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B18PA1: Thermodynamics

Dr N Hendrik Nahler
email: n.nahler@hw.ac.uk oce: G.30

2012/13

Introduction
About me
2012: Royal Society University Research Fellow, Heriot-Watt University 2007 2012: RS-URF, Durham University 2005 2007: Alexander von Humboldt Fellowship, UCSB 2003 2005: EU Marie Curie Fellowship, Bristol 2002: PhD in Molecular Physics, MPI for Fluid Dynamics, G ottingen
Thermodynamics N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

About my research
Photochemistry on water-ice surfaces at near-ambient conditions Molecule-surface dynamics: energy- and charge-transfer Development of spectroscopic methods

Thermodynamics
Where does it t in the big scheme?
Chemical thermodynamics is the study of the interrelation of heat and work with chemical reactions or with physical changes.
1 Thermodynamics N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 2

How much of a product is formed? Thermodynamics How much energy will be released/used? Thermodynamics How fast is it formed? Reaction Kinetics

Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Example
Thermodynamics Reaction Kinetics diamond graphite

" %

Thermodynamics and reaction kinetics


Thermodynamics all about if
If a reaction can occur. Applicable if a system is in stable or metastable equilibrium. If the driving force is sucient to enforce a favourable transformation.
Thermodynamics N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6

Reaction kinetics all about how


How fast a process can occur (rate of reaction). Applicable to systems in transition from non-equilibrium to equilibrium. How to overcome the energy barrier to go from the reactant to the product.

Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Example
Graphite has a lower Gibbs free energy than diamond and is therefore the thermodynamically favourable state. Large energy barrier to overcome. Reaction kinetics.

Lecture schedule
Thermodynamics

Week 1 3 4 9 10 11 12

Lecture 1&2 3&4 5&6 7&8 9 & 10 11 & 12 13 & 14

Topics Revision, 2nd Law of Thermodynamics 2nd and 3rd Laws of Thermodynamics Free energy and equilibrium Phase diagrams Ideal solutions Dilute solutions, equilibrium electrochemistry Equilibrium electrochemistry

N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Workshops in weeks 3, 4, 10, 11. Online quizzes every week after the lecture (together count 10% towards this term, 90% exam) Kinetics lectures (weeks 5 8), quizzes and workshops: Prof Ken McKendrick

Reading list
Textbook for this course
2 3 Thermodynamics

Thermodynamics: the rst law Thermodynamics: applications of the First Law Thermodynamics: the Second Law Physical equilibria: pure substances The properties of mixtures Chemical equilibrium: the principles Chemical equilibrium: equilibria in solutions Chemical equilibrium: electrochemistry

N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

4 5 6 7 8

Additional reading
Physical Chemistry (Atkins & de Paula), Chemistry (Housecroft & Constable), Basic chemical thermodynamics (Smith), Principles of thermodynamics (Kaufman)

Revision, 2nd Law of Thermodynamics


Thermodynamics N H Nahler

Key concepts
Internal energy change Enthalpy change Entropy change Gibbs free energy change U H S G

Laws of thermodynamics
1

Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

The internal energy, U , of an isolated system is constant. The entropy, S , of an isolated system tends to increase.

Goal: describe equilibrium using these key concepts.

Reading
Chapter 2 Thermodynamics: the rst law Chapter 3 Thermodynamics: applications of the First Law Chapter 4 Thermodynamics: the Second Law, pp. 83 93

System and Surrounding


System
The system is what we are interested in. Examples: reaction components, engine, biological cell.
Thermodynamics N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6

Surroundings
The surroundings is the universe apart from the system. This is where we mostly do our measurements. Open system Closed system Isolated system

Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

can exchange matter and energy with surroundings.

can only exchange energy with surroundings.

completely insulated from the surroundings.

The 1st Law of Thermodynamics


Thermodynamics

First law
The internal energy (U ) of an isolated system is constant.

N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10

Alternative denition
In chemical changes energy can be converted to one form or another but not destroyed.

