Thermodynamics

Module 1
Carnot cycle, Efficiency of heat engine, Entropy, entropy
calculations – Free energy, criteria for spontaneity, Free
energy as function of Temperature and Pressure.
Chemical potential – Fugacity - Activity coefficient –
Applications of free energy.
3rd law of thermodynamics – Absolute entropy.
 Thermodynamics
oThermodynamics is the study of the effects of work, heat, and energy on a
system
oThermodynamics is only concerned with macroscopic (large-scale) changes
and observations
oAll of thermodynamics can be expressed in terms of four quantities

a) Temperature (T)
b) Internal Energy (U)
c) Entropy (S)
d) Heat (Q)
 Classical vs Statistical
o Classical thermodynamics concerns the relationships between bulk properties of
matter. Nothing is examined at the atomic or molecular level.
o Statistical thermodynamics seeks to explain those bulk properties in terms of
constituent atoms. The statistical part treats the aggregation of atoms, not the
behavior of any individual atom

o The first law of thermodynamics is an extension of the law of conservation of energy

o The change in internal energy of a system is equal to the heat added to the system
minus the work done by the system
ΔU = Q - W
 Basics
o Thermodynamics deals with stability of systems. It tells us ‘what should happen?’.
o ‘Will it actually happen(?)’ is not the domain of thermodynamics and falls under the realm of
kinetics.
o To understand the laws of thermodynamics and how they work, first we need to get the terminology
right.
o Some of the terms may look familiar (as they are used in everyday language as well)- but their
meanings are more ‘technical’ and ‘precise’.
o System is region where we focus our attention (Au block in figure).
o Surrounding is the rest of the universe (the water bath at constant ‘temperature’).
o Universe = System + Surrounding (the part that is within the dotted line box in the figure below)
o More practically, we can consider the ‘Surrounding’ as the immediate neighbourhood of the system
(the part of the universe at large, with which the system ‘effectively’ interacts).
In this scheme of things we can visualize: a system, the surrounding and the universe at large.
o Things that matter for the surrounding: (i) T, (ii) P, (iii) ability to: do work, transfer heat, transfer
matter, etc. Parameters for the system: (i) Internal energy, (ii) Enthapy, (iii) T, (iv) P, (v) mass, etc.
 System and Surrounding

To a thermodynamic system two ‘things’ may be added/removed:

a) energy (in the form of heat &/or work)
b) matter.
An open system is one to which you can add/remove matter (e.g. a open beaker to which we can add
water). When you add matter- you also end up adding heat (which is contained in that matter).
A system to which you cannot add matter is called closed.
Though you cannot add/remove matter to a closed system, you can still add/remove heat (you can cool
a closed water bottle in fridge).
A system to which neither matter nor heat can be added/removed is called isolated.
A closed vacuum ‘thermos’ flask can be considered as isolated.
 System and Surroundings

Type of boundary Interactions Mass

Open All interactions possible (Mass, Work, Heat)

Closed Matter cannot enter or leave

Interactions possible
Semi-permeable Only certain species can enter or leave Work
Insulated Heat cannot enter or leave

Rigid Mechanical work cannot be done*

Heat
Isolated No interactions are possible**
 Basics
Matter is easy to understand and includes atoms, ions, electrons, etc.
Energy may be transferred (‘added’) to the system as heat, electromagnetic
radiation etc.
In TD the two modes of transfer of energy to the system considered are Heat and
Work.

