Thermodynamics

Reference: Atkins, 10th Edition, Chapter 2,3

1
 Main Topics
 Work, heat, and energy
 The internal energy
 Expansion work
 Heat Transactions
 Enthalpy
 Adiabatic changes
 Thermochemistry
 The Joule-Thomson effect
 Entropy
 Carnot cycle
 Spontaneity

2
 Thermodynamic Terminologies

 System; That portion of matter that

is selected for investigation. A
system can be open, closed, or
isolated. (As shown in Figure)

 Surroundings; Everything outside

the system.

 Universe; Surroundings + System

3
 Processes

 Process; Any transformation of a

system from one equilibrium
state to another over an interval
of time; Transfer of energy may
be involved. (As shown in Figure)

 Path of a process; The specific

series of equilibrium states
through which the system passes
during the process; Or the route
followed to make a change.

4
 Reversible process; A process in which the system is almost
in equilibrium with its surroundings at every stage of the
process.

 Irreversible process; A process in which the system is not in

equilibrium with its surroundings.

5
 State function; A property of a system (e.g. temperature,
pressure, volume, internal energy, enthalpy, entropy) that
has a unique value when a system is in a particular
thermodynamic state.

 It means that its value independent of any previous history

of the system. The value of a state function is independent of
pathway.

 State functions are always written using capital letters.

• Some examples of state functions are:

– T, P, V, E, H, and S Depend only on the initial and
final states
6
 Path function; A property (e.g. work, heat) that has a unique
value when a system is changing from one state to another
in a particular way (along a particular path).

• Examples of non-state functions are:

– q (heat), w, d (distance)
depend on the pathway

e.g.the altutide above sea level is a state function: Mount

Kinabalu is 4000 meter above sea level, there is an altitude
change of 4000 m, regardless of the route followed
 Equation of state; An equation that gives the value of a state
function in terms of independent variables of the system,
e.g. The ideal (or perfect) gas law: PV = nRT

7
 Extensive property; Proportional to the
amount of material present, e.g. volume,
energy and entropy.

 Intensive property; Independent of the

amount of material present, e.g.
temperature, pressure, refractive index and
chemical potential.

8
 Heat and Temperature

 What is the heat (q) of this room?

 This question has no answer. Heat is a path function. It is

measured during a change in state.

 What is the temperature (T) of this room?

 This question can be answered. Temperature is a state

function.

9
 The “Zeroth” Law of Thermodynamics

 When system A is in thermal equilibrium with another

system B – i.e. when A and B are in thermal contact and
there is no transfer of heat – and system A is also in thermal
equilibrium with system C, then system B must be in thermal
equilibrium with system C.

10
  The First Law of Thermodynamics
 Energy can be converted from one form to another with the interaction of
heat, work and internal energy, but it cannot be created nor destroyed,
under any circumstances

 There is a relationship between work (W), Heat (q) and the internal energy (U) of
a system as follows;

ΔU = q + W

 It means that the internal energy (U) of an isolated system is constant.

 This equation states that the change in the internal energy of a closed system is
equal to the energy that passes through its boundary as heat or work.

 Thus, q and W are positive if energy transferred into the system as work or heat &
q and W are negative if energy is lost.

 In another words, we view the flow of energy as work or heat from the system’s
perspective.
11
 Work (w)

 Work (w) is done when an object is

moved against an opposing force and
it is a path function.

 When a system does work, it

stimulated orderly motion in the
surroundings.

 For example, as seen in Figure, the

atoms here may be part of a weight
that is being raised.

 The ordered motion of the atoms in a

falling weight which does work on the
system.
12
 Energy

 The energy of a system is its capacity to do work.

 When work is done on a system, its capacity to do work is

increased, so the energy of the system is increased.

 When the system does work, its energy is reduced.

 In summary, when work is done on a system (w=positive),

so the energy increases (or we can say, internal energy,
ΔU = positive).

13
 Heat (q)
 When heat is transferred into a system,
its capacity to do work is increased, so
the energy of the system is increased.

 It can be shown by random motion of

the atoms called thermal motion. (As
shown in Figure)

 When the system releases heat, its

energy is reduced because it can do
less work than before. Heat is a path
function.

 It means that heat enter into system

(q=positive), energy increases, then
ΔU=positive.

