B18PA1: Thermodynamics

Dr N Hendrik Nahler
email: n.nahler@hw.ac.uk office: 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 fit 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

3

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 sufficient 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

83 – 93 . S .Reading list Textbook for this course 2 3 Thermodynamics Thermodynamics: the first 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 9 Additional reading Physical Chemistry (Atkins & de Paula). U . 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. Basic chemical thermodynamics (Smith). Chemistry (Housecroft & Constable). The entropy. Reading Chapter 2 Thermodynamics: the first law Chapter 3 Thermodynamics: applications of the First Law Chapter 4 Thermodynamics: the Second Law. of an isolated system is constant. pp. 2 Goal: describe equilibrium using these key concepts. Principles of thermodynamics (Kaufman) Revision. of an isolated system tends to increase.

N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Alternative definition In chemical changes energy can be converted to one form or another but not destroyed. 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. This is where we mostly do our measurements. completely insulated from the surroundings. Examples: reaction components. can only exchange energy with surroundings. engine. Classical mechanics Object falling off 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 . 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. The 1st Law of Thermodynamics Thermodynamics First law The internal energy (U ) of an isolated system is constant. biological cell.System and Surrounding System The system is what we are interested in.

q . to/from surroundings Work. potential energy etc. w = +ve and ∆U ↑. U The internal energy is made up of kinetic energy. rotational energy.g. w = −ve and ∆U ↓. w . Thermodynamics N H Nahler Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Changes in internal energy. If you quickly compress a gas it heats up e.g. spray can. ∆U ↑ for surroundings −→ system q = −ve . ∆U = q + w = q − p ∆V =q =0 for an ideal gas V = const. ∆U ↓ for system −→ surroundings equivalent for work. vibrational energy. ∆U Heat transfer. Compression To compress a gas work needs to be done by the surroundings on the system. work is done by the systems on the surroundings. 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. done on/by surroundings ∆U = q + w Sign convention for heat and work: q = +ve . bicycle pump.Internal Energy. w . If you quickly expand a gas it cools down e. Lecture 13 & 14 .

H If our chemistry happens in an open system then energy put into the system will be partly given back to surroundings. . 2. 56 – 59).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. Therefore we define 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 Definition of Enthalpy. pp.9. 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 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.

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. ∆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 . 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. Consequently dU and dH are exact differentials. ∆U .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 ). How big is the change in enthalpy.

is a measure of the molecular disorder of a system . The entropy.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 Hess’s Law of constant heat summation ∆r H (298 K) = − ∆r H (products. S. 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 different 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 defined in terms of the state function U . However. 298 K) − ◦ − ◦ Lecture 7 & 8 Lecture 9 & 10 (12) Lecture 11 & 12 Lecture 13 & 14 Example: find ∆f H for the reaction 2 NO(g) + O2 (g) given 1 2 N2 (g) 1 +2 O2 (g) 2 NO2 (g) ∆H1 = +90 kJ·mol−1 ∆H2 = −20 kJ·mol−1 ∆H3 = −86 kJ·mol−1 (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. S . 298 K) ∆r H (reactants. the entropy. it does not tell us about direction of change. It is defined in terms of a second state function.

or equal to. Lecture 1 & 2 Introduction Revision The Second Law Lecture 3 & 4 Alternative definition of the second law The total entropy. the heat flow divided by temperature. . Stot of a system (Ssys ) and surroundings (Ssur ) increases in the course of a spontaneous change. 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 definition of entropy. S Thermodynamics For a reversible change we define: dqrev T final 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. dS ≥ dQ T (17) Lecture 13 & 14 This applies for a natural process (irreversible). ∆Stot = ∆Ssys + ∆Ssur > 0 At equilibrium or for a reversible process. S .The 2nd Law of Thermodynamics (ii) Thermodynamics N H Nahler Second law The entropy. of an isolated system tends to increase.

6) A monoatomic perfect gas at a temperature Ti is expanded isothermally to twice its initial volume.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. (Atkins. 10 ◦C).0 dm3 at 250 K and 1. 4.12) 2 . what is the change in entropy? (Cp.m = 75. 4.m = 2 R . Assuming a body temperature of 36 ◦C.0 J·K−1 ? (Atkins. Into what volume must the gas be compressed to reduce the entropy by 10.00 atm is compressed isothermally. To what temperature should it be cooled to restore its entropy to its initial value? 3 CV .5 J·K−1 ·mol−1 ) 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.

1 bar steam (C 4) Lecture 11 & 12 Lecture 13 & 14 ∆vap H = 41 000 J·mol−1 . Melting at melting temperature. ∆vap S = 110 J·mol−1 ·K−1 3 Note that the vaporization entropy is much larger than the fusion entropy. (hydrogen bonding) Estimate the enthalpy of vaporization of bromine from its boiling temperature. Tf : ∆fus H (Tf ) ∆fus S = Tf Vaporization at the boiling temperature. Removal of heat freezes water.Entropy change: phase transition (i) Addition of heat evaporates water. 59. 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 J·mol−1 . Note the difference between the vaporization entropy and the predicted value from Trouton’s rule. ammonia and mercury. Tf = 273 K. 4 5 . Tb = 373 K. Hydrogen bonding and metal bonding in the latter lead to a higher order in the liquid phase and consequently to ∆vap S > 85 J·K−1 ·mol−1 . Entropy change: phase transition (ii) Examples 1 Thermodynamics N H Nahler Lecture 1 & 2 Melting of ice: ice 273 K. ∆fus S = 22 J·mol−1 ·K−1 2 Vaporization of water: water 373 K.2 ◦C. 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 Trouton’s rule (empirical) ∆vap S = ∆vap H (Tb ) ≈ 85 J·K−1 ·mol−1 Tb (26) Notable exceptions to the rule are water.

Ice is the more stable phase. S . The entropy. of an isolated system tends to increase.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. U . of an isolated system is constant. 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 2 3 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 find a reversible pathway. The entropy of a perfectly crystalline substance at T = 0 K is S = 0. Therefore the process is irreversible and ∆S (263 K) = ∆fus H (263 K) 263 K . Laws of thermodynamics 1 N H Nahler Lecture 1 & 2 The internal energy. (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.

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. Calculate the entropy change of the surroundings and the total entropy change (∆Stot > 0). Calculate the entropy change of the system. 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 . Lecture 13 & 14 .Example: the freezing of supercooled water 1 2 3 4 Construct reversible thermodynamic cycle Calculate entropy changes of individual changes.

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. 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. gases A and B are described by their partial volumes pA and pB in the mixture.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 ΔmixS / nR 0. 0.2 0 0 0. According to their mole fractions. (30) Entropy change: mixing of ideal gases (ii) Both gases A and B are under the same pressure p before mixing. The composition of a binary system is defined by one of the two mole fractions. .5 1 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Mole fraction of A.4 0. Consider mixing as an expansion of an ideal gas. 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) i 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.

We express Avogrado’s number as NAvo. Molecular: we measure disorder by the number of ways (microstates). A A A Lecture 11 & 12 Lecture 13 & 14 A B . W .g. . molecules can organise themselves.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. 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 B A B A A A A A B B B A A A B B B A A B B 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 = Avogadro’s number in this context. a gas is more disordered than a solid. Macroscopic: we measure disorder by entropy.

. . . ..How many arrangements are there? Thermodynamics Meet Jill and Jack N H Nahler A B 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 Let’s say we have NA Jills and N offices Number of ways of placing . . second Jill = N − 1 .. . . . . . 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 × . third Jill = N − 2 . . . first Jill = N . . 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 . .

. ... # # # # # # 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. Counting possibilities Thermodynamics N H Nahler To account for this overcounting.. .. 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 ... ..... . . For example. .. ..... . . .. ... identical configurations identical configurations identical configurations identical configurations identical configurations (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 Now we have overcounted the possibilities W Several different ways lead to the same microstate. NA molecules of A molecules of A molecules of A molecules of A molecules of A → → → 1 2 6 . how many ways of placing molecules on a given set of sites? 1 2 3 .... .. The six configurations constitute the same microstate.. . .