Heat and work are modes of transfer of energy and not ‘energy’ themselves.
o Once inside the system, the part which came via work and the part which came
via heat, cannot be distinguished.
o Before the start of the process and after the process is completed, the terms heat
and work are not relevant.
o From the above it is clear that, bodies contain internal energy and not heat (nor
work!).
o Matter when added to a system brings along with it some energy. The ‘energy
density’ (energy per unit mass or energy per unit volume) in the incoming matter
may be higher or lower than the matter already present in the system.
 Thermodynamic Processes
o Isothermal process → the process takes place at constant temperature (e.g. freezing of
water to ice at –10C)
o Isobaric → constant pressure
(e.g. heating of water in open air→ under atmospheric pressure)
o Isochoric → constant volume
(e.g. heating of gas in a sealed metal container)
o Reversible process → the system is close to equilibrium at all times (and infinitesimal
alteration of the conditions can restore the universe (system + surrounding) to the
original state. (Hence, there are no truly reversible processes in nature).
o Cyclic process → the final and initial state are the same. However, q and w need not be
zero.
o Adiabatic process → dq is zero during the process (no heat is added/removed to/from
the system)
o A combination of the above are also possible: e.g. ‘reversible adiabatic process’.
 Thermodynamic Processes
o An adiabatic process transfers no heat
therefore Q = 0; ΔU = Q – W
When a system expands adiabatically, W is positive (the system does work) so ΔU is negative.
When a system compresses adiabatically, W is negative (work is done on the system) so ΔU is positive.

o An isothermal process is a constant temperature process. Any heat flow into or out of the system must be slow
enough to maintain thermal equilibrium
For ideal gases, if ΔT is zero, ΔU = 0; therefore, Q = W
Any energy entering the system (Q) must leave as work (W)
o An isobaric process is a constant pressure process. ΔU, W, and Q are generally non-zero, but calculating the work
done by an ideal gas is straightforward
W = P·ΔV
Water boiling in a saucepan is an example of an isobar process
o An isochoric process is a constant volume process. When the volume of a system doesn’t change, it will do no work
on its surroundings. W = 0
ΔU = Q
Heating gas in a closed container is an isochoric process
Heat Capacity
o The amount of heat required to raise a certain mass of a material by a certain
temperature is called heat capacity
Q = mcxΔT
o The constant cx is called the specific heat of substance x, (SI units of J/kg·K)

Heat Capacity of an Ideal Gas:

o CV = heat capacity at constant volume

CV = 3/2 R
o CP = heat capacity at constant pressure
CP = 5/2 R
o For constant volume
Q = nCVΔT = ΔU

o The universal gas constant R = 8.314 J/mol·K

 The Zeroth Law of Thermodynamics
We have already discussed
the zeroth law, and include it
here for completeness:
If object A is in thermal
equilibrium with object C,
and object B is separately in
thermal equilibrium with
object C, then objects A and
B will be in thermal
equilibrium if they are placed
in thermal contact.
 The First Law of Thermodynamics
The change in internal energy of a closed system will be equal to the energy added to the system
minus the work done by the system on its surroundings.
This is the law of conservation of energy, written in a form useful to systems involving heat transfer.
If a system’s volume is constant, and heat is added, its internal energy increases.
 The First Law of Thermodynamics

If a system does work on the external world, and no heat is added, its internal energy decreases.
 The First Law of Thermodynamics
Combining these gives the first law of thermodynamics. The change in a system’s internal energy is related to the heat
Q and the work W as follows:

It is vital to keep track of the signs of Q and W.

 The First Law of Thermodynamics

The internal energy of the system depends only on its temperature. The work done and the heat
added, however, depend on the details of the process involved.
 Second Law of thermodynamics
o The first law of thermodynamics states that during any cycle that a system undergoes,
the cyclic integral of the heat is equal to the cyclic integral of the work.
o However, we know from our experience that because a proposed cycle does not violate
the first law does not ensure that the cycle will actually occur.
o It is this kind of experimental evidence that led to the formulation of the second law of
thermodynamics.
o In its broader significance the second law acknowledges that processes proceed in a
certain direction but not in the opposite direction.
o A hot cup of coffee cools by virtue of heat transfer to the surroundings, but heat will not
flow from the cooler surroundings to the hotter cup of coffee.
o Gasoline is used as a car drives up a hill, but the fuel level in the gasoline tank cannot be
restored to its original level when the car coasts down the hill.
Second Law of thermodynamics
o Statement:
“Heat can flow spontaneously from a hot object to a cold object; it will not
flow spontaneously from a cold object to a hot object”.
o The second law of thermodynamics introduces the notion of entropy (S), a measure of
system disorder (messiness)
o U is the quantity of a system’s energy, S is the quality of a system’s energy.
o If you watch a movie, how do you know that you are seeing events in the order they
occurred?
o If I drop a raw egg on the floor, it becomes extremely “disordered” (greater Entropy) –
playing the movie in reverse would show pieces coming together to form a whole egg
(decreasing Entropy) – highly unlikely!
o The 2nd Law helps determine the preferred direction of a process
o A reversible process is one which can change state and then return to the original state
o This is an idealized condition – all real processes are irreversible
 Second law of thermodynamics
o Identify the direction of a process. (ex: Heat can only transfer from a hot object to a cold object, not the
other around)