Classical mechanics
Object falling o a table Ekin = Harmonic oscillator Ekin = 1 2 1 mv = kx 2 = Epot 2 2 (2) 1 2 mv = mgh = Epot 2 (1)

Lecture 11 & 12 Lecture 13 & 14

Internal Energy, U
The internal energy is made up of kinetic energy, rotational energy, vibrational energy, potential energy etc.
Thermodynamics N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4

Changes in internal energy, U


Heat transfer, q , to/from surroundings Work, w , done on/by surroundings U = q + w Sign convention for heat and work: q = +ve , U for surroundings system q = ve , U for system surroundings equivalent for work, w . U = q + w = q p V =q =0 for an ideal gas V = const. for an isolated system (4) (5) (6) (3)

Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Work: ideal gas


Thermodynamics N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12

Expansion
When the gas expands, work is done by the systems on the surroundings, w = ve and U . If you quickly expand a gas it cools down e.g. spray can.

Compression
To compress a gas work needs to be done by the surroundings on the system, w = +ve and U . If you quickly compress a gas it heats up e.g. bicycle pump.

Lecture 13 & 14

Work in a chemical reaction


CuCO3 (s) + 2 HCl(aq)
solid liquid

CuCl2 (aq) + H2 O(l) + CO2 (g)


liquid liquid gas

(C 1)

Thermodynamics N H Nahler Lecture 1 & 2

open vessel at room temperature ideal gas law Remember the sign convention for work.

Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Enthalpy, H
If our chemistry happens in an open system then energy put into the system will be partly given back to surroundings. Therefore we dene a new quantity that avoids the complication of work of expansion by the system on the surroundings:
Thermodynamics N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6

Denition of Enthalpy, H
H = U + pV (7)

Lecture 7 & 8 Lecture 9 & 10

Change in enthalpy
At constant pressure: H = U + p V At constant pressure and no expansion work: H = q (9) (8)

Lecture 11 & 12 Lecture 13 & 14

Recall that the enthalpy varies with temperature, a concept which is expressed by the heat capacity (Atkins, 2.9, pp. 56 59).

State functions and heat capacity


Thermodynamics N H Nahler

The internal energy U and the enthalpy H are state functions (in contrast to path functions like w and q ). Consequently dU and dH are exact dierentials.
dU = U T
CV

Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4

dT +
V

U V

Lecture 5 & 6

dV (10)
T

Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

CV : Heat capacity at constant volume

dH =

H T
Cp

dT +
p

H p

dp (11)
T

Cp : Heat capacity at constant pressure

First law problem


Calculate the change in internal energy, U , when 1 mol of zinc is dissolved in aqueous hydrochloric acid at 298 K and atmospheric pressure given that the heat that is liberated is 151 000 J. How big is the change in enthalpy, H ?
Thermodynamics N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Thermochemistry
Change of enthalpy in chemical reactions
exothermic process endothermic process releases heat absorbs heat H < 0 H > 0
Thermodynamics N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6

Hesss Law of constant heat summation


r H (298 K) = r H (products, 298 K) r H (reactants, 298 K)

Lecture 7 & 8 Lecture 9 & 10

(12)

Lecture 11 & 12 Lecture 13 & 14

Example: nd f H for the reaction


2 NO(g) + O2 (g) given
1 2 N2 (g) 1 +2 O2 (g)

2 NO2 (g) H1 = +90 kJmol1 H2 = 20 kJmol1 H3 = 86 kJmol1

(C 2)

NO(g) N2 O4 (l)

N2 (g) + 2 O2 (g) 2 NO2 (g)

N2 O4 (l)

The 2nd Law of Thermodynamics (i)


Thermodynamics

The First Law states that energy is conserved when changes occur. It is dened in terms of the state function U . However, it does not tell us about direction of change.

N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Examples for natural directions of change


expansion of gas into vacuum spontaneous mixing of gases objects of dierent temperature brought into contact will equalize the temperature some reactions will occur spontaneously a ball bouncing will stop The Second Law is concerned with the direction of change. It is dened in terms of a second state function, the entropy, S . The entropy, S, is a measure of the molecular disorder of a system

The 2nd Law of Thermodynamics (ii)


Thermodynamics N H Nahler

Second law
The entropy, S , of an isolated system tends to increase.

Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4

Alternative denition of the second law


The total entropy, Stot of a system (Ssys ) and surroundings (Ssur ) increases in the course of a spontaneous change. Stot = Ssys + Ssur > 0 At equilibrium or for a reversible process, the total entropy is constant. Stot = 0 (13)

Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

(14)

Thermodynamic denition of entropy, S


Thermodynamics

For a reversible change we dene: dqrev T


nal

N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6

dS = S =

(15) dqrev T (16)

dS =
initial

Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12

Clausius inequality
The entropy change of the system must be greater than, or equal to, the heat ow divided by temperature. dS dQ T (17)

Lecture 13 & 14

This applies for a natural process (irreversible).