.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 Y Lecture 11 & 12 Lecture 13 & 14 1 1 0.1 . . ⇒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. we can not tell the difference between one Jack and another. ln N ! ≈ N ln N − N This approximation becomes more exact for large N .000 Y = ln N! Y = N ln N . ⇒ Adding the Jacks does not increase W any further.Counting possibilities Thermodynamics The remaining empty offices are all filled 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 difference between ’empty’ and ’empty’. NA molecules of A and NB molecules of B. We typically deal with N of the order of 1023 .1 1 10 N 100 0.N 10 100 1. Fortunately . Stirling's approximation 1 1. Stirling’s approximation The factorials are inconvenient for calculations.

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. ’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 . and R = kB NAvo.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 . 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: Sfinal = −nR (xA ln xA + xB ln xB ) B A B A A B A B B A A B ∆mix S = Sfinal − Sinitial = −nR (xA ln xA + xB ln xB ) We allow completely random mixing.

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 definitions The entropies of all perfectly crystalline substances are the same at T = 0.8 J·K−1 ·mol−1 If Sm (0) > 0 this is called the residual entropy. boiling point): − ◦ Sm (298 K) = 192 J·K−1 ·mol−1 Calculated entropy of CO (Boltzmann): − ◦ Sm (298 K) = 198 J·K−1 ·mol−1 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 ≈ 5.4 J·K−1 ·mol−1 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 . atoms and ions are regularly arranged with no disorder leading to S = 0. In the figure on the right. The Third-Law entropy or absolute entropy at any temperature.15 K for reference).Third law of Thermodynamics Third law A perfect crystal at T = 0 K has zero entropy. Sm is reported at a pressure of p = 1 bar and at the temperature of interest (often 298. the entropy follows from integrating the Cp /T curve. Residual entropy Measured entropy of CO (heat capacity. S (T ) can be calculated using heat capacity and phase-change data. At T = 0 for a perfect crystal. Water is another example with Sm (0) = k ln(3/2)NA = NA k ln(3/2) = R ln(3/2) ≈ 3. The − ◦ standard molar entropy.

Data at T = 298.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. we must always consider the total change of the system and the surroundings.j (reactants) (44) . Sm (H2 O(l)) = 70 J·K−1 ·mol−1 and ∆r H = −572 kJ·mol−1 ◦ Standard reaction entropy. ∆Sr− ◦ ∆Sr− = i − ◦ νi ∆Sm .15 K: Sm − ◦ − ◦ Sm (O2 (g)) = 205 J·K−1 ·mol−1 . We need to deal with this in chemistry but there are two other state functions that will be able to help us finding 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 J·K−1 ·mol−1 .i (products) − j − ◦ νj ∆Sm . 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.

describes the number of phases present in a system. (Gibbs) P = . Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase.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. 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. . . Phase diagram Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction 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. 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. constituent. constituent. .

. water NaCl solution NaCl iron oxide "rust" iron Lecture 5 & 6 Introduction Phase. . 45 (46) Spontaneous change/process: dGT . 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 Definition: G = H − TS and consequently: dG = dH − T dS − S dT = dH − T dS (T = const.) see equ. constituent.Phase. .) Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase. is the number of components in the system. 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.p ≤ 0 Equilibrium of a system at a fixed temperature and pressure corresponds to the minimum of the Gibbs free energy. Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Component A component is a chemically independent constituent of a system where C = . constituent and component (2) Constituent A constituent is a chemical species (ion or molecule) that is present in the system. constituent.

Change in Gibbs free energy We describe changes in an open systems where the pressure is constant with the Gibbs free energy.) in contact with a heat bath (T = const. N H Nahler Lecture 1 & 2 Lecture 3 & 4 Helmholtz free energy Definition: 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. (48) (49) Helmholtz free energy Constant temperature and volume Thermodynamics To describe a closed system (V = const. 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) . Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase. The adiabatic bomb calorimeter is such an example.) we cannot use the Gibbs free energy. p = const. 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.

component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 . However. the molar volume of gases strongly depends on pressure. 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. An empty gas cylinder has never been observed to spontaneously refill. The pressure dependence of G for an ideal gas pf Gm (pf ) = Gm (pi ) + RT ln pi Gas always expands into a vacuum. (54) Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase. constituent. (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 ) with∆T = Tf − Ti ∆Gm = −Sm ∆T p = const. (52) Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase. In general: ∆Gm = Gm (pf ) − Gm (pi ) with∆p = pf − pi ∆Gm = Vm ∆p T = const.Gibbs free energy: pressure dependence The (molar) Gibbs free energy varies with pressure.

Two phases have the same chemical potential at the transition temperature (equilibrium). 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 = µ chemical potential Note: this applies only to a pure substance dµ = ⇒ ∂µ ∂T ∂µ ∂T dT + p ∂µ ∂p ∂µ ∂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. solid. constituent. ∂µ ∂T = −Sm p N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase. liquid.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. component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 . Sm (s) < Sm (l) < Sm (v) The phase with the lower molar entropy is the stable phase at lower temperatures: T < Tf solid vs. The phase with the higher molar entropy is stable at higher temperatures: T > Tf liquid vs.

Important exception: for water Vm (l) < Vm (s). For most substances Vm (l) > Vm (s). T ) dµ(α) = dµ(β ) Using dµ = Vm dp − Sm dT it follows that Vm (α) dp − Sm (α) dT = Vm (β ) dp − Sm (β ) dT (Sm (β ) − Sm (α)) dT = (Vm (β ) − Vm (α)) dp Lecture 13 & 14 dp ∆trs S = dT ∆trs V Clapeyron equation (56) . 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. p . chemical potential. p . The phase with the lower molar volume (phase β ) is stable at higher pressures. component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams phase β phase α pressure.Chemical potential: variation with pressure Thermodynamics N H Nahler Vm > 0 for all substances The phase with the higher molar volume (phase α) is the stable phase at lower pressure. T ) = µ(β . constituent. High-pressure phases are denser than low-pressure phases. component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 µ(α. µ Lecture 1 & 2 ∂µ ∂p = Vm T 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 Clausius-Clapeyron . dp / dT > 0 but smaller than for the solid-liquid boundary. χ = ∆vap H R 1 1 − ∗ T T (ideal gas) (61) (62) (63) Introduction Phase. Volume change upon vaporization is large and positive. The molar entropy of melting is therefore ∆fus H /T . p p∗ Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 (57) Introduction Phase. 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. constituent.The solid-liquid boundary Thermodynamics N H Nahler Melting/fusion goes with a molar enthalpy change ∆fus H at temperature T . 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 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 (RT /p ) d ln p ∆vap H = dT RT 2 p = p ∗ e −χ . Volume change upon melting is mostly positive and small (exception: water!). dp ∆fus H = dT T ∆fus V Slope of solid-liquid boundary Entropy of melting is positive. constituent.

∆Vvap ≈ Vm (g )). N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase. Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 . Gas can only be liquefied below TC .. constituent. 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. Clausius-Clapeyron equation breaks down near critical point (ideal gas. 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.The gas-liquid critical point Thermodynamics Critical point ends the liquid-vapour equilibrium line. 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. ∆vap H (T ) = const. All three phases are in equilibrium at the triple point.

p ) . For any substance the liquid phase does not exist below the triple point pressure pt . 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. But is there a point at which all four phases exist in equilibrium? System of three equations with two unknowns (T . constituent. T . It also shows for a triple point: F = 0. p ) Gm (2. temperature. p ) does not have a solution. p ) Gm (3. mole fraction C : Number of components P : Number of phases Why can four phases not exist in equilibrium? As an example. There is only a single triple point for one value of T . p .g. T . F = C − P + 2 = 1 − 4 + 2 = −1 does not make sense. Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase. pressure. T . liquid tin. 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. T . p ) = G m (4. Lecture 13 & 14 Gm (1. constituent. the liquid phase does only exist above the triple point temperature Tt and below the critical temperature Tc . solid grey tin. p ) = Gm (3. T . tin can exist in four phases (solid white tin. vapour tin).Liquid phase Limitations For a substance with a volume increase from solid to liquid (most substances but not water). T . p ) = Gm (2.

component Free energy Chemical potential Phase boundaries Phase rule Phase diagrams Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 CO2 4 He . 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.Phase diagram of water Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Introduction Phase.