o Can be used to determine the “Quality” of the energy. (ex: A high-temperature energy source has a
higher quality since it is easier to extract energy from it to deliver useable work.)

o Can be used to exclude the possibilities of constructing 100% efficient heat engine and any perpetual-
motion machines. (Kevin-Planck statement and Clausius statement)

o Reversible processes and irreversibilities.

o Determine the theoretical limits for the performance of engineering systems. (ex: A Carnot engine is
theoretically the most efficient heat engine and its performance can be used to set as a standard for other
practical machines)
o A process can not happen unless it satisfies both the first and second laws of thermodynamics. The first
law characterizes the balance of energy which defines the “quantity” of energy. The second law defines
the direction which the process can take place and its “quality”.
o
 Second law Statements

Clausius statement : It states that heat cannot flow itself from a cold body
to a hot body spontaneously without the intervention of an external
energy.

Kelvin statement: It is impossible to take heat from a hot body and

convert it completely into work by a cyclic process without transferring a
part of heat to cold body.
Heat Engine
o A device which transforms heat into work is called a heat engine
o This happens in a cyclic process
o It is easy to produce thermal energy using work, but how does one produce
work using thermal energy?
o In a heat engine, mechanical energy can be obtained from thermal energy only
when heat can flow from a higher temperature to a lower temperature.
o Heat engines require a hot reservoir to supply energy (QH) and a cold reservoir
to take in the excess energy (QC)

QH is defined as positive, QC is negative

All irreversible processes are avoided while adhering to the 2nd Law
(isothermal and adiabatic only)
Heat Engine
A steam engine is one type of heat engine.

We will discuss only engines that run in a

repeating cycle; the change in internal energy
over a cycle is zero, as the system returns to its
initial state.
The high temperature reservoir transfers an
amount of heat QH to the engine, where part of
it is transformed into work W and the rest, QL,
is exhausted to the lower temperature
reservoir. Note that all three of these quantities
are positive.
Efficiency of a heat engine

The efficiency of the heat engine is the ratio of the work done to the
heat input:

Using conservation of energy to eliminate W, we find:

The Carnot Cycle
The different Cycles to examine the efficiency of a heat
engine are:

a) Otto Cycle
b) Diesel Cycle
c) Carnot Cycle
The Carnot engine was created to examine the efficiency of a heat engine. It is idealized, as
it has no friction.
Each leg of its cycle is reversible.
The Carnot cycle consists of:
•Isothermal expansion
•Adiabatic expansion
•Isothermal compression
•Adiabatic compression
 Carnot Cycle - Heat Engine

• Curve A (a → b): Isothermal expansion at TH

• Work done by the gas
• Curve B (b → c): Adiabatic expansion
• Work done by the gas
• Curve C (c → d): Isothermal compression at TC
• Work done on the gas
• Curve D (d → a): Adiabatic compression
• Work done on the gas
Area under PV curve

oThe area under the PV curve represents the quantity of work

done in a cycle

oWhen the curve goes right to left, the work is negative

oThe area enclosed by the four curves represents the net work
done by the engine in one cycle
 Efficiency of Carnot Engine
For an ideal reversible engine, the efficiency can be written in terms of
the temperature:

From this we see that 100% efficiency can be achieved only if the cold
reservoir is at absolute zero, which is impossible.