14
 The Internal Energy

 The total energy of a system is called the internal energy, U.

 U is the total kinetic + potential energy of the molecules

composing the system.

 The change in internal energy, ΔU, is the difference in internal

energy between two states.

 It means that, when the system changes from initial state (i)
with the internal energy, Ui to a final state (f) with the internal
energy, Uf;
ΔU = Uf - Ui
15
 Expansion Work

 Expansion work is the work arising from a change in volume.

 For example, as shown in the Figure, when a piston of area A moves out
through a distance dz, it sweeps out a volume dV=Adz.

16
 Expansion Work
 The external pressure, Pex is equivalent to a weight
pressing on the piston, the force opposing expansion is
F=PexA.

 Pex (the external pressure) is the pressure applied on the

system from outside the system. Thus;
Vf
W    ex dV
Vi

 The negative sign tells us that, when the system moves an

object against an opposing force, the internal energy of
the system doing the work will decrease

17
 Free Expansion

 At a constant external pressure;

w = - Pex (Vf – Vi) = Pex (Vi – Vf)

 “Free” expansion occurs when Pex = 0.

 Now, what is the value of w under conditions of free

expansion?

 This condition happens when a gas expands into the

vacuum.

18
 Expansion against Constant Pressure

 At a constant external pressure

throughout the expansion;
w = - Pex ΔV = Pex (Vi – Vf)

 For example, as shown in Figure,

the work done by a gas when it
expands against a constant external
pressure, is equal to the shaded
area.

 A chemical example of this

condition is the expansion of a gas
formed in a chemical reaction in a
container that can expand.

19
 Reversible Expansion

 System at equilibrium are poised to undergo reversible

change.

 Here, Pex is continuously changing but is never far from

the pressure of the system itself.

 In reversible expansion, Pex = Psys – dP ~ Psys

 Thus, dW = -Pex dV = -PsysdV

 In reversible compression; Pex = ?

20
 Isothermal Reversible Expansion

 The work done by a perfect gas when it expands reversibly &

isothermally is equal the area under the isotherm (P=nRT/V).

vf
W    rev dV
vi
Vf
dV Vf
W   nR    nR ln( )
Vi
V Vi

21
 Isothermal Reversible Expansion
 The work done during the irreversible expansion against the same
final pressure is equal to the rectangular area shown slightly darker.

 Note that the reversible work is GREATER than the irreversible work.

22
 Compression
Reversible Irreversible Reversible Irreversible Reversible Irreversible

W= 0 kJ/mol W= 0 kJ/mol W= 1.5 kJ/mol W= 5.6 kJ/mol W= 7.8 kJ/mol W= 28.5 kJ/mol

Expansion

W= 0 kJ/mol W= 0 kJ/mol W= -1.6 kJ/mol W= -0.7 kJ/mol W= -3 kJ/mol W= -1.2 kJ/mol

 Question. A sample consisting of 1 mol of Argon is expanded
isothermally at 0 C from 22.4 dm3 to 44.8 dm3. Calculate work for each
following processes;

 reversibly;

W = - nRT ln (Vf/ Vi)

= - (1 mol) (8.314 JK-1mol-1) (273 K) ln (44.8 / 22.4) = - 1573 J

Against a constant external pressure equal to the final pressure of the

gas;

W = -Pf ΔV where Pf = nRT / Vf

Pf = (1 mol) (8.314 JK-1mol-1) (273 K) / 44.8 dm3 = 50.66 Jdm-3
 
ΔV = Vf-Vi = 44.8 - 22.4 dm3 = 22.4 dm3
 
W = -(50.66 Jdm-3 x 22.4 dm3) = -1134 J
24
Example:
A cylinder of volume 2.00 L contains 0.100 mol He(g) at 30 oC.
Which process does more work on the system, compressing
the gas isothermally to 1.00 L with a constant pressure of 5.00
atm, or compressing it reversibly and isothermally to the same
final volume?

Solution

Isothermal irreversible compression

w = PexV = _ (5.00 atm) x ( _1.00 L) = +5.00 L atm

= +507 J (1 L atm = 101.325 J)

Isothermal reversible compression

w = _ nRT ln(Vfinal/Vintitial)
_ (0.100 mol) x (8.315 J K-1 mol-1) x (303 K) x ln 1.00L
=
2.00 L
= +175 J.
Thus the irreversible compression does more work.