1 and 6. Physical equilibrium So far we observed mass flow dn as a consequence of a phase transition. Consider the gas phase reaction: ν A A(g) + ν B B(g) ν C C(g) + ν D D(g) (C 8) Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 νi are the stochiometric numbers of a balanced reaction. 123–127 Extent of a chemical reaction ξ Thermodynamics N H Nahler ν A A(g) + ν B B(g) ν C C(g) + ν D D(g) Lecture 1 & 2 Lecture 3 & 4 The extent of a reaction ξ is defined so that any change by dξ changes the amount of any species J by: dξ = 1 dnJ νJ Extent of reaction (66) Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Note: the extent of a reaction is also referred to as the composition.Chemical equilibrium: reactions and mixtures Chemical equilibrium During a chemical reaction dn is caused by the (dis-)appearance of components. the chemical potential of A is equivalent to the partial molar Gibbs free energy of A. .2. How do partial molar volumes and partial molar Gibbs free energies in a mixture effect the equilibrium? Reading Chapter 7 Chemical equilibrium: The principles Chapter 6 The properties of mixtures. pp. Gm (A) = G (A)/nA . sections 6. Gibbs energy ∆G = µC νC ∆n + µD νD ∆n − µA νA ∆n − µB νB ∆n (67) Lecture 13 & 14 Remember that µA .

Reaction Gibbs free energy ∆r G If in equation 67 we divide by ∆n we obtain the reaction Gibbs energy ∆G ∆r G = = (µC νC + µD νD ) − (µA νA + µB νB ) (68) ∆n Or more general based on the extent of reaction when pressure and temperature are kept constant: ∆r G = ∂G ∂ξ (69) p .T Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 ∆r G < 0 forward reaction is spontaneous Lecture 11 & 12 Lecture 13 & 14 ∆r G > 0 reverse reaction is spontaneous ∆r G = 0 equilibrium Example: ammonia synthesis (1) Extent of reaction N2 (g) + 3 H2 (g) νN2 = −1 νH2 = −3 νNH3 = 2 ⇒ dξ = 1 1 1 dnN2 = dnH2 = dnNH3 −1 −3 2 2 NH3 (g) (C 9) Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Reaction Gibbs free energy dG = µN2 dnN2 + µH2 dnH2 + µNH3 dnNH3 = −µN2 dξ − 3µH2 dξ + 2µNH3 dξ = −µN2 − 3µH2 + 2µNH3 dξ ∆r G = −µN2 − 3µH2 + 2µNH3 Lecture 11 & 12 Lecture 13 & 14 .

Variation of ∆r G with ξ In general the chemical potential of a species J can be expressed with its activity aJ as: µJ = ◦ µ− J Thermodynamics N H Nahler + RT ln aJ (70) Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 ◦ where in the special case of mixtures of ideal gases aJ = pJ /p − is the partial pressure of J in respect to the standard pressure. ◦ With µJ = µ− J + RT ln pJ and pJ in bar follows: ∆r G = −µN2 − 3µH2 + 2µNH3 ◦ − ◦ = − µ− N2 + RT ln pN2 − 3 µH2 + RT ln pH2 Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 +2 ◦ µ− NH3 + RT ln pNH3 2 pNH 3 3 pN2 pH 2 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 ◦ − ◦ − ◦ = −µ− N2 − 3µH2 + 2µNH3 + RT ln ◦ ∆r G − ∆r G = − ◦ + RT ln Q (75) ◦ Standard reaction Gibbs energy ∆r G − ∆r G can be calculated from the standard Gibbs energies of formation: ◦ − ◦ − ◦ ∆r G − = ν Gm (products) − ν Gm (reactants) ◦ ◦ = ∆r H − − T ∆r S − ◦ − ◦ − ◦ − ◦ − ◦ ∆r G − = 2∆f GNH − ∆f GN − 3∆f GH = 2∆f GNH 3 2 2 3 (76) (77) . ∆r G = ◦ (µ− C νC + ◦ µ− D νD ) − ◦ (µ− A νA + ◦ µ− B νB ) + RT [νC ln aC + νD ln aD − νA ln aA − νB ln aB ] Where the first line is the standard reaction Gibbs energy : ◦ ◦ − ◦ − ◦ − ◦ ∆r G − = (µ− C νC + µD νD ) − (µA νA + µB νB ) (71) Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 (72) = − ◦ − ◦ − ◦ − ◦ Gm (C) · νC + Gm (D) · νD − Gm (A) · νA + Gm (B) · νB (73) Combining equations 71 and 73 and using logarithm rules: ·b n ln a = ln an and ln a + ln b − ln c = ln ac leads to: ∆r G = ∆r G − ◦ νC νD aC a + RT ln νA D νB aA aB (74) Example: ammonia synthesis (2) For ideal gases we can calculate the chemical potential directly.

Reaction quotient Q and equilibrium const. K At standard conditions: Partial pressures are all 1 bar 12 − ◦ ◦ − ◦ ∆r G = ∆r G + RT ln = ∆r G − = 2∆f GNH 3 3 1·1 Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Reaction quotient.00 − 3x NH3 0 +2x 2x Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 .00 − x H2 3.00 −x 1. Calculating an equilibrium composition Example: Ammonia synthesis Thermodynamics K= Species. Qequilibrium = K ∆r G = ∆r G − ◦ Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 (79) + RT ln K = 0 (80) (81) ◦ ∆r G − ln K = − RT We can now calculate the equilibrium composition of a reaction mixture from tables of thermodynamic data. Q Q= νC νD aC aD νA νB aA aB Lecture 7 & 8 (78) At equilibrium At equilibrium the reaction quotient Q is equivalent to the equilibrium constant K and ∆r G = 0.00 −3x 3. J Initial pJ / bar Change / bar Equilibrium pJ / bar 2 pNH 3 3 pN2 pH 2 N H Nahler = 977 Lecture 1 & 2 Lecture 3 & 4 N2 1. The equilibrium constant is dimensionless.

Kc related? K = Kc × = Kc × ◦ c− RT ◦ p− ∆νgas (83) ∆νgas Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 T 12. K and the equilibrium constant in terms of concentration. Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 . the effect of the disturbance. . Alternative wordings of Le Chatelier’s principle: When a system at equilibrium is disturbed. the equilibrium position will shift in the direction which tends to minimise. Kc = ? 5 Equilibria changes How does the equilibrium respond to changes in .8 × 10 . If a dynamic equilibrium is disturbed by changing the conditions. the position of equilibrium moves to counteract the change. Example: ammonia synthesis At T = 298 K the equilibrium constant is K = 5. 1 2 3 Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 concentration? pressure? temperature? Le Chatelier’s Principle Perturbation of a system at equilibrium will cause the equilibrium position to change in such a way as to tend to remove the perturbation. Any change in status quo prompts an opposing reaction in the responding system. or counteract.Equilibrium constant in terms of concentration.027 K (84) where ∆νgas = (νC + νD ) − (νA + νB ) with the standard ◦ ◦ concentration c − = 1 mol·dm−3 and standard pressure p − = 1 bar. . Kc [C]νC [D]νD Kc = [A]νA [B]νB (82) Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 How are the equilibrium constant in terms of activity.