Real engines have some frictional losses; the best achieve 60-80% of
the Carnot value of efficiency.
 Refrigerators, Air Conditioners, and Heat Pumps
These appliances can be thought of as heat
engines operating in reverse.
By doing work, heat is extracted from the cold
reservoir and exhausted to the hot reservoir.
Entropy and Second law of thermodynamics
Definition of the change in entropy S when an amount of heat Q is added:

Another statement of the second law of thermodynamics:

The total entropy of an isolated system never decreases.

Entropy is a measure of the disorder of a system.

This gives us yet another statement of the second law:
Natural processes tend to move toward a state of greater disorder.
Example: If you put milk and sugar in your coffee and stir it, you wind up with
coffee that is uniformly milky and sweet. No amount of stirring will get the
milk and sugar to come back out of solution.
Engine Efficiency
oThe thermal efficiency of a heat engine is
e = 1 + QC/QH

oThe “engine” statement of the 2nd Law:

it is impossible for any system to have an efficiency of 100% (e = 1)
[Kelvin’s statement]
oAnother statement of the 2nd Law:
It is impossible for any process to have as its sole result the transfer of
heat from a cooler object to a warmer object [Clausius’s statement]
Efficiency of Carnot Engine
Definition of the change in entropy S when an amount of heat Q is
added:

(15-8)

Another statement of the second law of thermodynamics:

The total entropy of an isolated system never decreases.
Irreversible processes (processes that proceed spontaneously in one direction but not
other) –
- inherent one-way processes in nature.
Perfume from an open bottle will spread throughout a room – the perfume molecules
will never spontaneous gather back into the bottle; miscible liquids left to themselves
always tend to mix, not to un-mix.
All irreversible changes S > 0  entropy is not a conserved quantity

Second law – when all systems taking part in a process are included, the entropy
remains constant or increases  no process is possible in which the total entropy
decreases, when all systems taking part in the process are included

For an adiabatic process: Q = 0

Q = 0  S = 0
Example

A mug of coffee cools from l00 °C to room

temperature 20 °C. The mass of the coffee
is m = 0.25 kg and its specific heat capacity
may be assumed to be equal to that of
water, c = 4190 J.kg-1.K-1.
Calculate the change in entropy
(i) of the coffee
(ii) of the surroundings and
(iii) of the coffee plus the surroundings
(the "universe").
Solution

The entropy of the coffee and of the surroundings will both

change.
In each case we consider the system of interest (first the coffee,
second the surroundings) and look at the corresponding
reversible change that takes the system from its initial to its
final state.

Note well that we are not claiming that the change occurred
reversibly, we are just imagining the reversible change so that
we can calculate the entropy change in the real situation.
(i) Coffee:
The coffee cools from l00 °C to 20 °C, i.e. from T1 = 373 K to
T2 = 293 K.
The transfer of energy Q from the coffee to its surroundings is given by the
relation Q = m c T , or dQ = m c dT, where m is the mass of the coffee, c the
specific heat capacity of the coffee and T the change in temperature of the
coffee while in contact with the reservoir/surroundings.

2 2 2
dQ mcdT 1
S     mc dT
1
T 1
T 1
T
 T2 
S  mc ln  
 T1 
S = (0.25)(4190) ln(293/373) J.K-1 = - 253 J.K-1 2nd Law??
(ii) Surroundings:
These remain at temperature 293 K while an irreversible flow of m c T occurs. Note
that this heat flow is calculated indirectly, in terms of coffee, where data needed for
this calculation is available, rather than from values directly associated with the
surroundings.

S = + |Q| / T = (m c |T|) / T

S = (0.25)(4190)(373 - 293)/293 = +286 J.K-1

Positive since heat flows into the surroundings.

38
(iii) Coffee plus surroundings:

Stotal = Scoffee + Ssurroundings = - 253 + 286 J.K-1

Stotal = + 33 J.K-1

As for all naturally occurring processes the net change in entropy is

positive.