Entropy change: heating


From equation 11 we know: dH dq = dT dT Cp dqrev = dT dS = T T T2 Cp dT S = T1 T Cp = (18) (19) (20)
Thermodynamics N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12

If Cp is independent of temperature (usually only over a small range): S = Cp ln T2 T1 (21)

Lecture 13 & 14

Example
You drink a glass of tap water (200 g, 10 C). Assuming a body temperature of 36 C, what is the change in entropy? (Cp,m = 75.5 JK1 mol1 )

Entropy change: expansion


The energy transferred as heat to a perfect gas when it undergoes reversible isothermal expansion is:
V2 V2
Thermodynamics N H Nahler Lecture 1 & 2

qrev = w =
V1

p dV =
V1

nRT V2 dV = nRT ln V V1

(22)

Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6

For the change in entropy in this process follows: V2 S = nR ln V1

(23)

Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Examples
1

A sample of carbon dioxide that initially occupies 15.0 dm3 at 250 K and 1.00 atm is compressed isothermally. Into what volume must the gas be compressed to reduce the entropy by 10.0 JK1 ? (Atkins, 4.6) A monoatomic perfect gas at a temperature Ti is expanded isothermally to twice its initial volume. To what temperature should it be cooled to restore its entropy to its initial value? 3 CV ,m = 2 R . (Atkins, 4.12)

Entropy change: phase transition (i)


Addition of heat evaporates water. Removal of heat freezes water. Melting at melting temperature, Tf : fus H (Tf ) fus S = Tf Vaporization at the boiling temperature, Tb : vap H (Tb ) vap S = Tb (24)
Thermodynamics N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8

(25)

Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Troutons rule (empirical)


vap S = vap H (Tb ) 85 JK1 mol1 Tb (26)

Notable exceptions to the rule are water, ammonia and mercury. Hydrogen bonding and metal bonding in the latter lead to a higher order in the liquid phase and consequently to vap S > 85 JK1 mol1 .

Entropy change: phase transition (ii)


Examples
1 Thermodynamics N H Nahler Lecture 1 & 2

Melting of ice: ice


273 K, 1 bar

water

(C 3)

Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10

fus H = 6000 Jmol1 , Tf = 273 K, fus S = 22 Jmol1 K1


2

Vaporization of water: water


373 K, 1 bar

steam

(C 4)

Lecture 11 & 12 Lecture 13 & 14

vap H = 41 000 Jmol1 , Tb = 373 K, vap S = 110 Jmol1 K1


3

Note that the vaporization entropy is much larger than the fusion entropy. Note the dierence between the vaporization entropy and the predicted value from Troutons rule. (hydrogen bonding) Estimate the enthalpy of vaporization of bromine from its boiling temperature, 59.2 C.

2nd and 3rd Laws of Thermodynamics


Thermodynamics

Key concepts
Entropy change S Absolute entropy Statistics and Thermodynamics Gibbs free energy change G Helmholtz energy change A Goal: describe equilibrium using these key concepts.

Laws of thermodynamics
1

N H Nahler Lecture 1 & 2

The internal energy, U , of an isolated system is constant. The entropy, S , of an isolated system tends to increase. The entropy of a perfectly crystalline substance at T = 0 K is S = 0.

Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Reading
Chapter 4 Thermodynamics: the Second Law To look further into concepts of Statistical Thermodynamics you can read Chapter 22 Statistical Thermodynamics

Entropy change: reversible and irreversible processes


Reversible change
Stot = Ssystem + Ssurrounding = 0 (27)
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12

Irreversible change
Stot = Ssystem + Ssurrounding > 0 To caculate S we need to nd a reversible pathway. (28)

Example: the freezing of supercooled water at T = 10 C


H2 O(l) H2 O(s) (C 5)

Lecture 13 & 14

Ice and water are not at equilibrium at 263 K. Ice is the more stable phase. Therefore the process is irreversible and S (263 K) = fus H (263 K) 263 K

Example: the freezing of supercooled water


1 2 3 4

Construct reversible thermodynamic cycle Calculate entropy changes of individual changes. Calculate the entropy change of the system. Calculate the entropy change of the surroundings and the total entropy change (Stot > 0).
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Entropy change: chemical reactions


Phase changes
solids liquids gases relatively ordered some order disordered low entropy medium entropy high entropy
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6

Changes in molecules
For a reaction with all molecules in the same phase x , the change in number of molecules is important: A(x) + B(x) C(x) (C 6)

Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12

Examples
NH2 (g) +HCl(g) NH4 Cl(s) S = ve 1 H2 (g) + 2 O2 (g) H2 O(l) S = ve + Ph2 CHCl+(in water) Ph2 CH (aq) + Cl (aq) S = ve Would guess S = +ve as number of particles increase but ions are solvated, meaning an ordering of water molecules around the ions.

