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Physical Chemistry
Ira N Levine
Tata McGraw Hill Education Pvt. Ltd., New York (2002).
Kinds of equilibrium.
Stable, Metastable, Unstable & Neutral equilibrium states.
Thermodynamic variables and potentials.
In this text only some aspects will be dealt with, readers may consult standard texts on
thermodynamics/thermostatics for a other aspects/detailed account.
Caution Note: In any chapter, amongst the first few pages (say 5 pages) there will be some ‘big picture’
overview information. This may lead to ‘overloading’ and readers who find this ‘uncomfortable’ may skip
particular slides in the first reading and come back to them later.
These slides are intended to set the stage for understanding the ‘purpose’ and ‘power’ of thermodynamics and its
Motivation ‘quantities’. Gibbs Free Energy (G) and Entropy (S) will be in special focus.
1
Let us start by performing the following (thought) experiment:
Heat a rod of Al from room temperature to 500C As expected the rod will expand
(A → B in figure below).
The expansion occurs because of two reasons:
1 Vibration of atoms (leading to an increase in average spacing between atoms→ the usual reason)
(A → M in figure below).
2 Increase in the concentration of vacancies* (a vacancy is created when a Al atom goes
to the surface and for every 4 vacancies created the volume equal to 1 unit cell is added).
(M → B in figure below).
The 2nd reason is of subtler origin and must be surprising to many readers. Additionally, it
is a smaller effect in terms of its contribution to the overall increase in length of the
specimen (see solved example link below- it is about 1 in 10000 effect).
Metal expands on
heating due to 2 different
physical reasons!
* It costs energy for the system to put vacancies (broken bonds, distortion to the lattice)
then why does the system tolerate vacancies?
Now let us perform another (thought) experiment to put in perspective the previous
experiment:
Heat a elastomer (cut rubber band) which has been stretched by a small weight by about
20C (room temperature + 20C) the stretched rubber band will contract!
The 2nd reason for the expansion of the Al rod is closely related to the contraction of the
stretched rubber band! occurs because of thermodynamic reasons (quantities like Gibbs
Free Energy (G) and Entropy (S)), which we shall learn in this chapter.
In the case of the heating of the Al rod- “how the vacancies form” is an issue of kinetics.
Kinetics will be dealt with in the topic of kinetics and chapter on Diffusion.
A ‘stretched’ elastomer
contracts on heating!
Motivation
2
Let us next consider the melting of a pure metal at its melting point (MP) (at constant T
and P) → by supplying heat to the sample of metal (so that the metal sample is only partly
molten). At the MP the liquid metal is in equilibrium with the solid metal.
The liquid has higher potential energy as well as higher kinetic energy (at the molecular level)
than the solid.
Then why does the liquid co-exist with the solid?
The answer to this question lies in the fact that internal energy is not the measure of
stability of the system (under the circumstances).
We will learn in this chapter that it is the Gibbs Free Energy (G). The molten metal has
higher energy (internal energy and enthalpy), but also higher Entropy. So the melting is
driven by an increase in Entropy of the system. The molten metal and the crystalline solid
metal have the same G → hence they co-exist in equilibrium.
Similarly we can consider the vaporization of water at 100C and 1 atm pressure.
Not only that steam has higher internal energy, but also that work has to be done against
atmospheric pressure to accommodate the higher volume of steam!
Stability and Equilibrium
Equilibrium refers to a state wherein there is a balance of ‘forces’*.
Nothing happens in a system in equilibrium (as there is no ‘motivation’).
(as we shall see equilibrium points have zero slope in a energy-parameter plot).
Stability relates to perturbations (usually small perturbations** about an equilibrium state)
(as we shall see stable relates to the curvature at the equilibrium points).
Note: nothing happens/changes in a
Kinds of Equilibrium system under equilibrium (at least
macroscopically)
Mechanical equilibrium
Thermal equilibrium
Reaction Equilibrium
Material Equilibrium
Phase Equilibrium
When conditions of reaction and phase equilibrium are satisfied, we have material
equilibrium.
The term thermodynamic equilibrium implies that, we have thermal, mechanical and
chemical equilibrium.
* Force has been used here in a generalized sense (as an agent which can cause changes)
** Perturbation is usually a small ‘force/displacement’ imposed in a short span of time.
Equilibrium with respect to conversion of set of chemical species to
another
Reaction equilibrium The fraction of reactants and products remains constant with time
Material equilibrium These are dynamic equilibria
Number of moles of each Phase equilibrium The fraction of various phases remains constant with time
substance (in the closed
system) remains constant Equilibrium with respect to transport of matter between phases of a
with time system (without conversion of one to another)
Thermal equilibrium
Thermodynamic Mechanical equilibrium
Equilibrium
Chemical equilibrium
Equilibrium in a Mechanical System
Let us start with a simple mechanical system (it is easier to visualize mechanical systems)
→ a rectangular block (Figure in next slide) (under an uniform gravitational potential).