39
Isothermal Process: T constant

S =  dQ / T S = Q / T
pV  n R T
n RT
In an isothermal expansion, p
heat Q must be added to V
keep T constant, in a process n R TdV  V2 
W   p dV    n R T ln  
where T is small dV  V1 
U  Q  W  0
Q = n R T ln( V2 / V1 )
 V2 
Q  W  n R T ln  
S = n R ln( V2 / V1 )  V1 
 V2   W 
   exp  
 1
V  n R T 
expansion: V2 > V1 ln(V2 /V1) > 0 S > 0
40
 Example
A stone of mass 1.0 kg is dropped into a lake of water from a
height of 3.0 m. Calculate the changes in entropy of the stone
and of the lake.
Solution

At first sight, this might seem to be a mechanics sum. But there will
be an energy transfer: potential energy of the stone to kinetic
energy of stone to internal energy of the lake. Changes in entropy
are associated with the energy transfers. Because of the size of the
lake, its temperature is effectively unchanged. We also assume that
there is
no difference between the temperatures of the air and the lake, so
the temperature of the stone is also unchanged.
Stone:
The initial and final thermal states (internal energy, temperature,
volume, etc.) are identical. The corresponding reversible change
to be considered is extremely simple - no change. This means
that the entropy change of the stone is zero.
Lake:

Take the energy that is transferred from the stone to the lake
as being equal to the original potential energy of the stone.
The corresponding reversible change is the transfer of heat
flow to the lake.

Increase of entropy, S = m g h / T

Assume

T = 300 K, m = 1.0 kg, g = 10 m.s-2 and h = 3.0 m

S = (1.0)(10)(3.0) / 300 = + 0.10 J.K-1

Practical Uses

oAutomobile engines, refrigerators, and air conditioners all work

on the principles laid out by the 2nd Law of Thermodynamics

oEver wonder why you can’t cool your kitchen in the hot summer
by leaving the refrigerator door open?

Feel the air coming off the back - you heat the air outside to cool the air
inside

See, you can’t break even!

Spontaneous Processes
o Processes that occur without outside intervention
o Spontaneous processes may be fast or slow
o Many forms of combustion are fast
o Conversion of graphite to diamond is slow
o Kinetics is concerned with speed, thermodynamics with the initial and
final state

o"In any spontaneous process there is always an increase in the

entropy of the universe"
o"The entropy of the universe is increasing"
oFor a given change to be spontaneous, Suniverse must be positive

Suniv = Ssys + Ssurr

Positional Entropy
The probability of occurrence of a particular state depends on the
number of ways (microstates) in which that arrangement can be
achieved
Ssolid < Sliquid << Sgas
Entropy and Temperature

Suniv = Ssys + Ssurr

o Entropy changes in the surrounding are primarily determined by heat flow
o The magnitude of entropy is dependent on the temperature
o The lower the temperature, the higher the impact to the surroundings of the transfer of
energy
Entropy and Exothermic Processes
o Exothermic process
DSsurr = positive, exothermic = more disorder in surroundings

o Endothermic process
DSsurr = negative, endothermic = less disorder in surroudings
Dssystem must increease to obey 2nd Law of Thermodynamics
Conditions for Spontaneous Process

oEntropy change for a process:

oDSuniv = DSsys + DSsurr > 0,  process is spontaneous
oDSuniv = DSsys + DSsurr = 0,  process is at equilibrium

oIf DSsys < 0, DSsurr > 0, and |DSsurr| > |DSsys|

oIf DSsurr < 0, DSsys > 0, and |DSsys| > |DSsurr|
Entropy and Temperature

Why is the sign different?

oThe enthalpy (H) concerns the system
oOur entropy here concerns the surroundings
oAs usual, temperatures must be in Kelvin
o 1st reaction
H = -125 kJ, 25 oC + 273 = 298 K
Ssurr = -125 kJ/298 K = 419 J/K
125 kJ = 125000 J
ssurr is positive, calculation refers to system
o 2nd reaction
H = 778 kJ, 25 oC + 273 = 298 K
S = 778 kJ/298 K = -2.61 kJ/K
(778 kJ = 778000 J)
Gibbs Free Energy
oFor a system at constant T & P. Gibbs free energy can be written as:
G = H – TS
oWhere H is enthalpy(kJ mol-1), S is entropy(J mol-1K-1) and T is
temperature (K)
Free Energy, G
G = H - TS
Typically defined as the energy available to perform work
G determines whether a process is spontaneous or not
(G = negative = spontaneous)
Takes into account enthalpy, entropy, and temperature
Symbol honors Josiah Gibbs (sometimes called Gibbs Free Energy or
Gibbs energy), a physics professor at Yale during the late 1800’s who
was important in developing much of modern thermodynamics
Energy Diagrams

