volume
n = amount of molecules
R = gas constant Step 1:
𝑝𝑉
p = pressure n= 𝑖 𝑖
𝑅𝑇𝑖
𝑉𝑓
Formula: ∆𝑆 = nR ln
𝑉𝑖
𝑉 𝑝𝑖𝑉𝑖 𝑉𝑓
∆𝑆 = nR ln 𝑉𝑓 ∆𝑆 = x R ln
𝑖 𝑅𝑇𝑖 𝑉𝑖
T𝑓
𝑆 Tf = 𝑆 Ti + Cp 𝑙𝑛
Ti 𝒑𝒊𝑽𝒊 𝑽𝒇
∆𝑺 = ln
𝑻𝒊 𝑽𝒊
4. Entropy changes accompanying specific processes
c. Heating
Given: Step 2:
T𝑓
ΔS = Change of Entropy 𝑆 Tf = 𝑆 Ti + Cp 𝑙𝑛
Ti
Ti = Temperature Initial T
𝑆 Tf - 𝑆 Ti = CV 𝑙𝑛 𝑓
Tf = Temperature Final Ti
T
Vi = Volume Initial ∆𝑆 = C𝑉 𝑙𝑛 T𝑓
i
Vf = Volume Final Cp,m - CV,m = R
Cp = Heat Capacity at constant pressure CV,m = R
CV = Heat Capacity at constant volume
n = amount of molecules 3 T𝑓
∆𝑆 = 𝑛 R 𝑙𝑛
R = gas constant 2 Ti
𝑝𝑉 3 T
p = pressure ∆𝑆 = 𝑖 𝑖 x R ln 𝑓
𝑅𝑇𝑖 2 Ti
𝟑
Formula: 𝒑𝒊𝑽𝒊 T
∆𝑺 = ln 𝒇 𝟐
𝑉
∆𝑆 = nR ln 𝑓 𝑻𝒊 Ti
𝑉𝑖
T
𝑆 Tf = 𝑆 Ti + Cp 𝑙𝑛 T𝑓
i
 Step 4:
4. Entropy changes accompanying specific processes Ti = 25oC
c. Heating K = oC + 273.15
Step 3: K = 25oC + 273.15
𝑝𝑉 𝑉
∆𝑆 = 𝑖 𝑖 ln 𝑓 K = 298 or 298.15
𝑇𝑖 𝑉𝑖
Tf = 100oC
3
𝑝𝑖𝑉𝑖 T K = oC + 273.15
∆𝑆 = ln 𝑓 2
K = 100oC + 273.15
𝑇𝑖 Ti
K = 373 or 373.15
3
𝑝𝑖𝑉𝑖 𝑉 𝑝𝑖𝑉𝑖 T 1 Pa m3 = 1 J
∆𝑆 = ln 𝑓 + ln 𝑓 2
𝑇𝑖 𝑉𝑖 𝑇𝑖 Ti p = 1 bar
100,000 𝑃𝑎
𝟑 p = 1 bar x 1 ba𝑟
𝒑𝒊𝑽𝒊 𝑽𝒇 T𝒇 p = 100,000 Pa or 1.00 x 105 Pa
∆𝑺 = ln 𝟐
𝑻𝒊 𝑽𝒊 Ti
Vi = 0.500 dm3
1 m3
Vi = 0.500dm3 x 0.001 dm3
Vi = 500 or 0.500 x 10-3 m3
Vf = 1.000 dm3
4. Entropy changes accompanying specific processes
c. Heating Step 5:
3
𝑝𝑖𝑉𝑖 𝑉𝑓 T𝑓
∆𝑆 = ln 2
𝑇𝑖 𝑉𝑖 Ti
3
1.00 x 105 Pa 𝑥 (0.500 x 10-3 m3 ) 1.000 dm3 373 K
∆𝑆 = x ln 0.500 dm3 298 K 2
298 K