25
 The Second Law of Thermodynamics

 We discussed that when the energy of a system changes

as a result of a temperature difference between the
system and its surroundings, the energy has been
transferred as heat.

 Based on the 2nd law of thermodynamics, heat can be

transferred spontaneously ONLY from a body at a higher
temperature to a body at a lower temperature.

26
 Heat Transactions

 We know that,
dU = dq + dWexp (expansion work) + dWe (any extra work)

 A system which kept at constant volume cannot do any

expansion work (Wexp = 0 ). So, at constant volume; dU =
dq or ΔU = qv

 ΔU can be measured by using adiabatic bomb

calorimeter in which qv=CΔT. Where, C is the “calorimeter
constant”.

27
 Calorimeter

 The bomb is the central vessel, which is

strong enough to withstand high
pressures.

 The calorimeter is the entire assembly

shown here.

 To ensure adiabaticity (q=0), the

calorimeter is immersed in a water bath
with a T continuously readjusted to that
of the calorimeter at each stage of the
combustion.

28
 Heat Capacity at Constant Volume (CV)

 At a constant volume; dU = dqV = CVdT

 U 
CV  
 T  V

 For polyatomic gases, the molar heat capacity at a constant volume

is Cv,m= 25 JK-1 mol-1.

 For monoatomic perfect gases, the molar heat capacity at a constant

volume, Cv,m= (3/2)R.

29
Cont’…

The internal energy of a system

increases as the temperature is raised.

This graph shows its variation as the

system is heated at constant volume.

The slope of the tangent to the

curve at any temperature is the heat
capacity at constant volume at that
temperature.

Note that, for the system illustrated

the heat capacity is greater at B than
A.

30
Cont’…

The internal energy of a system

varies with volume and temperature,
perhaps as shown here by the
surface.

The variation of the internal

energy with temperature at one
particular constant volume is
illustrated by the curve drawn
parallel to T.

The slope of this curve at any point

is the partial derivative. U
 
T V

31
 Enthalpy (H)
 As shown in Figure, when a system is
subjected to constant pressure and is free
to change its volume, some of the energy
supplied as heat may escape back into the
surroundings as work.

 In such a case, the change in internal

energy is smaller than the energy supplied
as heat.

In summary, the change in internal

energy is not equal to the heat supplied
when the system is free to change its
volume.

In this case, the heat supplied at constant

pressure is equal to another
thermodynamic property => H
  U  V 32
Cont’…

𝐻=𝑈+𝑃𝑉
d 𝐻=d𝑈 +𝑃 d𝑉 +𝑉 d 𝑃
We know that 𝑈=𝑞+𝑊 ;d𝑈 =d 𝑞+d 𝑊
The system is d 𝐻=d𝑞+d𝑊 +𝑃 d𝑉 +𝑉 d 𝑃
in equilibrium
with its d 𝑊 =− 𝑃 d𝑉 ;d 𝐻=d𝑞+𝑉 d 𝑃
surrounding
 At constant pressures; dH = dqp (no additional work)
 For measurable changes; ΔH = qp
 Heat Capacity at constant pressures (CP);

  
Cp   
  P
  C P 
33
 The Enthalpy of a Perfect Gas
V  nR
  U  V
  U  nR
  U  ng R

As shown in Figure, for gases, at a

given T, the slope of enthalpy versus T
is steeper than that of internal energy
versus T, and CP,m is larger than CV,m. Slope= heat capacity at constant pressure

 For an Ideal Gas the relationship

between heat capacities is given by;
𝐶𝑝= ( )
𝜕𝐻
𝜕𝑇 𝑝
For infinitesimal
changes of temp
d 𝐻=𝐶 𝑝 d𝑇
Cp-Cv = nR
For measurable ∆ 𝐻=𝐶 𝑝 ∆ 𝑇 34
For example;
Consider this reaction;
2H2 (g) + O2 (g) ⇾ 2 H2O (l)

 Answer.
 3 mol of gas-phase molecules is replaced by 2 mol of liquid-
phase molecules, so Δng = -3 mol.