The position of equilibrium moves to the left ([NH3 ] decreases). the position of equilibrium will move in such a way as to counteract the change: 1 2 Equilibrium will move so that [N2 ] decreases again. for example.Equilibria changes: concentration Suppose we have an equilibrium established in the ammonia synthesis: N2 (g) + 3 H2 (g) 2 NH3 (g) What happens when we . one of the reactants was a relatively expensive material whereas the other was cheap and plentiful. In general you might use this if. . . The position of equilibrium moves to the right ([NH3 ] increases). 1 increase the concentration of N2 ? 2 decrease the concentration of N2 ? Kc = [NH3 ] 2 3 Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 [N2 ][H2 ] According to Le Chatelier. Change in concentration Thermodynamics N H Nahler A+B AB Kc = [AB ] 5 = =5 [A][B ] 1·1 Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 C+D CD Kc = [CD ] 1 2 = = [C ][D ] 8 4·4 . Equilibrium will move so that [N2 ] increases again.

Equilibria changes: pressure Consider a dissociative reaction where α = extent of dissociation: A(g) 2 B(g) Start n 0 n(1 − α) 2αn Equ. n(1 − α) 2αn xi n(1 − α) + 2αn n(1 − α) + 2αn 2α 1−α 1+α 1+α 2 2 2 pB xB p K= = pA xA p 2 (2α) (1 + α) = p (1 + α)2 (1 − α) 4α2 = p 1 − α2 Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 α= 4p 1+ K −1 2 Equilibria changes: temperature At temperature T1 At temperature T2 ◦ ◦ ◦ ∆r G − ∆r H − ∆r S − ln K1 = − =− + RT1 RT1 R ◦ ◦ ◦ ∆r G − ∆r H − ∆r S − ln K2 = − =− + RT2 RT2 R Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 van’t Hoff equation ◦ ∆r H − ln K2 − ln K1 = R Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 1 1 − T1 T2 (85) Alternative expression of the van’t Hoff isochore: ◦ d ln K ∆r H − =− d(1/T ) R Lecture 13 & 14 (86) Exothermic reactions: T ↑ favours the reactants: K ↓ Endothermic reactions: T ↑ favours the products: K ↑ .

Concentration If the concentration of a reactant (solute or gas) is increased. Pressure If the pressure of an equilibrium system is increased.2 kJ·mol−1 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Change with pressure http://www.Equilibrium response Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 2 NO2 (g) brown N2 O4 (g) colour-less ◦− ∆f H − −57.youtube. then the equilibrium position shifts to reduce the pressure.com/watch?v=tlGrBcgANSY Le Chatelier’s Principle: summary Thermodynamics Perturbation of a system at equilibrium will cause the equilibrium position to change in such a way as to tend to remove the perturbation. If the temperature of an exothermic equilibrium system is increased. the equilibrium position shifts to use up the added reactants resulting in more products. the equilibrium position shifts to use up the heat by producing more reactants. N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 .youtube. Temperature If the temperature of an endothermic equilibrium system is increased. the equilibrium position shifts to use up the heat by producing more products.com/watch?v=PxJbp1SzGjY Change with temperature http://www.

Thermodynamic description of mixtures
Motivation
How can we describe the physical properties of a mixture? What is the chemical equilibrium of a mixture? How do thermodynamical properties change in a mixture of ideal gases?
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases

Mole fractions: System with J components
mole fraction of component J nJ xJ = ni number of moles ntotal nA + nB + · · · + nN xi = =1 ntotal xJ

(87)

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

i

Binary system with components A and B
nA nA + nB xA + xB = 1 xA = xB = 1 − xA xB = nB nA + nB (88)

Partial molar volume (1)
Thermodynamics

Aim
We want to be able to calculate the volume of any liquid mixture of two components A and B containing the amount nA of A and nB of B.
nB = 0 p, T = const.

N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Volume, V

V dV = = Vm,A dnA nA Vm,A molar volume of component A We can draw a similar plot for V against nB with nA = 0. V = VA nA + VB nB
Amount of A, nA

(89)

Partial molar volume
Definition of partial molar volume
The partial molar volume VJ of a substance J is defined as: VJ = ∂V ∂ nJ
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10

p ,T ,n

VA depends on the composition of the mixture. Note that the partial molar volume of A is negative at b . dV = ∂V ∂ nA
nA

dnA +
p ,T ,nB

∂V ∂ nB

dnB
p ,T ,nA

Lecture 11 & 12 Lecture 13 & 14

= VA dnA + VB dnB
nB nA nB

V =
0

VA dnA +
0

VB dnB = VA
0

dnA + VB
0

dnB

= VA nA + VB nB

Partial molar volume
Remember that V is a state function i.e. it does not matter if we first pour A into B or vice versa. For example: Add A first and then B or the other way round. The final volume will always be the same. We only have to know the partial volumes of the components in the target mixture in order to calculate the total volume of the mixture. While molar volumes are always positive, partial molar quantities can be negative: Example: limiting partial molar volume of MgSO4 in water is −1.4 cm3 ·mol−1 Addition of 1 mol of MgSO4 to a large quantity of water decreases the volume by 1.4 cm3 . The mixture contracts as salt breaks up , ions become hydrated, slight collapse The concept of partial molar quantities can be extended to any extensive state function. (Partial molar Gibbs energy)
Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Partial molar volume (2)
Thermodynamics

Example: water/ethanol mixture
H2 O VH2O (xEtOH = 0) ≈ 18 cm ·mol Water is added to water. The partial molar volume of water is just the molar volume of water. VH2O (xEtOH = 1) ≈ 14 cm3 ·mol−1 Water is added to a huge amount of ethanol. Every water molecule will be surrounded by ethanol molecules. EtOH Density: ρEtOH = 0.789 g·cm−3 Molar mass: MEtOH = 46.07 g·mol−1 Molar volume: Vm,EtOH = 58.4 cm3 ·mol−1
3 −1

N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

Partial molar Gibbs energies
Thermodynamics

p , T , nB = const.

N H Nahler

Chemical potential
The chemical potential of a component J in a mixture is defined as the partial molar Gibbs energy: µJ = ∂G ∂ nJ (90)
p ,T ,n

Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14

For a pure substance G = n Gm . It follows that: µ = Gm . In the same way as we have derived an equation for the total volume of a mixture, the total Gibbs energy of a binary mixture is: G = nA µA + nB µB (91)

and the ”appearance” or ”disappearance” of components due to chemical reactions. then the Gibbs free energy changes by dG = V dp − S dT + as before i new term N H Nahler Lecture 1 & 2 Lecture 3 & 4 µi dni (92) Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 The new term accounts for changes in number of moles due to e. For binary systems the equation simplifies to: dG = V dp − S dT + µA dnA + µB dnB (93) Lecture 11 & 12 Lecture 13 & 14 Gibbs-Duhem equation Thermodynamics Total Gibbs energy of a binary mixture G = nA µA + nB µB Infinitesimal change: dG = dnA µA + dnB µB + nA dµA + nB dµB From equation 93 with T . temperature and number of moles of each component change. follows: nA dµA + nB dµB = 0 From this special case of a binary mixture follows in general: ni dµi = 0 i N H Nahler (94) Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Gibbs-Duhem equation (95) The chemical potential of one component of a mixture cannot change independently of the chemical potentials of the other components.Fundamental equation of chemical thermodynamics Thermodynamics If the pressure. . phase changes chemical reactions The chemical potential is responsible for mass flow (dni ) from one phase to another. p = const.g.