Lecture 13 & 14

Entropy change: mixing of ideal gases (i)


How can we calculate the entropy change of a mixture of ideal gases? Is there actually a change in entropy? Ideal gases do not interact.
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Mole fractions: system with J components


mole fraction of component J nJ ni number of moles xJ = ntotal nA + nB + + nN xi = =1 ntotal nB xB = nA + nB xJ

(29)

Mole fractions: binary system with components A and B


nA xA = nA + nB xA + xB = 1 xB = 1 xA The two mole fractions are not independent from one another. The composition of a binary system is dened by one of the two mole fractions. (30)

Entropy change: mixing of ideal gases (ii)


Both gases A and B are under the same pressure p before mixing. According to their mole fractions, gases A and B are described by their partial volumes pA and pB in the mixture. Consider mixing as an expansion of an ideal gas.
0.6

Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6 Lecture 7 & 8

mixS / nR

0.4

0.2

0 0 0.5 1

Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Mole fraction of A, xA

mix S = nA R ln

pA pB nB R ln p p = nR (xA ln xA + xB ln xB )

(31) (32) (33)

mix S 0 Ideal gases always mix.

Mixing: statistical thermodynamics


Thermodynamics

Can we understand macroscopic behaviour from a molecular viewpoint?


We know that there is a conceptual link between molecular disorder and entropy e.g. a gas is more disordered than a solid. Macroscopic: we measure disorder by entropy. Molecular: we measure disorder by the number of ways (microstates), W , molecules can organise themselves. How can we relate S and W ? S = kB ln W (34)

N H Nahler Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

All we need to know to calculate S is W.

Mixing functions
Macroscopic thermodynamics
A (l) B (l)
Thermodynamics N H Nahler Lecture 1 & 2

Lecture 3 & 4

mix S = nR (xA ln xA + xB ln xB )
A (l) + B (l)

Molecular thermodynamics
B A B B A A A

Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10

A A A B

A B

A A A A A B B B A A A B B B A A B

What is the number of ways of placing NA molecules A into a cubic lattice with a total of N sites?
Note that NA = Avogadros number in this context. We express Avogrados number as NAvo. .

Lecture 11 & 12 Lecture 13 & 14

How many arrangements are there?


Thermodynamics

Meet Jill and Jack

N H Nahler

Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Counting possibilities
Lets say we have NA Jills and N oces
Number of ways of placing . . . . . . rst Jill = N . . . second Jill = N 1 . . . third Jill = N 2 ... . . . the NA th Jill = N (NA 1) = N NA + 1
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6 Lecture 7 & 8

Total number of ways W = W1 W2 W3 . . .


W = (N NA + 1) (N NA + 2) (N 1) N 1 2 3 (N NA ) (N NA + 1) (N 1) N = N! (N NA )! N! (N NA )! =W

Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Counting possibilities
Now we have overcounted the possibilities W
Several dierent ways lead to the same microstate. For example, in the case of:
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6

# # # # # #

1 1 2 2 3 3

# # # # # #

2 3 1 3 1 2

... ... ... ... ... ...

... ... ... ... ... ...

# # # # # #

3 2 3 1 2 1

Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

The three Jills (A molecules) are indistinguishable. The six congurations constitute the same microstate.

Counting possibilities
Thermodynamics N H Nahler

To account for this overcounting, how many ways of placing molecules on a given set of sites?
1 2 3 . . . NA molecules of A molecules of A molecules of A molecules of A molecules of A 1 2 6 . . . identical congurations identical congurations identical congurations identical congurations identical congurations (35)

Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6 Lecture 7 & 8

NA !

W =

N! (N NA )!NA !

Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

What about the Jacks (B molecules)? Does W change when they are included?