 Thus, at 298 K, when, RT = 2.48 kJ mol -1, the enthalpy and

internal energy changes taking place in the system are related by;
ΔHm – ΔUm = (-3 mol) x RT = -7.4 kJ mol-1

35
 Reversible Adiabatic Change
For a reversible adiabatic expansion of a perfect gas, P and V are
related by an expression that depends on the ratio of heat capacities.

 Reversible adiabatic expansion means reversible expansion in

thermally insulated container.

 As heat capacity is independent of volume; ΔU = Cv (Tf- Ti)

 Expansion is adiabatic (q=0); Wad = Cv ΔT

1/ c
 Thus, in general;  Vi 
 f  i 
V  
 f 
C
c  V ,m
R
Vi i c  V f  f c
V c  consant 36
Cont’…

As shown in Figure, the process

involves two steps;

 In the first step, the system expands

at constant T; there is no change in
internal energy if the system consists of
a perfect gas.

 In the second step, the temperature

of the system is reduced at constant
volume.

 Therefore, the overall change is the

sum of the changes for the two steps.

37
Cont’…
 An adiabat depicts the variation of P with V when a gas expands
adiabatically.

 Note that the pressure declines more steeply for an adiabat than it does for
isotherm because the temperature decreases in the former.
In an isothermal expansion,
energy flows into the system
as heat and maintains the
temperature, as a result the
pressure does not fall as much
as in adiabatic expansion

 f V f    iVi 
C p ,m
  CV , m
V   consant
38
Question.
Is the following statement true or false? Explain.
The heat of a system is changing during an adiabatic
process.

Answer.
False. During an adiabatic process, the change in the
heat of a system equals to 0.

39
 The Born-Haber Cycle for KCl at
298 K.

 Enthalpies changes are in kJ

mol-1.

 The steps;
1. Sublimation of K(s)
2. Dissociation of 1/2Cl2 (g)
3. Ionization of K(g)
4. Electron attachment to Cl(g)
5. Formation of solid from gas
6. Decomposition of compound.

40
41
 The Temperature Dependence of Reaction Enthalpies;
Kirchhoff's Law

2
  2     1    C p d 
1
T2
H (T2 )  H (T1 )   CP0 dT
0 0
T1

 r CP0  
Pr oducts
 CP0 ,m  
Re ac tan ts
 CP0 ,m

As shown in Figure, when T is increased, the enthalpy of the products and
the reactants both increase, but with different extents depends on the heat
capacities of the substances.
42
Question.
The standard entalphy of a formation of H2O (g) at 298 K is
-241.82 kJ mol-1. Estimate its valueat 100oC given the following
values of the molar heat capacities at constant pressure: H2O (g):
33.58 J K-1 mol-1; H2 (g): 28.84 J K-1 mol-1 ; O2: 29.37 J K-1 mol-1.
Assume that the heat capacities are independent of temperature

43
 Changes in Internal Energy

As shown in Figure, as the volume

and temperature of a system are
changed, the internal energy changes.

 Two Path can be seen; Path 1

(adiabatic)& Path 2 (non-adiabatic).

 It means they correspond to different

values of q and w but to the same value
of ΔU.

 The work & heat are path functions

but U is a state function. Thus,
f
U   dU
i
44
Cont’…
U  U (T , V )
 U   U 
dU    dV    dT
 V T  T V
 U 
   T
 V T
 U 
   CV
 T V
dU   T dV  CV dT

 The internal pressure, πT , is the slope of U with respect to V with the

temperature T held constant.

 or it can be stated that πT is a measure of cohesive forces in the sample.

45
 Changes in Internal Energy at Constant Pressure

dU   T dV  CV dT
dU dV
 T  CV
dT dT
 U   V 
   T    CV
 T  P  T  P
 The partial derivative on the right in the above expression is the
slope of the plot of volume against temperature (at constant P) which
is called the expansion coefficient.

1  V 
   Expansion coefficient
V  T  p
46
Cont’…

 Isothermal compressibility, κ
(kappa);
1  V 
     Isothermal compressibility
V  P T
 It is a measure of the fractional
change in volume when the
pressure is increased by a small
amount.

 The negative sign ensures that

the compressibility is a positive
quantity.

Because an increase of pressure,

implying a positive dP, brings about
a reduction of volume, a negative
dV.
47
Cont’…
 What does a large value for α mean?

 It means that the volume of the sample responds strongly to changes

in temperature.