The Gibbs energy of mixing of ideal gases (1) Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Gi = . . . . G = µA nA + µB nB ∆mix G = Gf − Gi We need to know the chemical potentials of the gases before and after mixing. . The Gibbs energy of mixing of ideal gases (2) Thermodynamics The molar free energy of an ideal gas is: p ◦ p− Since µ = Gm it follows that − ◦ Gm (p ) = Gm + RT ln N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 p ◦ µ = µ− + RT ln − p◦ The pressure is always given in ’bar’: ◦ µ = µ− + RT ln p ◦ = µ− + RT ln p 1 Before mixing: ◦ − ◦ Gi = µA nA + µB nB = nA (µ− A + RT ln p ) + nB (µB + RT ln p ) After mixing: ◦ − ◦ Gf = µA nA + µB nB = nA (µ− A + RT ln pA ) + nB (µB + RT ln pB ) . Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Gf = .

Other mixing functions What happens to the entropy and enthalpy of an ideal gas mixture? Thermodynamics N H Nahler Entropy ∆mix S = − ∂ ∆mix G ∂T p . Lecture 11 & 12 Lecture 13 & 14 . 42). The driving force comes entirely from the increase in entropy of the system.nA . Enthalpy From ∆G = ∆H − T ∆S ∆mix H = ∆mix G + T ∆mix S ∆mix H = 0 (98) The enthalpy of mixing is zero since there are no interactions between the gas molecules. With equation 30 and the ideal gas law: ∆mix G = xA nRT ln xA + xB nRT ln xB = nRT (xA ln xA + xB ln xB ) (96) ∆mix G ≤ 0 from xJ ≤ 1 Lecture 13 & 14 ⇒ Ideal gases always mix.The Gibbs energy of mixing of ideal gases (3) Thermodynamics ∆mix G = Gf − Gi = ◦ nA (µ− A N H Nahler + RT ln pA ) + ◦ nB (µ− B + RT ln pB ) Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 Lecture 11 & 12 ◦ − ◦ − (nA (µ− A + RT ln p ) + nB (µB + RT ln p )) pA pB = nA RT ln + nB RT ln p p ◦ − ◦ ∆mix G is independent of µ− A and µB .nB Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 = −nR (xA ln xA + xB ln xB ) (97) Lecture 7 & 8 Extent of a reaction Equilibrium constant Le Chatelier’s principle Partial molar quantities Mixing of ideal gases Lecture 9 & 10 ∆mix S ≥ 0 Note that we derived the entropy of mixing using statistical thermodynamics (molecular view) in lectures 3 & 4 (see equ.

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8 pp. p ) For the pure liquid A: ∗ ∗ − ◦ ∗ µ∗ A = µA (l) = µA (g) = µA + RT ln pA Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 (* denotes pure substance) In the presence of a solute B: µA = ◦ µ− A + RT ln pA (99) Lecture 13 & 14 Combining the last two equations: ◦ ∗ ∗ µ− A = µA − RT ln pA ∗ µA = µ∗ A − RT ln pA + RT ln pA pA = µ∗ (100) A + RT ln ∗ pA . 127 – 134 and pp.3. Reading Chapter 6 The properties of mixtures sections 6.Chemical potential of liquids Thermodynamics N H Nahler How to calculate the chemical potential of a liquid. 6. Lecture 13 & 14 Vapour-liquid equilibrium At equilibrium. 140 – 142. 6.4.5 and 6. the chemical potential of a substance in the vapour phase must be equal to its chemical potential in the liquid: µA (l) = µA (g. ◦ Ideal gas µ = µ− + RT ln p (single component) ◦ µA = µ− A + RT ln pA (ideal gas in a mixture) Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Based on the equation of state: Vm = RT /p Liquid We cannot calculate µ because we do not know the equation of state.

benzene / toluene) that: ∗ pA = xA · pA N H Nahler Lecture 1 & 2 Raoult’s law (103) Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 The presence of a second component (B) reduces the rate at which A molecules leave the surface of the liquid but does not inhibit the rate at which they return. The average energies of the A – A. B – B and A – B interactions are the same in an ideal solution.Ideal solutions Thermodynamics It has been found for closely related substances (e. . They are NOT zero! Remember that there are no intermolecular forces in an ideal gas.g. Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 Vapour pressure diagram Mixtures that follow Raoult’s law throughout the composition range are ideal solutions or ideal mixtures. rate of vaporization = k · xA rate of condensation = k · pA At equilibrium: k · xA = k · pA k ⇒ p A = xA k ∗ For the pure liquid: pA = pA and xA = 1 k ∗ ∗ pA = ⇒ pA = xA · pA k Raoult’s law Binary mixture Raoult’s law is valid for both components in a binary mixture: ∗ pA = xA · pA ∗ and pB = xB · pB Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 With Dalton’s law of partial pressures ptotal = pA + pB we can construct a vapour-pressure diagram.

∗ Gi =nA µ∗ A + nB µB N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Gf =nA (µ∗ A + RT ln xA ) + nB (µ∗ B + RT ln xB ) The average energies of the A – A.nB (105) (106) (107) (108) Lecture 13 & 14 . Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 Summary of chemical potentials ◦ µ(g) = µ− (g) + RT ln p ◦ µA (g) = µ− A (g) + RT ln pA ideal gas ideal gas in a mixture component in an ideal solution µA (l) = µ∗ A (l) + RT ln xA Ideal solutions: Gibbs energy of mixing Thermodynamics The Gibbs energy of mixing two liquids to form an ideal solution is calculated in the same way as for two ideal gases. B – B and A – B interactions are the same but not zero. ∆mix G = nRT (xA ln xA + xB ln xB ) ≤ 0 ∆mix S = −nR (xA ln xA + xB ln xB ) ≥ 0 ∆mix H = 0 ∆mix V = ∂ ∆mix G ∂p =0 T .nA .Chemical potential of liquids (2) Thermodynamics N H Nahler From equations 100 and 103 follows: µA = µ∗ A + RT ln xA (104) Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 The presence of a solute B lowers the chemical potential of the solvent A.

B–B Vapour pressure is less than ideal case (negative deviation from Raoult’s law). Raoult’s law still applicable for real mixtures if the mole fractions are close to one. For example: Acetone / CS2 A–B more attractive than A–A. The solvent molecules (A) are in an environment that differs only slightly from that of the pure solvent. A–B less attractive than A–A. xA 1 pA * N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 As xA → 1. .Real mixtures: deviations from Raoult’s law Thermodynamics If the average A–A. The red ellipse in the top figure shows the ideal solution regime. B–B Vapour pressure is greater than ideal case (positive deviation from Raoult’s law). the partial pressure of A (solvent) approaches the value expected for an ideal mixture. B–B and A–B interactions are not equal then the concepts of the ideal mixture fail. For example: Acetone / Chloroform N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 Behaviour close to pure substances Thermodynamics Pressure Real Ideal solution (Raoult) 0 Mole fraction of A.

97 × 104 12. However. ⇒ Raoult’s law Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 Henry’s law constants in water at 298 K K / atm O2 He Ne Ar 4. . Ideal-dilute solutions Thermodynamics N H Nahler 1 The solvent molecules (A) are in an environment that differs only slightly from that of the pure solvent.259 × 104 14. ⇒ Henry’s law The Henry’s law constant KB depends on the nature of substance A.955 × 104 The solute molecules (B) are in an environment totally unlike that in the pure substance (almost only B–A interactions). oxygen or anaesthetics in blood). xB 1 pB * Mixtures for which the solute (B) obeys Henry’s law and the solvent (A) obeys Raoult’s law are called ideal-dilute solutions.30 × 104 3.g. the constant of proportionality is not the vapour pressure of the pure substance but the Henry’s law constant (KB ): p B = xB K B (109) N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 Real Ideal solution (Raoult) 0 Mole fraction of B.Behaviour at small mole fractions: Henry’s law Thermodynamics Pressure Ideal dilute solution (Henry) KB For real mixtures the vapour pressure of the solute (B) is often proportional to its mole fraction. 2 Henry’s law is used for calculating the amounts of gas dissolved in liquids (e.