3
50 Pa m3 1.000 dm3 373 K
∆𝑆 = x ln 0.500 dm3 298 K 2
298 K

𝑃𝑎 𝑚3
∆𝑆 = 0.167785 𝐾 x ln 2 𝑥 1.40036
𝑃𝑎 𝑚3
∆𝑆 = 0.167785 𝐾 x ln 2.80071
𝑃𝑎 𝑚3
∆𝑆 = 0.17279 𝐾
𝑃𝑎 𝑚3 1𝐽
∆𝑆 = 0.17279 𝐾 x 𝑃𝑎 𝑚3
𝑱
∆𝑺 = 0.17279 or 0.173 𝑲
 Step 4:
4. Entropy changes accompanying specific processes Ti = 25oC
c. Heating K = oC + 273.15
SELF – TEST 3.4 K = 25oC + 273.15
K = 298 or 298.15
Step 3: Tf = -25oC
𝑝𝑉 𝑉 K = oC + 273.15
∆𝑆 = 𝑖 𝑖 ln 𝑓
𝑇𝑖 𝑉𝑖 K = -25oC + 273.15
3 K = 248 or 248.15
𝑝𝑖𝑉𝑖 T
∆𝑆 = ln 𝑓 2
𝑇𝑖 Ti
1 Pa m3 = 1 J
p = 1 bar
3
𝑝𝑖𝑉𝑖 𝑉 𝑝𝑖𝑉𝑖 T 100,000 𝑃𝑎
p = 1 bar x 1 ba𝑟
∆𝑆 = ln 𝑓 + ln 𝑓 2
𝑇𝑖 𝑉𝑖 𝑇𝑖 Ti p = 100,000 Pa or 1.00 x 105 Pa
𝟑
𝒑𝒊𝑽𝒊 𝑽𝒇 T𝒇 Vi = 0.500 dm3
∆𝑺 = ln 𝟐
𝑻𝒊 𝑽𝒊 Ti Vi = 0.500dm3 x
1 m3
0.001 dm3
Vi = 500 or 0.500 x 10-3 m3
Vf = 0.0500 dm3
4. Entropy changes accompanying specific processes
c. Heating SELF – TEST 3.4
Step 5:
3
𝑝𝑉 𝑉 T
∆𝑆 = 𝑖 𝑖 ln 𝑓 𝑓 2
𝑇𝑖 𝑉𝑖 Ti

3
1.00 x 105 Pa 𝑥 (0.500 x 10−3 m3 ) 0.0500 dm3 248 K
∆𝑆 = 298 K
x ln 0.500 dm3 298 K 2

3
50 Pa m3 0.0500 dm3 248 K
∆𝑆 = 298 K
x ln 0.500 dm3 298 K 2

𝑃𝑎 𝑚3
∆𝑆 = 0.167785 𝐾 x ln 0.1 x 0.75919
𝑃𝑎 𝑚3
∆𝑆 = 0.17 𝐾 x ln 0.0759
𝑃𝑎 𝑚3
∆𝑆 = -0.43831
𝐾
𝑃𝑎 𝑚3 1𝐽
∆𝑆 = -0.43831 𝐾 x 𝑃𝑎 𝑚3
𝑱
∆𝑺 = -0.43831 or -0.44 𝑲
4. Entropy changes accompanying specific processes
d. The measurement of entropy

• The entropy of a system at a temperature T is related to its entropy at T = 0 by

measuring its heat capacity Cp at different temperatures and evaluating the integral in this
T C dT
equation 𝑆 Tf = 𝑆(Ti) ‫׬‬T 𝑓 p , taking care to add the entropy of transition
i T
(ΔtrsH/Ttrs) for each phase transition between T = 0 and the temperature of interest. For
example, if a substance melts at Tf and boils at Tb, then its entropy above its boiling
temperature is given by