The potential energy (PE) of the system depends on the height of the centre of gravity
(CG).
The system has higher PE when it rests on face-A, than when it rests on face-B.
The PE of the system increases when one tilts it from C1 → C2 configuration. This
increase in potential energy is the ‘activation energy’ required.
In configurations such as C1,C2 & C3 the system will be in equilibrium (i.e. will not
change its configuration if there are no perturbations).
In configuration C2 the system has the highest energy (point B) and any small
perturbations to the system will take it downhill in energy → Unstable state.
Configuration C3 has the lowest energy (point C) and the system will return to this state if
there are small perturbations → the Stable state.
Configuration C1 also lies in an ‘energy well’ (like point C) and small perturbations will
tend to bring back the system to state C1. However this state is not the ‘global energy
minimum and hence is called a Metastable state.
Additionally, one can visualize a state of neutral equilibrium (C4), like a ball on a plane
(wherein the system is in a constant energy state with respect to configurations).
Mechanical Equilibrium of a Rectangular Block
We start by considering the mechanical equilibrium of a block- this is to get a first feel- additional concepts will be required
when dealing with condensed matter systems.
Ball on a plane
Neutral Equilibrium
Centre
Of
Gravity
C1 C2 C3 C4
C2 Unstable
Potential Energy = f(height of CG)
Activation
barrier
Stable
C1
Lowest CG of all possible
states
Metastable state Configuration C3
Points to be noted:
A system can exist in many states (as seen even for a simple mechanical system: block on a plane)
These states could be stable, metastable or unstable (or even neutral)
Using the relevant (thermodynamic) potential* the stability of the system can be characterized
(In the case of the block it is the potential energy, measured by the height of the CG for the case of the block on the plane)
System will ‘evolve’ towards the stable state provided ‘sufficient activation’ is provided
(in the current example the system will go from C1 to C3 by ‘sufficient jolting/shaking’ of the plane)
However, this aspect is not within the domain of thermodynamics.
Intensive properties are those which are independent of the size of the system
P, T
Extensive Properties are dependent on the quantity of material
V, E, H, S, G
Thermodynamic potentials and the relation between them
There are 4 important potentials (in some sense of equal stature).
These are:
Internal Energy (U), Enthalpy (H), Gibbs Free Energy (G), Helmholtz Free Energy (A).
The relation between these potentials and the state variables is as below.
The relevant thermodynamic potential which characterizes the stability of the system is
dependent on the state variables which are held constant (as in the table below).
The most conditions are one of Constant P and Constant T
→ Hence G (Gibbs Free Energy) is the most relevant thermodynamic potential.
However, we should remember that depending on the state variables being held constant
any one of the four potentials (U, H, F, G) could be the relevant potential. (i.e. all of the
potentials have the same ‘stature’).
dH TdS VdP
Constant V Constant P
dU TdS PdV
Constant S U H
dG SdT VdP
Constant T F G dA SdT PdV
* The main response.
Energy & Internal Energy
The total energy of a body is the sum of its kinetic energy (K), its potential energy (V) and
internal energy (U).
Let us consider a container of gas moving at a height ‘h’ from the ground at a velocity ‘v’.
The total energy of this system is (E) = K + V + U = (½ mv2)+(mgh)+U.
K & V are macroscopic quantities. U is related to the internal molecular structure (and the
details therein).
U consists of: molecular translational energy, molecular rotational energy, molecular
vibrational energy, energy due to electronic states, interaction energy between
molecules, relativistic rest- mass energy (mc2) arising from electrons and nucleons.
In most cases in thermodynamics K and V are ignored.
Gas v
h
1 Internal Energy (U)
T
H H 0 CP dT
0
T
H C dT
298
P
Entropy (S)
Entropy is perhaps one of the most profound and subtle concepts of nature.
Entropy can be understood looking at a Macroscopic picture (interpretation) or a
Microscopic picture (interpretation) (next slide).
Though these are different approaches to understand entropy– the result is the ‘same’
entropy.
In the Macroscopic view we ‘work’ at the system level and worry about observable
average quantities. In the Microscopic view we go into all the ‘details’ about the system.
The entropy of an isolated system will increase in a spontaneous process (cannot
spontaneously decrease)→ II law.
Since, the above can be applied to the entire universe (a large isolated system!**)→ the entropy
of the Universe will always increase (here we are not using the word ‘spontaneous’ as the Universe cannot be ‘coaxed’ into
doing a non-spontaneous processes!).
We had noted that the Boltzmann constant arises because we try to make a ‘unit’ Kelvin equal
to a unit C.