 Therefore;  U   V 
   T    CV
 T  P  T  P
1  V 
   
V  T  p
 U 
   V  T  CV
 T P

For a perfect gas, πT = 0, since there are no interactions between the

molecules, and thus the internal energy is independent of their
separation and independent of the volume of the sample.

 U 
   CV
 T  P
48
 The Joule-Thomson Effect (μ)

 This effect is important in liquefaction

of gases.

 The gas expands through the porous

barrier, which acts as a throttle, & the
whole apparatus is thermally insulated.

 This arrangement corresponds to an

isenthalpic expansion (expansion at
constant enthalpy).

 Heating or cooling of a gas depends on

the conditions.

49
Cont’…

 The thermodynamics basis of Joule-

Thomson expansion is;

 The pistons represent the upstream

& downstream gases, which maintain
constant pressures either side of the
throttle.

 Look at the transition from the top

diagram to the bottom diagram.

 It represents that the passage of a

given amount of gas through the
throttle occurs without change of
enthalpy.

50
Cont’…
     
H ( P, T ); dH    d    dT
     T  P
  
d    d   C d  If  d   0
   
  
  d   C d 
   
     
   C  
       
     
   C  ;    
     
d     C d   C d 

51
Question.
One mole of an ideal monoatomic gas at 25.0˚C is cooled and allowed to expand
from 1.00 dm3 to 10.00 dm3 against an external pressure of 1.00 bar. Calculate the
final temperature, work, heat, internal energy change and enthalpy change of this
process. (R = 8.314 x 10-2 dm3.bar.K-1.mol-1.)

Answer;
PV = nRT
1 bar (10 dm3) = 1 mol (8.314x10-2 dm3.bar.K-1.mol-1) T Thus; T = 120.3 K
1 bar = 105 Nm-2 Thus; 1 J = 1 Nm  
w = Pext (Vi – Vf) = 105 Nm-2 (1x10-3 m3 – 10x10-3 m3) = - 9000 J  
For monoatomic gas, Cv,m = (3/2)R
U = nCv,m T = 1 mol x 3/2 (8.314 J.mol-1.K-1) (120.3 K – 298 K) = -2216.1 J
q = U – w = -2216.1 J – (- 9000 J) = 6783.9 J
 
H = U + PV = - 3.70 kJ

52
Application

53
 Entropy
 The first law of thermodynamics ⇾ U (The internal energy). U is a state
function which tell us whether a change is permissible.

 Based on the second law of thermodynamics, heat can be transferred

spontaneously ONLY from a body at a higher temperature to a body at a
lower temperature.

 The second law of thermodynamics can also be expressed based on another

state function called entropy, S.

 Entropy is a measure of the energy dispersed in a process.

 The second law of thermodynamics uses entropy to identify the

spontaneous changes among those permissible changes.

 It stated that the entropy of an isolated system increases in the course of a

spontaneous changes; ΔStot > 0.
54
Spontaneous Processes

55
Reversible Processes vs.
Irreversible Processes

56
 The Thermodynamics Definition of Entropy
 It relates to the change in entropy (dS).

 It occurs as a result of a physical or a chemical change (generally; a

process)

 It comes from the idea that that how much energy is transferred as heat.

 Why? It is because heat stimulates random motion in the surroundings.

 Work stimulates uniform motion of atoms in the surroundings, thus it

doesn’t change their entropy.
dqrev
 Thus; dS 
T
f dq
S   rev
i T
57
 State Function

 State functions have the following quality,

for example;

U   dU 0
 Where the integral indicates any closed
path.

 Or we can say that the integral has an

exact value.

 In a thermodynamics cycle, the overall

change in a state function is zero.

58
 Carnot Cycle (Reversible Heat Transfer)
 The basic structure of a Carnot cycle is shown in
figure.

 In a four steps cycle,

 Step 1 (isothermal reversible expansion at Th),
step 2 (reversible adiabatic expansion at Th⇾Tc),
Step 3 (isothermal reversible compression at Tc),
step 4 (reversible adiabatic compression Tc⇾Th).
qh qc
 0
h c

 A general cycle may be divided into many

Carnot cycles;

dqrev
  sur
0

59
 Recall that a process is called adiabatic if no
heat is transferred in or out of the system.

 A general Carnot cycle can be divided into

small Carnot cycles as shown in Figure.