T𝒇 Cp(s)dT ∆𝒇𝒖𝒔𝑯 T Cp(1)dT ∆𝒗𝒂𝒑𝑯 T Cp(g)dT

𝑺 T = 𝑺 0 ‫׬‬0 + + ‫׬‬T 𝒃 + + ‫׬‬T
𝐓 𝑻𝒇 𝒇 𝑻 𝑻𝒃 𝒃 𝑻
4. Entropy changes accompanying specific processes
d. The measurement of entropy

• All the properties required, except S(0), can be measured

calorimetrically, and the integrals can be evaluated either
graphically or, as is now more usual, by fitting a polynomial to
the data and integrating the polynomial analytically. The
former procedure is illustrated in Fig. 3.14: the area under the
curve of Cp /T against T is the integral required. Because
dT/T = d ln T, an alternative procedure is to evaluate the area
under a plot of Cp against ln T.

• Debye extrapolation - In this method, Cp is measured down

to as low a temperature as possible, and a curve of the form
aT3 is fitted to the data. That fit determines the value of a, and
the expression Cp = aT3 is assumed valid down to T = 0.
Given:
S = Entropy
Sm = Molar Entropy
dT = Differential or delta of temperature
T = Temperature
Ti = Temperature Initial
Tf = Temperature Final
Cp = Heat Capacity at constant pressure
Step 1:
Formula: Cp = aT3
T𝑓 C dT T C dT
p
𝑆 Tf = 𝑆(Ti) න
p 𝑆 T =𝑆 0 +න
Ti T 0 T
T aT3dT
𝑆 T =𝑆 0 +න
0 T
T aT3dT
𝑆 T =𝑆 0 +න
0 T
T
𝑆 T =𝑆 0 + 𝑎 න T2dT
0
𝟏
𝑺 T =𝑺 0 + aT3
𝟑
Given:
S = Entropy
Sm = Molar Entropy
dT = Differential or delta of temperature
T = Temperature
Ti = Temperature Initial
Tf = Temperature Final
Cp = Heat Capacity at constant pressure
Step 2: Step 3:
1 1
𝑆 T = 𝑆 0 + aT3 𝑆 T =𝑆 0 + 𝐶 (𝑇)
3
3 𝑝
1 𝐽
aT3 is the heat capacity at the Sm 10K = Sm 0 + 0.43
3 𝐾 𝑚𝑜𝑙
temperature T
𝑱
Sm 10K = Sm 0 + 𝟎. 𝟏𝟒𝟑𝟑
𝑲 𝒎𝒐𝒍
1
𝑆 T =𝑆 0 + 𝐶 (𝑇)
3 𝑝
SELF – TEST 3.5
Given:
S = Entropy
Sm = Molar Entropy
dT = Differential or delta of temperature
T = Temperature
Ti = Temperature Initial
Tf = Temperature Final
Cp = Heat Capacity at constant pressure
Step 1:
Formula: Cp = aT3
T C dT
T𝑓 C dT 𝑆 T =𝑆 0 +න
p
p
𝑆 Tf = 𝑆(Ti) න 0 T
T TdT
Ti T 𝑆 T =𝑆 0 +න
0 T
T TdT
𝑆 T =𝑆 0 +න
0 T
T
𝑆 T =𝑆 0 + න dT
0
𝑆 T =𝑆 0 + T
𝑺 T =𝑺 0 + Cp(T)
5. Clausius inequality

• We recall that more energy flows as work under reversible conditions than under irreversible
conditions. That is, −dwrev ≥ −dw, or dw − dwrev ≥ 0. Because the internal energy is a state
function, its change is the same for irreversible and reversible paths between the same two states,
so we can also write:

dU = dq + dw = dqrev + dwrev

• It follows that dqrev − dq = dw − dwrev ≥ 0, or dqrev ≥ dq, and therefore that dqrev/T ≥ dq/T.
Now we use the thermodynamic definition of the entropy (eqn 3.1; dS = dqrev /T) to write the
equation below. This expression is the Clausius inequality.

𝒅𝒒
dS ≥
𝑻