• Left – A spontaneous reaction

– The products have a lower free energy (G) than the reactants (G < 0)
• Right – A nonspontaneous reaction
– The reactants have a higher free energy than the products (G > 0)
Free energy and reaction
G = 0?
– The reaction is at equilibrium

As a result
G < 0 The reaction is spontaneous.

G > 0 The reaction is nonspontaneous.

G = 0 The reaction mixture is at equilibrium.

-It’s not moving forward or reverse overall – multiple
processes, same speed
Dependence on Temperature

G = H - TS
oThere are two terms in the equation
oSpontaneity can change when the temperature changes.
oTemperature and spontaneity are not necessarily correlated.
oA reaction with a negative entropy (loss of randomness) would
be LESS spontaneous at higher temperatures – it doesn’t want
to happen, but is pushed by the extra heat.
 H, S, G and Spontaneity
G = H - TS
H is enthalpy, T is Kelvin temperature

Value of H Value of TS Value of G Spontaneity

Negative Positive Negative Spontaneous

Positive Negative Positive Nonspontaneous

Negative Negative ??? Spontaneous if the absolute value of
H is greater than the absolute value
of TS (low temperature)

Positive Positive ??? Spontaneous if the absolute value of

TS is greater than the absolute value
of H (high temperature)
 Example of Gibbs Energy

For the reaction at 298 K, the values of DH and DS are 58.03 kJ and
176.6 J/K, respectively. What is the value of DG at 298 K?

G = H - TS

G = 58.03 kJ – (298 K)(176.6 J/K)

G = 5.40 kJ Not spontaneous at this temperature

Example-2

Calculate the standard free-energy change at 25oC for the Haber

synthesis of ammonia using the given values for the standard enthalpy
and standard entropy changes:

N2(g) + 3H2(g) 2NH3(g) Ho = 92.2 kJ

So = 198.7 J/K

G = H  TS

G = 92.2 kJ  (298 K)(-198.7 J/K)(1 kJ/1000 J)

= -33.0 kJ
Example-3
o Iron metal can be produced by reducing iron(III) oxide with hydrogen:
Fe2O3(s) + 3 H2(g)  2 Fe(s) + 3 H2O(g)
H = +98.8 kJ; S = +141.5 J/K
(a) Is this reaction spontaneous under standard-state conditions at 25 °C?
(b) At what temperature will the reaction become spontaneous?

o To determine whether the reaction is spontaneous at 25 °C, we need to

determine the sign of G = H  TS. At 25 C (298 K), G for the reaction is
G = H  TS = (98.8 kJ)  (298 K)(0.1415 kJ/K)
= (98.8 kJ)  (42.2 kJ)
= 56.6 k
o Reaction is NOT spontaneous!
Example-3

At what temperature does this become spontaneous?

oAt temperatures above 698 K, the TS term becomes larger than H,
making the Gibbs energy negative and the process spontaneous

oWhy is this postive this time?

It should be understood that here we’re dealing with the system, not
the surroundings!
Effect of Temperature on DGo

Go = Ho - TSo

Example-1:
• For the reaction: N2(g) + 3H2(g)  2NH3(g),
Ho = -92 kJ and So = -199 J/K = -0.199 kJ/K

• At 25oC, TDSo = 298 K x (-0.199 J/K) = -59.3 kJ

• Go = Ho - TSo = -92 kJ – (-59.3 kJ) = -33 kJ;
•  reaction is spontaneous at 25oC

• At 250oC, TSo = 523 K x (-0.199 J/K) = -104 kJ;

• Go = Ho - TDSo = -92 kJ – (-104 kJ) = 12 kJ;
•  reaction is nonspontaneous at 250oC
Effect of Temperature on Go

Go = Ho – TSo

• Example-2:
• For the reaction: CH4(g) + H2O(g)  CO(g) + 3H2(g),
Ho = 206 kJ and So = 216 J/K = 0.216 kJ/K

• At 25oC, TSo = 298 K x (0.216 J/K) = 64.4 kJ

• Go = Ho - TSo = 206 kJ – 64.4 kJ = 142 kJ;
•  reaction is nonspontaneous at 25oC.