 As shown before, the function that

represented by the heat transferred divided
by temperature has the qualities of a state
function.

 Clausius called this function the entropy.

∮ 𝑑𝑆=0
𝑞 h 𝑞𝑐
∮ 𝑑𝑆= 𝑇 = 𝑇
h 𝑐
60
 The Clausius Inequality

 The definition of entropy is consistent with the second law. Recall that
more work is done when; |dWrev| ≥ |dW|

 Both values are negatives when energy leaves the system as work,
thus; - dWrev ≥ - dW or dW – dWrev ≥ 0

 U is a state function, so its change will be the SAME for irreversible &
reversible paths;
dU  dq  dW  dU  dqrev  dWrev  dW  dWrev  0
dqrev  dWrev  dq  dW
dqrev  dq  dW  dWrev  0
dqrev  dq  0  dqrev  dq
dqrev dq dq
  dS 
T T T
61
 Entropy Change in Irreversible Processes

 Irreversible change of state;

dU  dq  dW  dq  Pex dV
 Reversible change between same two states;

dqrev
dS   dU  dqrev  dWmax  TdS  PdV
T
 Equality gives a special requirement;

TdS  PdV  dq  Pex dV

TdS  dq   P  Pex  dV
62
 Irreversibility & Entropy change

 Look at this equation; TdS  dq   P  Pex  dV

 Possible conditions for actual processes;

 Condition 1; P > Pex ; dV > 0

 Condition 2; P < Pex ; dV < 0
 Condition 3; P = Pex ; dV = 0

 Under all conditions; -(Pex- P) dV ≥ 0

 In any actual process in an isolated system;

dS = 0 TdS ≥ 0

63
 Entropy Changes in Real Systems; A summary

 The change in the entropy determines whether the

process is spontaneous.

 The principal of Clausius;

The entropy of an isolated system will always
increase in a spontaneous process.

 Also known as the second law of thermodynamic.

64
 Entropy as State Function

 Any state function can be a function of any two other state

variables;

S  S T , V 
S  S T , P 
S  S  P, V 
S  S U , V 

 Each state function is a natural function of two specific

variables.

65
 Calculation of Entropy Changes

 We can calculate changes of entropy in a manner

analogous to other state variables;
S  S T ,V 
 S   S 
dS    dT    dV
 T V  V T
 You must know derivatives to carry out integration.
 It may also express entropy as a function of other
variables.
S  S T , P 
 S   S 
dS    dT    dP
 T  P  P T
66
 Maxwell Relations
 An infinitesimal change in a function f(x,y) can be written as; df = gdx +
hdy where g and h are functions of x and y.

 The mathematical criterion for df being an exact differential is that;

 g   h 
    
 y x  x y
 Because the fundamental equation; dU = TdS – PdV is an expression for
an exact differential, the function multiplying dS and dV (namely T and –
P) must pass this test.

 T   P 
     
V
 s  S V
 By this we can generate a relation between quantities that, at first sight,
would not seem to be related.
67
 Maxwell Relations from the Energy Functions

dU  TdS  PdV

dH  TdS  PdV

dA   SdT  VdP

dG   SdT  VdP
68
 Isothermal Expansion of a Perfect Gas

dqrev
dS 
T
f dq 1 f
S   rev
  dqrev
i T T i

Vf
qrev  Wrev  nRT ln
Vi
Vf
S  nR ln  Figure shows the logarithmic
Vi increase in entropy of a perfect
gas as it expands isothermally.

69
 Because entropy, S is a state function, ΔS is independent of the
path.

 Thus, this equation can be applied whether the change of state

occurs reversibly or irreversibility.

 But, as we know, dqsur = - dq

 Thus, Δstot = 0 (this is what we expect for a reversible process).

 If, the isothermal expansion occurs freely (W = 0), then q = 0

(ΔU = 0), thus Δssur = 0 Vf
Stot  nR ln
Vi

 So, in this case, Δstot ≥ 0, as we expected for an irreversible

process.
70
 Partial Derivatives of Energy

 Heat capacity at constant V can be defined based on

internal energy;
 U 
   CV
 T V

 Heat capacity at constant P can be defined based on

enthalpy;
 H 
   CP
 T  P

71
 Temperature Derivatives of Entropy
dqrev
 General form; dS 
T
 Constant volume; dU C
dS   V dT
T T
 S  CV
  
 T V T
 Constant pressure;
dH CP
dS   dT
T T
 S  CP
  
 T P T

 It is just like calculations of other state function changes.