Counting possibilities
Thermodynamics

The remaining empty oces are all lled up with Jacks (B molecules): N = NA + NB

N H Nahler Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change

In the same way as we are not able to tell the dierence between empty and empty, we can not tell the dierence between one Jack and another. Adding the Jacks does not increase W any further. W = N! N! S = kB ln (N NA )!NA ! (N NA )!NA ! (36)

Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

We now have a formula to calculate the entropy of any cubic lattice with N sites, NA molecules of A and NB molecules of B.

Stirlings approximation
The factorials are inconvenient for calculations. Fortunately . . . ln N ! N ln N N This approximation becomes more exact for large N . We typically deal with N of the order of 1023 .
Stirling's approximation
1 1,000 Y = ln N! Y = N ln N - N 10 100 1,000
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10

100

100

10

10

Lecture 11 & 12 Lecture 13 & 14

0.1 1 10 N 100

0.1

Entropy of mixing
Making use of the Stirling approximation
S = kB ln W = kB ln N! (N NA )!NA ! (37) (38) (39) + NA ln N NA N NA (40)
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6

= kB ln N ! ln(N NA )! ln NA ! = kB [N ln N N (N NA ) ln(N NA ) + (N NA ) NA ln NA + NA ] = kB N ln N NA N

Using mole fractions: xA = NA /N and xB = (N NA )/N . xA = kB N ln xB + xA ln = kB N [(1 xA ) ln xB + xA ln xA ] xB = kB N (xA ln xA + xB ln xB ) Using N = nNAvo. and R = kB NAvo. S = nR (xA ln xA + xB ln xB ) (42) (41)

Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Entropy of mixing: S = nR (xA ln xA + xB ln xB )


Thermodynamics N H Nahler

Before mixing: Sinitial = S (xA = 1) + S (xB = 1) = 0


A A A A A A B B B B B B

Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6

After mixing: Snal = nR (xA ln xA + xB ln xB )


B A B A A B A B B A A B mix S = Snal Sinitial = nR (xA ln xA + xB ln xB ) We allow completely random mixing. Macroscopic thermodynamics mix S = nR (xA ln xA + xB ln xB )

Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

only one out of the possible arrangements

Third law of Thermodynamics


Third law
A perfect crystal at T = 0 K has zero entropy.
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Alternative denitions
The entropies of all perfectly crystalline substances are the same at T = 0. At T = 0 for a perfect crystal, atoms and ions are regularly arranged with no disorder leading to S = 0. The Third-Law entropy or absolute entropy at any temperature, S (T ) can be calculated using heat capacity and phase-change data. In the gure on the right, the entropy follows from integrating the Cp /T curve. The standard molar entropy, Sm is reported at a pressure of p = 1 bar and at the temperature of interest (often 298.15 K for reference).

Residual entropy
Measured entropy of CO (heat capacity, boiling point): Sm (298 K) = 192 JK1 mol1 Calculated entropy of CO (Boltzmann): Sm (298 K) = 198 JK1 mol1 Where does this discrepancy come from? Orientation at T = 0 K means N molecules of CO can be arranged in W = 2N ways leading to Sm (0) = k ln 2NA = NA k ln 2 = R ln 2 5.8 JK1 mol1 If Sm (0) > 0 this is called the residual entropy. Water is another example with Sm (0) = k ln(3/2)NA = NA k ln(3/2) = R ln(3/2) 3.4 JK1 mol1
Thermodynamics N H Nahler

CO

Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change

H2 O

Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Equilibrium and direction of change


What do we know so far about entropy and the direction of change?
isolated system non-isolated system dSsystem > 0 dSsystem + dSsurroundings > 0 spontaneous spontaneous
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4

Clausius inequality
dS dq T (system) (43)

It is an inequality for spontaneous irreversible change but an equality for a reversible change where the equilibrium is maintained.

Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10

Implications of entropy
Whenever considering the implications of entropy for a non-isolated system, we must always consider the total change of the system and the surroundings. We need to deal with this in chemistry but there are two other state functions that will be able to help us nding the direction of change by focussing on the system alone: G : Change in Gibbs free energy A: Change in Helmholtz energy (less common)

Lecture 11 & 12 Lecture 13 & 14

Standard reaction entropy and direction


Example
Thermodynamics

2 H2 (g) + O2 (g)

H2 O(l)

(C 7)

N H Nahler Lecture 1 & 2 Lecture 3 & 4 Introduction Irreversible change Chemical reactions Mixing Possibilities Mixing functions Third law Direction of change Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

(H2 (g)) = 131 JK1 mol1 , Data at T = 298.15 K: Sm Sm (O2 (g)) = 205 JK1 mol1 , Sm (H2 O(l)) = 70 JK1 mol1 and r H = 572 kJmol1

Standard reaction entropy, Sr


Sr = i i Sm ,i (products) j j Sm ,j (reactants)

(44)

Free energy and physical equilibrium


Key concepts
Gibbs free energy change G Helmholtz energy change A Phase boundaries: temperature and pressure Phase stability triple and critical point Goal: describe the phase of a component based on the Gibbs free energy.

Phase diagram

Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Reading
Chapter 4 Thermodynamics: the Second Law Chapter 5 Physical equilibria: pure substances

Phase, constituent and component (1)


Thermodynamics N H Nahler

Phase
A phase is a state of matter that is uniform throughout, not only in chemical composition but also in physical state. (Gibbs) P = . . . describes the number of phases present in a system.

Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

P=1 single phase solid liquid gas

P=2 phase mixture solid/solid solid/liquid solid/gas etc.

Phase, constituent and component (2)


Constituent
A constituent is a chemical species (ion or molecule) that is present in the system.
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4

Component
A component is a chemically independent constituent of a system where C = . . . is the number of components in the system.
water NaCl solution NaCl iron oxide "rust" iron

Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10

ice

Lecture 11 & 12 Lecture 13 & 14

P=2 C =1

P=2 C =2

P=1 C =2

Gibbs free energy


From the Clausius inequality: dQ dS and T T dS dH T dS dH 0 dH T dS 0 (45)
Thermodynamics N H Nahler

dH = dQ

(p = const.)

Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Gibbs free energy


Denition: G = H TS and consequently: dG = dH T dS S dT = dH T dS (T = const.) see equ. 45 (46)

Spontaneous change/process: dGT ,p 0 Equilibrium of a system at a xed temperature and pressure corresponds to the minimum of the Gibbs free energy.

Change in Gibbs free energy


We describe changes in an open systems where the pressure is constant with the Gibbs free energy.
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Combining 1st and 2nd law


dU = dQ p dV dU = T dS p dV dG = dH S dT T dS = dU + p dV + V dp S dT T dS = T dS p dV + p dV + V dp S dT T dS dG = V dp S dT (47) and dH = dQ + V dp

Temperature and pressure dependence of G


The free energy is a state function: Pressure dependence: Temperature dependence: G =V p G = S T T = const. p = const. (48) (49)

Helmholtz free energy


Constant temperature and volume
Thermodynamics

To describe a closed system (V = const.) in contact with a heat bath (T = const.) we cannot use the Gibbs free energy. The adiabatic bomb calorimeter is such an example.

N H Nahler Lecture 1 & 2 Lecture 3 & 4

Helmholtz free energy


Denition: A = U TS and consequently: dA = dU T dS S dT = dq p dV T dS S dT = T dS p dV T dS S dT dA = p dV S dT (50)

Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Maximum work
Considering the total change in entropy one can show that the Helmholtz free energy is a measure for the maximum work that can be performed by a system: A w (51)

Gibbs free energy: pressure dependence


The (molar) Gibbs free energy varies with pressure. In general: Gm = Gm (pf ) Gm (pi ) withp = pf pi Gm = Vm p T = const. (52)
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8

Note: The molar volume of liquids and solids does change very little with pressure. However, the molar volume of gases strongly depends on pressure.

The pressure dependence of G for an ideal gas


pf Gm (pf ) = Gm (pi ) + RT ln pi Gas always expands into a vacuum. An empty gas cylinder has never been observed to spontaneously rell. (53)

Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Gibbs free energy: temperature dependence


The (molar) Gibbs free energy varies with temperature: Gm = Gm (Tf ) Gm (Ti ) withT = Tf Ti Gm = Sm T p = const. (54)
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Chemical potential of pure substances


Thermodynamics

Spontaneous process: dG < 0


dG = G T G T dT +
p

N H Nahler Lecture 1 & 2

G p

Lecture 3 & 4

dp
T

Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12

= S
p

and

G p

=V
T

molar free energy Gm = chemical potential


Note: this applies only to a pure substance d = T T dT +
p

p p

Lecture 13 & 14

dp
T

(55)