Examples of real liquid mixtures Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 ∗ K B > pB ∗ K A > pA ∗ KB < pB ∗ KA < pA Unfavourable A–B interactions Favourable A–B interactions Chemical potential of a non-ideal liquid mixture How can we calculate the chemical potential of a component in a non-ideal liquid mixture? Ideal-dilute solution (Henry) KB Thermodynamics N H Nahler Lecture 1 & 2 Ideal solution regime: pB = pB µB (l) = µ∗ B (l) + RT ln ∗ pB = µ∗ B (l) + RT ln xB ∗ xB pB Pressure Non- ideal pB * Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 (110) 0 Ideal solution (Raoult) Mole fraction of B. xB 1 ∗ Ideal-dilute solution regime: pB = xB KB µB (l) = µ∗ B (l) + RT ln pB KB ∗ = µ (l) + RT ln B ∗ ∗ +RT ln xB pB pB new standard state (111) General non-ideal liquid mixture Trick: We take the equation for the ideal mixture and replace xB with the activity (or effective mole fraction aB ). µB (l) = µ∗ B (l) + RT ln aB (112) .

The composition of the vapour phase is the same as for the original liquid phase. Point c (dew-point line): 1 phase present (vapour). Vapour pressure diagrams Phase rule F =C −P +2 Gibbs phase rule (116) F : Variance. ∗ µB = µ∗ B + RT ln aB = µB + RT ln xB + RT ln γB ideal mixture correction term (115) The activity coefficient varies with p . More volatile component dominates in the vapour phase. T . ∗ ∗ ∗ ptotal = pA + pB = pB + pA − pB xA Point a: 1 phase present (liquid) Point b (bubble-point line): Evaporation starts (2 phases). aB → xB and hence γB → 1 (ideal solution regime). C : Components. Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 . and the mole fraction. xB 1 Activity and mole fraction aB = γB · xB (114) Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 Ideal mixtures: γB = 1 Non-ideal mixtures: γB < 1 or γB > 1 As xB → 1.Activity ideal pB * Activity and pressure aB = pB ∗ pB (113) Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Pressure Non- pB aB = p * B 0 Mole fraction of B. P : Phases in equilibrium A binary mixture (C = 2) for which we keep the temperature constant: F = 3 − P . Degrees of freedom are then the pressure and the composition.

ptotal ∗ ∗ · pB pA = ∗ (118) ∗ − p∗ y pB + pA A B The lever rule Vertical line: isopleth constant composition Horizontal lines in 2-phase region: tie lines nα lα = nβ lβ Lever rule (119) Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 . yA = pA ptotal ∗ pB Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 yB = 1 − yA + ∗ (pA Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 ptotal = − ∗ pB ) xA ∗ pA = xA · pA It follows: ∗ xA · p A yA = ∗ ∗ − p∗ x pB + pA A B Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 (117) The vapour is richer in the more volatile component.Composition of the vapour Question: At which pressure is the dew-line crossed? We need to know ptotal = f (yA ) where yA is the mole fraction of A in the vapour phase.

Temperature-composition diagrams Thermodynamics A phase diagram can be used to discuss the process of fractional distillation. Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 Vapour phase diagram Example: hexane/heptane mixtures (1) Thermodynamics 1 Label the regions of the phase diagrams as to which phase(s) is (are) present. the boiling and condensation cycle is repeated successively. N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Fractional distillation In a simple condensation the vapour is withdrawn and condensed. We change the y-axis in the phase diagram: p → T with p = const. In fractional distillation. Note that the liquid phase is now in the lower part of the diagram. heptane: 100 ◦C How would you obtain pure heptane? A few steps depending on initial mixture Infinite number of steps N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 2 3 4 . Most volatile component? hexane heptane What are the boiling temperatures of pure hexane and heptane? hexane: 100 ◦C. heptane: 65 ◦C hexane: 65 ◦C.

Examples: acetone / chloroform or nitric acid / water Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 . A–B interactions stabilise the liquid. If deviations are significant enough: Vapour pressure exhibits minimum (temperature maximum). Fractionation by distillation not possible.3 if half of the liquid phase is vaporised during each distillation step? 4 5 6 Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 2 Negative azeotropes A–B more attractive than A–A.8 ? 1 2 3 What is the number of plates required to go from xheptane = 0.3 from a mixture with xheptane = 0.Vapour phase diagram Example: hexane/heptane mixtures (2) Thermodynamics N H Nahler 1 What is the number of ’theoretical plates’ required to obtain a mixture with xheptane = 0. Azeotrope: Evaporation occurs without change in composition (xA = yA ). B–B Vapour pressure is less than ideal case (negative deviation from Raoult’s law).8 to xheptane = 0.

Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Chemical potential of liquids Ideal solutions Ideal-dilute solutions Henry’s law Activity Phase diagrams Azeotropes Lecture 11 & 12 Lecture 13 & 14 Chemical potential of gases and liquids µ(g) = µ (g) + RT ln ideal gas − ◦ p ◦ p− µ(g) = µ (g) + RT ln real gas − ◦ f ◦ p− µA (g) = µA (g) + RT ln pA ideal gas in a mixture − ◦ µA (l) = µA (l) + RT ln ∗ pA ∗ pA component in a liquid mixture µA (l) = µA (l) + RT ln xA ideal liquid mixture and ideal solution regime ∗ µB = µB id. Examples: ethanol / water or dioxane / water Not possible to obtain pure ethanol by distillation of ethanol / water mixtures. B–B Vapour pressure is greater than ideal case (positive deviation from Raoult’s law).-dil. A–B interactions destabilise the liquid. + RT ln xB µA = µA + RT ln aA non-ideal liquid mixture ∗ ideal-dilute solution regime .Positive azeotropes A–B less attractive than A–A. If deviations are significant enough: Vapour pressure exhibits maximum (temperature minimum).

5 295.0624 0.5 62.1 652.0 654.8 331.1212 0.7 505.9191 0.7 492.0 512.4 447.9 634.9 490.6 419.5702 0.5 564.3 pacetone (Torr) 343.8 441.1857 0.0 512.3 .0 313.5 232.7 379.7 191.6 207.7220 0.9407 0.2 254.0 0 ptotal (Torr) 343.8 602.6 645.4 274.8280 0.4 328.4 103.2 123.9692 1 pCS2 (Torr) 0 110.2869 0.1 180.1 614.Henry’s law constant of a CS2 / acetone mixture at 298 K xCS2 0 0.5 464.1 595.4058 0.2 553.7 258.0 502.

1 and 9. nB divided by the volume of the solution. You may want to refer to chapter 10 to revise the protonation and deprotonation in acid/base solutions. Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 Molality The molality.Electrolyte solutions Thermodynamics What is different in electrolyte solutions? The solute dissociates into ions. nB divided by the mass of solvent A used to prepare the solution: nB bB = (121) mA Units of bB are mol·kg−1 and often denoted as 1 m = 1 mol·kg−1 Mole fraction The third quantity measuring concentration is the mole fraction. Measures of concentration Molar concentration The molar concentration is commonly called molarity. nB to the total amount of the solution n: nB xB = (122) n . 193 – 200. The unit 1 mol·cm−3 is also reported as 1 M and read ’molar’. The ions experience long-range interaction (Coulomb interaction) Solutions of a single ion (positive or negative) cannot be prepared. How do we determine the chemical potential and equilibrium of an electrolyte solution? N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 Reading Chapter 9 Chemical equilibrium: electrochemistry sections 9. Note that the volume V is the total volume of the solution not just of the solvent. V : nB cB = (120) V Units of cB are mol·cm−3 or commonly mol·L−1 . cB of a solute B in a solution is the amount of B. The molar concentration. bB of a substance B in a solution is the amount of B. xB (unitless) relating the amount of B.2 pp.

mole fraction Variation with temperature Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Variation with mole fractions Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 Standard states Ions in solutions Note: Unless stated otherwise we discuss aqueous solutions at a temperature of 25 ◦C. molality. AB(s) − A+ aq + Baq Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 (C 10) .Molar concentration. Greater electrical conductivity compared to non-electrolyte. Acetic acid is a weak electrolyte → partially ionised. Example: NaCl is a strong electrolyte → completely ionised. Thermodynamics N H Nahler Solutions of electrolytes Components are ionised to some degree in solution.