 Integrate appropriate derivatives over the range to find the change in entropy.
72
 Entropy of Mixing of Ideal Gases

 Consider volume change of an ideal gas when the

temperature is constant. i shows any components in the
system. Calculate the entropy of the system;

V V
 S   P   S   P 
2 2

    S     dV     dV
 V T  T V V1 
V T V1 
T V
V final V final
 Si   P 
Si     dV     dV
Vinitial 
V T Vinitial 
T V
V final
nR  V final 

Vinitial
V
dV  nR ln  
 Vinitial 

73
Cont’…

 Consider the process of mixing of ideal gases;

two separated gases are allowed to
intermingle as shown in Figure.

 The entropy change for the system is the

SUM of the entropy changes for the gases;

S  S A  S B
 VA  VB   VA  VB 
 nR ln    nR ln  
 VA   VB 

 This is a positive quantity; mixing of ideal

gases is a spontaneous process.

74
 Entropy Change upon a Phase Change

 Phase change is accompanied by a change in the enthalpy, ΔHϕ, called the latent
enthalpy of transition. A phase change occurs at a specific temperature, Tϕ. Thus;
entropy change; H 
S 
T
 Look at Table 3.2. Note that a
wide range of liquids give
approximately the same
standard entropy of
vaporization.

 This empirical observation is

called Trouton ‘s rule. But
exception is water. Why?

75
 Summary
 Evaluate derivatives to determine state function changes.

 Some derivatives are measured quantities such as CP, CV, α, κ, …

 Others determined from equation of state.

 Entropy derivatives are determined from definitions of reversible

heat.

 Calculate changes by integration of derivatives.

 Entropy changes at phase transitions evaluated by the definition of

entropy.

76
77
 The Third Law of Thermodynamics

 It defines the entropy at a specific set of conditions, namely T = 0 K.

 The entropy of all pure, crystalline substances is the same at the

absolute zero of temperature. That entropy is assigned the value of
zero; S(0) = 0.

 Nernst heat theorem; the entropy change accompanying any physical or

chemical transformation approaches zero as the temperature
approaches zero: ΔS⇾0 as T⇾0 when all the substances involved are
perfectly ordered.

 Note that it does not say that the entropy of every substance is zero at
these conditions.

78
Cont’…

 Entropies reported on the basis in which

S(0) = 0 are called Third-Law entropies.

 By rules, when the substance is in its

standard state at the temperature T, the
standard (Third-Law) entropy is denoted
Sθ(T).

 Then, the standard reaction entropy Sθ(T), is

defined like the standard reaction enthalpy.

r S  
Products
 Sm  
Reac tan ts
 Sm

79
Debye Theory of Heat Capacity of Crystalline Solids

 You need to know the heat capacity at any temperatures

to define entropy.

 But it is difficult to measure that for T near 0 K.

 Thus, we use a theoretical evaluation of low temperature

heat capacity introduced by Debye;

CP T   AT 3
 Debye considered the solid a group of vibrating atoms in
a lattice.

80
 Methodology for Using Debye Theory to Obtain
Standard Entropy

 Evaluate integral in two parts (0⇾T0 & T0⇾T)

T0
C P T  T
C P T 
S  T   S   0    dT   dT
0
T T0
T
 Evaluation using Debye theory;

C P T  T
C P T 
S  T   S   0    dT
3 T0
T
 The remaining integral is calculated numerically.

81
 Reference State
 By rules, the absolute values of state
functions must tie to some reference
point.

 For example, one must define the

constant, Sθ(0) in an equation like;

 S  CP
  
 T  P T
T
C 
T 
S T   S  0   
  P
dT  As shown, the variation of Cp/T with T
0
T for a sample is used to evaluate entropy,
which is equal to the area beneath the
 Then, the entropy at all other upper curve up to the corresponding T,
temperature is found through this plus the entropy of each phase
equation. transition passed.

82
 Reference State for Real Gases

 The standard state for any gas is the equivalent ideal

gas at 1 bar.

 This will result in a “tricky” evaluation of entropy of the

real gas.