• At 1200 K, TSo = 1200 K x (0.216 J/K) = 259 kJ;

• Go = Ho - TSo = 206 kJ – 259 kJ) = -53 kJ;
•  reaction is spontaneous at 1200 K
G under Nonstandard Conditions

• Free energy change also depends on concentrations

and partial pressures;
• Under nonstandard conditions (Pi not 1 atm),
G = Go + RTlnQp,

Consider the reaction: N2(g) + 3H2(g)  2NH3(g),

(PNH3 ) 2
Qp =
(PN2 )(PH2 ) 3

Under standard condition, PN2 = PH2 = PNH3 = 1 atm, Qp = 1;

lnQp = 0, and G = Go
G of reaction under nonstandard condition

Consider the following reaction at 250oC:

N2(g) + 3H2(g)  2NH3(g),
where, PN2 = 5.0 atm, PH2 = 15 atm, and PNH3 = 5.0 atm

Qp = 52/(5 x 153) = 1.5 x 10-3

lnQp = ln(1.5 x 10-3 ) = -6.5

Under this condition, G = Go + RTlnQp;

(For this reaction at 250oC, calculated Go = 12 kJ)
 G = 12 kJ + (0.008314 kJ/T x 523 K x (-6.5))
= 12 kJ – 28 kJ = -16 kJ  spontaneous reaction
Entropy Changes in Chemical Reactions
oConstant Temperature and Pressure
oReactions involving gaseous molecules
oThe change in positional entropy is dominated by the relative
numbers of molecules of gaseous reactants and products

Typically, more moles of gas, more entropy

Calculating Entropy Change in a Reaction

S 0
reaction   np S 0
products   nr S o
reactants

oCalculates standard entropy of a reaction, uses standard entropies

of compounds
oEntropy is an extensive property (a function of the number of
moles)
oGenerally, the more complex the molecule, the higher the
standard entropy value
Chemical Potential
o chemical potential of a species is energy that can be absorbed or released due to a change of
the particle number of the given species,
e.g. in a chemical reaction or phase transition
o The chemical potential of a species in a mixture is defined as the rate of change of free energy of
a thermodynamic system with respect to the change in the number of atoms or molecules of the
species that are added to the system.
mi = (G / ni)

Where mi is the chemical potential of a certain component in a system and Dni is the change in
moles of that component. For a system at equilibrium, mi is the same in all phases.
The chemical potential, µ, of a component in a solution can be thought of in many ways:
1. A measure of the "escaping tendency" for a component in a solution;
2. A measure of the reactivity of a component in a solution;
3. The chemical potential of a component in a solution is defined as the rate at which the internal
energy of the solution increases as the number of moles of the component in question increases,
for a given entropy and volume of the solution.
Activity and Fugacity (for a gas):
Fugacity can be defined as the apparent (or effective) concentration of a species as
opposed the actual concentration.
They are a measure of the departure of a system from ideal behavior and need to be
taken into account even when dealing with relatively dilute solutions.
Activity (or fugacity) is related to concentration through the activity coefficient (gi ).
g i = ai / m i
Where ai is the activity and mi is the actual concentration.
Incorporating the chemical potential into the activity yields the following equation:
mi = mi0 + RT ln(ai)
Where mi0 is the chemical potential of component i in its standard state.
Third Law of Thermodynamics
o"The entropy of a perfect crystalline solid at O K is zero" (NO disorder,
since everything is in perfect position)

o No movement = 0 K

o No disorder = no entropy (S = 0)