µi of the solution in respect of activity: µi = ◦ µ− i Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 + RT ln ai (123) where the activity. ai is defined in respect of the molality and activity coefficient: ai = γi · bi (124) Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 Mean quantities p q s s s Ionic activity ai = a± = a+ · a− = γ± · b± p q Mean ionic molality b± = b+ · b− 1/s s± = (p p · q q ) 1/s = s± · bi with . Opposing charges attract each other while same charges repel each other. Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Activity and chemical potential We define the chemical potential. all measurements on the solution will lead to mean quantities including cations and anions. Electrolyte Strong long-range Coulombic interactions.01m aqueous solution of Mg3 (PO4 )2 Mean ionic activity coefficients (1) Our solution is always composed of cations and anions. Example: 0.Interactions and molality Interactions Non-electrolyte Weak short-range interactions often only van-der-Waals. Consequently. Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 Molality Consider the solvation of a general strong electrolyte dissociating by the equation: Mp Xq (s) z+ z− pMaq + qXaq (C 11) This solution will behave as a solution of molality (p + q )bMp Xq where bMp Xq is the nominal molality of the solution.

02 m solution of ZnCl2 How can we determine the mean ionic activity coefficient. Shielded ions have a lower energy (chemical potential) than unshielded ions in an ideal solution (γ < 1). Note that the DHLL uses log x = log10 x rather than ln x . Debye-H¨ uckel theory How can we calculate mean activity coefficients? Debye-H¨ uckel theory: assumptions Ions in solution are surrounded by an ionic atmosphere of counter charges.509 for water at 25 ◦C. I = (127) Lecture 13 & 14 .Mean ionic activity coefficients (2) Mean quantities Thermodynamics Mean ionic activity coefficient q p · γ− γ± = γ+ 1/s N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 (125) Chemical potential ◦ µi = µ− i + sRT ln (γ± · s± · bi ) ◦ With the arithmetic mean µ− i = p µ+ + q µ− Lecture 7 & 8 (126) Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 Example: bi = 0. In general A ∝ ( r T )−3/2 . The mean activity coefficient depends on the solution (dielectric constant) and the temperature. Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Debye-H¨ uckel limiting law (DHLL) log γ± = −A|z+ · z− |I 1/2 With the ionic strength 1 2 2 ◦ z+ pbi + z− qbi /b − (128) 2 And the constant A = 0. γ± ? Due to the strong Coulombic interactions an approach similar to Henry’s law will even fail for dilute solutions. proportional to the dielectric constant r and the temperature T .

..51|z+ · z− | I √ − 0. For the specific case of aqueous solutions at room temperature this is often expressed as the Davies equation: log γ± = −0. Extended Debye-H¨ uckel law (1) Thermodynamics The Debye-H¨ uckel limiting law (DHLL) only applies for dilute solutions. When concentrations exceed 1 × 10−3 mol·dm−3 ion-ion interactions become even more important and it is better to use the empirical . Myron Kaufman The linear fits are according to the Debye-H¨ uckel limiting law. N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Extended Debye-H¨ uckel law A|z+ · z− |I 1/2 log γ± = − + CI 1 + BI 1/2 (129) Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 where B and C are dimensionless parameters.Measured mean ionic activity coefficients Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 from: Principles of Thermodynamics.30I 1+ I √ (130) .

Myron Kaufman It can be seen that γ± usually increases for higher concentrations and may then even exceed 1. in disagreement with the Debye-H¨ uckel theory.05 m HCl solution Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 .Extended Debye-H¨ uckel law (2) Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 from: Principles of Thermodynamics. This happens due to: Example: activity of a 0.

25 ◦C Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 .0 m acetic acid solution.Example: pH of a 0.05 m HCl solution pH = − log aH+ (131) Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 Example: pH of a 1.

A. L and inversely proportional to the cross-sectional area.00 Example: acidity constant from the conductivity Question: The molar conductivity of 0.60 Anions OH – Cl – – NO3 2– SO4 19. 1/2 Λm = Λ◦ m − κc Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 (133) Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 Limiting molar conductivity Λ◦ m = λ+ + λ− (134) Ionic conductivities λ+ and λ− in mS·m2 ·mol−1 Cations H+ Na+ K+ Mg 2+ 34. pKa of acetic acid (weak acid)? Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 . What is the acidity constant.91 7.01 7.Molar conductivity Molar conductivity in respect to concentration: κ (132) Λm = c Empirical Kohlrausch law for strong electrolytes (fully dissociated into ions): Resistance U ρL = I A Proportional to the length of sample.01 mol·dm−3 CH3 COOHaq is 1. R= Conductivity κ = ρ−1 which is expressed in Ω−1 ·m−1 or S·m−1 where 1 S = 1 Ω−1 .65 mS·m2 ·mol−1 .96 5.35 10.15 16.64 7.

Mobility of H+ and H3 O+ in aqueous solution.g.19 Cl 7.23 ·10−8 m2 ·s−1 ·V−1 . a lower viscosity of the solution. Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 A higher charge. u u= ez 6πη a (135) Ionic mobilities in water at 298 K in 10−8 m2 ·s−1 ·V−1 Cations Anions + H 36. η . their hydrodynamic radius decreases due to decreasing hydration. 25 ◦C u (H+ (H3 O+ )) = 36. Proton mobility in water Thermodynamics A very important exception from the ionic mobility based on the size of the ion is the very high proton mobility in water. we need to consider an effective radius including the entire object (e.50 SO4 8.41 2+ 2– Mg 5.Ionic mobility Drift velocity Ions travelling through a solution with an external electric field E will settle into a limiting velocity defined by the acceleration caused by the electric field and a deceleration caused by the viscosity of the solution.64 + – Na 5.92 + – K 7. The proton travels along a chain of H2 O molecules. lead to a higher mobility of the ion in solution. This is down to a very different mechanism for conduction: N H Nahler Lecture 1 & 2 Lecture 3 & 4 Grotthus mechanism The proton travels from one H2 O molecule to the next and from there to the next. a. and a smaller radius of the ion.23 OH – 20. It is an effective motion. Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Concentration Ionic solutions Debye-H¨ uckel theory Ionic equilibrium Migration of ions Lecture 13 & 14 The proton motion is not a real motion of a single proton through the aqueous solution. Ionic mobility. with hydrating water molecules).62 NO3 7. Although the radius increases for Group 1 cations down the group.29 Rather than using the pure radius of the ion in question. z . This is called the hydrodynamic radius.

two electronic conductors (metal or graphite) dipping into .Equilibrium electrochemistry Electrochemical cells Electrochemical potential = Chemical potential + Electrostatic potential Different types of electrodes Combination of electrodes form electrochemical cells Thermodynamic data from electrochemical cells Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Applications Batteries: Car starter batteries Batteries: Li-Ion cells Fuel cells Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications Reading Chapter 9 Chemical equilibrium: electrochemistry sections 9. . an electrolyte (ionic conductor) two electrodes made by the conductor and its surrounding electrolyte The electrodes may be in two different electrode compartments (left figure) where a salt bridge (or membrane) allows ion flow across the electrodes. 200 – 210.9 pp. The electrodes may share the same electrolyte (right figure). N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications . . Electrochemical cells Thermodynamics Electrochemical cell consists of . .3 and 9. .