 The evaluation from the reference state requires one to

integrate through a point which the real and ideal gas
have in common.

83
Cont’…

 The entropy of a real gas is a sum of terms;

P2 P2
 S   V   S   V 
   
 P T
  S 
 T  P
P  P  dP  P   T  dP
1 T 1 P

S T , P   S  T   S  S  T   Sideal  S real

 P
 V   Vm 
S T , P   S m T     m  dP     dP
P0 
T  P ,ideal 0
T  P ,real

P
 R  Vm  
S T , P   S 
ideal T        dP
0
P  T  P ,real 

84
 Summary

 Reference values of state functions specified.

 The third law of thermodynamics defines the entropy at a

specific state (pure crystalline material, 0 K).

 Values at other states found by integration.

 Debye’s theory determines entropy changes at low T.

 Reference state of gases is defined for ideal gas at 1 bar;

 Integrate through P = 0
 “Correction” terms for nonideality

85
 Spontaneity under Arbitrary Conditions

 At constant U and V, the criterion for spontaneity is;

 S U ,V 0

 But this is not a convenient set of conditions.

 Often There are some constraints such as constant P and T,

or constant T and V.

 Consider idea from physics: minimization of energy.

86
 Free-energy Functions

 Specify energy and entropy considerations in a system.

 Helmholtz free-energy A, of a state;

A = U – TS

 Gibbs free-energy G, of a state;

G = H – TS = U + PV –TS

 Thus, both energy minimization and entropy maximization are

considered simultaneously.

87
 Differential Helmholtz Free-Energy & Spontaneity

 By definition; A  U  TS
dA  dU  TdS  SdT  dU  dq  dW
dA  dq  dW  TdS  SdT
dA   dq  TdS   Pex dV  SdT
 Under constant V and constant T conditions;

dA  dq  TdS
 For spontaneity under constant V and constant T conditions, this
equation must be negative;
 dAT ,V 0

88
 Differential Gibbs Free-Energy & Spontaneity

 By definition; G  H  TS
dG  dH  TdS  SdT  H  U  PV
 dU  PdV  VdP  TdS  SdT U  q  W
 dq  dW  PdV  VdP  TdS  SdT
  dq  TdS    Pex  P  dV  VdP  SdT
 Under constant T & constant P conditions;

dG  dq  TdS
 For spontaneity under constant T & constant P conditions, this
must be negative;
 dG T , P  0
 This is like minimizing excess energy in a physical system.

89
 Helmholtz Free-energy in Reversible Process

 Helmholtz free-energy in a process;

dA   dq  TdS   dW  SdT
 At constant T;

dA   dq  TdS   dW

 Under reversible conditions; dqrev = TdS

dA  dWmax

 The Helmholtz free-energy change represents the maximum

work in the process.

90
 Gibbs Free-energy in Reversible Process

 Gibbs free-energy Change;

dG   dq  TdS   dW  PdV  VdP  SdT

 At constant T and constant P;

dG   dq  TdS   dW  PdV

 Under reversible conditions; dqrev= TdS and PdV= - dWmax,mech

dG  dW  dWmax,mech

 The Gibbs free-energy change represents the work in the

excess of the reversible mechanical work of a process.

91
 Free-energy Changes

 Helmholtz free-energy A;

dA   SdT  PdV
 Gibbs free-energy G;

dG   SdT  VdP
 Recall that how entropy depends on temperature to
evaluate free energy change;

 S   S 
S  S T , V   dS    dT    dV
 T V  V  P
 S   S 
S  S T , P   dS    dT    dP
 T P  P T
92
 Evaluation by Integration

 Evaluate changes of a function such as A or G in a process

requires evaluating an integral of a derivative;

T2 V2

A    S T dT   P V dV
T1 V1
T2 P2

G    S T dT   V  P dP
T1 P1

93
 Summary

 Spontaneity under specific conditions demands certain changes in state functions.

 Free-energy functions specify spontaneity under common conditions;

 Related to work;
 ΔA is maximum work in a process.
 dA T ,V  0
 ΔG is excess work (above maximum) in a process.  dG T , P  0
 Thus, we must calculate changes, ΔA and/or ΔG, to determine spontaneity of a
process & make predictions.

 Constant U and V;  dS U ,V 0

 Maxwell relations provide connection between derivatives to allow proper

integration.
94
95