Suppose we measured temperature in terms of ‘’, then entropy would be a pure number.
Q&A Are the two definitions of entropy (the classical one defined by equation (1) & the
statistical mechanics one defined by equation (2)) identical?
Clearly they are not identical as equation (1) deals with S (i.e. changes in entropy), while
equation (2) deals with S (the absolute value).
However, the quantity ‘S’ being referred to both the equations is the same. In fact the third
law of thermodynamics establishes this link.
Qrev
Sthermal
T
(1) S config k ln (2)
Qrev
* Thermal entropy as defined before as :
Sthermal Continued...
T
Say you want to measure the mass of a person (let the person called Sukriti). This can be done in two
ways: (i) Sukriti stands on a weighing machine and this gives her mass (MSukriti) or (ii) she counts the
number of atoms of various types in her body (NO, NC, NFe, etc.) and then she multiplies these numbers
with their respective atomic masses and sums the results to get the total mass of her body (N OmO +
NCmC + NFemFe +..... = MSukriti).
By both ways we get the mass of Sukriti (MSukriti)
In method (i) in which we sit at the boundary of the system (called Sukriti) and need not know the
microscopic details of the person, while in method (ii) we have all the microscopic (atomic composition)
details and use this to compute the mass of Sukriti. Clearly we should not add the two methods of
obtaining masses (to get the ‘total’ mass of Sukriti).
Mass of Sukriti
O, N, Fe,...
25 kg
Funda Check How do I understand the microscopically degenerate states?
Note that some set of variables are kept constant for a system. E.g.: (i) number of moles of matter,
volume and temperature (NVT) or (ii) NPT or (iii) NVE, etc.
The microstates have to be enumerated keeping these variables constant.
Let us consider a NVE system. A classroom of students where the number of students, the volume of
the room and the energy of the students are constant.
Let the classroom have 50 students with a total energy of 100 U* (i.e. an average of 2 U per student).
This energy can be distributed amongst the students in many ways.
Way-1: all the 50 students jump with 2U.
Way-2: 25 students jump with 4U and the remaining are quiet.
Way-3: 25 students are jumping with 2U and 25 are rotating with 2U.
Etc.
So there are many ways that the 100U energy can be distributed amongst the students.
This represents the microstates in energy.
A B 6 6.5.4
Unmixed state
6
C3 20
3 3 3.2.1
Two boxes separated by a barrier
initially
Unmixed state
18 mixed states
2 unmixed states
State-A
State-B
N!
Smix k ln k ln (1) Smix k ln k ln
N!
( N nA )! nA !
A
( n )! (nB
)!
This formula N!
Smix k ln k ln (1)
A
( n )! (nB
)!
This formula can be simplified using the Stirling’s approximation (wherein the factorials can be replaced)
n
n
An useful formula for evaluating ln(factorials) is the Stirling’s approximation: n ! ~ 2 n
e
Ln(r !) r ln(r ) r r! r ~ asymptotically equal, e = 2.718…
Let us consider a binary alloy (disordered solid solution) with two components A & B in mole fractions XA
and XB. The entropy change on the formation of the alloy can be written as below using the equation (1).
N! XA
nA n
XB B
Smix k ln k ln k ln( N !) {ln(nA !) ln(nB !)} N N
(nA )! (nB )!
X A XB 1
Smix k {N ln( N ) N } {nA ln(nA ) nA} {nB ln(nB ) nB }
nA nB N
Smix k {N ln( N )} {nA ln(nA )} {nB ln(nB )}
Smix k {N ln( N )} {NX A ln( NX A )} {NX B ln( NX b )}
Smix k {N ln( N )} {NX A (ln( N ) ln( X A ))} {NX B (ln( N ) ln( X b ))}
At the melting point of a material when heat is supplied (Q) to the material it does not lead to an increase in the
temperature. Instead, the absorbed heat leads to melting i.e. the energy goes into breaking of bonds in the solid and
consequently a transformation in the state of the material (solid → liquid). The entire process of melting takes place
at a constant temperature (Tm). The heat absorbed is called the Latent Heat of Fusion (Hfusion).
Suppose we take a mole of Al atoms in crystalline form and melt the same, then the change in entropy can be
calculated as below.
In the solid state the atoms are fixed on a lattice (of course with vibrations!) and this represents a ‘low entropy’ state.
On melting the entropy of the system increases as the atoms are free to move around and many configurations are
possible. From this point of view often Entropy is considered as a measure of disorder (however, it must be clear
that the phrase ‘measure of disorder’ is used with an understanding of the context).
Data: Enthalpy of fusion (Hf) = 10.67 kJ/mole, Melting Point (Tm) = 933.4 K (660.25C)
Q H f 10.67 103
Smelting Al 11.43 J / K / mole
T Tm 933.4
What is the entropy of mixing 0.5 mole of A with 0.5 mole of B on a mole of lattice sites (N 0 sites)?