M. Metal electrode as source/sink of electrons. Supplies electrons to the circuit. anode is connected to positive terminal as electrons need to be withdrawn. Solution contains X− ions. M. Higher potential. When connected to an external power supply. Hydrogen electrode: Pt(s)|H2 (g)|H+ (aq) N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Metal-insoluble salt electrode Metal electrode. Electric neutrality is preserved by cations and anions travelling in opposite directions (salt bridge or directly to electrodes). with Ox and Red in solution. M|MX|X – Example: Ag(s)|AgCl(s)|Cl – (aq) Lecture 11 & 12 Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications Redox electrode Inert metal electrode. covered with insoluble salt. Cathode Where reduction takes place. MX. Ox + ν e − Red with Q = aRed /aOx Example: Pt(s)|Fe 2+ (aq)|Fe 3+ (aq) .Electrodes (1) Thermodynamics Anode Where oxidation takes place. N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications Electrodes (2) Gas electrode Thermodynamics Gas in equilibrium with its ions in solutions. Often a catalyst. Opposite for cathode.

Electrode concentration cell Different electrode concentrations e. oxidation. A double vertical bar denotes an interface without junction potential (membrane. oxidation: Zn(s) Zn 2+ (aq) + 2 e – Cathode. A vertical bar denotes an interface between phases. reduction: Cu 2+ (aq) + 2 e – Overall reaction: Zn(s)+Cu 2+ (aq) Cu(s) Zn 2+ (aq)+Cu(s) Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications . Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications Electrolytic cell Non-spontaneous reaction is driven by external DC source. Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Daniell cell The two electrodes consist of copper in contact with copper(II)sulfate solution and zinc in contact with zinc sulfate solution. different pressures at gas electrodes. Examples: dry cells. Fuel cell Is a galvanic cell where the reagents are continuously supplied from the outside. Anode. salt bridge). mercury cells. Right side: Cathode.g. The two electrodes are separated by a porous membrane. nickel-cadmium and lithium ion cells. Electrolyte concentration cell Same electrolyte in both electrode compartments but different concentrations. Produces electricity as a result of the spontaneous reaction happening inside. Reagents: H2 + O2 or 2 CH3 OH + 3 O2 Cell types (2) Cell notation Pt(s)|H2 (g)|HCl(aq)|AgCl(s)|Ag(s) Zn(s)|ZnSO4 (aq)||CuSo4 (aq)|Cu(s) Left side: Anode. reduction.Cell types (1) Galvanic cell Also called voltaic cell.

− ◦ If Ecell > 0 then K > 1 − ◦ If Ecell < 0 then K < 1 ⇒ ⇒ products favoured reactants favoured Example: − ◦ The standard potential of the Daniell Cell is EDaniell = +1. p = const. ν electrons are exchanged. The electric work w performed by this charge travelling to the cathode in an electric field Ecell is −ν · e · NA · Ecell . Q . K . What is the equilibrium constant? . It allows us to measure and calculate equilibrium constants of most reactions involving ions. the charge of 1 mol of H+ : F = e · NA = 96 485 C·mol−1 Useful: At room temperature we can calculate RT /F = 0.) follows: ∆r G = −ν eNA Ecell (136) Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications Nernst equation − ◦ Ecell = Ecell − RT ln Q νF (137) with the Faraday constant.0257 V Cells at equilibrium An electrochemical cell at equilibrium fulfils ∆r G = 0 and the reaction quotient. With wmax = ∆G (T .10 V.Cell potential How can we relate the work performed by an electrochemical cell with the Gibbs energy? When the redox reaction is balanced. Using equations 136 and 137 we derive: − ◦ 0 = Ecell − − ◦ ν FEcell ln K = RT Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 RT ln K νF (138) Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications We will see that this important relationship does not only allow us to calculate equilibrium constants of electrochemical cells. is replaced by the equilibrium constant. Therefore for one mole of reactants ν NA electrons are exchanged with a charge of ν (−e )NA .

Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications Standard hydrogen electrode (SHE) Pt(s)|H2 (g)|H+ (aq) Or: 2 H+ + 2 e – H2 ◦ E− = 0 at all T ◦ E− = 0 at all T The standard potential for the SHE is defined as zero and provides a reference for all other standard potentials of half-reactions. Example: standard potentials Rules Standard potentials are added up similar to Hess’s law where you have to take the stochiometry into account. Reverse the sign to obtain the standard reduction potential. Note: In older sources you will find the standard oxidation potential. Zn 2+ + 2 e – Zn If we define a reference half cell then we can measure all other half cells in respect to that standard half cell. The number of electrons in the overall reaction need to be balanced. The standard (reduction) potential of the individual half cells cannot be independently measured e.g.Standard Potentials Measuring of cell potentials A galvanic cell is made-up from two half cells which both contribute to the overall cell potential. In general the standard potential of the galvanic cell is the difference between the right cell (reduction) and the left cell (oxidation): − ◦ − ◦ − ◦ = ER − EL (139) Ecell Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications Ag(s)|AgBr(s)|NaBr(aq)||NaCl(aq)|Cl2 (g)|Pt(s) .

∆r G − .10 and 9.11) . Ecell . and standard ◦ free energy. 9. Thermodynamics Cell: Cu(s)|CuCl2 (aq)|AgCl(s)|Ag(s) N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications Equilibrium constants and activities Standard formation energies (see example) Equilibrium constants (see example) Activity coefficients: from accurate measurement (or table) of ◦ E− and then a measurement of E as a function of concentration of the cell electrolyte yields the reaction quotient Q (Nernst equation). Enthalpy and entropy: E ∂ ∂ (T −1 ) T − ◦ − ◦ Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications ◦ ∆r H − = −ν F (140) p ◦ ∆r S − = ∆r H − ∆r G T ∂ ∆r G =− = νF ∂T p ◦ ∂E − ∂T (141) p Determination of pH (Atkins.− ◦ Example: standard potential. Elements of Physical Chemistry.

Example: Standard formation energy Thermodynamics ◦ ∆f G − (Cl− ) from the Pt|H2 (g)|HCl(aq)|Cl2 (aq)|Pt cell N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications Example: Equilibrium constant Equilibrium constant of the disproportionantion reaction 2 Cu+ (aq) Cu(s) + Cu 2+ (aq) at 298 K Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications .

Electrodes: Pb powder. . The energy density is 15 times larger than that of a lead storage battery. Electrolyte: concentrated H2 SO4 .04 V Typically six cells are used in series (12 V).7 V Li has a low atomic mass making for light batteries.Car starter battery Why are they still used? The lead-sulfuric acid cell has a standard potential of 2. They made the progress of laptops. Anode LiCoO2 (s) Li1-n CoO2 (s) + ne – CLix Li1-n CoO2 (s) + CLix Cathode C(s) + nLi+ + ne – Overall LiCoO2 (s) + C(s) Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications Li-ion batteries belong to the group of rechargeable secondary cells. PbO and PbSO4 supported on a Pb frame. Li-ion batteries are also used as energy storage in hybrid cars. Can provide high current (up to 100 A required). mobile phones and tablet computers possible. 500–1500 full recharge cycles. 2– Anode Pb(s) + SO4 (aq) PbSO4 (s) + 2 e – 2– Cathode PbO2 (s) + 4 H+ (aq) + SO4 + 2e – PbSO4 (s) + 2 H2 O(l) Overall PbO2 (s)+Pb(s)+2 H2 SO4 2 PbSO4 (s)+2 H2 O(l) Thermodynamics N H Nahler Lecture 1 & 2 Lecture 3 & 4 Lecture 5 & 6 Lecture 7 & 8 Lecture 9 & 10 Lecture 11 & 12 Lecture 13 & 14 Electrochemical cells Electrodes Cell potentials Measurement of thermodynamic properties Applications Pb|PbSO4 (s)|H2 SO4 (aq)|PbSO4 (s)|PbO2 (s)|Pb Laptops and electric cars: Li-Ion cells Thermodynamics N H Nahler Why are they so popular? High cell potential: 3.