= Sm
p

and

= Vm
T

Chemical potential: variation with temperature


Thermodynamics

Sm > 0 for all substances (T > 0 K) The phase with the lowest chemical potential is the most stable one. Sm (s) < Sm (l) < Sm (v) The phase with the lower molar entropy is the stable phase at lower temperatures: T < Tf solid vs. liquid. The phase with the higher molar entropy is stable at higher temperatures: T > Tf liquid vs. solid. Two phases have the same chemical potential at the transition temperature (equilibrium). T = Sm
p

N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Chemical potential: variation with pressure


Thermodynamics N H Nahler

Vm > 0 for all substances The phase with the higher molar volume (phase ) is the stable phase at lower pressure. The phase with the lower molar volume (phase ) is stable at higher pressures. High-pressure phases are denser than low-pressure phases. For most substances Vm (l) > Vm (s). Important exception: for water Vm (l) < Vm (s).
chemical potential,

Lecture 1 & 2

= Vm
T

Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams

phase phase pressure, p

Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Phase boundaries
Thermodynamics N H Nahler

At a phase transition the chemical potentials of two coexisting phases are equal:

Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12

(; p , T ) = ( ; p , T ) d() = d( ) Using d = Vm dp Sm dT it follows that Vm () dp Sm () dT = Vm ( ) dp Sm ( ) dT (Sm ( ) Sm ()) dT = (Vm ( ) Vm ()) dp

Lecture 13 & 14

dp trs S = dT trs V

Clapeyron equation

(56)

The solid-liquid boundary


Thermodynamics N H Nahler

Melting/fusion goes with a molar enthalpy change fus H at temperature T . The molar entropy of melting is therefore fus H /T . dp fus H = dT T fus V Slope of solid-liquid boundary Entropy of melting is positive. Volume change upon melting is mostly positive and small (exception: water!).
p p

Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6

(57)

Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12

dp =

fus H 1 dT fus V T T fus H T p = p + ln fus V T

Lecture 13 & 14

(58) (59)

The liquid-vapour boundary


The entropy of vaporization at temperature T is equal to vap H /T . dp vap H = dT T vap V Slope of solid-liquid boundary (60)
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6

Entropy of vaporization is positive. Volume change upon vaporization is large and positive. dp / dT > 0 but smaller than for the solid-liquid boundary. dp vap H = dT T (RT /p ) d ln p vap H = dT RT 2 p = p e ; = vap H R 1 1 T T (ideal gas) (61) (62) (63)

Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Clausius-Clapeyron

The gas-liquid critical point


Thermodynamics

Critical point ends the liquid-vapour equilibrium line. Gas can only be liqueed below TC . Clausius-Clapeyron equation breaks down near critical point (ideal gas, vap H (T ) = const., Vvap Vm (g )).

N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Temperature increase

gas

gas

supercritical fluid

liquid

liquid

liquid density decrease vapour density increase

The solid-vapour boundary and triple point


Thermodynamics

The Clausius-Clapeyron equation can also be used to calculate the solid-vapour boundary. dp sub H = dT T sub V Slope of solid-vapour boundary (64)

N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8

sub H = fus H + vap H

Triple point
At the triple point all three coexistence curves intersect. All three phases are in equilibrium at the triple point.

Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Liquid phase
Limitations
For a substance with a volume increase from solid to liquid (most substances but not water), the liquid phase does only exist above the triple point temperature Tt and below the critical temperature Tc . For any substance the liquid phase does not exist below the triple point pressure pt .
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

The Gibbs phase rule


Phase rule
F =C P +2 (65)
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12

F : Number of degrees of freedom e.g. pressure, temperature, mole fraction C : Number of components P : Number of phases

Why can four phases not exist in equilibrium?


As an example, tin can exist in four phases (solid white tin, solid grey tin, liquid tin, vapour tin). But is there a point at which all four phases exist in equilibrium? System of three equations with two unknowns (T , p ) does not have a solution. F = C P + 2 = 1 4 + 2 = 1 does not make sense. It also shows for a triple point: F = 0. There is only a single triple point for one value of T , p .

Lecture 13 & 14 Gm (1, T , p ) = Gm (2, T , p ) Gm (2, T , p ) = Gm (3, T , p ) Gm (3, T , p ) = G m (4, T , p )

Phase diagram of water


Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Phase diagram of CO2 and He


Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase, constituent, component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

CO2

He