Solved
Example
Data: k 1.38 1023 J / K
The initial configurational entropy of solid A and Solid B (unmixed) is zero. This is because the
atoms of solid A (and similarly solid B) are indistinguishable and hence these A and B atoms in a
lattice of N0/2 sites represent just one configurational state, which implies that the entropy is zero.
Using: S config k ln N Cn
N!
Ln(r !) r ln(r ) r
A
( N nA )! (nA )!
N0 N0
2
N N N N N
k N0 ln N0 N 0 2 0 ln 0 0 k N 0 ln N 0 N 0 ln 0 k N 0 ln N 0 ln 0
2 2 2 2 2
k N 0 ln 2
We have noted that all the internal energy change may not be available as heat for us (some
may be used up to do work to accommodate the products of say a combustion process) and
we introduced the concept of enthalpy for this.
Needless to say, only a spontaneous process can be used for extracting work out of a
system. (For a driven process we have to supply work!).
In a spontaneous process the entropy of the universe has to increase (2nd law of TD rephrased).
So: (Ssystem+Ssurrounding) > 0.
(E.g. If heat enters the system from the surrounding then Ssystem will be positive, while Ssurrounding will be negative).
If entropy is constant in a process, then the direction (condition) for spontaneity is obvious
→ it is the direction in which the internal energy (U) or enthalpy (H) decreases. It is the
‘entropy tax’ which is making things difficult.
As pointed out before we will like to make computations of spontaneity, purely looking at
system based variables.
Under two conditions it is possible to write the condition for spontaneity of a process,
purely based on the system variables.
If the process is carried out under constant T, V.
If the process is carried out under constant T, P.
At constant V there can be no expansion work and if there is no other form of work (magnetic,
electrical etc.) then this energy will lead to an increase in the internal energy of the system (U).
U
S 0 T S U 0 or equivalently U T S 0
T
Note that we do not have to write Ureversible as U is a state function (depends only on the
initial and final states). Zero at constant T
P
Piston
Q
Heat flow
direction T
T
3 Helmholtz Free Energy (A or F)
H
P
C
e
G H TS ( E PV ) TS Sl
op
CP
0
(dq PdV ) PdV VdP TdS SdT
TdS VdP TdS SdT 298 K
Pure Metal Pure Metal
0 T (K) 0 T (K)
dG VdP SdT dG
S At T = 0 K, S = 0 J/K the slope of the G versus T curve at T = 0 is zero
dG P SdT dT P
Summary
H increases with T (with positive curvature).
The Slope of the G vs T curve at 0K is zero.
The curvature (G-T curve) is always negative.
On ‘heating’ the H increases but G decreases
Revisit of the plots
H curve
G curve
What happens during a phase transformation (say a solid to liquid transformation- melting)?
Needless to say, there is no time involved here (and hence we cannot talk about heating or
cooling). All we can comment is on the relative stability of the two phases involved (the solid
and the liquid) at various temperatures. From this we can arrive at the stability regimes of the
two phases (with T). (We often show this ‘as if’ some process is actually taking place– as shown with the red lines in the figure).
Since there are two phases involved, we need two H vs. T and two G vs T curves.
Tm
id
l
So
H
Enthalpy of fusion
0 298 T (K)
G
So
Solid lines correspond to the li d
Li
How long will the solid take to melt if heated above the melting point?
Will the liquid freeze if cooled below Tm?
The above questions do not come under the preview of equilibrium thermodynamics.
Some of these questions will be taken up for study in the chapter on phase transformations.
Funda Check Why is water stable at 10C, does it not have higher ‘energy’ than ice?
True that ice has higher internal energy than water. But, internal energy (U) is not the
measure of stability of a material system at constant T and P → it is the Gibbs free energy
(G). Note that ‘at constant temperature’ does not mean that the system cannot exchange
energy with the surrounding (i.e., the system can exchange energy with the surrounding).
Hence, we have to compare the Gibbs free energy of water and ice at 10C (& 1 atm). The
phase which has a lower G will be ‘stable’.
Ice has a lower enthalpy and a lower entropy, while water has a higher enthalpy with a
higher entropy.
G = H TS.
Enthalpy cost not offset by entropy
Below 0C
benefit, hence G > 0 (i.e. ice stable)
Gwater Gice ( H water H ice ) T ( Swater Sice )
Positive Positive Enthalpy cost offset by entropy benefit,
Above 0C
hence G < 0 (i.e. water stable)
Steam (with even higher entropy and enthalpy) becomes stable only at even higher temperatures (T > 100C).
Additional point to note: below 0C (say at 5C) ice is stable, but we can cool water to this temperature (i.e. undercool) and hold it for a
while (how long depends on other things).